CN112744798B - Production method of high-water-solubility monoammonium phosphate - Google Patents
Production method of high-water-solubility monoammonium phosphate Download PDFInfo
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- CN112744798B CN112744798B CN202011583245.3A CN202011583245A CN112744798B CN 112744798 B CN112744798 B CN 112744798B CN 202011583245 A CN202011583245 A CN 202011583245A CN 112744798 B CN112744798 B CN 112744798B
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Abstract
The invention provides a production method of high-water-solubility monoammonium phosphate, which comprises the following steps: a) Mixing phosphoric acid and a chelating agent, and reacting to obtain acid liquor; b) Taking part of the acid liquor obtained in the step A), introducing ammonia gas for reaction, and neutralizing until the pH value is 4.0-5.0 to obtain neutralized slurry; c) Adding the neutralized slurry into the residual acid liquor to obtain mixed slurry with the pH value of 1.0-3.0; d) And continuously introducing ammonia gas into the mixture to neutralize until the pH value is 4.0-4.5, and drying to obtain a monoammonium phosphate product. The method for preparing the monoammonium phosphate comprises the steps of neutralizing the part, added with the phosphoric acid dissolved with a small amount of the chelating agent, and then adding the rest phosphoric acid dissolved with a small amount of the chelating agent to perform reverse adjustment to reduce the pH value of the monoammonium phosphate slurry.
Description
Technical Field
The invention belongs to the technical field of fertilizer preparation, and particularly relates to a production method of high-water-solubility monoammonium phosphate.
Background
Most of the high water-solubility water-soluble fertilizer monoammonium phosphate is produced by adopting a wet-process phosphoric acid ammonia introduction neutralization impurity removal process, namely an industrial grade monoammonium phosphate production process. The wet-process phosphoric acid can produce the high-water-solubility water-soluble fertilizer monoammonium phosphate by main process flows of desulfurization pretreatment, neutralization impurity removal, phosphoric acid concentration, monoammonium phosphate crystallization and the like. The process flow is complex, the requirement on equipment is high, and particularly the separation of neutralized filter residue and the crystallization of monoammonium phosphate. 0.4-0.6 ton of fertilizer grade monoammonium phosphate can be produced when 1 ton of industrial grade monoammonium phosphate is produced, the total nutrient content of the fertilizer grade monoammonium phosphate is low, the caking property is strong, the packaging, the storage and the transportation are not facilitated, and the integral utilization rate of the fertilizer grade monoammonium phosphate is low. Under the environmental protection pressure in the future, fertilizer grade monoammonium phosphate may face the risk of being eliminated.
If wet-process phosphoric acid is directly used for producing water-soluble fertilizer monoammonium phosphate without impurity removal treatment, the defects are as follows: low total nutrient content of the product, low comprehensive utilization rate of phosphorus, strong caking property, high content of water-insoluble substances (G4), and the like. In addition, in the production process, because the insoluble phosphate generated by the metal impurities and the phosphoric acid has the characteristics of high viscosity and the like, the monoammonium phosphate slurry has poor fluidity and is not beneficial to the transportation and drying of the slurry.
In the phosphate fertilizer and compound fertilizer product, namely, the product upgrading is realized by reducing the content of the water-insoluble substance of monoammonium phosphate in volume 34 of first phase Europe in 1 month in 2019, citric acid or EDTA is selected as a complexing agent, the addition amount of the citric acid or EDTA is 80kg/t and 50kg/t respectively, the content of the water-insoluble substance of the product can be controlled to be below 5 percent, but the cost is increased by 400-600 yuan/t, and the cost of the raw materials is obviously increased.
Chinese patent CN111662098A discloses a monoammonium phosphate suspension containing medium and trace elements and a preparation method thereof. The method comprises the following steps: a. carrying out chelation reaction: mixing concentrated phosphoric acid with a chelating agent and a suspending agent, heating to 50-120 ℃, stirring and reacting for 30-60 min to obtain a chelated solution; wherein, the concentrated phosphoric acid contains medium trace elements; b. ammoniation reaction: introducing ammonia gas into the chelated solution until the pH value is 4.0-5.5, and reacting at the constant temperature of 80-120 ℃ for 20-60 min to obtain high-temperature monoammonium phosphate feed liquid containing medium and trace elements; c. cooling and forming: and cooling the high-temperature monoammonium phosphate feed liquid containing the medium trace elements to obtain the monoammonium phosphate suspended fertilizer containing the medium trace elements. The chelating agent selected by the invention is ethylenediamine tetraacetic acid or citric acid, the dosage of the chelating agent is large, the cost is high, the water insoluble content in the final product is still at a high level, and the concentration of phosphorus pentoxide (in weight percentage) in wet-process phosphoric acid is diluted due to the large dosage of the chelating agent, so that the total nutrient of the water-soluble fertilizer is low.
Disclosure of Invention
The invention aims to provide a production method of high-water-solubility monoammonium phosphate, which is a method for neutralizing part of added phosphoric acid dissolved with a small amount of chelating agent and then adding the rest phosphoric acid dissolved with a small amount of chelating agent to perform reverse adjustment to reduce the pH value of monoammonium phosphate slurry, so that water insoluble substances (G4) in water-soluble monoammonium phosphate directly produced from wet-process phosphoric acid can be controlled within 1 percent, the total nutrient is high, and the requirements of macroelement water-soluble fertilizer standards (NY/T1107-2020) can be met.
The invention provides a production method of high-water-solubility monoammonium phosphate, which comprises the following steps:
a) Mixing phosphoric acid and a chelating agent, and reacting to obtain acid liquor;
b) Taking part of the acid liquor obtained in the step A), introducing ammonia gas for reaction, and neutralizing until the pH value is 4.0-5.0 to obtain neutralized slurry;
c) Mixing the neutralized slurry with the residual acid liquor to obtain mixed slurry with the pH value of 1.0-3.0;
d) And continuously introducing ammonia gas into the mixture to neutralize until the pH value is 4.0-4.5, and drying to obtain a monoammonium phosphate product.
Preferably, the phosphoric acid is wet-process phosphoric acid;
p in the phosphoric acid 2 O 5 The mass fraction of (A) is 20-38%.
Preferably, the chelating agent is one or more of ammonium formate, polyamino polyether methylene phosphonic acid, 2-phosphonobutane-1,2,4 tricarboxylic acid and diethylenetriamine pentaacetic acid;
the dosage of the chelating agent is 5-15 kg/t of monoammonium phosphate product.
Preferably, the reaction temperature of the step A) is 20-110 ℃; the reaction time of the step A) is 20-60 min.
Preferably, the reaction temperature in the step B) is 80-120 ℃, and the reaction time is 20-80 min.
Preferably, the mass of the partial acid liquid in the step B) is 45-65% of that of the acid liquid in the step A).
Preferably, in the step D), after neutralization, atomization and drying are sequentially performed to obtain a monoammonium phosphate product.
Preferably, the air inlet temperature for atomization is 150-180 ℃; the air outlet temperature is 80-110 ℃.
Preferably, the drying temperature is 50-80 ℃, and the drying time is 30-180 min.
The invention provides a production method of high-water-solubility monoammonium phosphate, which comprises the following steps: a) Mixing phosphoric acid and a chelating agent, and reacting to obtain acid liquor; b) Taking part of the acid liquor obtained in the step A), introducing ammonia gas for reaction, and neutralizing until the pH value is 4.0-5.0 to obtain neutralized slurry; c) Adding the neutralized slurry into the residual acid solution to obtain mixed slurry with the pH value of 1.0-3.0; d) And continuously introducing ammonia gas into the mixture to neutralize until the pH value is 4.0-4.5, and drying to obtain a monoammonium phosphate product. The invention prepares the monoammonium phosphate by adding the phosphoric acid part dissolved with a small amount of chelating agent for neutralization, then adding the residual phosphoric acid dissolved with a small amount of chelating agent for back regulation to reduce the pH value of the monoammonium phosphate slurry, and the action principle is as follows: the insoluble phosphate is increased along with the increase of the pH value of the monoammonium phosphate slurry, the chelating effect of the chelating agent is close to the limit by neutralizing most of the phosphoric acid to the pH value of 4.0-5.0, and the generated insoluble phosphate is further dissolved because the added phosphoric acid can reduce the pH value of the monoammonium phosphate slurry system after the chelating agent is added. The phosphoric acid with the chelating agent continues to act, so that the generation of insoluble phosphate is greatly reduced in the subsequent neutralization process, and the content of water-insoluble substances in the monoammonium phosphate is well controlled. On the other hand, the reaction mechanism is changed due to the change of the neutralization mode of the monoammonium phosphate slurry, the pH value of the raw monoammonium phosphate slurry is a gradually rising process, and the generated precipitate is determined. By controlling the pH value of the monoammonium phosphate slurry to rise firstly, then reduce and rise secondly, most of the finally generated precipitate is dissolved in water, and the water solubility of monoammonium phosphate is ensured. The water solubility of the monoammonium phosphate produced by the method is far higher than that of the monoammonium phosphate obtained by direct neutralization. The verification proves that: the water insoluble substance (G4) in the monoammonium phosphate produced by adopting the mode of reversely adjusting the pH value can be controlled within 1 percent, and the water insoluble substance (G4) in the monoammonium phosphate produced by adopting the mode of directly neutralizing is 2 to 5 percent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a water solubility test of monoammonium phosphate prepared in examples 1 and 2 of the present invention, the left figure is the monoammonium phosphate in example 1, and the right figure is the monoammonium phosphate in example 2;
FIG. 2 is a water solubility test of monoammonium phosphate prepared in examples 3 and 4 of the present invention, the left graph is the monoammonium phosphate in example 3, and the right graph is the monoammonium phosphate in example 4;
FIG. 3 is a water solubility test of monoammonium phosphate prepared in examples 5 and 6 of the present invention, the left graph showing the monoammonium phosphate in example 5, and the right graph showing the monoammonium phosphate in example 6;
FIG. 4 is a water solubility test of monoammonium phosphates prepared in comparative example 1 and comparative example 2 of the present invention, the left figure being the monoammonium phosphate in comparative example 1, and the right figure being the monoammonium phosphate in comparative example 2;
FIG. 5 is a water solubility test of monoammonium phosphate prepared in comparative example 3 of the present invention.
Detailed Description
The invention provides a production method of high-water-solubility monoammonium phosphate, which comprises the following steps:
a) Mixing phosphoric acid and a chelating agent, and reacting to obtain acid liquor;
b) Taking part of the acid liquor obtained in the step A), introducing ammonia gas for reaction, and neutralizing until the pH value is 4.0-5.0 to obtain neutralized slurry;
c) Adding the neutralized slurry into the residual acid liquor to obtain mixed slurry with the pH value of 1.0-3.0;
d) And continuously introducing ammonia gas into the mixture to neutralize until the pH value is 4.0-4.5, and drying to obtain a monoammonium phosphate product.
In the present invention, the phosphoric acid is preferably wet-process phosphoric acid, in which P is present in the wet-process phosphoric acid 2 O 5 The mass fraction of (A) is 20-38%.
In the present invention, the chelating agent complexes with the metal cation to form a stable water-soluble complex, thereby reducing the water-insoluble content of the product. Particularly, the chelating agent is added into phosphoric acid before ammonia gas is neutralized, so that the chelating agent can fully exert the effect of chelating metal cations, and the generation of insoluble phosphate or citrate soluble phosphate is greatly reduced.
In the invention, the chelating agent is one or more of ammonium formate, polyamino polyether methylene phosphonic acid, 2-phosphonic butane-1,2,4 tricarboxylic acid and diethylenetriamine pentaacetic acid; the chelating agent is used in an amount of 5 to 15kg/t of the monoammonium phosphate product, more preferably 10 to 15kg/t of the monoammonium phosphate product, such as 5kg/t of the monoammonium phosphate product, 6kg/t of the monoammonium phosphate product, 7kg/t of the monoammonium phosphate product, 8kg/t of the monoammonium phosphate product, 9kg/t of the monoammonium phosphate product, 10kg/t of the monoammonium phosphate product, 11kg/t of the monoammonium phosphate product, 12kg/t of the monoammonium phosphate product, 13kg/t of the monoammonium phosphate product, 14kg/t of the monoammonium phosphate product, and 15kg/t of the monoammonium phosphate product, preferably within a range having any of the above values as an upper limit or a lower limit.
The type and amount of chelating agent added can directly affect the total nutrient and water insoluble content of the monoammonium phosphate product. When the conventional chelating agent citric acid or EDTA is selected, if the addition amount of the chelating agent citric acid or EDTA is less, the water insoluble matter content of the monoammonium phosphate product is still at a higher level; if the addition amount is more, the cost is increased, and the phosphoric acid is diluted, so that the total nutrient of the monoammonium phosphate product is reduced more. The unconventional chelating agent used in the invention can avoid the defects of the conventional chelating agent, the dosage of the unconventional chelating agent is small, and the dosage of the compounded chelating agent is 5 kg/t-15 kg/t, so that the content of the water insoluble substances in the monoammonium phosphate product can be reduced.
In the present invention, the temperature of the reaction, i.e., the temperature of the wet-process phosphoric acid, is preferably 20 to 110 ℃, preferably 30 to 100 ℃, such as 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ and 110 ℃, and is preferably a range value having any of the above values as an upper limit or a lower limit. The reaction time is preferably 20 to 60min, more preferably 30 to 50min, such as 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, and preferably any of the above values is used as an upper limit or a lower limit.
After the acid liquor is obtained, preferably, part of the acid liquor is taken and introduced with ammonia gas for neutralization reaction until the pH value is 4.0-5.0, so as to obtain neutralized slurry.
According to the invention, ammonia gas is preferably introduced into 45-65% of the total mass of the acid solution, preferably 50-60%, such as 45%, 50%, 55%, 60%, 65%, and preferably a range value with any value as an upper limit or a lower limit.
In the present invention, the neutralization reaction temperature of the partial acid solution is preferably 80 to 120 ℃, more preferably 90 to 110 ℃, such as 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ and 120 ℃, and is preferably a range value having any of the above values as an upper limit or a lower limit. The time for the neutralization reaction of the partial acid solution is preferably 20 to 80min, more preferably 30 to 70min, such as 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min and 80min, and is preferably a range value taking any value of the above as an upper limit or a lower limit.
And then adding the obtained neutralized slurry into the residual acid liquor, wherein the pH value of the obtained mixed slurry is 1.0-3.0.
In the present invention, the neutralized slurry is preferably added to the residual acid solution, or the residual acid solution may be added to the neutralized slurry, and the mixing time of the neutralized slurry and the residual acid solution is controlled to be 60 to 180min, more preferably 80 to 150min, such as 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min, and 180min, preferably any value thereof is used as an upper limit or a lower limit. The temperature of the reaction of the neutralized slurry with the residual acid solution is preferably 60 to 100 ℃, more preferably 70 to 90 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃, and is preferably a range value with any value as an upper limit or a lower limit.
And (3) continuously introducing ammonia gas into the obtained mixed slurry, carrying out neutralization reaction until the pH value is 4.0-5.0, and then atomizing and drying the slurry to obtain a monoammonium phosphate product.
In the invention, the inlet air temperature of the atomization is preferably 150-180 ℃, and more preferably 160-170 ℃; the outlet air temperature is preferably 80 to 110 ℃, and more preferably 90 to 100 ℃.
The drying temperature is preferably 50-80 ℃, more preferably 60-70 ℃, and the drying time is preferably 30-180 min, more preferably 50-150 min, and most preferably 80-120 min.
In the high water-soluble monoammonium phosphate prepared by the method of the invention, the effective P is 2 O 5 + total N is more than or equal to 68.0%, water insoluble matter (G4) is less than 1.0%, moisture absorption rate is less than or equal to 2.0%, and water content is less than 1.0%.
The invention provides a production method of high-water-solubility monoammonium phosphate, which comprises the following steps: a) Mixing phosphoric acid and a chelating agent, and reacting to obtain acid liquor; b) Taking part of the acid liquor obtained in the step A), introducing ammonia gas for reaction, and neutralizing until the pH value is 4.0-5.0 to obtain neutralized slurry; c) Adding the neutralized slurry into the residual acid solution to obtain mixed slurry with the pH value of 1.0-3.0; d) And continuously introducing ammonia gas into the mixture to neutralize until the pH value is 4.0-4.5, and drying to obtain a monoammonium phosphate product. The invention prepares the monoammonium phosphate by adding the phosphoric acid dissolved with the chelating agent to reduce the pH value of the monoammonium phosphate slurry by reverse regulation, and the action principle is as follows: the insoluble phosphate is increased along with the increase of the pH value of the monoammonium phosphate slurry, the chelating effect of the chelating agent is close to the limit by neutralizing most of the phosphoric acid to the pH value of 4.0-5.0, and the generated insoluble phosphate is further dissolved because the added phosphoric acid can reduce the pH value of the monoammonium phosphate slurry system after the chelating agent is added. The phosphoric acid with the chelating agent continues to act, so that the generation of insoluble phosphate is greatly reduced in the subsequent neutralization process, and the content of water-insoluble substances in the monoammonium phosphate is well controlled. On the other hand, the reaction mechanism is changed due to the change of the neutralization mode of the monoammonium phosphate slurry, the pH value of the raw monoammonium phosphate slurry is a gradually rising process, and the generated precipitate is determined. By controlling the pH value of the monoammonium phosphate slurry to rise firstly, then reduce and rise secondly, most of the finally generated precipitate is dissolved in water, and the water solubility of monoammonium phosphate is ensured. The water solubility of the monoammonium phosphate produced by the method of the invention is far higher than that of the monoammonium phosphate obtained by direct neutralization. The test proves that: the water insoluble substance (G4) in the monoammonium phosphate produced by the mode of reversely adjusting the pH value can be controlled within 1 percent, and the water insoluble substance (G4) in the monoammonium phosphate produced by the mode of directly neutralizing is 2 to 5 percent.
In order to further illustrate the present invention, the following examples are provided to describe the method for producing highly water-soluble monoammonium phosphate in detail, but should not be construed as limiting the scope of the present invention.
The phosphoric acid raw material components used in examples and comparative examples are shown in table 1.
TABLE 1 chemical composition of phosphoric acid starting material (wt/%)
| P 2 O 5 | CaO | MgO | Fe 2 O 3 | Al 2 0 3 | SO 3 | |
| Example 1 | 28.76 | 0.10 | 1.29 | 0.88 | 0.73 | 1.52 |
| Example 2 | 34.66 | 0.13 | 1.39 | 0.96 | 0.78 | 1.59 |
| Example 3 | 36.51 | 0.14 | 1.40 | 0.95 | 0.81 | 1.66 |
| Example 4 | 30.10 | 0.12 | 1.31 | 0.89 | 0.80 | 1.57 |
| Example 5 | 25.61 | 0.11 | 1.12 | 0.74 | 0.63 | 1.42 |
| Example 6 | 25.61 | 0.11 | 1.12 | 0.74 | 0.63 | 1.42 |
| Comparative example 1 | 37.59 | 0.13 | 1.33 | 0.90 | 0.85 | 1.48 |
| Comparative example 2 | 28.71 | 0.10 | 1.31 | 0.90 | 0.83 | 1.54 |
| Comparative example 3 | 32.75 | 0.13 | 1.32 | 0.88 | 0.74 | 1.62 |
Example 1
a. 1000g of phosphoric acid with phosphorus pentoxide content of 28.76% is taken, the temperature is 75 ℃, 2.1g of ammonium formate and 1.6g of polyamino polyether methylene phosphonic acid are respectively added under stirring, and then stirring is continued for 30min.
b. And (b) taking 450g of the acid liquor obtained in the step (a), introducing ammonia gas for neutralization, controlling the pH value of the water-soluble fertilizer slurry to be 4.0-5.0, and continuing to react for 30min.
c. Slowly adding the acid liquor remaining in the step a into the water-soluble fertilizer slurry obtained in the step b, controlling the adding time to be 1-2h, controlling the reaction time to be 80-100 ℃, and finally controlling the pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 1.3.
d. And c, continuously introducing ammonia gas into the slurry obtained in the step c for neutralization, controlling the end point pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 4.0-4.5, reacting for 20-40min, and atomizing and drying to obtain the water-soluble fertilizer monoammonium phosphate. Wherein the air inlet temperature of the atomization tower is 150-180 ℃, and the air outlet temperature is 80-110 ℃; the oven temperature is 50-80 deg.C, and the drying time is 30-80min.
The water-insoluble content (G4) of the water-soluble fertilizer monoammonium phosphate produced by the method described in example 1 was 0.32%.
Example 2
a. 1000g of phosphoric acid with phosphorus pentoxide content of 34.66% is taken, the temperature is 93 ℃, 1.5g of polyamino polyether methylene phosphonic acid, 2.6g of 2-phosphonic butane-1,2,4 tricarboxylic acid and 1.8g of diethylenetriamine pentaacetic acid are respectively added under the stirring condition, and the stirring is continued for 25min.
b. And (b) taking 600g of the acid liquor obtained in the step (a), introducing ammonia gas for neutralization, controlling the pH value of the water-soluble fertilizer slurry to be 4.0-5.0, and continuing to react for 20min.
c. Slowly adding the acid liquor remaining in the step a into the water-soluble fertilizer slurry obtained in the step b, controlling the adding time to be 1-2h, controlling the reaction time to be 80-100 ℃, and finally controlling the pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 2.7.
d. And c, continuously introducing ammonia gas into the slurry obtained in the step c for neutralization, controlling the end point pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 4.0-4.5, reacting for 20-40min, and atomizing and drying to obtain the water-soluble fertilizer monoammonium phosphate. Wherein the air inlet temperature of the atomization tower is 150-180 ℃, and the air outlet temperature is 80-110 ℃; the oven temperature is 50-80 deg.C, and the drying time is 30-80min.
The water-insoluble (G4) content of the water-soluble fertilizer monoammonium phosphate produced according to the method described in example 2 was 0.10%.
Example 3
a. 1000g of phosphoric acid with phosphorus pentoxide content of 36.51% are taken, the temperature is 88 ℃, 4.2g of 2-phosphonobutane-1,2,4 tricarboxylic acid is added under stirring, and the stirring is continued for 20min.
b. And (b) taking 500g of the acid liquor obtained in the step (a), introducing ammonia gas for neutralization, controlling the pH value of the water-soluble fertilizer slurry to be 4.0-5.0, and continuing to react for 20min.
c. Slowly adding the acid liquor remaining in the step a into the water-soluble fertilizer slurry obtained in the step b, controlling the adding time to be 1-2h, controlling the reaction time to be 80-100 ℃, and finally controlling the pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 2.4.
d. And c, continuously introducing ammonia gas into the slurry obtained in the step c for neutralization, controlling the end point pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 4.0-4.5, reacting for 20-40min, and atomizing and drying to obtain the water-soluble fertilizer monoammonium phosphate. Wherein the air inlet temperature of the atomization tower is 150-180 ℃, and the air outlet temperature is 80-110 ℃; the oven temperature is 50-80 deg.C, and the drying time is 30-80min.
The water-insoluble (G4) content of the water-soluble fertilizer monoammonium phosphate produced according to the method described in example 3 was 0.48%.
Example 4
a. 1000g of phosphoric acid with phosphorus pentoxide content of 30.10% is taken, the temperature is 81 ℃, 3.4g of polyamino polyether methylene phosphonic acid and 1.4g of 2-phosphonic butane-1,2,4 tricarboxylic acid are respectively added under the stirring condition, and the stirring is continued for 25min.
b. And (b) taking 500g of the acid liquor obtained in the step (a), introducing ammonia gas for neutralization, controlling the pH value of the water-soluble fertilizer slurry to be 4.0-5.0, and continuing to react for 25min.
c. Slowly adding the acid liquor remaining in the step a into the water-soluble fertilizer slurry obtained in the step b, controlling the adding time to be 1-2h, controlling the reaction time to be 80-100 ℃, and finally controlling the pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 2.2.
d. And c, continuously introducing ammonia gas into the slurry obtained in the step c for neutralization, controlling the end point pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 4.0-4.5, reacting for 20-40min, and atomizing and drying to obtain the water-soluble fertilizer monoammonium phosphate. Wherein the air inlet temperature of the atomizing tower is 150-180 ℃, and the air outlet temperature is 80-110 ℃; the oven temperature is 50-80 deg.C, and the drying time is 30-80min.
The water-insoluble content (G4) of the water-soluble fertilizer monoammonium phosphate produced by the method described in example 4 was 0.26%.
Example 5
a. 1000g of phosphoric acid with 25.61 percent of phosphorus pentoxide is taken, the temperature is 73 ℃, 0.8g of ammonium formate, 1.4g of polyamino polyether methylene phosphonic acid, 1.1g of 2-phosphonic butane-1,2,4 tricarboxylic acid and 0.5g of diethylenetriamine pentaacetic acid are respectively added under the stirring condition, and the stirring is continued for 30min.
b. And (b) taking 650g of the acid liquor obtained in the step (a), introducing ammonia gas for neutralization, controlling the pH value of the water-soluble fertilizer slurry to be 4.0-5.0, and continuing to react for 20min.
c. Slowly adding the acid liquor remaining in the step a into the water-soluble fertilizer slurry obtained in the step b, controlling the adding time to be 1-2h, controlling the reaction time to be 80-100 ℃, and finally controlling the pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 2.8.
d. And c, continuously introducing ammonia gas into the slurry obtained in the step c for neutralization, controlling the end point pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 4.0-4.5, reacting for 20-40min, and atomizing and drying to obtain the water-soluble fertilizer monoammonium phosphate. Wherein the air inlet temperature of the atomization tower is 150-180 ℃, and the air outlet temperature is 80-110 ℃; the oven temperature is 50-80 deg.C, and the drying time is 30-80min.
The water-insoluble content (G4) of the water-soluble fertilizer monoammonium phosphate produced by the method in example 5 is 0.16%.
Example 6
The same acid solution as in example 5, the same type and amount of chelating agent as in example 2, and the same conditions for controlling the reaction process as in example 2 were used.
a. 1000g of phosphoric acid with 25.61 percent of phosphorus pentoxide is taken, the temperature is 73 ℃, 1.8g of polyamino polyether methylene phosphonic acid, 3.1g of 2-phosphonobutane-1,2,4 tricarboxylic acid and 2.2g of diethylenetriamine pentaacetic acid are respectively added under the stirring condition, and the stirring is continued for 25min.
b. And (b) taking 600g of the acid liquor obtained in the step (a), introducing ammonia gas for neutralization, controlling the pH value of the water-soluble fertilizer slurry to be 4.0-5.0, and continuing to react for 20min.
c. Slowly adding the acid liquor remaining in the step a into the water-soluble fertilizer slurry obtained in the step b, controlling the adding time to be 1-2h, controlling the reaction time to be 80-100 ℃, and finally controlling the pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 2.7.
d. And c, continuously introducing ammonia gas into the slurry obtained in the step c for neutralization, controlling the end-point pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 4.0-4.5, reacting for 20-40min, atomizing and drying to obtain the water-soluble fertilizer monoammonium phosphate. Wherein the air inlet temperature of the atomization tower is 150-180 ℃, and the air outlet temperature is 80-110 ℃; the oven temperature is 50-80 deg.C, and the drying time is 30-80min.
The water-insoluble content (G4) of the water-soluble fertilizer monoammonium phosphate produced by the method described in example 6 was 0.09%.
Comparative example 1
a. 1000g of phosphoric acid with a phosphorus pentoxide content of 37.59% are taken at a temperature of 95 ℃.
b. And (b) introducing the acid liquor obtained in the step (a) into ammonia gas for neutralization, and controlling the pH value of the water-soluble fertilizer slurry to be 4.0-4.5.
c. And c, atomizing and drying the slurry obtained in the step b to obtain the water-soluble fertilizer monoammonium phosphate. Wherein the air inlet temperature of the atomizing tower is 150-180 ℃, and the air outlet temperature is 80-110 ℃; the oven temperature is 50-80 deg.C, and the drying time is 30-80min.
The water-insoluble (G4) content of the water-soluble fertilizer monoammonium phosphate produced according to the method described in comparative example 1 was 7.72%.
Comparative example 2
a. Taking 1000g of phosphoric acid with the phosphorus pentoxide content of 28.71%, at the temperature of 70 ℃, respectively adding 2.1g of chelating agent ammonium formate, 1.7g of diethylenetriamine pentaacetic acid and 2.8g of polyamino polyether methylene phosphonic acid under the stirring condition, and then continuing to stir for 25min.
b. And (b) introducing the acid liquor obtained in the step (a) into ammonia gas for neutralization, and controlling the pH value of the water-soluble fertilizer slurry to be 4.0-4.5.
c. And c, atomizing the slurry obtained in the step b, and drying to obtain the water-soluble fertilizer monoammonium phosphate. Wherein the air inlet temperature of the atomizing tower is 150-180 ℃, and the air outlet temperature is 80-110 ℃; the oven temperature is 50-80 deg.C, and the drying time is 30-80min.
The water-insoluble content (G4) of the water-soluble fertilizer monoammonium phosphate produced by the method described in comparative example 2 was 3.51%.
Comparative example 3
a. 1000g of phosphoric acid having a phosphorus pentoxide content of 32.75% are taken at a temperature of 84 ℃.
b. And (b) taking 600g of the acid liquor obtained in the step (a), introducing ammonia gas for neutralization, controlling the pH value of the water-soluble fertilizer slurry to be 4.0-5.0, and continuing to react for 20min.
c. Slowly adding the acid liquor remaining in the step a into the water-soluble fertilizer slurry obtained in the step b, controlling the adding time to be 1-2h, controlling the reaction time to be 80-100 ℃, and finally controlling the pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 2.7.
d. And c, continuously introducing ammonia gas into the slurry obtained in the step c for neutralization, controlling the end-point pH value of the water-soluble fertilizer monoammonium phosphate slurry to be 4.0-4.5, reacting for 20-40min, atomizing and drying to obtain the water-soluble fertilizer monoammonium phosphate. Wherein the air inlet temperature of the atomizing tower is 150-180 ℃, and the air outlet temperature is 80-110 ℃; the oven temperature is 50-80 deg.C, and the drying time is 30-80min.
The water-insoluble (G4) content of the water-soluble fertilizer monoammonium phosphate produced according to the method described in comparative example 3 was 5.28%.
FIGS. 1 to 3 show the water solubility test of the monoammonium phosphate in examples 1 to 5 at a mass concentration of 1%, and FIGS. 4 to 5 show the water solubility test of the water-soluble fertilizer monoammonium phosphate in comparative examples 1 to 3 at a mass concentration of 1%, from FIGS. 1 to 5, it can be seen that the water-soluble fertilizer monoammonium phosphate prepared by the method of the present invention has excellent water solubility, and the monoammonium phosphate product in the comparative example has poor water solubility.
The chemical composition of the water-soluble monoammonium phosphate fertilizer products of the examples and comparative examples are shown in table 2.
TABLE 2 chemical composition and moisture absorption (wt/%) of monoammonium phosphate as water-soluble fertilizer
TABLE 3 chemical composition of water-soluble fertilizer monoammonium phosphate
As can be seen from the examples and comparative examples, the optimal formula for adding the chelating agent into the wet-process phosphoric acid is to use the three chelating agents of polyamino polyether methylene phosphonic acid, 2-phosphonic butane-1,2,4 tricarboxylic acid and diethylene triamine pentaacetic acid in a matching way, and the water-insoluble (G4) of the water-soluble fertilizer monoammonium phosphate can be reduced to be less than 0.1 percent. The produced water-soluble fertilizer meets (actually is superior to) NY/T1107-2020 macroelement water-soluble fertilizer standard requirements.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A production method of high water-solubility monoammonium phosphate comprises the following steps:
a) Mixing phosphoric acid and a chelating agent, and reacting to obtain acid liquor;
the chelating agent is polyamino polyether methylene phosphonic acid, 2-phosphonic butane-1,2,4 tricarboxylic acid and diethylenetriamine pentaacetic acid, and the dosage of the chelating agent is 5-15 kg/t monoammonium phosphate product;
b) Taking part of the acid liquor obtained in the step A), introducing ammonia gas for reaction, and neutralizing until the pH value is 4.0-5.0 to obtain neutralized slurry;
c) Mixing the neutralized slurry with the residual acid liquor to obtain mixed slurry with the pH value of 1.0-3.0;
d) And continuously introducing ammonia gas into the mixed slurry to neutralize until the pH value is 4.0-4.5, and drying to obtain a monoammonium phosphate product.
2. The production method according to claim 1, wherein the phosphoric acid is wet-process phosphoric acid;
p in the phosphoric acid 2 O 5 The mass fraction of (A) is 20-38%.
3. The production method according to claim 1, wherein the reaction temperature in step A) is 20 to 110 ℃; the reaction time of the step A) is 20-60 min.
4. The production method according to claim 1, wherein the reaction temperature in the step B) is 80 to 120 ℃ and the reaction time is 20 to 80min.
5. The production method according to claim 1, characterized in that the mass of the partial acid liquid in the step B) is 45-65% of the mass of the acid liquid in the step A).
6. The production method according to claim 1, wherein in the step D), after the neutralization, the atomization and the drying are sequentially carried out to obtain the monoammonium phosphate product.
7. The production method according to claim 6, wherein the inlet air temperature for atomization is 150-180 ℃; the air outlet temperature is 80-110 ℃.
8. The production method according to claim 6, wherein the drying temperature is 50 to 80 ℃ and the drying time is 30 to 180min.
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