阅读说明：本技术 一种磷酸铵肥料的生产方法 (Production method of ammonium phosphate fertilizer ) 是由 王辛龙 许德军 许德华 杨林 张志业 钟本和 于 2020-06-23 设计创作，主要内容包括：本发明涉及一种磷酸铵肥料的生产方法,属于肥料技术领域。本发明解决的技术问题是提供一种磷酸铵肥料的生产方法,其工艺简单成本低。该方法通过螯合-氨化-造粒工艺,得到磷酸铵肥料。本发明方法,制备工艺简单,操作安全,生产成本低,可适用于各种浓度的湿法磷酸。本发明可有效提高磷酸铵中水溶磷含量及活化植物生长过程中所必需的中微量元素。本发明可充分利用湿法磷酸中的杂质离子,如铁、镁、钙等,防止在肥料配置过程中磷元素沉淀。本发明制备的产品水溶磷含量高,含植物生长过程中所必需的中微量元素,产品无毒无害,对环境友好,可广泛应用于农业。(The invention relates to a production method of an ammonium phosphate fertilizer, belonging to the technical field of fertilizers. The invention aims to provide a production method of an ammonium phosphate fertilizer, which has simple process and low cost. The method obtains the ammonium phosphate fertilizer through a chelation-ammoniation-granulation process. The method has the advantages of simple preparation process, safe operation and low production cost, and is suitable for wet-process phosphoric acid with various concentrations. The invention can effectively improve the content of water-soluble phosphorus in ammonium phosphate and activate the medium trace elements necessary in the growth process of plants. The invention can fully utilize impurity ions in the wet-process phosphoric acid, such as iron, magnesium, calcium and the like, and prevent phosphorus element from precipitating in the process of preparing the fertilizer. The product prepared by the invention has high water-soluble phosphorus content, contains medium and trace elements necessary for the plant growth process, is nontoxic and harmless, is environment-friendly, and can be widely applied to agriculture.)

1. The production method of the ammonium phosphate fertilizer is characterized by comprising the following steps:

a. carrying out chelation reaction: mixing wet-process phosphoric acid and a chelating agent, keeping the temperature at 30-120 ℃, and reacting at a constant temperature for 10-120 min to obtain a chelating solution;

b. ammoniation reaction: introducing ammonia gas into the chelating solution for neutralization until the neutralization degree is 0.5-2.0, and reacting for 30-60 min to obtain an ammonium phosphate-containing material;

c. and (3) granulation: and granulating the ammonium phosphate-containing material to obtain the ammonium phosphate fertilizer.

2. The method for producing a compound fertilizer according to claim 1, characterized in that: the pH value of the wet-process phosphoric acid is less than or equal to 0.5.

3. The method for producing a compound fertilizer according to claim 1, characterized in that: in the step a, the chelating agent is at least one of citric acid, EDTA and ammonium polyphosphate.

4. The method for producing a compound fertilizer according to claim 1, characterized in that: in the step a, the dosage of the chelating agent is 1.0-1.5 times of the theoretical dosage required by the chelation reaction of the medium trace elements in the wet-process phosphoric acid.

5. The method for producing a compound fertilizer according to claim 1, characterized in that: and a, keeping the temperature at 90 ℃ and reacting for 30min at constant temperature.

6. The method for producing a compound fertilizer according to claim 1, characterized in that: in step b, the reaction is carried out for 30 min.

7. The method for producing a compound fertilizer according to claim 1, characterized in that: and c, granulating by spraying or drum granulating.

8. The method for producing a compound fertilizer according to claim 7, characterized in that: in the step c, an ammonium phosphate product which mainly comprises monoammonium phosphate is prepared in a slurry spraying granulation mode.

9. The method for producing a compound fertilizer according to claim 1, characterized in that: and c, preparing an ammonium phosphate product mainly containing diammonium phosphate in a drum granulation mode in the ammonia atmosphere.

Technical Field

The invention relates to a production method of an ammonium phosphate fertilizer, belonging to the technical field of fertilizers.

Background

Ammonium phosphate is a high-quality macroelement basic fertilizer and has been widely used in agriculture at home and abroad. In recent years, with the transformation requirements of the chemical fertilizer industry in China and the continuous development of water and fertilizer integration technology in agriculture, the requirement on the content of water-soluble phosphorus in the ammonium phosphate fertilizer is higher and higher. The grade of phosphate ore in China is poor, and wet-process phosphoric acid contains a large amount of impurity ions such as iron, magnesium, calcium, manganese and the like, so that the content of water-insoluble substances in the slurry-process ammonium phosphate product is high, and the content of water-soluble phosphorus is low. Such ammonium phosphate products have been increasingly unable to meet the agricultural needs of our country. To increase the water soluble phosphorus content of ammonium phosphate products, wet-process phosphoric acid is often purified to reduce its impurity ion content or new processes are developed to increase the water soluble phosphorus content of ammonium phosphate products.

The Chinese patent with application number 201910095327.4 discloses a production method for increasing the water-soluble phosphorus content of citrate soluble phosphorus fertilizer, namely urea sulfate is used for converting citrate soluble phosphorus in the citrate soluble phosphorus fertilizer into water-soluble phosphorus through the steps of mixing, curing and the like, thereby increasing the water-soluble phosphorus content. The process has the advantages of long flow, complex operation, long required time and higher production cost.

The Chinese patent application No. 201610664630.8 discloses a method for converting citrate soluble phosphorus into water soluble phosphorus, which is to dissolve citrate soluble phosphorus by strong acid and then add an activator, a stabilizer and the like to obtain stable water soluble phosphorus slurry. The process needs strong acid such as sulfuric acid and nitric acid, and the obtained water-soluble phosphorus slurry is strong acid and is not beneficial to agricultural application.

The Chinese patent with application number 201310396218.9 discloses a method for producing fully water-soluble monoammonium phosphate by using wet-process phosphoric acid, namely, solid-liquid separation is carried out on slurry after wet-process phosphoric acid ammonification reaction, and filtrate is concentrated and dried to obtain fully water-soluble monoammonium phosphate. The method has long process flow, white fertilizer can be generated in the production process, and the yield of phosphorus is low.

The Chinese patent with application number 201410245006.5 discloses a method for producing fully water-soluble monoammonium phosphate and co-producing magnesium ammonium phosphate by using wet-process phosphoric acid, namely, the fully water-soluble monoammonium phosphate and magnesium ammonium phosphate products are prepared by the wet-process phosphoric acid through the steps of three times of ammoniation reaction, aging, solid-liquid separation, concentration, crystallization and the like. The monoammonium phosphate product prepared by the method has high water-soluble phosphorus content, but the process is complex, white fertilizer and ammonium magnesium phosphate are byproducts, and the phosphorus yield is low.

The Chinese patent with application number 201610705632.7 discloses a method for producing fully water-soluble diammonium phosphate by wet-process phosphoric acid, namely, preparing diammonium phosphate by the wet-process phosphoric acid through the steps of primary neutralization reaction, solid-liquid separation, concentration, secondary neutralization reaction, drying and the like. The method has the advantages of complex process, white fertilizer produced in the production process, low phosphorus yield and high production cost.

The Chinese patent with application number CN201410033591.2 discloses a water-soluble phosphate fertilizer and a preparation method thereof, namely, phosphate rock powder is used as a raw material, and crystal lattices of hydroxyl-like materials are inserted, so that the phosphate rock is completely converted into the water-soluble phosphate fertilizer containing calcium, magnesium, iron and the like. The method effectively utilizes metal ions in the phosphorite, has high phosphorus yield, but has the disadvantages of complex process, difficult operation, high energy consumption and high production cost, and is not beneficial to industrial production. The method improves the water-soluble phosphorus content of the ammonium phosphate product, reduces the yield of phosphorus in the wet-process phosphoric acid, wastes metal ions in the wet-process phosphoric acid, increases the production cost of the ammonium phosphate, and is easy to react with the metal ions in the soil after application to produce insoluble phosphate and reduce the utilization rate of phosphorus.

Chinese patent application No. 201210154344.9 discloses a method for producing macroelement water-soluble fertilizer, adding a specific chelating agent into crude phosphoric acid for chelation, and then introducing ammonia gas to adjust the pH value to 5-6 to obtain water-soluble phosphate fertilizer; mixing and granulating the water-soluble phosphate fertilizer, the water-soluble nitrogenous fertilizer and the water-soluble potash fertilizer, and drying and cooling to obtain the macroelement fully water-soluble fertilizer. Although the method can prepare the macroelement water-soluble fertilizer by taking the crude phosphoric acid as the raw material, the specific chelating agent is needed, so that the components of the chelating agent are complex and the cost is high.

The Chinese patent application with the application number of 201910339366.4 discloses a preparation method of full water-soluble monoammonium phosphate containing medium and trace elements, wherein wet-process phosphoric acid is used as a raw material, and a secondary ammoniation technology is adopted to obtain the full water-soluble monoammonium phosphate.

Disclosure of Invention

Aiming at the defects, the invention provides a production method of an ammonium phosphate fertilizer, which has simple process and low cost.

The production method of the ammonium phosphate fertilizer comprises the following steps:

a. carrying out chelation reaction: mixing wet-process phosphoric acid and a chelating agent, keeping the temperature at 30-120 ℃, and reacting at a constant temperature for 10-120 min to obtain a chelating solution;

b. ammoniation reaction: introducing ammonia gas into the chelating solution for neutralization until the neutralization degree is 0.5-2.0, and reacting for 30-60 min to obtain an ammonium phosphate-containing material;

c. and (3) granulation: and granulating the ammonium phosphate-containing material to obtain the ammonium phosphate fertilizer.

In one embodiment, the wet-process phosphoric acid used has a pH of 0.5 or less.

In one embodiment, in step a, the chelating agent is at least one of citric acid, EDTA and ammonium polyphosphate.

In one embodiment, in the step a, the amount of the chelating agent is 1.0 to 1.5 times of the theoretical amount of the medium trace elements in the wet-process phosphoric acid required for the chelating reaction.

In one embodiment, the temperature is kept at 90 ℃ during chelation, and the reaction is carried out for 30min at constant temperature.

In one embodiment, step b is reacted for 30 min.

In step c, the granulation is spray granulation or drum granulation.

In step c, as an embodiment, the ammonium phosphate product mainly comprising monoammonium phosphate is prepared by means of slurry spraying granulation.

As an embodiment, in step c, ammonium phosphate products mainly comprising diammonium phosphate are prepared by drum granulation in an ammonia atmosphere.

Compared with the prior art, the invention has the following advantages:

1. the invention takes wet-process phosphoric acid as a raw material, has simple preparation process, does not need special chelating agent, and can prepare ammonium phosphate products only by one-step ammoniation reaction.

2. The preparation method can adapt to wet-process phosphoric acid raw materials with various concentrations, the water-soluble phosphorus content in the product is high, and different types of ammonium phosphate products can be prepared by adjusting the process conditions.

3. The invention fully utilizes impurity ions in the wet-process phosphoric acid and improves P₂O₅And the utilization rate of impurity ions is reduced, and the production cost is reduced.

4. The ammonium phosphate fertilizer contains medium and trace elements essential for plant growth, and the product is non-toxic, harmless, environment friendly and may be used widely in agriculture.

Detailed Description

The production method of the ammonium phosphate fertilizer comprises the following steps:

a. carrying out chelation reaction: mixing wet-process phosphoric acid and a chelating agent, keeping the temperature at 30-120 ℃, and reacting at a constant temperature for 10-120 min to obtain a chelating solution;

b. ammoniation reaction: introducing ammonia gas into the chelating solution for neutralization until the neutralization degree is 0.5-2.0, and reacting for 30-60 min to obtain an ammonium phosphate-containing material;

c. and (3) granulation: and granulating the ammonium phosphate-containing material to obtain the ammonium phosphate fertilizer.

The method directly adopts the phosphoric acid containing wet process as the raw material, chelates the medium and trace metal elements in the phosphoric acid containing wet process by using a chelating agent, obtains ammonium phosphate slurry containing medium and trace elements through ammoniation reaction, and prepares the ammonium phosphate fertilizer containing medium and trace elements through granulation, thereby providing medium and trace elements necessary in the growth process for plants. The method is simple and has low cost. The invention adopts the chelation technology to chelate part of metal ions in wet-process phosphoric acid so as to improve that the metal ions are not precipitated by phosphorus in the phosphoric acid ammoniation process, thereby greatly improving the content of water-soluble phosphorus in the product while improving the utilization rate of phosphorus and metal ions.

As one embodiment, the wet-process phosphoric acid is industrial wet-process phosphoric acid, and the pH value is below 0.5. The concentration of the wet-process phosphoric acid can be the wet-process phosphoric acid produced by any factory in China at present.

Step a is a chelation reaction process, namely adding a chelating agent and chelating medium and trace elements in the wet-process phosphoric acid. The invention aims to improve the metal ions and P in wet-process phosphoric acid₂O₅Utilization of water soluble phosphorus and ammonium phosphate products, and chelating agents commonly used in the art are therefore suitable for use in the present invention, for example, ethylenediaminetetraacetic acid (EDTA), disodium ethylenediaminetetraacetic acid (EDTA-2Na), tetrasodium ethylenediaminetetraacetate (EDTA-4Na), diammonium ethylenediaminetetraacetic acid, triammonium ethylenediaminetetraacetate, dimethylenetriaminepentaacetic acid, potassium hydrogenethylenediaminetetraacetate, disodium dihydroethylenediaminetetraacetate dihydrate, diethylenetriaminepentaacetic acid (DTPA), pentasodium diethylenetriaminepentaacetate (DTPA-5Na), Triethylenediamine (TEDA), propylenediaminetetraacetic acid (PDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), trisodium hydroxyethylethylenediaminetriacetic acid (HEDTA-3Na), hydroxyethylethylenediamine (AEEA), trisodium hydroxyethylethylenediaminetetraacetate, sodium dihydroxyethylglycinate, sodium nitrilotriacetate, nitrilotriacetic acid, nitrilotriacetic acid trisodium salt monohydrate, hydroxyethyldiphosphonic acid, ethylenediamine diphthaloacetic acid (EDDHA), ethylenediamine diphthalacetic acid sodium acetate (EDDHA-Na), hydroxyethylidene diphosphonic acid and potassium, sodium, ammonium salts thereof, aminotrimethylene phosphonic acid and potassium, sodium, ammonium salts thereof, ethylenediamine tetramethylene phosphonic acid and potassium, sodium, ammonium salts thereof, diethylenetriamine pentamethylene phosphonic acid and potassium, sodium, ammonium salts thereof, 2-phosphonic butane-1, 2, 4-tricarboxylic acid and potassium, sodium, ammonium salts thereof, polyol phosphates, 2-hydroxyphosphonic acid and potassium, sodium, ammonium salts thereof, hexamethylenediamine tetramethylene phosphonic acid and potassium, sodium, ammonium salts thereof, polyamino polyether methylene phosphonic acid and potassium, sodium, ammonium salts thereof, bis 1, 6-hexylenediamine pentamethylene phosphonic acid and potassium, sodium, ammonium salts thereof, triethylenetetramine hexaacetic acid and potassium, sodium, ammonium salts thereof, Sodium, ammonium salts, dihydroxyethylglycine and its potassium, sodium, ammonium salts, 2-oxoacetoxymalonic acid and its potassium, sodium, ammonium salts, 2-oxoacetoxybutyric acid and its potassium, sodium, ammonium salts, 1,2,3, 4-cyclopentanetetracarboxylic acid and its potassium, sodium, ammonium saltsSalts, acetic acid and its potassium, sodium, ammonium salts, citric acid, potassium citrate, monosodium citrate, phytic acid, gluconic acid, sodium gluconate, potassium gluconate, glucose-lactone, sodium pyrophosphate, sodium tripolyphosphate, potassium pyrophosphate, (poly) polyphosphate, (poly) sodium polyphosphate, (poly) ammonium polyphosphate, hexametaphosphoric acid, sodium hexametaphosphate, potassium hexametaphosphate, ammonium hexametaphosphate, glucoheptonic acid and its potassium, sodium, ammonium salts, sorbitol syrup, carboxymethyloxysuccinic acid, carboxymethyltartaric acid, tartaric acid and its sodium salts, tartaric acid and its potassium salts, naphthalenetrisulfonic acid, maleic acid, amino acids and its potassium, sodium, ammonium salts, lignosulfonic acid and its soluble salts, valeric acid, pentenoic acid, pentasodium pentenoate, humic acid and its potassium, sodium, ammonium salts, oxalic acid and its potassium, sodium, ammonium salts, alginic acid and its potassium, sodium, ammonium salts, sugar alcohols, mannitol, xylitol, malic acid and its potassium, sodium, ammonium salts, fulvic acid and its potassium, sodium, ammonium salts, lignosulfonic acid and its potassium, sodium, ammonium salts, HBED, EDDMA, polyacrylic acid and its potassium, sodium, ammonium salts, polyethylene glycol, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malonic acid, fumaric acid, citric acid, ascorbic acid, succinic acid, glycolic acid, polymethacrylic acid, hydrolyzed polymaleic anhydride, maleic acid-acrylic acid copolymers, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid multipolymers, hydroxypropyl acrylate copolymers, acrylic acid-acrylate-phosphonic acid-sulfonate tetrapolymers, acrylic acid-acrylate-sulfonate terpolymers, carboxylate-sulfonate-nonionic terpolymers, polyepoxysuccinic acid (sodium), polyaspartic acid (sodium), ethylenediamine, 2,2' -bipyridine, 1, 10-phenanthroline, amino sodium triacetate, iminodiacetic acid, tetrasodium iminodisuccinate, trisodium ethylenediamine disuccinate (IDS), waste acid or filter mud in sugar industry, furfural and waste residues thereof, high-concentration organic waste liquid discharged in alcohol and monosodium glutamate production, fermentation waste liquid, livestock manure and biogas slurry thereof, amino acid waste liquid, pyroligneous liquor, oligosaccharide, dunaliella salina polysaccharide, xanthan gum, yeast waste liquid and the like.

In some embodiments, the chelating agent is at least one of citric acid, EDTA, ammonium polyphosphate.

The addition amount of the chelating agent is related to the content of water-soluble phosphorus in the ammonium phosphate, and the more the addition amount of the chelating agent is, the more trace elements are chelated, the higher the content of water-soluble phosphorus in the ammonium phosphate product is, and vice versa. Preferably, the dosage of the chelating agent is 1.0-1.5 times of the theoretical dosage required by the chelation reaction of the medium trace elements in the wet-process phosphoric acid, then in the step b, the clear solution is obtained after the wet-process phosphoric acid is subjected to ammoniation reaction, the dosage of the chelating agent can completely chelate impurity ions in the wet-process phosphoric acid, and the content of water-soluble phosphorus in the ammonium phosphate product can be increased to 100%.

In one embodiment, the temperature is kept at 90 ℃ during chelation, and the reaction is carried out for 30min at constant temperature.

And b, an ammoniation reaction process, namely adding ammonia gas to a certain neutralization degree (0.5-2.0) and reacting for a certain time. The resulting liquid is a slurry or clear solution containing ammonium phosphate. The solution contains impurity ions in the wet-process phosphoric acid, such as Fe, Mg, Ca, Mn, Cu, Zn, and the like.

In a specific embodiment, the amination reaction in step b has a reaction time of 30 min.

The step c is a granulation process, and the common method for preparing the solid from the solution is suitable for the invention. As an embodiment, the ammonium phosphate product is produced by spray granulation or drum granulation.

In a specific embodiment, the ammonium phosphate product mainly containing monoammonium phosphate is prepared by adopting a slurry spraying granulation mode.

In another embodiment, ammonium phosphate products based on diammonium phosphate are produced by drum granulation under ammonia atmosphere.

The temperature of the chelating reaction, the amination reaction and the concentration of the wet-process phosphoric acid are not limited in the present invention, and any temperature below the boiling point of the wet-process phosphoric acid is suitable for the present invention. When the temperature rises, the reaction rate is accelerated, and in order to accelerate the reaction rate, improve the production efficiency and comprehensively consider the problem of energy consumption, the preferable reaction temperature is 30-120 ℃.

The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.