阅读说明：本技术 一种连续活化腐植酸复合肥料的生产方法及应用 (Production method and application of continuously activated humic acid compound fertilizer ) 是由 陈俊阳 林枫 吴柱刚 魏素君 于 2021-08-23 设计创作，主要内容包括：本发明涉及一种连续活化腐植酸复合肥料的生产方法及应用,属于肥料技术领域,生产方法包括如下步骤：第一次活化：将褐煤通过研磨,并通入氨水,得到褐煤匀浆；第二次活化：将褐煤匀浆与稀硫酸混合,得到预混料；第三次活化：将预混料与复合肥原料均匀混合、造粒；第四步、造粒完成后,进行烘干、冷却、筛分。本发明以褐煤为原料,通过球磨粉碎褐煤,引起褐煤内部分子结构发生变化,化学键断裂,含氧官能团数量增加,有利于腐植酸的活化。通过氨水和腐植酸在球磨机中均匀混合,增大了反应接触面,生成腐植酸铵,然后通过添加稀硫酸,加速腐植酸铵的生成,降低腐植酸复合肥料生产成本。(The invention relates to a production method and application of a continuously activated humic acid compound fertilizer, belonging to the technical field of fertilizers, wherein the production method comprises the following steps: first activation: grinding lignite, and introducing ammonia water to obtain lignite homogenate; and (3) second activation: mixing the lignite homogenate with dilute sulfuric acid to obtain a premix; and (3) activating for the third time: uniformly mixing the premix and the compound fertilizer raw materials, and granulating; and fourthly, after granulation is finished, drying, cooling and screening. The invention takes the lignite as a raw material, and the lignite is crushed by ball milling, so that the molecular structure in the lignite is changed, the chemical bond is broken, the number of oxygen-containing functional groups is increased, and the activation of humic acid is facilitated. The ammonia water and the humic acid are uniformly mixed in the ball mill, so that the reaction contact surface is increased, the humic acid ammonium is generated, then the dilute sulfuric acid is added, the generation of the humic acid ammonium is accelerated, and the production cost of the humic acid compound fertilizer is reduced.)

1. A production method of continuously activated humic acid compound fertilizer is characterized by comprising the following steps:

first step, first activation: conveying lignite into an industrial ball mill through a conveying belt, introducing ammonia water, grinding for 15-20min, and grinding the lignite into uniform slurry to obtain lignite slurry;

step two, second activation: adding the lignite homogenate into a granulator, adding dilute sulfuric acid, uniformly mixing the lignite homogenate with the dilute sulfuric acid, and stirring for 2-4 hours at the temperature of 90-95 ℃ to obtain a premix;

step three, activating for the third time: uniformly mixing the premix and the compound fertilizer raw materials, controlling the air temperature of a head of a granulator to be 500-;

and fourthly, after granulation is finished, drying, cooling and screening are carried out, and the compound fertilizer produced by continuously activating humic acid is obtained.

2. The method for producing the continuously activated humic acid compound fertilizer as claimed in claim 1, wherein the mass fraction of the ammonia water is 5-15%; the solid-liquid ratio of the lignite to the ammonia water is 3-5 g: 1 mL.

3. The method for producing continuously activated humic acid compound fertilizer as claimed in claim 1, wherein the mass fraction of the dilute sulphuric acid is 50-65%, and the volume ratio of the dilute sulphuric acid to the lignite homogenate is 1: 5-10.

4. The method for producing the continuously activated humic acid compound fertilizer as claimed in claim 1, wherein the compound fertilizer raw material is prepared by the following steps:

heating and melting urea, adding ammonium sulfate and potassium sulfate to obtain a compound, mixing the compound and an auxiliary agent, and granulating by using a traditional granulator to obtain a compound fertilizer raw material.

5. The method for producing the continuously activated humic acid compound fertilizer as claimed in claim 1, wherein the raw materials of the compound fertilizer comprise 30-50 parts by weight of urea, 8-10 parts by weight of ammonium sulfate, 22-30 parts by weight of potassium sulfate and 7-10 parts by weight of an auxiliary agent.

6. The method for producing the continuously activated humic acid compound fertilizer as claimed in claim 4, wherein the auxiliary agent is prepared by the following steps:

step S11, mixing sodium alginate and water, then adding sodium hydroxide to adjust the pH value to 7-9, then adding a mixture of adipic acid and acetic anhydride, and stirring and reacting for 1.5-3.5h at the temperature of 40-60 ℃ to obtain a solid a;

and step S12, mixing the solid a with water, adjusting the pH value to 8 by using sodium hydroxide, adding an octenyl succinic anhydride solution, and stirring for reacting for 3 hours to obtain the assistant.

7. The application of the continuously activated humic acid compound fertilizer produced by the method of claim 1 in lettuce planting.

Technical Field

The invention belongs to the technical field of fertilizers, and particularly relates to a production method and application of a continuously activated humic acid compound fertilizer.

Background

The humic acid compound fertilizer is an organic-inorganic compound fertilizer, and has the effects of improving soil, storing water and keeping fertilizer, improving the utilization rate of the fertilizer and the like as a fertilizer synergist in agricultural production.

The prior invention patent provides a production mode of humic acid compound fertilizer: 1) the invention patent CN101768019B provides a technology for preparing humic acid fertilizer by degrading and activating natural organic materials in a reaction kettle, decompressing and blasting, and concentrating, wherein the reaction conditions are that the temperature is 80-175 ℃, the pressure is 3-12.5 atmospheric pressures, the light wave is 400nm ultraviolet light, the weight percentage of a hydrolytic agent KOH is 2.5-20%, and an oxidant TiO is₂3-12.5% by weight of a directing agent FeSO₄0.3-3% by weight, the water solubility of the final finished product is greatly improved; 2) the invention patent CN106316693A discloses a biological humic acid fertilizer which is prepared by taking edible fungus chaff, apple pomace, soybean molasses, a modifying agent, a complex enzyme and a complex microbial inoculum as main raw materials and performing enzymolysis and microbial fermentation on the main raw materials.

The above patents have high requirements on environment and long reaction time, and are not beneficial to industrial continuous production, so that the method is difficult to realize in industrial production. In the production process of the humic acid compound fertilizer, the raw material generally selected by the humic acid is lignite which is a mineral coal with the lowest coalification degree and contains humic acid soluble in alkali liquor, the content of active humic acid is low, and the application effect in agriculture is not obvious.

Disclosure of Invention

The invention aims to provide a production method and application of a continuously activated humic acid compound fertilizer.

The purpose of the invention can be realized by the following technical scheme:

a production method of continuously activated humic acid compound fertilizer comprises the following steps:

first step, first activation: conveying lignite into an industrial ball mill through a conveying belt, introducing ammonia water, grinding for 15-20min, and grinding the lignite into uniform slurry to obtain lignite slurry;

step two, second activation: conveying the lignite homogenate into a granulator through an ore pulp pump, adding dilute sulfuric acid into a mixing reactor with a distribution pipe, uniformly mixing the lignite homogenate and the dilute sulfuric acid in the rotating process, and stirring for 2-4 hours at the temperature of 90-95 ℃ to obtain a premix; the activation is promoted by utilizing the temperature of acid-base reaction;

step three, activating for the third time: uniformly mixing the premix with the compound fertilizer raw materials in a granulator, controlling the air temperature of the head of the granulator to be 500-600 ℃, the material temperature to be 70-80 ℃ and the material temperature of the tail of the granulator to be 50-55 ℃, carrying out three times of activation on humic acid, and introducing ammonia acid through a tubular reactor according to a production target formula to adjust the pH value and supplement nitrogen.

And fourthly, after granulation is finished, drying, cooling and screening are carried out, and the compound fertilizer produced by continuously activating humic acid is obtained.

Further, the mass fraction of the ammonia water is 5-15%; the solid-liquid ratio of the lignite to the ammonia water is 3-5 g: 1 mL.

Further, the mass fraction of the dilute sulfuric acid is 50-65%, and the volume ratio of the dosage of the dilute sulfuric acid to the dosage of the lignite homogenate is 1: 5-10.

Further, the compound fertilizer raw material is prepared by the following steps:

heating and melting urea, adding ammonium sulfate and potassium sulfate to obtain a compound, mixing the compound and an auxiliary agent, properly adding water, and granulating by using a traditional granulator to obtain the raw material of the compound fertilizer.

Furthermore, the raw materials of the compound fertilizer comprise 30-50 parts of urea, 8-10 parts of ammonium sulfate, 22-30 parts of potassium sulfate and 7-10 parts of an auxiliary agent by weight.

Further, the auxiliary agent is prepared by the following steps:

step S11, mixing sodium alginate and water, adding sodium hydroxide to adjust the pH value to 7-9, adding a mixture of adipic acid and acetic anhydride, stirring and reacting at 40-60 ℃ for 1.5-3.5h, adding absolute ethyl alcohol after the reaction is finished, precipitating a solid, and then carrying out vacuum filtration to obtain a solid a; adipic acid and acetic anhydride are subjected to a crosslinking reaction with alcoholic hydroxyl groups on sodium alginate, and ester bonds obtained after crosslinking have stronger bonding strength than hydrogen bonds between original sodium alginate molecules, so that the viscosity is improved on one hand, and the stability is improved on the other hand.

And step S12, mixing the solid a with water, adjusting the pH value to 8 by using sodium hydroxide, adding an octenyl succinic anhydride solution, stirring for reacting for 3 hours, then adding a 1mol/L hydrochloric acid solution to adjust the pH value to 6, carrying out vacuum filtration, washing a filter cake by using an ethanol aqueous solution with the volume fraction of 60% and distilled water in sequence, and after washing is finished, drying to constant weight at 50 ℃ to obtain the auxiliary agent. Unreacted hydroxyl on the solid a reacts with octenyl succinic anhydride, hydrophilic carboxyl and lipophilic alkenyl long chain are introduced, and after the hydrophilic carboxyl and the lipophilic alkenyl long chain have amphiphilic characteristics, the hydrophilic carboxyl and the lipophilic alkenyl long chain are more beneficial to compounding and mixing with substances.

Further, the mixture of adipic acid and acetic anhydride in step S11 is adipic acid and acetic anhydride in a molar ratio of 1: 1, the dosage ratio of sodium alginate to water is 1 g: 10 mL; the mass ratio of the sodium alginate to the mixture of adipic acid and acetic anhydride is 100: 7-9;

the octenyl succinic anhydride solution in step S12 was octenyl succinic anhydride and isopropyl alcohol in a ratio of 1 g: 10mL of the mixture is mixed; the using ratio of the solid a to the water is 1 g: 20 mL; the using amount mass ratio of the solid a to the octenyl succinic anhydride is 100: 3-5.

The continuously activated humic acid compound fertilizer prepared by the method is applied to lettuce planting.

The invention has the beneficial effects that:

the invention takes the lignite as a raw material, and the lignite is crushed by ball milling, so that the molecular structure in the lignite is changed, the chemical bond is broken, the number of oxygen-containing functional groups is increased, and the activation of humic acid is facilitated.

The ammonia water and the humic acid are uniformly mixed in the ball mill, so that the reaction contact surface is enlarged, the humic acid ammonium is generated, and then the reaction temperature is increased by adding the dilute sulfuric acid, and the generation of the humic acid ammonium is accelerated.

In order to improve the content of active humic acid in lignite and realize continuous industrial production, the invention provides a production process for producing a compound fertilizer by activating humic acid so as to reduce the production cost of the humic acid compound fertilizer, and an auxiliary agent is added into the raw materials of the prepared compound fertilizer to improve the granulation integrity, wherein the auxiliary agent takes sodium alginate as a raw material and is easy to chelate with N, P, K and the like to obtain chelate molecules which are easy to be absorbed by plants and have biological activity, so that the absorption efficiency of the crops on nutrient elements is enhanced, and the fertilizer loss is effectively reduced.

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

Preparing an auxiliary agent:

step S11, mixing sodium alginate and water, adding sodium hydroxide to adjust the pH value to 7, adding a mixture of adipic acid and acetic anhydride, stirring and reacting for 1.5 hours at the temperature of 40 ℃, adding absolute ethyl alcohol after the reaction is finished, separating out a solid, and then carrying out vacuum filtration to obtain a solid a; wherein the mixture of adipic acid and acetic anhydride is adipic acid and acetic anhydride in a molar ratio of 1: 1, the dosage ratio of sodium alginate to water is 1 g: 10 mL; the mass ratio of the sodium alginate to the mixture of adipic acid and acetic anhydride is 100: 7;

and step S12, mixing the solid a with water, adjusting the pH value to 8 by using sodium hydroxide, adding an octenyl succinic anhydride solution, stirring for reacting for 3 hours, then adding a 1mol/L hydrochloric acid solution to adjust the pH value to 6, carrying out vacuum filtration, washing a filter cake by using an ethanol aqueous solution with the volume fraction of 60% and distilled water in sequence, and after washing is finished, drying to constant weight at 50 ℃ to obtain the auxiliary agent. Wherein the octenyl succinic anhydride solution is prepared by mixing octenyl succinic anhydride and isopropanol according to a ratio of 1 g: 10mL of the mixture is mixed; the using ratio of the solid a to the water is 1 g: 20 mL; the using amount mass ratio of the solid a to the octenyl succinic anhydride is 100: 3.

example 2

Preparing an auxiliary agent:

step S11, mixing sodium alginate and water, adding sodium hydroxide to adjust the pH value to 9, adding a mixture of adipic acid and acetic anhydride, stirring and reacting for 3.5 hours at the temperature of 60 ℃, adding absolute ethyl alcohol after the reaction is finished, separating out a solid, and then carrying out vacuum filtration to obtain a solid a; wherein the mixture of adipic acid and acetic anhydride is adipic acid and acetic anhydride in a molar ratio of 1: 1, the dosage ratio of sodium alginate to water is 1 g: 10 mL; the mass ratio of the sodium alginate to the mixture of adipic acid and acetic anhydride is 100: 9;

and step S12, mixing the solid a with water, adjusting the pH value to 8 by using sodium hydroxide, adding an octenyl succinic anhydride solution, stirring for reacting for 3 hours, then adding a 1mol/L hydrochloric acid solution to adjust the pH value to 6, carrying out vacuum filtration, washing a filter cake by using an ethanol aqueous solution with the volume fraction of 60% and distilled water in sequence, and after washing is finished, drying to constant weight at 50 ℃ to obtain the auxiliary agent. Wherein the octenyl succinic anhydride solution is prepared by mixing octenyl succinic anhydride and isopropanol according to a ratio of 1 g: 10mL of the mixture is mixed; the using ratio of the solid a to the water is 1 g: 20 mL; the using amount mass ratio of the solid a to the octenyl succinic anhydride is 100: 5.

example 3

Preparing raw materials of a compound fertilizer:

heating and melting urea, adding ammonium sulfate and potassium sulfate to obtain a compound, mixing the compound and an auxiliary agent, properly adding water, and granulating by using a traditional granulator to obtain the raw material of the compound fertilizer. Wherein, the raw materials of the compound fertilizer comprise 30 parts of urea, 8 parts of ammonium sulfate, 22 parts of potassium sulfate and 7 parts of auxiliary agent by weight; the adjuvant was prepared as in example 2.

Example 4

Preparing raw materials of a compound fertilizer:

heating and melting urea, adding ammonium sulfate and potassium sulfate to obtain a compound, mixing the compound and an auxiliary agent, properly adding water, and granulating by using a traditional granulator to obtain the raw material of the compound fertilizer. Wherein the raw materials of the compound fertilizer comprise 50 parts of urea, 10 parts of ammonium sulfate, 30 parts of potassium sulfate and 10 parts of an auxiliary agent by weight; the adjuvant was prepared as in example 2.

Example 5

A production method of continuously activated humic acid compound fertilizer comprises the following steps:

first step, first activation: conveying lignite into an industrial ball mill through a conveying belt, introducing ammonia water, grinding for 15min, and grinding the lignite into uniform slurry to obtain lignite slurry;

step two, second activation: conveying the lignite homogenate into a granulator through an ore pulp pump, adding dilute sulfuric acid into a mixing reactor with a distribution pipe, uniformly mixing the lignite homogenate and the dilute sulfuric acid in the rotating process, and stirring for 2 hours at the temperature of 90 ℃ to obtain a premix; the activation is promoted by utilizing the temperature of acid-base reaction;

step three, activating for the third time: uniformly mixing the premix with the compound fertilizer raw materials in a granulator, controlling the air temperature of the head of the granulator to be 500 ℃, the material temperature to be 70 ℃ and the material temperature at the tail of the granulator to be 50 ℃, and carrying out three-time activation on humic acid.

And fourthly, after granulation is finished, drying, cooling and screening are carried out, and the compound fertilizer produced by continuously activating humic acid is obtained.

Wherein the mass fraction of the ammonia water is 5%; the solid-liquid ratio of the lignite to the ammonia water is 3 g: 1 mL; the mass fraction of the dilute sulfuric acid is 50%, and the volume ratio of the dosage of the dilute sulfuric acid to the dosage of the lignite homogenate is 1: 10; the compound fertilizer raw material was prepared as in example 4.

Example 6

A production method of continuously activated humic acid compound fertilizer comprises the following steps:

first step, first activation: conveying lignite into an industrial ball mill through a conveying belt, introducing ammonia water, grinding for 18min, and grinding the lignite into uniform slurry to obtain lignite slurry;

step two, second activation: conveying the lignite homogenate into a granulator through an ore pulp pump, adding dilute sulfuric acid into a mixing reactor with a distribution pipe, uniformly mixing the lignite homogenate and the dilute sulfuric acid in the rotating process, and stirring for 3 hours at the temperature of 92 ℃ to obtain a premix; the activation is promoted by utilizing the temperature of acid-base reaction;

step three, activating for the third time: uniformly mixing the premix with the compound fertilizer raw materials in a granulator, controlling the air temperature of the head of the granulator to be 550 ℃, the material temperature to be 75 ℃ and the material temperature of the tail of the granulator to be 52 ℃, and carrying out three-time activation on humic acid.

And fourthly, after granulation is finished, drying, cooling and screening are carried out, and the compound fertilizer produced by continuously activating humic acid is obtained.

Wherein the mass fraction of the ammonia water is 10 percent; the solid-liquid ratio of the lignite to the ammonia water is 4 g: 1 mL; the mass fraction of the dilute sulfuric acid is 55%, and the volume ratio of the dosage of the dilute sulfuric acid to the dosage of the lignite homogenate is 1: 8; the compound fertilizer raw material was prepared as in example 4.

Example 7

A production method of continuously activated humic acid compound fertilizer comprises the following steps:

first step, first activation: conveying lignite into an industrial ball mill through a conveying belt, introducing ammonia water, grinding for 20min, and grinding the lignite into uniform slurry to obtain lignite slurry;

step two, second activation: conveying the lignite homogenate into a granulator through an ore pulp pump, adding dilute sulfuric acid into a mixing reactor with a distribution pipe, uniformly mixing the lignite homogenate and the dilute sulfuric acid in the rotating process, and stirring for 4 hours at the temperature of 95 ℃ to obtain a premix; the activation is promoted by utilizing the temperature of acid-base reaction;

step three, activating for the third time: uniformly mixing the premix with the compound fertilizer raw materials in a granulator, controlling the air temperature of the head of the granulator to be 600 ℃, the material temperature to be 80 ℃ and the material temperature of the tail of the granulator to be 55 ℃, and carrying out three times of activation on humic acid.

And fourthly, after granulation is finished, drying, cooling and screening are carried out, and the compound fertilizer produced by continuously activating humic acid is obtained.

Wherein the mass fraction of the ammonia water is 15%; the solid-liquid ratio of the lignite to the ammonia water is 5 g: 1 mL; the mass fraction of the dilute sulfuric acid is 50%, and the volume ratio of the dosage of the dilute sulfuric acid to the dosage of the lignite homogenate is 1: 5; the compound fertilizer raw material was prepared as in example 4.

Comparative example 1

Compared with example 6, the first activation was not performed, and the remaining raw materials and preparation process were kept unchanged.

Comparative example 2

Compared with example 6, the second activation was not performed, and the rest of the raw materials and the preparation process were kept unchanged.

The samples prepared in the examples 5-7 and the comparative examples 1-2 are tested, the vegetable greenhouse is tested, the plant spacing is 18-20 cm, the row spacing is 25-30 cm, and the variety of the lettuce is as follows: greenish green and beautiful, oil green lettuce, the fertilization period is 20 days, the fertilization amount is 6 kg/mu, the fertilization is carried out for three times, 20 days after the third fertilization, and the average plant height, the average plant weight and the yield increase are recorded.

The test results are shown in table 1 below:

TABLE 1

As can be seen from the above table 1, the continuously activated humic acid compound fertilizer prepared by the invention has good use effect on vegetable planting.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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.