Production process of plant growth regulator-containing macroelement water-soluble fertilizer

Abstract

The application discloses a production process of a plant growth regulator-containing macroelement water-soluble fertilizer, and comprises the following steps: selecting macroelement components containing at least two of nitrogen, phosphorus and potassium, a specific plant growth regulator, a functional additive containing a porous nano adsorption carrier and a molecular stabilizer, and deionized water; loading the regulator on the nano carrier by vacuum impregnation or spray adsorption to form an intermediate, mixing the intermediate with a fertilizer base liquid under the protection of inert gas, high-speed shearing and high-pressure nano homogenization dispersion, vacuum low-temperature concentration, low-temperature drying and low-temperature airflow crushing, and finally, nitrogen charging or vacuum packaging. The process realizes that the retention rate of active ingredients of the regulator is greater than or equal to 95%, the retention rate is greater than or equal to 90% after 90-day accelerated storage, the product is fast in dissolution, uniform in dispersion, low in hygroscopicity, suitable for large-scale production, and efficient in playing the synergistic effect of "nutrient supply + growth regulation".

Description

Technical Field

[0001] This invention relates to the field of agricultural fertilizer production technology, specifically to a production process for a water-soluble fertilizer containing plant growth regulators and macro-elements. Background Technology

[0002] The combination of plant growth regulators and water-soluble fertilizers containing macronutrients is an important development direction for modern agriculture to achieve the integration of "nutrition + regulation" and improve fertilizer efficiency. By adding trace amounts of highly efficient plant growth regulators (such as brassinolide, S-inducer, etc.) to water-soluble fertilizers, essential nutrients can be provided to crops while their growth and development are directionally regulated, enhancing their resistance to stress, thereby achieving increased yield and improved quality.

[0003] However, combining extremely low amounts (typically 1 to 1 / 10,000,000) of plant growth regulators with high concentrations of macro-element inorganic salts (nitrogen, phosphorus, potassium, etc.) and processing them into physicochemically stable solid water-soluble fertilizer products faces a series of long-standing technical bottlenecks in existing technologies: Chemical stability challenges: Most plant growth regulators are organic active substances, and their molecular structures are easily damaged in high-ionic-strength inorganic salt solutions, undergoing degradation, isomerization, or complexation reactions with metal ions, leading to a sharp decline in biological activity. Especially in subsequent processing steps involving temperature increases, such as concentration and drying, heat-sensitive regulator components are prone to decomposition and inactivation, resulting in a very low retention rate of active ingredients in the final product, severely impacting the product's effectiveness and consistency.

[0004] The challenges of physical uniformity and dispersibility: Due to their extremely small dosage, plant growth regulators are difficult to distribute evenly within a large solid fertilizer matrix. Conventional, simple physical mixing easily leads to the "agglomeration" or uneven distribution of the regulator in the finished product, resulting in excessively high or low local concentrations during application. This not only leads to unstable efficacy but may even cause phytotoxicity to crops due to excessively high local concentrations. Furthermore, this non-uniformity also prevents the regulator from dispersing quickly and evenly in water during dissolution.

[0005] Storage stability challenges: Even if mixing is achieved in the early stages of processing, the hygroscopic salts and trace modifiers remain in close contact for extended periods during storage, accelerating the slow degradation of active ingredients. Furthermore, water-soluble fertilizer powders produced using conventional processes are prone to absorbing moisture and clumping, further impacting the product's physical stability and ease of application.

[0006] Current production processes mostly involve directly dissolving regulators in the aqueous phase and then simply mixing them with fertilizer solutions, or dry mixing them with solid fertilizers. The former cannot solve the problem of chemical degradation during processing and storage, while the latter cannot solve the problem of uniform distribution. Although some technologies have attempted to add common carriers or adjuvants, none of them have fundamentally achieved effective physical isolation and protection of active ingredients throughout the entire processing (especially in high-temperature and high-salt environments) and during storage, nor have they achieved uniform dispersion at the nanoscale. Therefore, improvements are urgently needed. Summary of the Invention

[0007] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a production process for water-soluble fertilizers containing macronutrients and plant growth regulators. This process utilizes key technologies such as porous nanocarrier loading, inert gas protection, multi-stage homogeneous dispersion, and low-temperature processing. It achieves the advantages of efficient retention, uniform dispersion, and long-term product stability of active ingredients, solving problems in the production of water-soluble fertilizers containing macronutrients and plant growth regulators, including poor chemical stability of plant growth regulators, easy degradation during processing, uneven distribution in the finished product, loss of active ingredients during storage, and easy agglomeration of powder.

[0008] (II) Technical Solution To achieve the above objectives, the present invention provides the following technical solution: A production process for a water-soluble fertilizer containing plant growth regulators and macro-elements includes the following steps: S1 Raw Material Selection: Select macro-element components, plant growth regulator components, functional additives, and deionized water as raw materials; The macro-elemental components include at least two of nitrogen source, phosphorus source, and potassium source. The nitrogen source is selected from one or more of urea, ammonium nitrate, and ammonium sulfate. The phosphorus source is selected from one or more of potassium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium polyphosphate. The potassium source is selected from one or more of potassium chloride, potassium sulfate, and potassium nitrate. The plant growth regulator component is selected from one or more of brassinolide, S-inducer, paclobutrazol, and others, and its proportion in the total mass of the raw materials is 0.001% to 0.1%. The functional adjuvant comprises a porous nano-adsorbent carrier and a molecular stabilizer. The porous nano-adsorbent carrier is selected from one or more of modified nano-silica, mesoporous carbon, porous starch, and sepiolite powder, with a specific surface area of ​​200-600 m² / g and an average pore size of 2-50 nm. The mass ratio of the plant growth regulator component to the porous nano-adsorbent carrier is 1:50 to 1:200. The molecular stabilizer is selected from one or more of cyclodextrin, sodium lignosulfonate, and polyvinylpyrrolidone, and is used to form inclusion complexes or spatial barriers with plant growth regulator molecules during loading.

[0009] S2 raw material pretreatment: S2.1 The macro-element components are crushed and sieved to a particle size of 80-120 mesh to ensure subsequent dissolution efficiency; S2.2 Loading of plant growth regulators: The plant growth regulator components are dissolved in a portion of deionized water, and the temperature is controlled at 25~40℃ and the stirring rate is 100~200 r / min to obtain a uniform regulator stock solution; the regulator stock solution is mixed with the porous nano-adsorbent carrier under stirring, and vacuum impregnation or spray adsorption is used to allow the regulator molecules to fully enter the pores of the carrier to obtain a loaded regulator intermediate; wherein the vacuum impregnation conditions are: temperature 25-35℃, vacuum degree -0.08 to -0.095 MPa, and impregnation time 2-4 h.

[0010] S3 Mixing and Reaction: The pretreated macro-element components are added to the reactor, along with the remaining deionized water, and stirred until completely dissolved to form a fertilizer base solution. Under inert gas (nitrogen or argon) protection, the loaded regulator intermediate is slowly added to the fertilizer base solution, along with the remaining functional additives. The reaction temperature is controlled at 30-45℃, and the stirring rate is 300-500 r / min. The reaction is carried out at a constant temperature for 1.5-2.5 h to prevent the active ingredients from oxidizing and degrading upon contact with air.

[0011] S4 Deep Homogeneous Dispersion: The reacted mixture is transported to a homogenizer and first subjected to high-speed shear dispersion, with the rotation speed controlled at 8000-15000 r / min and the time at 10-20 min, to break up the initial agglomerates; then high-pressure nano-homogenization is performed, with the pressure controlled at 60-100 MPa and the number of cycles at 3-5, to achieve nanoscale uniform dispersion of the loaded regulator intermediate in the fertilizer system, resulting in a homogeneous and stable suspension.

[0012] S5 Low-Temperature Concentration and Solidification: The suspension is concentrated under vacuum at low temperature, with the concentration temperature controlled at 40-55℃ and the vacuum degree not lower than -0.08 MPa, until the solid content of the slurry is 65%-80%, reducing the impact of high temperature on the active ingredients; then the slurry is introduced into a low-temperature continuous belt dryer or a vacuum freeze dryer for dehydration and solidification, with the drying temperature controlled not higher than 60℃, until the material moisture content is ≤3%, to obtain a porous solid material.

[0013] S6 Finished Product Preparation: The porous solid material is subjected to low-temperature airflow pulverization, with the inlet air temperature controlled at ≤20℃ to ensure that the particle size D90 of the pulverized material is ≤15μm; then it is sieved through a 200-400 mesh screen to remove a small amount of large particle impurities; finally, it is metered and packaged in a nitrogen-filled or vacuum environment to avoid moisture absorption and oxidation of active ingredients, thus obtaining the finished product of water-soluble fertilizer containing plant growth regulators and macro-elements.

[0014] (III) Beneficial Effects Compared with the prior art, the present invention provides a production process for a water-soluble fertilizer containing plant growth regulators and macro-elements, which has the following beneficial effects: 1. Significantly improves the retention rate of active ingredients: By loading plant growth regulators onto porous nano-adsorbent carriers, combined with the inclusion and spatial barrier effects of molecular stabilizers, physical isolation and chemical protection of active ingredients are achieved. With the addition of inert gas protection, vacuum low-temperature concentration and low-temperature drying, low-temperature pulverization and other low-temperature processing techniques, the degradation and damage of plant growth regulators by high-salt environments, high-temperature conditions and oxygen are effectively avoided, so that the processing retention rate of active ingredients of plant growth regulators in the final product is ≥95%, solving the core problem of easy failure of active ingredients in existing processes.

[0015] 2. Achieving uniform dispersion and application safety: Through a multi-stage homogenization process of "high-speed shear dispersion + high-pressure nano-homogenization", the intermediate of the loaded regulator is dispersed to the nanoscale, ensuring its uniform distribution in the fertilizer system and avoiding the agglomeration problem caused by conventional mixing; the finished product can be quickly dissolved and uniformly dispersed after being diluted with water, and there will be no local concentration that is too high or too low during application, which not only ensures the stability of the regulatory effect, but also reduces the risk of phytotoxicity.

[0016] 3. Enhanced product storage stability: The porous structure of the loaded regulator intermediate can isolate the active ingredients from macro-element salts for a long time, reducing interactions during storage; the porous solid material obtained by low-temperature drying and the nitrogen-filled / vacuum packaging method effectively reduce the risk of moisture absorption and clumping of the finished product; after accelerated storage for 90 days at 50℃ and 75% relative humidity, the retention rate of plant growth regulator active ingredients in the product is ≥90%, which is significantly better than existing process products and extends the product shelf life.

[0017] 4. Balancing production efficiency and product quality: The parameters of each step in this process are clear and highly operable, making it suitable for large-scale production. The dissolution efficiency of the pretreatment of macro-elements, the synergistic effect of multi-stage homogenization and low-temperature processing, ensure both the product's water solubility (complete dissolution within 3 minutes in 20℃ water) and the synergistic effect of nutrients and active ingredients, achieving an integrated function of "nutrient supply + growth regulation". Detailed Implementation

[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] Example 1 Raw material selection: Major elemental components: 30 kg of urea (nitrogen source), 45 kg of potassium dihydrogen phosphate (phosphorus source + potassium source), and 20 kg of potassium nitrate (potassium source); Plant growth regulator components: brassinolide 0.005 kg; Functional additives: 0.5 kg of modified nano-silica (specific surface area 350 m² / g, average pore size 15 nm) and 1.5 kg of β-cyclodextrin (molecular stabilizer); 50kg of deionized water.

[0020] Raw material pretreatment: S2.1 Crush urea, potassium dihydrogen phosphate, and potassium nitrate separately and pass them through a 100-mesh sieve for later use; S2.2 Take 10 kg of deionized water, heat it to 30 °C, add brassinolide, stir and dissolve at 150 r / min to obtain the regulator mother liquor; mix the regulator mother liquor with modified nano silica, place it in a vacuum impregnation tank, control the temperature at 30 °C and the vacuum degree at -0.09 MPa, impregnate for 3 h, filter and dry to obtain the supported regulator intermediate.

[0021] Mixing and reaction: The pretreated macro-element components were put into the reactor, and the remaining 40 kg of deionized water was added. After stirring and dissolving, a fertilizer base solution was formed. Nitrogen gas was introduced for protection, and the loaded regulator intermediate and β-cyclodextrin were slowly added. The temperature was controlled at 35℃ and the stirring rate at 400 r / min. The reaction was carried out at a constant temperature for 2 hours.

[0022] Deep homogenization and dispersion: The mixed reaction solution is transported to a homogenizer and first dispersed at high speed of 12000 r / min for 15 min, and then homogenized at high pressure of 80 MPa for 4 times to obtain a suspension.

[0023] Low-temperature concentration and solidification: The suspension was concentrated under vacuum at low temperature, with the temperature controlled at 50℃ and the vacuum degree at -0.09MPa, until the solid content was 70%; then, it was dried at 55℃ using a vacuum freeze dryer until the water content was 2.5%, resulting in a porous solid material.

[0024] Preparation of finished product: The porous solid material is subjected to low-temperature airflow pulverization (inlet air temperature 15℃), and the particle size D90 after pulverization is 12μm; it is then passed through a 300-mesh sieve and metered and packaged in a nitrogen-filled environment to obtain the finished product.

[0025] Example 2 Raw material selection: Major elemental components: ammonium nitrate (nitrogen source) 25kg, ammonium polyphosphate (phosphorus source) 30kg, potassium sulfate (potassium source) 35kg; Plant growth regulator components: S-inducer 0.01 kg; Functional additives: 1.5 kg of mesoporous carbon (specific surface area 500 m² / g, average pore size 20 nm) and 2 kg of sodium lignosulfonate (molecular stabilizer); 60kg of deionized water.

[0026] Raw material pretreatment: S2.1 Ammonium nitrate, ammonium polyphosphate, and potassium sulfate are pulverized and then passed through a 120-mesh sieve; S2.2 Take 15 kg of deionized water, heat it to 35 °C, and stir at 180 r / min to dissolve S-inducer to obtain the regulator mother liquor; mix the regulator mother liquor with mesoporous carbon, and use spray adsorption to make the mother liquor uniformly adhere to the surface of mesoporous carbon, and dry it to obtain the supported regulator intermediate.

[0027] Mixing and reaction: Add the macro-element components to the reactor, add the remaining 45 kg of deionized water to dissolve them, purge with argon gas, add the supported regulator intermediate and sodium lignosulfonate, control the temperature at 40℃ and the stirring rate at 450 r / min, and react at a constant temperature for 2 h.

[0028] Deep homogeneous dispersion: First, disperse at high speed of 15000 r / min for 12 min, then homogenize at high pressure of 90 MPa for 4 times to obtain a suspension.

[0029] Low-temperature concentration and solidification: Vacuum low-temperature concentration at 50℃ and vacuum degree -0.085 MPa, concentrated to a solid content of 75%; then dried at 55℃ using a low-temperature continuous belt dryer to a moisture content of 2%, yielding porous solid material.

[0030] Preparation of finished product: Low-temperature airflow pulverization (inlet temperature 18℃), particle size D90=10μm; after sieving through a 400-mesh sieve, vacuum packaging is used to obtain the finished product.

[0031] Example 3 Raw material selection: Major elemental components: Ammonium sulfate (nitrogen source) 20kg, diammonium hydrogen phosphate (phosphorus source) 35kg, potassium chloride (potassium source) 30kg; Plant growth regulator components: Coronavirus 0.008 kg; Functional additives: sepiolite powder (specific surface area 250 m² / g, average pore size 30 nm) 1.2 kg, polyvinylpyrrolidone (molecular stabilizer) 1.8 kg; 55kg of deionized water.

[0032] Raw material pretreatment: S2.1 After crushing the large number of elemental components, pass them through a 100-mesh sieve; S2.2 Take 12 kg of deionized water and dissolve the coronary spores at 30 °C with stirring at 150 r / min to obtain the regulator mother liquor; mix it with sepiolite powder and place it in a vacuum impregnation tank at 32 °C and a vacuum of -0.09 MPa for 3 h to obtain the supported regulator intermediate.

[0033] Mixing and reaction: The macro-element components were dissolved in the remaining 43 kg of deionized water. Under nitrogen protection, the supported regulator intermediate and polyvinylpyrrolidone were added. The reaction was carried out at 38 °C and 420 r / min for 2.5 h.

[0034] Deep homogeneous dispersion: high-speed shear dispersion at 10000 r / min for 18 min, followed by high-pressure nano-homogenization at 70 MPa 5 times to obtain a suspension.

[0035] Low-temperature concentration and solidification: Vacuum concentration at 45℃ to a solid content of 72%, followed by vacuum freeze drying to a moisture content of 2.8%, yielding a porous solid material.

[0036] Product preparation: Low-temperature airflow pulverization (inlet temperature 16℃), particle size D90=13μm; after 250 mesh sieving, nitrogen filling and packaging are used to obtain the finished product.

[0037] Experimental Example To verify the superiority of the process of this invention, a control group (using existing conventional processes: plant growth regulators are directly dissolved and mixed with fertilizer solution, followed by conventional high-temperature concentration and spray drying) was set up for performance comparison with the finished products of Examples 1, 2, and 3 of this invention. The test indicators and results are as follows: Judgment criteria: The retention rate of active ingredients during processing is ≥90% as excellent, 80%~90% as good, and <80% as unqualified. After accelerated storage, an active ingredient retention rate of ≥85% is considered excellent, 75%~85% is considered good, and <75% is considered unqualified. Dissolution time ≤3min is excellent, 3~5min is good, and >5min is unacceptable; A moisture absorption rate of ≤3% is excellent, 3%~5% is good, and >5% is unqualified; The dispersion uniformity CV ≤ 5% is excellent, 5%~10% is good, and > 10% is unacceptable.

[0038] Experimental conclusions: The finished products of Examples 1, 2, and 3 of this invention are significantly superior to the control group in terms of active ingredient retention rate, storage stability, dissolution rate, and dispersion uniformity, fully meeting the excellent standards and verifying the technical advantages of this process.

[0039] Typical Case The product from Example 1 of this invention was applied to tomato cultivation, with 5 kg per acre, diluted 1000 times with water, for root irrigation. A control group (using conventional processing) and a blank control group (without water-soluble fertilizer) were also included. Results showed:

[0040] The germination rate of tomatoes produced by this invention is increased by 12%, plant height increases by 15%, and stress resistance (drought resistance and disease resistance) is significantly enhanced. The harvest was brought forward by 7 days, the weight of individual fruits increased by 18%, the total yield increased by 22%, and the soluble solids content of the fruits increased by 3.5%. The total tomato yield of the control group increased by 8%, but the stress resistance showed no significant improvement. The blank control group did not exhibit the aforementioned effects of increasing yield and improving quality.

[0041] This case demonstrates that the water-soluble fertilizer produced by the process of this invention can effectively exert the synergistic effect of "nutrition + regulation" due to the full retention and uniform distribution of active ingredients, thus significantly improving crop planting benefits.

[0042] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A production process for a water-soluble fertilizer containing plant growth regulators and macro-elements, characterized in that, Includes the following steps: S1 Raw Material Selection: The raw materials include macro-element components, plant growth regulator components, functional additives, and deionized water; the macro-element components include at least two of nitrogen source, phosphorus source, and potassium source; the functional additives include at least one porous nano-adsorbent carrier. S2 raw material pretreatment: S2.1 The macro-elemental components are crushed and sieved; S2.2 Loading of plant growth regulators: The plant growth regulator components are dissolved in a portion of deionized water to obtain a regulator stock solution; the regulator stock solution is mixed with the porous nano-adsorption carrier under stirring, and vacuum impregnation or spray adsorption is performed to load the regulator into the pores of the carrier to obtain a loaded regulator intermediate; S3 Mixing and Reaction: The pretreated macro-element components are put into the reaction vessel, the remaining deionized water is added, and the mixture is stirred until completely dissolved to form a fertilizer base solution; under inert gas protection, the loaded regulator intermediate is slowly added to the fertilizer base solution, and other functional adjuvants are added at the same time, and the reaction conditions are controlled to carry out a constant temperature reaction. S4 Deep Homogeneous Dispersion: The reaction mixture is transported to a homogenizer and subjected to high-speed shear dispersion and high-pressure nano-homogenization in sequence to obtain a homogeneous and stable suspension; S5 Low-temperature concentration and solidification: The suspension is concentrated under vacuum at low temperature to obtain a paste or high-solids slurry; then the slurry is introduced into a low-temperature continuous belt dryer or a vacuum freeze dryer for dehydration and solidification to obtain a porous solid material; S6 Finished Product Preparation: The porous solid material is subjected to low-temperature airflow pulverization, sieving, metering, and packaging to obtain a finished water-soluble fertilizer containing plant growth regulators and macro-elements; wherein, the packaging is carried out in a nitrogen-filled or vacuum environment.

2. The production process of a water-soluble fertilizer containing plant growth regulators and macro-elements according to claim 1, characterized in that, In step S1, the porous nano-adsorbent carrier is selected from one or more of modified nano-silica, mesoporous carbon, porous starch, and sepiolite powder, with a specific surface area of ​​200-600 m² / g and an average pore size of 2-50 nm.

3. The production process of a water-soluble fertilizer containing plant growth regulators and macro-elements according to claim 1, characterized in that, In step S1, the plant growth regulator component is selected from one or more of brassinolide, S-inducer, paclobutrazol, and paclobutrazol; and the mass ratio of the plant growth regulator component to the porous nano-adsorbent carrier is 1:50 to 1:

200.

4. The production process of a water-soluble fertilizer containing plant growth regulators and macro-elements according to claim 1, characterized in that, In step S1, the functional adjuvant further includes a molecular stabilizer, which is selected from one or more of cyclodextrin, sodium lignosulfonate, and polyvinylpyrrolidone, and is used to form inclusion complexes or spatial barriers with plant growth regulator molecules during loading.

5. The production process of a water-soluble fertilizer containing plant growth regulators and macro-elements according to claim 1 is characterized in that, In step S2.2, the conditions for vacuum impregnation are: temperature 25-35℃, vacuum degree -0.08 to -0.095 MPa, and impregnation time 2-4 h.

6. The production process of a water-soluble fertilizer containing plant growth regulators and macro-elements according to claim 1, characterized in that, In step S3, the isothermal reaction temperature is 30-45℃, the reaction time is 1.5-2.5 h, and the stirring rate is 300-500 r / min; the inert gas is nitrogen or argon.

7. The production process of a water-soluble fertilizer containing plant growth regulators and macro-elements according to claim 1, characterized in that, In step S4, the high-speed shear dispersion is performed at a rotation speed of 8000-15000 r / min for 10-20 min; the high-pressure nano-homogenization is performed at a pressure of 60-100 MPa for 3-5 cycles.

8. The production process of a water-soluble fertilizer containing plant growth regulators and macro-elements according to claim 1, characterized in that, In step S5, the vacuum low-temperature concentration temperature is 40-55℃, the vacuum degree is not lower than -0.08 MPa, and the concentration is carried out until the solid content of the slurry is 65%-80%; the low-temperature drying temperature is not higher than 60℃, and the drying is carried out until the moisture content of the material is ≤3%.

9. The production process of a water-soluble fertilizer containing plant growth regulators and macro-elements according to claim 1, characterized in that, In step S6, the inlet temperature of the low-temperature airflow pulverizer is ≤20℃, and the particle size D90 of the pulverized material is ≤15μm; the sieving particle size is 200-400 mesh.

10. The production process of a water-soluble fertilizer containing plant growth regulators and macro-elements according to claim 1, characterized in that, In the final product, the processing retention rate of the active ingredients of plant growth regulators is ≥95%, and after accelerated storage for 90 days at a temperature of 50℃ and a relative humidity of 75%, the retention rate of active ingredients is ≥90%.

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