Amino acid organic water-soluble fertilizer and preparation method thereof

Abstract

The application relates to the technical field of organic water-soluble fertilizers, and discloses an amino acid organic water-soluble fertilizer and a preparation method thereof. The amino acid organic water-soluble fertilizer comprises the following components in weight: 40-50 parts of amino acid concentrate, 10-15 parts of organic matter, 20-25 parts of macroelement, 5-8 parts of medium element, 3-5 parts of polyaspartic acid, 4-6 parts of trace element, 0.4-0.6 parts of beneficial microbial agent, 2-4 parts of quaternary ammonium salt-based silicon dioxide, 0.2-0.3 parts of indole acetic acid and 0.5-1 part of synergist. The amino acid organic water-soluble fertilizer of the application uses waste animal and plant protein as raw material, has the advantages of environmental protection and low cost, and is superior to the commercially available product which depends on chemical synthesis of amino acid; through a multi-step enzymolysis (alkaline protease + acidolysis + papain / cellulase) process, the waste protein is efficiently converted into small molecule amino acid, the limitation of traditional single-enzyme hydrolysis is broken, more comprehensive free amino acid is released, and the plant absorption rate is significantly improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic water-soluble fertilizer, in particular to an amino acid organic water-soluble fertilizer and a preparation method thereof. BACKGROUND

[0002] In recent years, with the development of facility agriculture and precision fertilization technology, water-soluble fertilizer has become a research hotspot due to its efficient absorption and environmental friendliness. Long-term use of traditional chemical fertilizers can easily lead to soil compaction, salinization and environmental pollution, while conventional organic fertilizers have problems such as slow nutrient release and low active ingredients. Amino acid water-soluble fertilizer, as a new type of functional fertilizer, can directly participate in plant metabolism by providing small-molecule organic nitrogen sources, and has growth promotion and stress resistance functions, but its application still faces the following bottlenecks:

[0003] Insufficient amino acid source and activity: most products use chemical synthesis or single enzymatic process to prepare amino acids, which have wide molecular weight distribution and low free amino acid content, resulting in poor plant absorption and utilization rate;

[0004] Poor nutrient synergy: in traditional formulations, macronutrients and micronutrients are simply physically mixed, which can easily cause antagonism or precipitation, and lack of slow-release carriers, resulting in nutrient loss;

[0005] Single function: most commercially available products focus on nutrient supply, ignoring the microorganism-plant-soil interaction mechanism, and have limitations in disease resistance, root promotion, quality improvement and other comprehensive functions;

[0006] Low utilization rate of waste resources: animal and plant protein waste (such as soybean meal and fish meal) is often treated as low-value raw material and cannot be efficiently converted into high-value fertilizer components.

[0007] In the prior art, although some studies have tried to improve fertilizer efficiency by using complex microorganisms, adding chelating agents or plant growth regulators, most of them are limited to single function improvement. In addition, for fruits and corns that require high sugar accumulation and lodging resistance, traditional fertilizers cannot meet the dual demands of quality and yield.

[0008] Chinese patent application CN104030741B discloses an acidic organic fertilizer and a preparation method thereof, which effectively solves the problems of insufficient soil fertility, supplement of fertilizer, avoids soil compaction, effectively improves soil alkalinity, and has high specificity, but the nutrition needs to be improved. SUMMARY

[0009] In view of the deficiencies of the prior art, the amino acid organic water-soluble fertilizer provided by the present application has the advantages of efficient nutrient supply, disease resistance and yield increase, and waste resource utilization. The present application provides the following technical solutions: the amino acid organic water-soluble fertilizer comprises the following components by weight: 40-50 parts by weight of an amino acid concentrate, 10-15 parts by weight of organic matter, 20-25 parts by weight of macroelements, 5-8 parts by weight of meso-elements, 3-5 parts by weight of polyaspartic acid, 4-6 parts by weight of microelements, 0.4-0.6 parts by weight of beneficial microbial inoculants, 2-4 parts by weight of quaternary ammonium salt-based silicon dioxide, 0.2-0.3 parts by weight of indole acetic acid, and 0.5-1 part by weight of a synergist.

[0010] Further, the amino acid concentrate is prepared from waste animal and plant proteins through enzymatic hydrolysis and acid hydrolysis, and the total amino acid content in the amino acid concentrate is greater than or equal to 70%.

[0011] Further, the organic matter is any one or more of humic acid, potassium fulvate, and alginic acid.

[0012] Further, the macroelements include any one or more of nitrogen, phosphorus, and potassium.

[0013] The meso-elements include at least calcium and magnesium.

[0014] The microelements include at least boron, zinc, manganese, iron, copper, and molybdenum.

[0015] Further, the beneficial microorganisms are any one or more of Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus megaterium, Bacillus mycoides, and Bacillus licheniformis.

[0016] Further, the preparation method of the amino acid concentrate is as follows:

[0017] S11: After the waste animal and plant proteins are crushed, deionized water is added, the solution is adjusted to be alkaline, and alkaline protease is added for hydrolysis; after hydrolysis, the primary peptide solution is obtained by filtration;

[0018] S12: Dilute hydrochloric acid is added to the primary peptide solution, the pH is adjusted to 2.0-3.0, and the solution is acid-hydrolyzed at 80°C for 2 hours to break the large molecular peptide chains into a small molecular amino acid solution;

[0019] S13: After the small molecular amino acid solution is cooled, papain and cellulase are added for hydrolysis to further release free amino acids; after enzyme inactivation, the solution is cooled, concentrated, and spray-dried to obtain the amino acid concentrate.

[0020] Further, in step S11, the waste animal and plant proteins include multiple types of soybean meal, fish meal, and feathers; the ratio of the amount of the waste animal and plant proteins to the amount of deionized water is 1: (3-5), and the amount of the alkaline protease is 0.5-1% of the solution.

[0021] The papain and cellulase are used in an amount of 0.3-0.5% and 0.2-0.4% of the small molecule amino acid solution respectively in step S11.

[0022] Further, the preparation method of the quaternary ammonium salt-based silicon dioxide is as follows:

[0023] S21: 5-9 parts by weight of (dimethylaminomethyl) phenol and 2-4 parts by weight of pyromellitic anhydride are added to 1,4-dioxane solvent and stirred uniformly, then 0.03-0.032 parts by weight of pyridine catalyst is added thereto, and the temperature is raised to 70-80°C for stirring reaction for 6-8h, after the reaction, the solvent is removed by reduced pressure concentration, washed with diethyl ether, and recrystallized in dichloromethane to obtain intermediate 1;

[0024] S22: 12-15 parts by weight of chloroacetic acid and 9-10 parts by weight of intermediate 1 are added to N,N-dimethylformamide solvent, and nitrogen protection is performed, and the reaction is performed at 75-90°C, after the reaction is completed, distilled under reduced pressure, washed and dried to obtain intermediate 2;

[0025] S23: 5-8 parts by weight of hydroxylated silicon dioxide and 4-7 parts by weight of intermediate 2 are added to a reactor containing N,N-dimethylformamide, and stirred and mixed, and 0.02-0.024 parts by weight of p-toluenesulfonic acid catalyst is further added thereto, and the reaction is performed at 50-70°C for 4-5h, after the reaction is completed, distilled under reduced pressure, washed and dried to obtain quaternary ammonium salt-based silicon dioxide.

[0026] Further, the weight ratio of (dimethylaminomethyl) phenol to pyromellitic anhydride in step S21 is (1-2.5):1; and the weight of the pyridine catalyst is 0.8-1.5% of the pyromellitic anhydride;

[0027] The weight ratio of chloroacetic acid to intermediate 1 in step S22 is (1.2-1.6):1;

[0028] The weight ratio of hydroxylated silicon dioxide to intermediate 2 in step S23 is (1-1.3):1; and the weight of the pyridine catalyst is 0.5-1.2% of the intermediate 2.

[0029] Further, the preparation method of the amino acid organic water-soluble fertilizer comprises the following steps:

[0030] S1: After the amino acid concentrate is dissolved in deionized water, organic matter is added, beneficial microorganism inoculum is inoculated, and fermentation is performed to obtain a fermentation liquor;

[0031] S2: Polyaspartic acid and chelated trace elements are sequentially added to the fermentation liquor, and stirred and reacted to form stable chelates;

[0032] S3: adding macroelements, mesoelements, quaternary ammonium salt-based silicon dioxide, indole acetic acid, potassium chloride, synergist into the chelate, stirring and spray drying to obtain solid water-soluble fertilizer or directly blending into liquid water-soluble fertilizer.

[0033] Beneficial technical effects

[0034] (1) The amino acid organic water-soluble fertilizer of the present application uses waste animal and plant protein (soybean meal, fish meal, chicken feather) as raw material, has environmental protection and low cost, and is superior to commercially available products which rely on chemical synthesis of amino acids; through multi-step enzymatic hydrolysis (alkaline protease + acid hydrolysis + papain / cellulase) process, the waste protein is efficiently converted into small molecule amino acids, breaking through the limitations of traditional single enzyme hydrolysis, releasing more comprehensive free amino acids, and significantly improving the plant absorption rate;

[0035] (2) In the present application, the quaternary ammonium salt contained in the quaternary ammonium salt-based silicon dioxide can provide nitrogen element, enhance fertilizer efficiency, and improve soil structure; and the quaternary ammonium salt can combine with mineral particles in the soil to promote the formation of soil aggregate structure, increase the porosity and aeration of the soil, and the silicon oxide can also improve the permeability of the soil; the organic silicon and the quaternary ammonium salt endow the water-soluble fertilizer with slow-release, adsorption and ion exchange functions, which can reduce nutrient loss and enhance the stability of the fertilizer;

[0036] (3) The combination of polyaspartic acid and trace elements in chelation forms a stable chelate, prolongs the nutrient release period, improves the utilization rate, and the synergistic effect of indole acetic acid and microbial agents promotes root development and soil activation, and enhances stress resistance DETAILED DESCRIPTION

[0037] At 20℃, anhydrous ethanol and ammonia water with a mass fraction of 30% were added to a reactor containing deionized water, then 7.2g of tetraethyl orthosilicate was added, stirred for 3h, mixed uniformly, filtered, dried, and then the obtained product was placed in a sodium hydroxide solution, heated in a water bath at 70℃ for 4h, cooled to room temperature, washed with deionized water, and dried to obtain hydroxylated silicon dioxide.

[0038] Example 1

[0039] The amino acid organic water-soluble fertilizer comprises the following components by weight: 40 parts by weight of amino acid concentrate, 10 parts by weight of organic matter, 25 parts by weight of macroelements, 6 parts by weight of mesoelements, 5 parts by weight of polyaspartic acid, 5 parts by weight of trace elements, 0.4 parts by weight of beneficial microorganisms, 2 parts by weight of quaternary ammonium salt-based silicon dioxide, 0.2 parts by weight of indole acetic acid, and 0.7 parts by weight of synergist.

[0040] The organic matter is humic acid and alginic acid.

[0041] The macroelements include 10 parts by weight of urea, 5 parts by weight of potassium dihydrogen phosphate, 10 parts by weight of potassium chloride;

[0042] The medium elements include 3 parts by weight of EDTA-Ca, 3 parts by weight of EDTA-Mg;

[0043] The trace elements include 2 parts by weight of EDTA-Fe, 1 part by weight of manganese sulfate, 1 part by weight of zinc sulfate, and 1 part by weight of copper sulfate;

[0044] The microorganism includes 0.3 parts by weight of Bacillus subtilis and 0.1 parts by weight of Bacillus amyloliquefaciens.

[0045] The synergist is an alkyl glycoside quaternary ammonium salt.

[0046] The preparation method of the amino acid concentrate is as follows:

[0047] S11: The waste animal and plant protein (soybean meal and fish meal in a weight ratio of 1:1) is crushed to 80 mesh, deionized water is added in a weight ratio of 1:3, sodium hydroxide is added to adjust the pH to 8.0, 0.5% alkaline protease is added, and hydrolysis is carried out at 55°C for 4 hours. After hydrolysis, the primary peptide solution is obtained by filtration;

[0048] S12: Dilute hydrochloric acid is added to the primary peptide solution to adjust the pH to 2.0, and acid hydrolysis is carried out at 80°C for 2 hours to break the large molecular peptide chains into small molecular amino acid solutions;

[0049] S13: The small molecular amino acid solution is cooled to 40°C, 0.3% papain and 0.2% cellulase are added for hydrolysis for 6 hours to further release free amino acids. After the enzyme is inactivated at 60°C for 30 min, the solution is cooled, concentrated, and spray dried to obtain an amino acid concentrate.

[0050] The preparation method of the quaternary ammonium salt-based silicon dioxide is as follows:

[0051] S21: 5 parts by weight of (dimethylaminomethyl) phenol and 2 parts by weight of pyromellitic anhydride are added to 20 mL of 1,4-dioxane, stirred uniformly, then 0.03 parts by weight of pyridine catalyst is added, heated to 70°C, stirred for 6h, after reaction, the solvent is removed under reduced pressure, washed with diethyl ether, recrystallized in dichloromethane to obtain intermediate 1;

[0052] S22: 12 parts by weight of chloroacetic acid and 9 parts by weight of intermediate 1 are added to 16 mL of N,N-dimethylformamide solvent, nitrogen is introduced for protection, and reaction is carried out at 75°C. After the reaction is completed, the product is distilled under reduced pressure, washed and dried to obtain intermediate 2;

[0053] S23: 5 parts by weight of hydroxylated silicon dioxide and 4 parts by weight of intermediate 2 are added to a reactor equipped with 25 mL of N,N-dimethylformamide, the mixture is stirred, 0.02 parts by weight of p-toluenesulfonic acid catalyst is added thereto, it is reacted at 50°C for 4 h, after the end of the reaction it is distilled under reduced pressure, washed and dried to obtain quaternary ammonium salt-based silicon dioxide.

[0054] The preparation method of the amino acid organic water-soluble fertilizer is

[0055] S1: After the amino acid concentrate is dissolved in 1 times ionized water, organic matter is added, beneficial microbial inoculants are inoculated, and fermentation is carried out at 30°C for 48 h to obtain a fermentation liquor;

[0056] S2: Polyaspartic acid and chelated trace elements are sequentially added to the fermentation liquor, and stirred for 1 h to form a stable chelate;

[0057] S3: After a large amount of elements, medium elements, quaternary ammonium salt-based silicon dioxide, indole acetic acid, potassium chloride, and synergist are added to the chelate and stirred for 1 h, spray drying is carried out to obtain a solid water-soluble fertilizer.

[0058] Example 2

[0059] The amino acid organic water-soluble fertilizer comprises the following components by weight: 45 parts by weight of amino acid concentrate, 12 parts by weight of organic matter, 22 parts by weight of large amount of elements, 5 parts by weight of medium amount of elements, 4 parts by weight of polyaspartic acid, 5 parts by weight of trace elements, 0.5 parts by weight of beneficial microorganisms, 4 parts by weight of quaternary ammonium salt-based silicon dioxide, 0.3 parts by weight of indole acetic acid, and 0.5 parts by weight of synergist;

[0060] The organic matter comprises 8 parts by weight of alginic acid and 4 parts by weight of potassium fulvic acid;

[0061] The large amount of elements comprises 8 parts by weight of urea, 5 parts by weight of potassium dihydrogen phosphate, and 9 parts by weight of potassium chloride;

[0062] The medium amount of elements comprises 3 parts by weight of EDTA-Ca and 2 parts by weight of EDTA-Mg;

[0063] The trace elements comprise 1 part by weight of EDTA-Fe, 1 part by weight of manganese sulfate, 1 part by weight of zinc sulfate, 0.5 parts by weight of copper sulfate, and 0.5 parts by weight of ammonium molybdate;

[0064] The beneficial microorganisms are 0.3 parts by weight of Bacillus subtilis and 0.2 parts by weight of Bacillus megaterium;

[0065] The synergist is an alkyl glycoside quaternary ammonium salt.

[0066] The preparation method of the amino acid concentrate is as follows:

[0067] S11: The waste animal and plant protein (soybean meal, fish meal, chicken feather weight ratio 1:1:1) is crushed to 80 mesh, 1:3 deionized water is added according to weight ratio, sodium hydroxide is added to adjust pH to 9, 0.5% alkaline protease is added, hydrolysis at 55℃ for 3 hours, after hydrolysis, the primary peptide solution is obtained by filtration;

[0068] S12: Add dilute hydrochloric acid to the primary peptide solution, adjust pH to 3, acid hydrolysis at 80℃ for 3 hours, break the large molecular peptide chain into small molecular amino acid solution;

[0069] S13: The small molecular amino acid solution is cooled to 40℃, 0.3% papain and 0.3% cellulase are added for hydrolysis for 6 hours, further releasing free amino acids, heating to 60℃ for 30min to inactivate the enzyme, then the solution is cooled, concentrated, spray dried to obtain amino acid concentrate.

[0070] The preparation method of the quaternary ammonium salt-based silicon dioxide is:

[0071] S21: 9 parts by weight of (dimethylaminomethyl) phenol and 4 parts by weight of pyromellitic anhydride are added to 25 mL of 1,4-dioxane, stirred uniformly, then 0.032 parts by weight of pyridine catalyst is added, heated to 80℃ and stirred for 8h, after reaction, the solvent is removed by reduced pressure concentration, washed with diethyl ether, recrystallized in dichloromethane to obtain intermediate 1;

[0072] S22: 15 parts by weight of chloroacetic acid and 10 parts by weight of intermediate 1 are added to 24 mL of N,N-dimethylformamide solvent, protected by nitrogen, reacted at 75-90℃, after the reaction is completed, distilled under reduced pressure, washed and dried to obtain intermediate 2;

[0073] S23: 8 parts by weight of hydroxylated silicon dioxide and 7 parts by weight of intermediate 2 are added to a reactor containing 30 mL of N,N-dimethylformamide, stirred and mixed, 0.024 parts by weight of p-toluenesulfonic acid catalyst is further added, reacted at 70℃ for 5h, after the reaction is completed, distilled under reduced pressure, washed and dried to obtain quaternary ammonium salt-based silicon dioxide.

[0074] The preparation method of the amino acid organic water-soluble fertilizer is

[0075] S1: The amino acid concentrate is added to deionized water to dissolve, then organic matter is added, inoculated with beneficial microorganism inoculum, fermented at 30℃ for 48 hours to obtain fermentation liquor;

[0076] S2: Polyaspartic acid and chelated trace elements are sequentially added to the fermentation liquor, stirred and reacted for 1 hour to form stable chelate;

[0077] S3: adding macroelements, mesoelements, quaternary ammonium salt-based silicon dioxide, indoleacetic acid, potassium chloride, synergist into the chelate, stirring for 1 hour, and then spray drying to obtain a solid water-soluble fertilizer.

[0078] Example 3

[0079] The amino acid organic water-soluble fertilizer comprises 50 parts by weight of an amino acid concentrate, 15 parts by weight of organic matter, 20 parts by weight of macroelements, 7 parts by weight of mesoelements, 3 parts by weight of polyaspartic acid, 4 parts by weight of trace elements, 0.6 parts by weight of beneficial microorganisms, 3 parts by weight of quaternary ammonium salt-based silicon dioxide, 0.2 parts by weight of indoleacetic acid, and 1 part by weight of synergist.

[0080] The organic matter comprises 8 parts by weight of alginic acid and 4 parts by weight of potassium fulvate.

[0081] The macroelements comprise 8 parts by weight of urea, 5 parts by weight of potassium dihydrogen phosphate, and 9 parts by weight of potassium chloride.

[0082] The mesoelements comprise 3 parts by weight of EDTA-Ca and 2 parts by weight of EDTA-Mg.

[0083] The trace elements comprise 1 part by weight of EDTA-Fe, 1 part by weight of manganese sulfate, 1 part by weight of zinc sulfate, 0.5 part by weight of copper sulfate, and 0.5 part by weight of ammonium molybdate.

[0084] The beneficial microorganisms comprise 0.3 parts by weight of Bacillus subtilis and 0.2 parts by weight of Bacillus megaterium.

[0085] The synergist is an alkyl glycoside quaternary ammonium salt.

[0086] The preparation method of the amino acid concentrate is as follows:

[0087] S11: grinding waste animal and plant proteins (soybean meal and chicken feathers at a weight ratio of 2:1) to 80 mesh, adding deionized water at a weight ratio of 1:3, adding sodium hydroxide to adjust the pH to 8.5, adding 0.1% alkaline protease, and hydrolyzing at 55°C for 2 hours; filtering the hydrolyzed solution to obtain a primary peptide solution;

[0088] S12: adding dilute hydrochloric acid to the primary peptide solution to adjust the pH to 2.0, and acidizing at 80°C for 2 hours to break the large molecular peptide chains into a small molecular amino acid solution;

[0089] S13: cooling the small molecular amino acid solution to 40°C, adding 0.5% papain and 0.2% cellulase for hydrolysis for 5 hours to further release free amino acids, heating to 60°C to inactivate the enzymes for 30 minutes, and then cooling, concentrating, and spray drying the solution to obtain an amino acid concentrate.

[0090] The preparation method of the quaternary ammonium salt-based silicon dioxide is as follows:

[0091] (1) 6 parts by weight of (dimethylaminomethyl) phenol and 3 parts by weight of pyromellitic anhydride were added to 24 mL of 1,4-dioxane, stirred uniformly, and then 0.031 parts by weight of a pyridine catalyst was added thereto, warmed to 75°C, and stirred for 7 h. After the reaction, the solvent was removed by concentration under reduced pressure, washed with diethyl ether, and recrystallized in dichloromethane to obtain an intermediate 1;

[0092] (2) 13 parts by weight of chloroacetic acid and 9.5 parts by weight of the intermediate 1 were added to 20 mL of N,N-dimethylformamide solvent, and the reaction was performed under nitrogen protection at 80°C. After the reaction was completed, the product was distilled under reduced pressure, washed, and dried to obtain an intermediate 2;

[0093] (3) 6 parts by weight of hydroxylated silica and 5 parts by weight of the intermediate 2 were added to a reactor containing 27 mL of N,N-dimethylformamide, and stirred and mixed. Then, 0.022 parts by weight of a p-toluenesulfonic acid catalyst was added thereto, and the reaction was performed at 60°C for 4 h. After the reaction was completed, the product was distilled under reduced pressure, washed, and dried to obtain a quaternary ammonium salt-based silica.

[0094] The preparation method of the amino acid organic water-soluble fertilizer is

[0095] S1: After the amino acid concentrate was dissolved in 1 times ionized water, an organic matter was added, and a beneficial microorganism inoculant was inoculated, and then fermentation was performed at 30°C for 48 h to obtain a fermentation broth;

[0096] S2: Polyaspartic acid and chelated micro- and trace elements were sequentially added to the fermentation broth, and stirred and reacted for 1 h to form a stable chelate;

[0097] S3: After a large amount of elements, a medium amount of elements, a quaternary ammonium salt-based silica, indole acetic acid, potassium chloride, and a synergist were added to the chelate and stirred for 1 h, spray drying was performed to obtain a solid water-soluble fertilizer.

[0098] Example 4

[0099] The amino acid organic water-soluble fertilizer includes 42 parts by weight of an amino acid concentrate, 12 parts by weight of an organic matter, 25 parts by weight of a large amount of elements, 5 parts by weight of a medium amount of elements, 5 parts by weight of polyaspartic acid, 4 parts by weight of micro- and trace elements, 0.5 parts by weight of a beneficial microorganism, 2 parts by weight of a quaternary ammonium salt-based silica, 0.3 parts by weight of indole acetic acid, and 0.7 parts by weight of a synergist.

[0100] The organic matter includes 8 parts by weight of alginic acid and 4 parts by weight of potassium fulvate.

[0101] The large amount of elements includes 9 parts by weight of urea, 6 parts by weight of potassium dihydrogen phosphate, and 9 parts by weight of potassium chloride.

[0102] The microelement includes 1 part by weight of EDTA-Fe, 1 part by weight of manganese sulfate, 1 part by weight of zinc sulfate, 0.5 part by weight of copper sulfate and 0.5 part by weight of ammonium molybdate;

[0103] The microelement includes 1 part by weight of EDTA-Fe, 1 part by weight of manganese sulfate, 1 part by weight of zinc sulfate, 0.5 part by weight of copper sulfate and 0.5 part by weight of ammonium molybdate;

[0104] The microelement includes 1 part by weight of EDTA-Fe, 1 part by weight of manganese sulfate, 1 part by weight of zinc sulfate, 0.5 part by weight of copper sulfate and 0.5 part by weight of ammonium molybdate;

[0105] The synergist is alkyl polyglycoside quaternary ammonium salt.

[0106] The preparation method of the amino acid concentrate is as follows:

[0107] S11: The waste animal and plant protein (fish meal, chicken feather, weight ratio 2:1) is crushed to 80 mesh, deionized water is added at a weight ratio of 1:3, sodium hydroxide is added to adjust the pH to 8.0, 0.1% alkaline protease is added, and hydrolysis is carried out at 55°C for 2 hours. After hydrolysis, the primary peptide solution is obtained by filtration;

[0108] S12: Dilute hydrochloric acid is added to the primary peptide solution, the pH is adjusted to 2.4, and acid hydrolysis is carried out at 80°C for 2 hours to break the large molecular peptide chains into small molecular amino acid solution;

[0109] S13: The small molecular amino acid solution is cooled to 40°C, 0.5% papain and 0.3% cellulase are added for hydrolysis for 5 hours to further release free amino acids. After the enzyme is inactivated at 60°C for 30 min, the solution is cooled, concentrated, and spray dried to obtain the amino acid concentrate.

[0110] The preparation method of the quaternary ammonium salt-based silicon dioxide is as follows:

[0111] (1) 5 parts by weight of (dimethylaminomethyl) phenol and 2 parts by weight of pyromellitic anhydride are added to 20 mL of 1,4-dioxane, stirred uniformly, then 0.03 parts by weight of pyridine catalyst is added, heated to 70°C and stirred for 6h, after reaction, the solvent is removed by reduced pressure concentration, washed with diethyl ether, recrystallized in dichloromethane to obtain intermediate 1;

[0112] (2) 15 parts by weight of chloroacetic acid and 10 parts by weight of intermediate 1 are added to 24 mL of N,N-dimethylformamide solvent, nitrogen is introduced for protection, and reaction is carried out at 75-90°C. After the reaction is completed, the product is distilled under reduced pressure, washed and dried to obtain intermediate 2;

[0113] (3) 6 parts by weight of hydroxylated silicon dioxide and 5 parts by weight of intermediate 2 were added to a reactor containing 27 mL of N,N-dimethylformamide, mixed with stirring, 0.022 parts by weight of p-toluenesulfonic acid catalyst was further added thereto, and the reaction was continued at 60°C for 4 h, after which distillation was performed under reduced pressure, washed, and dried to obtain a quaternary ammonium salt-based silicon dioxide.

[0114] The preparation method of the amino acid organic water-soluble fertilizer is: adding water into a stirring tank, then continuously adding amino acid, organic matter, macroelement, meso-element, trace element, beneficial microorganism, quaternary ammonium salt-based silicon dioxide, indole acetic acid, and potassium chloride, stirring for 22 min, and obtaining the amino acid organic water-soluble fertilizer after the end.

[0115] The preparation method of the amino acid organic water-soluble fertilizer is

[0116] S1: After dissolving the amino acid concentrate in 1 times ionized water, the organic matter was added, the beneficial microorganism inoculant was inoculated, and the fermentation was carried out at 30°C for 48 hours to obtain a fermentation liquor;

[0117] S2: Polyaspartic acid and chelated meso-trace elements were sequentially added to the fermentation liquor, and stirred and reacted for 1 hour to form a stable chelate;

[0118] S3: The chelate was added with macroelement, meso-element, quaternary ammonium salt-based silicon dioxide, indole acetic acid, potassium chloride, and synergist, and after stirring for 1 hour, the solid water-soluble fertilizer was obtained by spray drying.

[0119] Example 5

[0120] The amino acid organic water-soluble fertilizer includes 48 parts by weight of amino acid concentrate, 12 parts by weight of organic matter, 20 parts by weight of macroelement, 5 parts by weight of meso-element, 3 parts by weight of polyaspartic acid, 5 parts by weight of trace element, 0.6 parts by weight of beneficial microorganism, 3 parts by weight of quaternary ammonium salt-based silicon dioxide, 0.2 parts by weight of indole acetic acid, and 0.7 parts by weight of synergist.

[0121] The organic matter includes 6 parts by weight of alginic acid and 6 parts by weight of potassium fulvate;

[0122] The macroelement includes 8 parts by weight of urea, 5 parts by weight of potassium dihydrogen phosphate, and 7 parts by weight of potassium chloride;

[0123] The meso-element includes 3 parts by weight of EDTA-Ca and 2 parts by weight of EDTA-Mg;

[0124] The trace element includes 1 part by weight of EDTA-Fe, 1 part by weight of EDTA-Zn, 0.8 parts by weight of manganese sulfate, 0.7 parts by weight of zinc sulfate, 0.5 parts by weight of copper sulfate, 0.5 parts by weight of ammonium molybdate, and 0.5 parts by weight of boric acid;

[0125] The probiotic is 0.3 parts by weight of Bacillus subtilis and 0.2 parts by weight of Paenibacillus mucilaginosus.

[0126] The synergist is alkyl polyglycoside quaternary ammonium salt.

[0127] The preparation method of the amino acid concentrate is:

[0128] S11: The waste animal and plant protein (soybean meal, fish meal, chicken feather, weight ratio 1:1:1) is crushed to 80 mesh, deionized water is added at a weight ratio of 1:3, sodium hydroxide is added to adjust the pH to 8.2, 0.1% alkaline protease is added, and hydrolysis is carried out at 55°C for 2 hours. After hydrolysis, the primary peptide solution is obtained by filtration;

[0129] S12: Add dilute hydrochloric acid to the primary peptide solution, adjust the pH to 2.6, and acid hydrolyze at 80°C for 2 hours to break the large molecular peptide chain into a small molecular amino acid solution;

[0130] S13: The small molecular amino acid solution is cooled to 40°C, 0.3% papain and 0.2% cellulase are added, and hydrolysis is carried out for 5 hours to further release free amino acids. After heating to 60°C for 30 min to inactivate the enzyme, the solution is cooled, concentrated, and spray dried to obtain an amino acid concentrate.

[0131] The preparation method of the quaternary ammonium salt-based silicon dioxide is:

[0132] (1) Add 9 parts by weight of (dimethylaminomethyl) phenol and 4 parts by weight of pyromellitic anhydride to 25 mL of 1,4-dioxane, stir uniformly, then add 0.032 parts by weight of pyridine catalyst, heat to 80°C and stir for 8h, then remove the solvent by reducing pressure after reaction, wash with diethyl ether, and recrystallize in dichloromethane to obtain intermediate 1;

[0133] (2) Add 13 parts by weight of chloroacetic acid and 9.5 parts by weight of intermediate 1 to 20 mL of N,N-dimethylformamide solvent, protect with nitrogen, and react at 80°C. After the reaction is completed, distill under reduced pressure, wash and dry to obtain intermediate 2;

[0134] (3) Add 5 parts by weight of hydroxylated silicon dioxide and 4 parts by weight of intermediate 2 to a reactor containing 25 mL of N,N-dimethylformamide, stir and mix, then add 0.02 parts by weight of p-toluenesulfonic acid catalyst, react at 50°C for 4h, then distill under reduced pressure after the reaction is completed, wash and dry to obtain quaternary ammonium salt-based silicon dioxide.

[0135] The preparation method of the amino acid organic water-soluble fertilizer is

[0136] S1: After the amino acid concentrate is dissolved in 1 times ionized water, organic matter is added, and beneficial microbial inoculants are inoculated, and then fermentation is carried out at 30°C for 48 hours to obtain a fermentation liquor;

[0137] S2: Polyaspartic acid and chelated trace elements are sequentially added to the fermentation liquor, and stirred for 1 hour to form a stable chelate;

[0138] S3: After a large amount of elements, medium elements, quaternary ammonium salt-based silicon dioxide, indole acetic acid, potassium chloride, and synergist are added to the chelate and stirred for 1 hour, spray drying is performed to obtain a solid water-soluble fertilizer.

[0139] Comparative Example 1

[0140] The difference between this comparative example and Example 5 is that the amino acid concentrate is prepared according to the preparation method of the patent with publication number CN 108610193A. The specific preparation method is as follows:

[0141] a. 70 parts of soybean cake and 15 parts of cottonseed cake are crushed, and then 5 parts of fish meal is uniformly mixed with the crushed soybean cake and cottonseed cake. Water is then added to adjust the water content to 55%, and a mixture one is obtained;

[0142] b. 20 parts of alfalfa grass are cut and added to the mixture one, and then uniformly mixed to obtain a mixture two;

[0143] c. 1 part of a biological inoculant and 5 parts of rice bran are uniformly mixed to obtain a mixture three. The storage period of the rice bran is three months, and the biological inoculant is a commercially available Jinbao amino acid foliar fertilizer inoculant;

[0144] d. The mixture two is mixed into the mixture three, and then sealed in a fermentation cylinder for fermentation. The specific fermentation process is as follows: when the fermentation temperature reaches 60°C, it is maintained for 40 hours, and then the fermentation material is loosened and sealed for fermentation. When the temperature again reaches 60°C, it is maintained for 40 hours, and then the fermentation material is loosened again. The above process is repeated until the temperature of the fermentation material no longer rises, i.e. the fermentation is completed. The fermentation material is turned over four times;

[0145] e. The fermentation product is filtered, concentrated, and spray dried to obtain an amino acid concentrate;

[0146] The preparation method of the amino acid organic water-soluble fertilizer comprises:

[0147] S1: The amino acid concentrate is placed in red sugar water, stirred, and then allowed to stand for 15 days. Amino acid stock solution is obtained by suction filtration. The weight ratio of the amino acid concentrate to the red sugar water is 1:1, and the concentration of the red sugar water is 9%.

[0148] S2: Polyaspartic acid and chelated trace elements are sequentially added to the amino acid stock solution, and stirred to form a stable chelate;

[0149] S3: adding macroelements, mesoelements, quaternary ammonium salt-based silicon dioxide, indoleacetic acid, potassium chloride, synergist into the chelate, stirring, and then spray drying to obtain a solid water-soluble fertilizer.

[0150] Comparative Example 2

[0151] The difference between this comparative example and Example 5 is that the amino acid concentrate is prepared by the preparation method of the patent with publication number CN 108610193A, and the specific preparation method is as follows:

[0152] (1) animal fresh bones or bone residues, animal internal organ residues, bean residues are mixed according to a mass ratio of 5:3:2, 5 times of water is added, and the mixture is cooked under a pressure of 0.2 Mpa for 5 h, and then filtered to obtain a cooking liquid;

[0153] (2) the cooking liquid obtained in step (1) is cooled to room temperature, then sodium carbonate is added to adjust the pH to 7.2, 5% of the total weight of the cooking liquid is added to the cooking liquid, and the mixture is enzymatically hydrolyzed at 40-45°C for 8 h, then 25% of the total weight of the cooking liquid is added to the cooking liquid, and the mixture is enzymatically hydrolyzed at 40-45°C for 10 h; then the supernatant is obtained by precipitation and filtration, 6% of the total weight of the cooking liquid is added to the supernatant, and the mixture is enzymatically hydrolyzed at 40-45°C for 10 h; then sulfuric acid solution is added to adjust the pH to 2, and the mixture is acid-decomposed at 100°C for 10 h, then the mixture is filtered to remove impurities, 20% of the total weight of the cooking liquid is added to the mixture, and the mixture is fermented at 40-45°C for 9 h; finally, 10% of hydrochloric acid solution (the pH of the added hydrochloric acid solution is 4) is added to the mixture, and the mixture is acid-decomposed at 100°C for 12 h to obtain the acid-decomposed liquid;

[0154] (3) the acid-decomposed liquid obtained in step (2) is cooled, concentrated, and spray-dried to obtain the amino acid concentrate.

[0155] Comparative Example 3

[0156] The difference between this comparative example and Example 5 is that the papain and cellulase in step S13 are replaced by the same amount of trypsin.

[0157] Comparative Example 4

[0158] The difference between this comparative example and Example 5 is that polyaspartic acid is not added.

[0159] Comparative Example 5

[0160] The difference between this comparative example and Example 5 is that indoleacetic acid is not added.

[0161] Comparative Example 6

[0162] The difference between this comparative example and Example 5 is that quaternary ammonium salt-based silicon dioxide is not added.

[0163] Comparative Example 7

[0164] The amino acid water-soluble fertilizer is purchased from Henan Johnson Agricultural Science and Technology Development Co., Ltd., Ca+Mg≥30 g / L, and amino acid≥100 g / L.

[0165] Amino acid determination

[0166] 0.1 g of the amino acid concentrate prepared in Examples 1-5 and Comparative Examples 1-3 was added to 100 mL of water for dissolution, filtered using a 0.22 μm nylon filter to remove particulate impurities. The amino acids in the sample were quantitatively analyzed by a full-automatic amino acid analyzer, and all the determination results were the average of three results. The determination results are shown in Table 1.

[0167] Table 1 Amino acid composition and content (mg / g) in the amino acid concentrate prepared in Examples 1-5 and Comparative Examples 1-3

[0168]

[0169] The amino acid organic water-soluble fertilizer of the present application adopts a three-step hydrolysis process of alkaline protease + dilute hydrochloric acid hydrolysis + papain / cellulase, which can more efficiently release small molecule amino acids compared to the use of single trypsin.

[0170] Field test

[0171] The amino acid organic water-soluble fertilizers of Application Examples 1-5 and Comparative Examples 1-7 were subjected to field tests. The tests were conducted from May to September 2024 in Qingzhou City, Weifang City, Shandong Province, which has a temperate monsoon climate. The annual rainfall mainly concentrates in June-September, the annual average rainfall is about 600-800 mm, the annual average temperature is about 12-14℃, and the planting system is winter wheat-summer corn rotation. The soil type of the test site is brown soil, and the basic physicochemical properties are shown in Table 1. The test adopted a randomized block design, and each test set was arranged in 3 repeated treatment areas. The area of each treatment area was 4m x 5m = 20m 2The planting density is 3500 plants per mu, the planting variety is fruit corn of Brittle Sweet 89, base fertilizer is organic fertilizer + compound fertilizer, the organic fertilizer is 2500 kg per mu, the compound fertilizer is balanced compound fertilizer (15-15-15), the use amount of the compound fertilizer is about 40 kg per mu, the earlily applied fertilizer is applied before the tassel, the amount of the urea is 20 kg per mu, the potassium dihydrogen phosphate solution (concentration 0.3%) is sprayed twice in the maturation period, the spraying amount of each time is 40 L per mu, and the interval time of each spraying is 7 days. The amino acid organic water-soluble fertilizer is diluted 1500 times, 50 L per mu, and the Brittle Sweet 89 fruit corn seedlings are sprayed once every 15 days after the emergence for 7-8 times, the growth of the Brittle Sweet 89 fruit corn is observed, the average plant height, the number of diseases and insect pests, the fruit weight of the fruit corn and the sweetness of the fruit corn are recorded, the sweetness of the fruit corn is detected according to NY / T523-2002, and the diseases and insect pests of the corn seedlings are judged according to DB33T 943.3-2014.

[0172] Table 1 basic physicochemical properties of the test soil

[0173]

[0174] Table 1: Fertilizer performance test.

[0175]

[0176] As shown in Table 1, the amino acid organic water-soluble fertilizer is rich in nutrition, can prevent pests, and can improve the quality of fruits.

[0177] The above disclosed preferred embodiments of the present application are only used to help explain the present application. The preferred embodiments do not describe all the details, and the application is not limited to the specific embodiments described. Obviously, according to the content of the specification, many modifications and changes can be made. The specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present application, so that those skilled in the art can well understand and utilize the present application.

Claims

1. Amino acid organic water-soluble fertilizer, characterized in that, The composition comprises the following weight components: 40-50 parts by weight of amino acid concentrate, 10-15 parts by weight of organic matter, 20-25 parts by weight of macroelement, 5-8 parts by weight of medium element, 3-5 parts by weight of polyaspartic acid, 4-6 parts by weight of trace element, 0.4-0.6 parts by weight of beneficial microbial agent, 2-4 parts by weight of quaternary ammonium salt-based silicon dioxide, 0.2-0.3 parts by weight of indole acetic acid, and 0.5-1 part by weight of synergist; The amino acid concentrate is prepared from waste animal and plant proteins through enzymatic hydrolysis and acid hydrolysis, and the total amino acid content in the amino acid concentrate is greater than or equal to 70%; The preparation method of the amino acid concentrate comprises the following steps: S11: crushing the waste animal and plant proteins, adding deionized water, adjusting the solution to be alkaline, and adding alkaline protease for hydrolysis; after hydrolysis, filtering to obtain a primary peptide solution; S12: adding dilute hydrochloric acid to the primary peptide solution, adjusting the pH to 2.0-3.0, and acid hydrolyzing at 80℃ for 2 hours to break the large molecular peptide chains into small molecular amino acid solution; S13: after cooling the small molecular amino acid solution, adding papain and cellulase for hydrolysis to further release free amino acids, and after enzyme inactivation, cooling, concentrating, and spray drying the solution to obtain the amino acid concentrate; In step S11, the waste animal and plant proteins include multiple kinds of soybean meal, fish meal, and feather; the ratio of the amount of the waste animal and plant proteins to the amount of deionized water is 1: (3-5), and the amount of the alkaline protease is 0.5-1% of the solution; In step S13, the amounts of the papain and the cellulase are 0.3-0.5% and 0.2-0.4% of the small molecular amino acid solution, respectively; The preparation method of the quaternary ammonium salt-based silicon dioxide comprises the following steps: S21: adding 5-9 parts by weight of (dimethylaminomethyl) phenol and 2-4 parts by weight of pyromellitic anhydride to 1,4-dioxane solvent, stirring uniformly, then adding 0.03-0.032 parts by weight of pyridine catalyst thereto, heating to 70-80℃, stirring and reacting for 6-8 hours, after the reaction, removing the solvent under reduced pressure, washing with ethyl ether, recrystallizing in dichloromethane, and obtaining intermediate 1; S22: adding 12-15 parts by weight of chloroacetic acid and 9-10 parts by weight of intermediate 1 to N,N-dimethylformamide solvent, protecting by nitrogen gas, and reacting at 75-90℃; after the reaction is completed, distilling under reduced pressure, washing, and drying to obtain intermediate 2; S23: adding 5-8 parts by weight of hydroxylated silicon dioxide and 4-7 parts by weight of intermediate 2 to a reactor containing N,N-dimethylformamide, stirring and mixing, continuously adding 0.02-0.024 parts by weight of p-toluenesulfonic acid catalyst thereto, and reacting at 50-70℃ for 4-5 hours; after the reaction is completed, distilling under reduced pressure, washing, and drying to obtain quaternary ammonium salt-based silicon dioxide.

2. The amino acid organic water soluble fertilizer according to claim 1, characterized in that, The organic matter is any one or more of humic acid, potassium fulvate, and alginic acid.

3. The amino acid organic water soluble fertilizer according to claim 1, characterized in that, The macroelement is any one or more of nitrogen, phosphorus, and potassium; The medium element at least includes EDTA-Ca and EDTA-Mg. The microelements at least include EDTA-Fe or EDTA-Zn, manganese sulfate, zinc sulfate, copper sulfate, ammonium molybdate and boric acid.

4. The amino acid organic water soluble fertilizer according to claim 3, characterized in that, The beneficial microbial agent is any one or more of Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus megaterium, Bacillus mycoides and Bacillus licheniformis.

5. The amino acid organic water soluble fertilizer according to claim 4, characterized in that, The weight ratio of the (dimethylaminomethyl) phenol to pyromellitic anhydride in step S21 is (1-2.5):1; the weight of the pyridine catalyst is 0.8-1.5% of the pyromellitic anhydride; The weight ratio of the chloroacetic acid to the intermediate 1 in step S22 is (1.2-1.6):1; The weight ratio of the hydroxylated silicon dioxide to the intermediate 2 in step S23 is (1-1.3):1; the weight of the pyridine catalyst is 0.5-1.2% of the intermediate 2.

6. A process for the preparation of the amino acid organic water soluble fertilizer as claimed in any one of the claims 5, wherein the process comprises the steps of: The method comprises the following steps: S1: after dissolving the amino acid concentrate in deionized water, adding organic matter, inoculating beneficial microbial agent, and performing fermentation to obtain fermentation liquor; S2: adding polyaspartic acid and chelated microelements into the fermentation liquor in sequence, stirring and reacting to form stable chelate; S3: adding macroelements, residual microelements, quaternary ammonium salt-based silicon dioxide, indole acetic acid, potassium chloride and synergist into the chelate, stirring, and then spray drying to obtain solid water-soluble fertilizer or directly blending to obtain liquid water-soluble fertilizer.

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