Amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate

An amino acid organic water-soluble fertilizer, prepared by cross-linking chitosan quaternary ammonium salt and cellulose to encapsulate earthworm enzymatic hydrolysate in a microgel, solves the problems of long-lasting effect and dispersibility of traditional organic water-soluble fertilizers, and improves stability and antibacterial properties, ensuring the normal operation of the fertilization system and the long-term use of the fertilizer.

CN119822890BActive Publication Date: 2025-11-11GUANGDONG ZHONGSHI LONGTAI LOW CARBON TECH CO LTD
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Patent Information

Application Number
CN202510036602.0
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2025-01-09
Publication Date
2025-11-11
Estimated Expiration
2045-01-09

AI Technical Summary

Technical Problem

Traditional organic water-soluble fertilizers suffer from problems such as insufficient duration of action, easy deterioration, and unstable microgel dispersion, resulting in low fertilization efficiency and microbial contamination.

Method used

Microgels were prepared by cross-linking chitosan quaternary ammonium salt and cellulose, and earthworm enzymatic hydrolysate was encapsulated to produce an amino acid organic water-soluble fertilizer. Slow release was achieved through hydrogen and ionic bonds in the microgel, the release rate was controlled by adjusting the pH value, and the positive charge of the quaternary ammonium salt was used to improve dispersibility and antibacterial properties.

Benefits of technology

It achieves stability and slow-release effect of amino acid organic water-soluble fertilizer, prevents nozzle clogging, extends shelf life, and improves fertilization efficiency and antibacterial properties.

✦ Generated by Eureka AI based on patent content.

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Abstract

This invention discloses an amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate. The amino acid organic water-soluble fertilizer is obtained by encapsulating earthworm enzymatic hydrolysate and nitrogen, phosphorus, and potassium organic materials in a microgel. The microgel is obtained by cross-linking chitosan quaternary ammonium salt and cellulose with a cross-linking agent. The positively charged quaternary ammonium salt structure in the microgel plays a role in dispersion, stabilization, and antibacterial action. The encapsulation of the organic water-soluble fertilizer provides a slow-release effect, preventing fertilizer loss. The resulting microgel has a particle size of 1-20 μm, making it easy to spray.
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Description

Technical Field

[0001] This invention belongs to the field of water-soluble fertilizer technology, specifically relating to an amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate. Background Technology

[0002] Earthworms contain more than ten kinds of proteolytic enzymes. Under suitable temperatures of 50-60 ℃ and pH of 7.0-7.5, earthworms can use their own enzymes to hydrolyze proteins, resulting in a nutrient-rich hydrolysate. This hydrolysate mainly includes 18 kinds of free amino acids, short peptides, small molecule proteins, and chelated trace elements such as iron, copper, manganese, and zinc. These components have significant effects on increasing crop yield, improving the quality of agricultural products, and enhancing the disease resistance of plants. Therefore, earthworm hydrolysate has been developed into various amino acid-containing fertilizers.

[0003] Currently, organic water-soluble fertilizers mainly suffer from the following problems: 1) Although organic fertilizers have a longer effect time than inorganic fertilizers, traditional fertilizers generally lack a long-lasting effect, requiring multiple applications; 2) Incomplete inactivation leads to microbial contamination and spoilage. Microgels are colloidal particles with a certain three-dimensional network structure, formed by cross-linking of biopolymer molecules. The interconnections between polymer molecules mainly include covalent bonds, van der Waals forces, hydrophobic interactions, hydrogen bonds, and ionic bonds. Through the protective effect of the microgel matrix, active substances can be effectively isolated from the external environment, thus greatly reducing the risk of denaturation and inactivation of active substances due to environmental changes, and also enabling slow release. Chitosan is a natural polysaccharide with a structure similar to cellulose, possessing good biocompatibility and biodegradability, making it a suitable substrate for microgel modification. However, due to its large molecular weight, it easily forms strong hydrogen bonds within and between molecules, making it difficult to dissolve in water and organic solvents, which greatly limits its application. Microcapsule solutions have the problem of unstable dispersion, which may lead to precipitation or stratification, causing blockage during spraying and affecting fertilization efficiency. Summary of the Invention

[0004] To overcome the shortcomings of the prior art, the present invention provides an amino acid organic water-soluble fertilizer based on earthworm hydrolysate encapsulated in a microgel. The microgel is obtained by cross-linking chitosan quaternary ammonium salt and cellulose with a cross-linking agent. The microgel carries a positive charge and plays a role in dispersion and stabilization. The organic water-soluble fertilizer is encapsulated and plays a role in slow release, preventing fertilizer loss. The obtained microgel has a particle size of 1~20 μm and is easy to spray.

[0005] The technical solution to achieve the objective of this invention is as follows: an amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate, characterized in that the amino acid organic water-soluble fertilizer is obtained by encapsulating earthworm enzymatic hydrolysate and nitrogen, phosphorus, and potassium organic materials in a microgel; the preparation method of the earthworm enzymatic hydrolysate is as follows:

[0006] S1. Clean the live earthworms, remove impurities, expel the internal organs, drain the water, and then freeze them quickly.

[0007] S2. The obtained frozen earthworms were enzymatically hydrolyzed in a water bath for 4-5 h at a temperature of 45-55 ℃ and a pH of 7.0-7.5.

[0008] S3. After centrifugation, 1-2 wt% of water-soluble mold inhibitor was added to the supernatant to obtain earthworm enzymatic hydrolysis stock solution;

[0009] The microgel is obtained by cross-linking chitosan quaternary ammonium salt and cellulose with a cross-linking agent at pH 5.0 to 9.0; the microgel particle size is 1 to 20 μm.

[0010] The resulting solids can be recycled as feed.

[0011] Preferably, the nitrogen, phosphorus, and potassium organic materials are obtained from agricultural waste through one or more methods, including composting, fermentation, pyrolysis, hydrothermal treatment, and microbial transformation; the agricultural waste is at least one of wheat straw, rice straw, corn straw, vegetable residues, fruit tree branches, and rice husks.

[0012] Preferably, the quick-freezing temperature in step S1 is -20 to -10 ℃; the enzyme required for enzymatic hydrolysis in step S2 is a proteolytic enzyme from earthworms; and the centrifugation speed in step S3 is 1000 to 2000 rpm.

[0013] Preferably, the chitosan quaternary ammonium salt is prepared as follows:

[0014] Add 0.2 parts of chitosan and 8-10 parts of 1-allyl-3-methylimidazolium chloride ionic liquid to a three-necked flask, heat and stir in an oil bath at 75-85 °C until the chitosan is completely dissolved. Add 0.4-0.6 parts of glycidyltrimethylammonium chloride to the flask and stir at 75-85 °C for 7-8 h. Then add a mixed solution of ethanol and acetone to the flask to precipitate the chitosan quaternary ammonium salt. Filter the mixed solution to obtain the chitosan quaternary ammonium salt filter cake. Wash the cake at least twice with a mixed solution of ethanol and acetone to remove 1-allyl-3-methylimidazolium chloride and glycidyltrimethylammonium chloride. Dry the cake to obtain the chitosan quaternary ammonium salt.

[0015] Preferably, the cellulose is bacterial cellulose; and the crosslinking agent is sodium tetraborate.

[0016] Preferably, the preparation method of the amino acid organic water-soluble fertilizer is as follows:

[0017] 1) After diluting the earthworm enzymatic hydrolysate, disperse nitrogen, phosphorus, potassium, and organic materials in it and sonicate for 5-10 min. Adjust the pH to 5.0-9.0, add chitosan quaternary ammonium salt and cellulose, stir for 10-20 min, slowly add the crosslinking agent dissolved in water to the system, stir for 10-16 h and then take it out.

[0018] 2) After homogenizing with a homogenizer for 2-3 minutes, the microgel suspension is ultrasonically crushed for 8-10 minutes, the pH value is adjusted, and after passing through a 200-300 mesh sieve, amino acid organic water-soluble fertilizer is obtained.

[0019] Preferably, the earthworm enzymatic hydrolysate in step 1) is diluted 300-500 times; the mass ratio of chitosan quaternary ammonium salt, cellulose, and cross-linking agent is (8-10):1:(8-20); the total mass of chitosan quaternary ammonium salt, cellulose, and cross-linking agent is 15-20 wt% of the amino acid organic water-soluble fertilizer; and the mass of nitrogen, phosphorus, and potassium organic materials is 5-10 wt% of the amino acid organic water-soluble fertilizer.

[0020] Preferably, the homogenizer speed in step 2) is 8000~10000 rpm; the ultrasonic crushing power is 360~400 W, running for 3 seconds and stopping for 3 seconds under ice bath conditions; and the pH value is 4~10.

[0021] Beneficial effects

[0022] This invention offers the following beneficial effects: It provides an amino acid-based organic water-soluble fertilizer with high stability, good slow-release effect, and antibacterial and antiseptic properties, based on earthworm enzymatic hydrolysate. The effective components of the amino acid-based organic water-soluble fertilizer are encapsulated through hydrogen and ionic bonds in the microgel, and the slow-release rate is controlled by adjusting the pH value. The quaternary ammonium salt structure gives the microgel containing the amino acid-based organic water-soluble fertilizer a positive charge, making it less prone to aggregation in water, thus improving the dispersibility and stability of the fertilizer, preventing clogging of nozzles or pipes, and ensuring the normal operation of the fertilization system. The quaternary ammonium salt also has a certain antibacterial effect, further inhibiting the reproduction of bacteria, fungi, and algae that may be present in the water-soluble fertilizer, extending the fertilizer's shelf life and preventing spoilage. Attached Figure Description

[0023] Figure 1 This describes the preparation route of the microgels of the present invention;

[0024] Figure 2 The infrared spectra of chitosan, chitosan quaternary ammonium salt and microgel of the present invention are shown.

[0025] 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] Unless otherwise specified, the experimental methods used in the embodiments are conventional methods, and the materials and reagents used are commercially available unless otherwise specified.

[0027] The raw materials and equipment used in the embodiments and comparative examples are described below:

[0028] Water-soluble mold inhibitor: Main components include aflatoxin B1 decomposing mold, Bacillus subtilis, Bacillus licheniformis, lactic acid bacteria, bio-complex enzyme, and glucose oxidase, purchased from Xinweimu;

[0029] Chitosan: Deacetylation degree ≥95%, Product No. A001827, purchased from Jianglai Biotechnology;

[0030] 1-Allyl-3-methylimidazolium chloride: Product No. 1039111, purchased from Shanghai Haohong Biomedical Technology Co., Ltd.

[0031] Glycidyltrimethylammonium chloride: Product No. 1228799, purchased from Shanghai Haohong Biomedical Technology;

[0032] Cellulose: Bacterial cellulose, 50-100 nm in diameter, purchased from Guilin Qihong Technology Co., Ltd.

[0033] Chitosan quaternary ammonium salt:

[0034] 0.2 parts of chitosan and 8 parts of 1-allyl-3-methylimidazolium chloride ionic liquid were added to a three-necked flask and heated and stirred at 80 °C until the chitosan was completely dissolved. 0.4 parts of glycidyltrimethylammonium chloride were added to the flask and stirred at 80 °C for 8 h. A mixed solution of ethanol and acetone was added to the flask to precipitate chitosan quaternary ammonium salt. The mixed solution was filtered to obtain a chitosan quaternary ammonium salt filter cake. The filter cake was washed three times with a mixed solution of ethanol and acetone to remove 1-allyl-3-methylimidazolium chloride and glycidyltrimethylammonium chloride. The filter cake was then dried to obtain chitosan quaternary ammonium salt.

[0035] JIUPIN-1200E Ultrasonic Destroyer: Wuxi Jiuping Instrument Co., Ltd.

[0036] Earthworm enzymatic hydrolysate

[0037] S1. Clean the live earthworms, remove impurities, expel the internal organs, drain the water, and then quickly freeze them at -20 ℃.

[0038] S2. The obtained frozen earthworms were enzymatically hydrolyzed in a water bath for 4 h at a temperature of 50 ℃ and a pH of 7.0.

[0039] S3. After centrifugation at 1000 rpm, 1.5 wt% of water-soluble mold inhibitor was added to the supernatant to obtain the earthworm enzymatic hydrolysis stock solution.

[0040] A method for preparing an amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate

[0041] Example 1

[0042] 1) After diluting the earthworm enzymatic hydrolysate 400 times, disperse 8 wt% of nitrogen, phosphorus, and potassium organic materials (based on the total mass of amino acid organic water-soluble fertilizer) in it and sonicate for 5 min. Adjust the pH to 9.0, add chitosan quaternary ammonium salt and cellulose, stir for 10 min, and slowly add the cross-linking agent dissolved in water dropwise to the system. The mass ratio of chitosan quaternary ammonium salt, cellulose, and cross-linking agent is 9:1:8, and the total mass of chitosan quaternary ammonium salt, cellulose, and cross-linking agent is 18 wt% of the amino acid organic water-soluble fertilizer. Stir for 12 h and then remove the solution.

[0043] 2) After homogenizing at 8000 rpm for 2 min, the microgel suspension was ultrasonically crushed for 8-10 min, the pH was adjusted to 6.5, and after passing through a 300-mesh sieve, amino acid organic water-soluble fertilizer was obtained.

[0044] Example 2

[0045] Compared with the preparation method in Example 1, the difference is that in step 1), the mass ratio of chitosan quaternary ammonium salt, cellulose and crosslinking agent is 9:1:16.

[0046] Example 3

[0047] Compared with the preparation method in Example 1, the difference is that in step 1), the mass ratio of chitosan quaternary ammonium salt, cellulose and crosslinking agent is 9:1:20.

[0048] Example 4

[0049] Compared with the preparation method in Example 1, the difference is that in step 2), the homogenizer speed of 8000 rpm is replaced with 9000 rpm.

[0050] Example 5

[0051] Compared with the preparation method in Example 1, the difference is that in step 2), the homogenizer speed of 8000 rpm is replaced with 10000 rpm.

[0052] Example 6

[0053] Compared with the preparation method in Example 1, the difference is that step 1) adjusting the pH to 9.0 is replaced with adjusting the pH to 7.

[0054] Example 7

[0055] Compared with the preparation method in Example 1, the difference is that step 1) adjusting the pH to 9.0 is replaced with adjusting the pH to 5.

[0056] Comparative Example 1

[0057] Compared with the preparation method in Example 1, the difference is that in step 1), the chitosan quaternary ammonium salt is replaced with chitosan.

[0058] Comparative Example 2

[0059] Compared with the preparation method in Example 1, the difference is that step 2) does not involve homogenization and crushing.

[0060] Comparative Example 3

[0061] The preparation method is as follows: dilute the earthworm enzymatic hydrolysate 400 times, disperse nitrogen, phosphorus, and potassium organic materials in it, and sonicate for 5 minutes to obtain amino acid organic water-soluble fertilizer.

[0062] Comparative Example 4

[0063] Compared with the preparation method in Example 1, the difference is that step 1) adjusting the pH to 9.0 is replaced by adjusting the pH to 11.0.

[0064] Comparative Example 5

[0065] Compared with the preparation method in Example 1, the difference is that step 1) adjusting the pH to 9 is replaced with adjusting the pH to 3.0.

[0066] The following are the test methods for performance parameters involved in this invention:

[0067] Fourier transform infrared spectroscopy (FTIR) measurement: Model Spectrum two, PerkinElmer, USA;

[0068] Particle size: S3500 laser particle size analyzer, Microtrac, USA. Particle size test data is before sieving.

[0069] Release rate: The same batch of air-dried soil was collected and placed in containers of 15 cm*15 cm*15 cm. 10 ml of organic water-soluble fertilizer was sprayed on the soil surface, and the soil moisture was kept at 60%. The soil was placed at room temperature. At 1, 10, 20 and 30 days, a cylindrical sampler with a diameter of 0.5 cm and a height of 15 cm was used to extract the soil with aqueous solution. The results were tested according to the industry standard NTY1975-2010 "Determination of Free Amino Acid Content in Water-Soluble Fertilizers".

[0070] Antibacterial activity test: The inoculated Staphylococcus aureus and Escherichia coli were transferred to a constant temperature shaker at 37 ℃ and 130 r for 18 h to 24 h. The bacterial solution was diluted with 0.03 mol / L phosphate (PBS) buffer to 3×105 CFU / mL to 4×105 CFU / mL. 0.2 g of the sample from the example and comparative example was added to an Erlenmeyer flask, and 100 μL of the diluted bacterial solution was added. The mixture was shaken and cultured at 24 ℃ and 150 r / min for 18 h to 24 h. The shaken bacterial solution was diluted 10 times. 100 μL of the bacterial solution from each dilution gradient was spread onto an agar plate. Two plates were spread in parallel for each dilution gradient. After incubation at 37 ℃ for 24 h, the colonies on the plates were counted. The plate without any added components was the control group. The antibacterial rate was calculated using formula (1).

[0071] (1)

[0072] In the formula: For antibacterial rate; This represents the colony count in the control group; The colony counts are for the examples and comparative tests.

[0073] Dispersion stability test: Observe after 180 days whether it is stable and whether there is turbidity or precipitation.

[0074] Field fertilizer efficiency experiment on tomatoes: Using the same amount and frequency of fertilizer application, the effects on the vitamin V of the fruit were compared. c The yield increase was measured and statistically analyzed using the 2,6-dichlorophenol titration method, the sugar-acid ratio (anthrone colorimetric method for determining soluble total sugar, acid-base neutralization titration method for determining titratable acid), and the yield increase compared to the application of an equal amount of water.

[0075] From the appendix Figure 2 It can be seen that the infrared spectra of quaternary ammonium chitosan and chitosan are not significantly different, with quaternary ammonium chitosan showing a similar pattern at 1653 cm⁻¹. -1 and 1483 cm -1 There are two strong peaks; the former represents the stretching motion of the NH group in the tertiary amine, and the latter represents the stretching motion of the CH group in -N(CH3)3; in the spectrum of the microgel, the peak at 1670 cm⁻¹ is... -1 The vibrational peak of -OH is due to the stretching motion of C=O, which is 3441 cm⁻¹. -1 Redshifted to 3272cm -1 1323 cm -1 and 690 cm -1 For the stretching vibration of BOB and the bending vibration of BOC.

[0076] Table 1. Average particle size and antibacterial activity determination of examples and comparative examples.

[0077]

[0078] As shown in Table 1, the particle size, antibacterial rate, sustained-release effect, and dispersion stability of Examples 1-7 are all excellent. Data from Examples 1-3 show that with increasing crosslinking agent dosage, the particle size of the microcapsules encapsulating amino acid organic water-soluble fertilizer first increases and then decreases, and the amino acid release rate also first decreases and then increases. This is because increasing the crosslinking density makes the microcapsule network structure more compact, improving the loading capacity for amino acids. However, when the microgel network density is too high, the steric hindrance increases, leading to a decrease in encapsulation efficiency and thus an increase in the release rate. Data from Examples 1, 4, and 5 show that the higher the homogenizer speed, the smaller the microcapsule particle size and the slower the release rate. During homogenization, shear... Shear force can refine microgels, thereby reducing particle size. The release rate is slower because homogenization improves the dispersibility of microgels. Data from Examples 1, 6, and 7 show that within the pH range of 5 to 9, the higher the pH, the lower the release rate. At pH 9.0, most amino acids in earthworms carry a negative charge, and chitosan quaternary ammonium salt has a high adsorption capacity for amino acids, resulting in a high encapsulation rate. When the pH is 5, the negative charge of amino acids decreases, and the adsorption capacity of chitosan quaternary ammonium salt for amino acids decreases, thus reducing the encapsulation rate. Data from Comparative Example 1 shows that the dispersion stability and antibacterial properties of microgels after replacing chitosan quaternary ammonium salt with chitosan are not as good as those in Examples 1-7, while the release rate is slightly increased. The data from Comparative Example 2 show that the gel particles without homogenization and fragmentation are too large, falling outside the 1-20 μm range, and are therefore unsuitable for spray systems. Since Comparative Example 3 was not encapsulated, sustained release and particle size testing were not performed. Comparative Examples 4 and 5 show that both excessively high and low pH values ​​reduce the encapsulation efficiency, leading to an increased release rate. When the pH is too high, the positive charge of the chitosan quaternary ammonium salt decreases, and the dispersibility also decreases. When the pH is too low, some amino acids begin to carry a positive charge, resulting in a decrease in the encapsulation efficiency.

[0079] Table 2. Field fertilizer efficiency experiments corresponding to the examples and comparative examples.

[0080]

[0081] As shown in Table 2, the fertilizer effect test data indicates that a good slow-release effect is essential for improving the fertilizer effect of tomatoes. Data from Examples 1-7 and Comparative Examples 1, 4, and 5 show that within a certain range, as the slow-release effect increases, the V of the resulting fruit increases. c The sugar-acid ratio gradually increased, and the fruit yield also improved. Data from Comparative Example 1 shows that direct spraying of unencapsulated amino acid organic water-soluble fertilizer can also increase the vitamin C content of the fruit. c The sugar-acid ratio and yield were compared, but the effect was not as good as that of Examples 1-7 of the present invention; since the particle size of Comparative Example 2 was too large and not suitable for spraying system, no experimental control was conducted.

[0082] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. An amino acid-based organic water-soluble fertilizer based on earthworm enzymatic hydrolysate, characterized in that, The amino acid organic water-soluble fertilizer is obtained by encapsulating earthworm enzymatic hydrolysate and nitrogen, phosphorus, and potassium organic materials in a microgel; the preparation method of the earthworm enzymatic hydrolysate is as follows: S1. Clean the live earthworms, remove impurities, expel the internal organs, drain the water, and then freeze them quickly. S2. The obtained frozen earthworms were enzymatically hydrolyzed in a water bath for 4-5 h at a temperature of 45-55 ℃ and a pH of 7.0-7.

5. S3. After centrifugation, water-soluble mold inhibitors are added to the supernatant to obtain earthworm enzymatic hydrolysis stock solution; The microgel is obtained by cross-linking chitosan quaternary ammonium salt and cellulose with a cross-linking agent at pH 5.0~9.0; the microgel particle size is 1~20 μm. Chitosan and solvent were added to a reaction vessel and heated and stirred until the chitosan was completely dissolved. Glycidyltrimethylammonium chloride was added to the reaction vessel and stirred. After the reaction was completed, post-processing was performed to obtain chitosan quaternary ammonium salt. The cellulose is bacterial cellulose; the crosslinking agent is sodium tetraborate.

2. The amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate as described in claim 1, characterized in that, The nitrogen, phosphorus, and potassium organic materials are obtained from agricultural waste through one or more methods, including composting, fermentation, pyrolysis, hydrothermal treatment, and microbial transformation; the agricultural waste is at least one of wheat straw, rice straw, corn straw, vegetable residues, fruit tree branches, and rice husks.

3. The amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate as described in claim 1, characterized in that, In step S1, the quick-freezing temperature is -20 to -10 ℃; in step S2, the enzyme required for enzymatic hydrolysis is a proteolytic enzyme from earthworms; in step S3, the centrifugation speed is 1000 to 2000 rpm, and the amount of water-soluble mold inhibitor added is 1 to 2 wt%.

4. The amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate as described in claim 1, characterized in that, The mass ratio of chitosan, solvent, and glycidyltrimethylammonium chloride is 1:(40~50):(2~3); the stirring temperature is 75~85℃, and the stirring time is 7~8 h; the solvent is 1-allyl-3-methylimidazolium chloride ionic liquid; the post-treatment operation is to add a mixed solution of ethanol and acetone into a flask to precipitate chitosan quaternary ammonium salt, filter the mixed solution to obtain chitosan quaternary ammonium salt filter cake, wash it at least twice with a mixed solution of ethanol and acetone to remove impurities, and dry it to obtain chitosan quaternary ammonium salt.

5. An amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate as described in any one of claims 1 to 4, characterized in that, The preparation method of the amino acid organic water-soluble fertilizer is as follows: 1) After diluting the earthworm enzymatic hydrolysate, disperse nitrogen, phosphorus, potassium, and organic materials in it and sonicate for 5-10 min. Adjust the pH to 5.0-9.0, add chitosan quaternary ammonium salt and cellulose, stir for 10-20 min, slowly add the crosslinking agent dissolved in water to the system, stir for 10-16 h and then take it out. 2) After homogenizing with a homogenizer for 2-3 minutes, the microgel suspension is ultrasonically crushed for 8-10 minutes, the pH value is adjusted, and after passing through a 200-300 mesh sieve, amino acid organic water-soluble fertilizer is obtained.

6. The method for preparing an amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate as described in claim 5, characterized in that, The earthworm enzymatic hydrolysate in step 1) is diluted 300-500 times; the mass ratio of chitosan quaternary ammonium salt, cellulose, and cross-linking agent is (8-10):1:(8-20); the total mass of chitosan quaternary ammonium salt, cellulose, and cross-linking agent is 15-20 wt% of the amino acid organic water-soluble fertilizer; and the mass of nitrogen, phosphorus, and potassium organic materials is 5-10 wt% of the amino acid organic water-soluble fertilizer.

7. The method for preparing an amino acid organic water-soluble fertilizer based on earthworm enzymatic hydrolysate as described in claim 5, characterized in that, The homogenizer speed in step 2) is 8000~10000 rpm; the ultrasonic crushing power is 360~400 W, running for 3 seconds and stopping for 3 seconds under ice bath conditions; the pH value is 4~10.

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