Amino acid water-soluble fertilizer and preparation process thereof

Abstract

The invention discloses an amino acid water-soluble fertilizer and a preparation process thereof, and relates to the technical field of water-soluble fertilizer preparation. The nutrient solution is prepared from the following raw materials: 35 to 45 parts of compound amino acid, 8 to 12 parts of monopotassium phosphate, 3 to 4 parts of potassium sulfate, 1.5 to 2 parts of disodium calcium ethylenediamine tetraacetate, 1.2 to 1.8 parts of EDTA (Ethylene Diamine Tetraacetic Acid) chelated magnesium, 0.3 to 0.7 part of chelated zinc, 0.1 to 0.3 part of zinc sulfate, 2 to 3 parts of citric acid-monopotassium phosphate buffer solution, 2 to 3 parts of algal polysaccharide, 0.5 to 1 part of mannitol, 2 to 4 parts of potassium fulvate, 1 to 2 parts of chitosan oligosaccharide and 0.5 to 1 part of nano silicon dioxide. 0.5-1 part of polyaspartic acid; 1-2 parts of a dispersing agent; the compound amino acid raw materials comprise 60-70% of fish scale protein water-soluble amino acid and 30-40% of bamboo shoot protein water-soluble amino acid; the amino acid water-soluble fertilizer provided by the invention can effectively improve the nutrient absorption efficiency of crops and promote the growth of the crops.

Description

Technical Field

[0001] This application relates to the field of water-soluble fertilizer preparation technology, and particularly to an amino acid water-soluble fertilizer and its preparation process. Background Technique

[0002] Water-soluble fertilizers, abbreviated as water-soluble fertilizers, are a type of multi-component compound fertilizer that can be completely dissolved in water, with good solubility and no residue. Compared with traditional varieties such as superphosphate and granulated compound fertilizers, water-soluble fertilizers have significant advantages. They have a fast dissolution rate and a high absorption and utilization rate by crops. More importantly, water-soluble fertilizers can be applied to modern agricultural irrigation facilities such as sprinkler irrigation and drip irrigation to achieve the integration of water and fertilizer, carry fertilizer with water, and improve the fertilization efficiency. They play an important role in improving fertilizer utilization efficiency, saving agricultural water, reducing environmental pollution, and improving crop quality.

[0003] Amino acids are promoters and catalysts for the synthesis of various enzymes in plants, and have a significant promoting effect on plant growth, especially photosynthesis. Amino acid fertilizers can increase the content of various nutrient elements required in plants, accelerate the accumulation of dry matter, and regulate the ratio of macronutrients, micronutrients, and various nutrient components, thereby promoting the normal growth of plants. Amino acid-containing water-soluble fertilizers are the main products of the application of amino acids in agriculture. Their main component is free amino acids, and according to the nutrient requirements of different plants, medium and trace plant nutrient elements are added, which is a dual-effect fertilizer for supplementing amino acids and trace elements.

[0004] Although amino acid water-soluble fertilizers have been widely used in the agricultural field, their nutrient absorption efficiency still needs to be improved. Plants absorb amino acids mainly through the cell membranes on the roots and leaf surfaces. Since the molecular weight of amino acids in traditional amino acid water-soluble fertilizers is usually large, exceeding 1000 Da, this large molecular weight limits the ability of amino acids to be rapidly absorbed by crops, thereby affecting the overall nutrient absorption efficiency, which can lead to insufficient nutrient supply and affect the growth and development of crops. Summary of the Invention

[0005] In order to solve the above technical problems, this application provides an amino acid water-soluble fertilizer and its preparation process.

[0006] The amino acid water-soluble fertilizer provided by this application adopts the following technical scheme:

[0007] An amino acid water-soluble fertilizer, the raw materials of which by weight include 35-45 parts of compound amino acids, 8-12 parts of potassium dihydrogen phosphate, 3-4 parts of potassium sulfate, 1.5-2 parts of calcium disodium ethylene diamine tetraacetate, 1.2-1.8 parts of EDTA chelated magnesium, 0.3-0.7 parts of chelated zinc, 0.1-0.3 parts of zinc sulfate, 2-3 parts of citric acid-potassium dihydrogen phosphate buffer, 2-3 parts of seaweed polysaccharide, 0.5-1 part of mannitol, 2-4 parts of potassium humate, 1-2 parts of chitosan oligosaccharide, 0.5-1 part of nano-silica, 0.5-1 part of polyaspartic acid, and 1-2 parts of dispersant;

[0008] The compound amino acid raw materials include 60-70% of fish scale protein water-soluble amino acids and 30-40% of bamboo shoot protein water-soluble amino acids by mass percentage;

[0009] The molecular weight of the compound amino acid is 200-1000Da.

[0010] Preferably, the molecular weight of the chitosan oligosaccharide is 1-5kDa.

[0011] Preferably, the preparation method of the compound amino acid includes the following steps:

[0012] S1. Boil the carp scales in pure water for 15-30 min and then crush them, filter out the water to make fish scale homogenate; add pure water to the fish scale homogenate, and then add compound protease A at an addition amount of 3000-5000 U / g, and perform water bath enzymatic hydrolysis for 4-8 h. After the enzymatic hydrolysis reaction ends, perform water bath treatment at 90-95 °C for 10-15 min to inactivate the protease, and filter to obtain fish scale protein water-soluble amino acids;

[0013] S2. Wash and crush the bamboo shoot processing waste, add pure water for cell wall breaking and pulping, and then add compound protease B at an addition amount of 5000-7000 U / g, and perform water bath enzymatic hydrolysis for 4-8 h. After the enzymatic hydrolysis reaction ends, perform water bath treatment at 90-95 °C for 10-15 min to inactivate the protease, and filter to obtain bamboo shoot protein water-soluble amino acids;

[0014] S3. After the obtained fish scale protein water-soluble amino acids and bamboo shoot protein water-soluble amino acids are respectively treated by an anti-pollution ultrafiltration membrane and a nanofiltration membrane, the fish scale protein water-soluble amino acids and bamboo shoot protein water-soluble amino acids are mixed to obtain compound amino acids.

[0015] Preferably, the compound protease A includes flavor protease and neutral protease; the mass ratio of the flavor protease to the neutral protease is 1:0.9-1.1.

[0016] Preferably, the compound protease B includes cellulase, pectinase, and acidic protease; the mass ratio of the cellulase, pectinase, and acidic protease is 1:0.8-1.2:1-1.3.

[0017] Preferably, the preparation method of the anti-fouling ultrafiltration membrane comprises the following steps:

[0018] Immerse the brominated polyether ether ketone ultrafiltration membrane in an aqueous solution of 2-[2-(dimethylamino)ethoxy]ethanol with a mass fraction of 10-15 wt% and soak it at room temperature for 20-24 h; after completion, take out the ultrafiltration membrane and repeatedly wash it with deionized water to remove the unreacted 2-[2-(dimethylamino)ethoxy]ethanol attached to the surface, thus obtaining the anti-fouling ultrafiltration membrane.

[0019] Preferably, the raw materials of the brominated polyether ether ketone ultrafiltration membrane are prepared from the following raw materials in parts by weight: 14-16 parts of PEEK-Br polymer, 2-4 parts of polyvinylpyrrolidone, and 80-90 parts of N-methylpyrrolidone.

[0020] Preferably, the preparation method of the PEEK-Br polymer comprises the following steps:

[0021] S1. By weight, mix 4-6 parts of methylhydroquinone, 10-13 parts of 4,4'-dihydroxybenzophenone, 6-7 parts of anhydrous potassium carbonate, 40-50 parts of N,N-dimethylacetamide, and 17-25 parts of toluene evenly, then slowly raise the temperature to 140-150 °C to remove water for 4-5 h. After the water removal is completed, slowly raise the temperature of the system to 160-170 °C and separate the excess toluene, and then maintain the system at 160-170 °C for 8-10 h and then discharge. After crushing the product with a crusher, wash it with deionized water by reflux for several times and wash it with ethanol by reflux for several times, filter and vacuum dry it at 60-70 °C for 8-10 h to obtain PEEK-CH3;

[0022] S2. Add 8-10 parts of the obtained PEEK-CH3 to 250-300 parts of 1,1,2,2-tetrachloroethane and stir until dissolved, then continuously stir for 30-50 min in a nitrogen atmosphere to remove the oxygen in the solution; add 0.4-0.5 parts of benzoyl peroxide and 4-6 parts of N-bromosuccinimide to the system, continue to stir at room temperature for 20-30 min and then raise the temperature to 80-90 °C, react for 5-7 h and then cool to room temperature and discharge; crush the product and ultrasonically wash it in absolute ethanol for several times, filter and vacuum dry it at 60-70 °C for 8-10 h to obtain the PEEK-Br polymer.

[0023] Preferably, the preparation method of the brominated polyether ether ketone ultrafiltration membrane comprises the following steps:

[0024] The PEEK-Br polymer, polyvinylpyrrolidone, and N-methylpyrrolidone were magnetically stirred until completely dissolved to obtain a casting solution; the casting solution was degassed at 45-55 °C, the degassed casting solution was poured onto a clean glass plate, scraped into a film with a scraper, and left standing in air for 30-45 s, then quickly placed in a coagulation bath until the nascent film separated from the glass plate; the nascent film was soaked in deionized water, and the deionized water was changed every 6-8 h. After multiple replacements, an asymmetric pore structure was formed in the film, and thus a polyetheretherketone bromide ultrafiltration membrane was obtained.

[0025] The present application also provides a preparation process for an amino acid water-soluble fertilizer, adopting the following technical solution:

[0026] A preparation process for an amino acid water-soluble fertilizer includes the following steps:

[0027] Calcium disodium ethylene diamine tetraacetate, EDTA chelated magnesium, chelated zinc, and zinc sulfate were added to the compound amino acid, and a citric acid-potassium dihydrogen phosphate buffer solution was added. The temperature was controlled at 40-50 °C, and a chelation reaction was carried out for 2-3 h; subsequently, seaweed polysaccharide, mannitol, potassium humate, and chitosan oligosaccharide were added and mixed evenly by a homogenizer, and then potassium dihydrogen phosphate, potassium sulfate, nano-silica, polyaspartic acid, and a dispersant were added. After stirring evenly, an amino acid water-soluble fertilizer was obtained.

[0028] In summary, the present application includes at least one of the following beneficial technical effects:

[0029] 1. The present application uses a compound of fish scale protein water-soluble amino acid and bamboo shoot protein water-soluble amino acid as the main substances in the amino acid water-soluble fertilizer for crops. Among them, fish scale protein is rich in collagen, and the contents of lysine, proline, etc. are relatively high in its amino acid composition; bamboo shoot protein is rich in glutamic acid, aspartic acid, etc. The compound of these animal and plant dual-source amino acids can provide a more comprehensive variety of amino acids, meet the needs of plants for various amino acids at different growth stages, and promote plant growth;

[0030] 2. The present application uses calcium disodium ethylene diamine tetraacetate, EDTA chelated magnesium, chelated zinc, and zinc sulfate as chelated elements such as in the amino acid water-soluble fertilizer. The cell membrane on the surface of plant roots has higher permeability to chelated metal ions, enabling these ions to enter plant cells more quickly, meeting the needs of crops for these trace elements; at the same time, it also avoids the formation of insoluble precipitates of metal ions such as calcium with groups such as phosphate groups in the soil, effectively improving the stability of the fertilizer efficiency of the water-soluble fertilizer.

[0031] 3. In this application, 2-[2-(dimethylamino)ethoxy]ethanol is grafted onto the surface of a brominated polyether ether ketone ultrafiltration membrane to obtain a surface quaternary ammonium salt-modified ultrafiltration membrane, which effectively improves the hydrophilicity of the ultrafiltration membrane surface, improves the permeability and anti-fouling performance of the membrane, thereby effectively intercepting macromolecular protein residues and preventing pollutants such as proteins from adsorbing on the ultrafiltration membrane surface and affecting the permeability of the ultrafiltration membrane; after treatment with the anti-fouling ultrafiltration membrane and nanofiltration membrane, controlling the amino acid molecular weight at 200-1000 Da effectively improves the absorption efficiency of crops. Detailed implementation mode

[0032] The following further elaborates on this application in conjunction with examples.

[0033] The chemical reagents used in the preparation examples, examples, and comparative examples provided by the present invention are all commercially available products, and their trademarks and manufacturers are as follows:

[0034] Calcium disodium edetate, Shanghai Macklin Biochemical Co., Ltd., E832428;

[0035] Chelated zinc, Hubei Weishi Chemical Reagent Co., Ltd.;

[0036] EDTA chelated magnesium, Shandong Pingju Biotechnology Co., Ltd.;

[0037] Oligochitosan, Shanghai Yuansheng Biotechnology Co., Ltd., molecular weight 3000 Da;

[0038] Nanofiltration membrane, Dalton Membrane Technology (Shenzhen) Co., Ltd., DA-NF200-400.

[0039] Preparation Example 1

[0040] S1. After mixing 4 g of methylhydroquinone, 10 g of 4,4'-dihydroxybenzophenone, 6 g of anhydrous potassium carbonate, 40 g of N,N-dimethylacetamide, and 17 g of toluene evenly, slowly heat the mixture to 140 °C to remove water for 4 h. After the water removal is completed, slowly heat the system to 160 °C and separate the excess toluene. Then maintain the system at 160 °C for 8 h and discharge the product. After crushing the product with a pulverizer, wash it with deionized water by refluxing 3 times and with ethanol by refluxing 3 times, filter, and vacuum dry at 60 °C for 8 h to obtain PEEK-CH3;

[0041] S2. Add 8 g of the obtained PEEK-CH3 to 250 g of 1,1,2,2-tetrachloroethane, stir until dissolved, and continuously stir for 30 min under a nitrogen atmosphere to remove the oxygen in the solution; add 0.4 g of benzoyl peroxide and 4 g of N-bromosuccinimide to the system, continue to stir at room temperature for 20 min, then raise the temperature to 80 °C, react for 5 h, then cool to room temperature, and discharge; crush the product, ultrasonically wash it 3 times in absolute ethanol, filter and vacuum dry it at 60 °C for 8 h to obtain the PEEK-Br polymer;

[0042] S3. Dissolve 14 g of the PEEK-Br polymer, 2 g of polyvinylpyrrolidone and 80 g of N-methylpyrrolidone by magnetic stirring to obtain a casting solution; remove the bubbles from the casting solution at 45 °C, pour the degassed casting solution onto a clean glass plate, scrape it into a film with a 150-μm scraper and let it stand in the air for 30 s, then quickly place it in a coagulation bath until the nascent film detaches from the glass plate; soak the nascent film in deionized water and change the deionized water every 6 h. Replace it multiple times to form an asymmetric pore structure in the film, that is, obtain the brominated polyether ether ketone ultrafiltration membrane;

[0043] S4. Immerse the brominated polyether ether ketone ultrafiltration membrane in an aqueous solution of 2-[2-(dimethylamino)ethoxy]ethanol with a mass fraction of 10 wt% and soak it at room temperature for 20 h; after completion, take out the ultrafiltration membrane and repeatedly wash it with deionized water to remove the unreacted 2-[2-(dimethylamino)ethoxy]ethanol attached to the surface, that is, obtain the anti-fouling ultrafiltration membrane.

[0044] Preparation Example 2

[0045] S1. Mix 5 g of methylhydroquinone, 11.5 g of 4,4'-dihydroxybenzophenone, 6.5 g of anhydrous potassium carbonate, 45 g of N,N-dimethylacetamide and 21 g of toluene evenly, slowly raise the temperature to 145 °C to remove water for 4.5 h, after the water removal is completed, slowly raise the temperature of the system to 160 °C and separate the excess toluene, then maintain the system at 165 °C for 9 h and then discharge. After crushing the product with a crusher, wash it 4 times by refluxing with deionized water and 4 times by refluxing with ethanol, filter and vacuum dry it at 65 °C for 9 h to obtain PEEK-CH3;

[0046] S2. Add 9 g of the obtained PEEK-CH3 to 275 g of 1,1,2,2-tetrachloroethane, stir until dissolved, and continuously stir for 40 min under a nitrogen atmosphere to remove the oxygen in the solution; add 0.45 g of benzoyl peroxide and 5 g of N-bromosuccinimide to the system, continue to stir at room temperature for 25 min, then raise the temperature to 85 °C, react for 6 h, then cool to room temperature, and discharge; crush the product, ultrasonically wash it 4 times in absolute ethanol, filter and vacuum dry it at 65 °C for 9 h to obtain the PEEK-Br polymer;

[0047] S3. Dissolve 15 g of PEEK-Br polymer, 3 g of polyvinylpyrrolidone and 85 g of N-methylpyrrolidone by magnetic stirring to obtain a casting solution; remove air bubbles from the casting solution at 50 °C, pour the degassed casting solution onto a clean glass plate, scrape it into a film with a 150-μm doctor blade and let it stand in air for 40 s, then quickly put it into a coagulation bath until the nascent film detaches from the glass plate; soak the nascent film in deionized water and change the deionized water every 7 h. Replace it multiple times to form an asymmetric pore structure in the film, thus obtaining a polyetheretherketone bromide ultrafiltration membrane;

[0048] S4. Soak the polyetheretherketone bromide ultrafiltration membrane in an aqueous solution of 2-[2-(dimethylamino)ethoxy]ethanol with a mass fraction of 12 wt% at room temperature for 22 h; after completion, take out the ultrafiltration membrane and repeatedly wash it with deionized water to remove the unreacted 2-[2-(dimethylamino)ethoxy]ethanol attached to the surface, thus obtaining an anti-fouling ultrafiltration membrane.

[0049] Preparation Example 3

[0050] S1. Mix 6 g of methylhydroquinone, 13 g of 4,4'-dihydroxybenzophenone, 7 g of anhydrous potassium carbonate, 50 g of N,N-dimethylacetamide and 25 g of toluene evenly, then slowly raise the temperature to 150 °C to remove water for 5 h. After the water removal is completed, slowly raise the temperature of the system to 170 °C and separate the excess toluene, then maintain the system at 170 °C for 10 h and then discharge. Crush the product with a pulverizer and wash it by refluxing with deionized water 5 times and refluxing with ethanol 5 times, filter and vacuum dry at 70 °C for 10 h to obtain PEEK-CH3;

[0051] S2. Add 10 g of the prepared PEEK-CH3 to 300 g of 1,1,2,2-tetrachloroethane and stir until dissolved, then continuously stir for 50 min under a nitrogen atmosphere to remove oxygen in the solution; add 0.5 g of benzoyl peroxide and 6 g of N-bromosuccinimide to the system, continue to stir at room temperature for 30 min and then raise the temperature to 90 °C, react for 7 h and then cool to room temperature, and discharge; crush the product and ultrasonically wash it 5 times in absolute ethanol, filter and vacuum dry at 70 °C for 10 h to obtain a PEEK-Br polymer;

[0052] S3. Dissolve 16 g of PEEK-Br polymer, 4 g of polyvinylpyrrolidone and 90 g of N-methylpyrrolidone by magnetic stirring to obtain a casting solution; remove the bubbles from the casting solution at 55 °C, pour the degassed casting solution onto a clean glass plate, scrape it into a film with a 150-μm blade and let it stand in air for 45 s, then quickly put it into a coagulation bath until the nascent film detaches from the glass plate; soak the nascent film in deionized water and change the deionized water every 8 h. Replace it multiple times to form an asymmetric pore structure in the film, thus obtaining a polyether ether ketone bromide ultrafiltration membrane;

[0053] S4. Immerse the polyether ether ketone bromide ultrafiltration membrane in an aqueous solution of 2-[2-(dimethylamino)ethoxy]ethanol with a mass fraction of 15 wt% and soak it at room temperature for 24 h; after completion, take out the ultrafiltration membrane and repeatedly wash it with deionized water to remove the unreacted 2-[2-(dimethylamino)ethoxy]ethanol attached to the surface, thus obtaining an anti-fouling ultrafiltration membrane.

[0054] Example 1

[0055] S1. Boil 2 g of carp scales in pure water for 15 min, then crush them, filter out the water, and make fish scale homogenate; add 10 g of pure water to the fish scale homogenate, and then add compound protease A at an addition amount of 3000 U / g, and perform enzymatic hydrolysis treatment in a water bath at 40 °C for 4 h. After the enzymatic hydrolysis reaction is completed, perform water bath treatment at 90 °C for 10 min to inactivate the protease, and filter to obtain water-soluble amino acids of fish scale protein; in this example, the compound protease A used includes flavor protease and neutral protease, and the mass ratio is 1:0.9;

[0056] S2. Wash 2 g of bamboo shoot processing waste, then crush it, add 20 g of pure water for cell wall breaking and pulping, and then add compound protease B at an addition amount of 5000 U / g, and perform enzymatic hydrolysis treatment in a water bath at 40 °C for 4 h. After the enzymatic hydrolysis reaction is completed, perform water bath treatment at 90 °C for 10 min to inactivate the protease, and filter to obtain water-soluble amino acids of bamboo shoot protein; in this example, compound protease B includes cellulase, pectinase, and acidic protease, and the mass ratio is 1:0.8:1;

[0057] S3. After the obtained water-soluble amino acids of fish scale protein and water-soluble amino acids of bamboo shoot protein are respectively treated with the anti-fouling ultrafiltration membrane and nanofiltration membrane prepared in Preparation Example 1, control the molecular weight of the amino acids to be 200-1000 Da. After mixing the water-soluble amino acids of fish scale protein and water-soluble amino acids of bamboo shoot protein, a composite amino acid is obtained, in which the water-soluble amino acids of fish scale protein account for 60% and the water-soluble amino acids of bamboo shoot protein account for 40%;

[0058] S4. Add 1.5 g of calcium disodium edetate, 1.2 g of EDTA chelated magnesium, 0.3 g of chelated zinc, and 0.1 g of zinc sulfate to 35 g of the compound amino acid prepared in S3. Add 2 g of citric acid - potassium dihydrogen phosphate buffer solution, control the temperature at 40 °C, and carry out chelation reaction for 2 h. Then add 2 g of seaweed polysaccharide, 0.5 g of mannitol, 2 g of potassium fulvate, and 1 g of chitosan oligosaccharide. After mixing evenly with a homogenizer, add 8 g of potassium dihydrogen phosphate, 3 g of potassium sulfate, 0.5 g of nano - silicon dioxide, 0.5 g of polyaspartic acid, and 1 g of dispersant sodium dodecyl benzene sulfonate. After stirring evenly, an amino acid water - soluble fertilizer is obtained.

[0059] Example 2

[0060] S1. Boil 3 g of carp scales in pure water for 22 min, then crush them, filter out the water, and make fish scale homogenate. Add 15 g of pure water to the fish scale homogenate, and then add compound protease A at an addition amount of 4000 U / g. Carry out enzymatic hydrolysis treatment in a water bath at 45 °C for 6 h. After the enzymatic hydrolysis reaction ends, carry out water bath treatment at 92.5 °C for 13 min to inactivate the protease. After filtration, fish scale protein water - soluble amino acids are obtained. In this example, the compound protease A used includes flavor protease and neutral protease, and the mass ratio is 1:1.

[0061] S2. Wash 3 g of bamboo shoot processing waste, then crush it, add 30 g of pure water for cell wall breaking and pulping, and then add compound protease B at an addition amount of 6000 U / g. Carry out enzymatic hydrolysis treatment in a water bath at 45 °C for 6 h. After the enzymatic hydrolysis reaction ends, carry out water bath treatment at 92.5 °C for 13 min to inactivate the protease. After filtration, bamboo shoot protein water - soluble amino acids are obtained. In this example, the compound protease B includes cellulase, pectinase, and acidic protease, and the mass ratio is 1:1:1.15.

[0062] S3. After the obtained fish scale protein water - soluble amino acids and bamboo shoot protein water - soluble amino acids are respectively treated with the anti - pollution ultrafiltration membrane and nanofiltration membrane prepared in Preparation Example 2, control the molecular weight of the amino acids to be 200 - 1000 Da. After mixing the fish scale protein water - soluble amino acids and bamboo shoot protein water - soluble amino acids, compound amino acids are obtained, wherein the fish scale protein water - soluble amino acids account for 60% and the bamboo shoot protein water - soluble amino acids account for 40%.

[0063] S4. Add 1.5 g of calcium disodium edetate, 1.2 g of EDTA chelated magnesium, 0.3 g of chelated zinc, and 0.1 g of zinc sulfate to 35 g of the compound amino acid obtained in S3. Add 2 g of citric acid - potassium dihydrogen phosphate buffer solution, control the temperature at 40 °C, and carry out chelation reaction for 2 h. Subsequently, add 2 g of seaweed polysaccharide, 0.5 g of mannitol, 2 g of fulvic acid potassium, and 1 g of chitosan oligosaccharide. After mixing evenly with a homogenizer, add 8 g of potassium dihydrogen phosphate, 3 g of potassium sulfate, 0.5 g of nano - silicon dioxide, 0.5 g of polyaspartic acid, and 1 g of dispersant sodium dodecylbenzenesulfonate. After stirring evenly, an amino acid water - soluble fertilizer is obtained.

[0064] Example 3

[0065] S1. Boil 4 g of carp scales in pure water for 30 min, then crush them, filter out the moisture, and make fish scale homogenate. Add 20 g of pure water to the fish scale homogenate, and then add compound protease A at an addition amount of 5000 U / g. Carry out enzymatic hydrolysis treatment in a water bath at 50 °C for 8 h. After the enzymatic hydrolysis reaction ends, carry out water bath treatment at 95 °C for 15 min to inactivate the protease, and filter to obtain water - soluble amino acids of fish scale protein. In this example, the compound protease A used includes flavor protease and neutral protease, and the mass ratio is 1:1.1;

[0066] S2. Wash 2 g of bamboo shoot processing waste, then crush it, add 20 g of pure water for cell wall - breaking pulping, and then add compound protease B at an addition amount of 5000 U / g. Carry out enzymatic hydrolysis treatment in a water bath at 40 °C for 4 h. After the enzymatic hydrolysis reaction ends, carry out water bath treatment at 90 °C for 10 min to inactivate the protease, and filter to obtain water - soluble amino acids of bamboo shoot protein. In this example, the compound protease B includes cellulase, pectinase, and acidic protease, and the mass ratio is 1:0.8:1;

[0067] S3. After the obtained water - soluble amino acids of fish scale protein and water - soluble amino acids of bamboo shoot protein are respectively treated with the anti - pollution ultrafiltration membrane and nanofiltration membrane prepared in Preparation Example 3, control the molecular weight of the amino acids to be 200 - 1000 Da. After mixing the water - soluble amino acids of fish scale protein and water - soluble amino acids of bamboo shoot protein, a compound amino acid is obtained, wherein the water - soluble amino acids of fish scale protein account for 60% and the water - soluble amino acids of bamboo shoot protein account for 40%;

[0068] S4. Add 1.5 g of calcium disodium edetate, 1.2 g of EDTA chelated magnesium, 0.3 g of chelated zinc, and 0.1 g of zinc sulfate to 35 g of the compound amino acid prepared in S3. Add 2 g of citric acid - potassium dihydrogen phosphate buffer solution, control the temperature at 40 °C, and carry out chelation reaction for 2 h. Subsequently, add 2 g of seaweed polysaccharide, 0.5 g of mannitol, 2 g of potassium fulvate, and 1 g of chitosan oligosaccharide. After mixing evenly with a homogenizer, add 8 g of potassium dihydrogen phosphate, 3 g of potassium sulfate, 0.5 g of nano - silica, 0.5 g of polyaspartic acid, and 1 g of dispersant sodium dodecyl benzene sulfonate. After stirring evenly, an amino acid water - soluble fertilizer is obtained.

[0069] Example 4

[0070] S1. Boil 2 g of carp scales in pure water for 15 min, then crush them, filter out the water, and make fish scale homogenate. Add 10 g of pure water to the fish scale homogenate, and then add compound protease A at an addition amount of 3000 U / g. Carry out enzymatic hydrolysis treatment at 40 °C for 4 h. After the enzymatic hydrolysis reaction ends, carry out water - bath treatment at 90 °C for 10 min to inactivate the protease. After filtration, fish scale protein water - soluble amino acids are obtained. In this example, the compound protease A used includes flavor protease and neutral protease, and the mass ratio is 1:0.9.

[0071] S2. Wash 2 g of bamboo shoot processing waste, then crush it, add 20 g of pure water for cell wall breaking and pulping, and then add compound protease B at an addition amount of 5000 U / g. Carry out enzymatic hydrolysis treatment at 40 °C for 4 h. After the enzymatic hydrolysis reaction ends, carry out water - bath treatment at 90 °C for 10 min to inactivate the protease. After filtration, bamboo shoot protein water - soluble amino acids are obtained. In this example, the compound protease B includes cellulase, pectinase, and acidic protease, and the mass ratio is 1:0.8:1.

[0072] S3. After the obtained fish scale protein water - soluble amino acids and bamboo shoot protein water - soluble amino acids are respectively treated with the anti - pollution ultrafiltration membrane and nanofiltration membrane prepared in Preparation Example 1, control the molecular weight of the amino acids to be 200 - 1000 Da. After mixing the fish scale protein water - soluble amino acids and bamboo shoot protein water - soluble amino acids, compound amino acids are obtained, wherein the fish scale protein water - soluble amino acids account for 60% and the bamboo shoot protein water - soluble amino acids account for 40%.

[0073] S4. Add 1.75 g of calcium disodium edetate, 1.5 g of EDTA chelated magnesium, 0.5 g of chelated zinc, and 0.2 g of zinc sulfate to 40 g of the compound amino acid prepared in S3. Add 2.5 g of citric acid - potassium dihydrogen phosphate buffer solution, control the temperature at 45 °C, and carry out chelation reaction for 2.5 h. Subsequently, add 2.5 g of seaweed polysaccharide, 0.75 g of mannitol, 3 g of potassium fulvate, and 1.5 g of chitosan oligosaccharide. After mixing evenly with a homogenizer, add 10 g of potassium dihydrogen phosphate, 3.5 g of potassium sulfate, 0.75 g of nano - silica, 0.75 g of polyaspartic acid, and 1.5 g of dispersant sodium dodecyl benzene sulfonate. After stirring evenly, an amino acid water - soluble fertilizer is obtained.

[0074] Example 5

[0075] S1. Boil 2 g of carp scales in pure water for 15 min, then crush them, filter out the moisture, and make fish scale homogenate. Add 10 g of pure water to the fish scale homogenate, and then add compound protease A at an addition amount of 3000 U / g. Carry out enzymatic hydrolysis treatment at 40 °C for 4 h. After the enzymatic hydrolysis reaction ends, carry out water - bath treatment at 90 °C for 10 min to inactivate the protease. After filtration, fish scale protein water - soluble amino acids are obtained. The compound protease A used in this example includes flavor protease and neutral protease, and the mass ratio is 1:0.9.

[0076] S2. Wash 2 g of bamboo shoot processing waste, then crush it, add 20 g of pure water for cell wall breaking and pulping, and then add compound protease B at an addition amount of 5000 U / g. Carry out enzymatic hydrolysis treatment at 40 °C for 4 h. After the enzymatic hydrolysis reaction ends, carry out water - bath treatment at 90 °C for 10 min to inactivate the protease. After filtration, bamboo shoot protein water - soluble amino acids are obtained. The compound protease B in this example includes cellulase, pectinase, and acid protease, and the mass ratio is 1:0.8:1.

[0077] S3. After the obtained fish scale protein water - soluble amino acids and bamboo shoot protein water - soluble amino acids are respectively treated with the anti - pollution ultrafiltration membrane and nanofiltration membrane prepared in Preparation Example 1, control the molecular weight of the amino acids to be 200 - 1000 Da. After mixing the fish scale protein water - soluble amino acids and bamboo shoot protein water - soluble amino acids, compound amino acids are obtained, wherein the fish scale protein water - soluble amino acids account for 60% and the bamboo shoot protein water - soluble amino acids account for 40%.

[0078] S4. Add 2 g of calcium disodium ethylenediaminetetraacetate, 1.8 g of EDTA chelated magnesium, 0.7 g of chelated zinc, and 0.3 g of zinc sulfate to 45 g of the compound amino acid prepared in S3, add 3 g of citric acid - potassium dihydrogen phosphate buffer solution, control the temperature at 50 °C, and carry out chelation reaction for 3 h; then add 3 g of seaweed polysaccharide, 1 g of mannitol, 4 g of potassium fulvate, and 2 g of chitosan oligosaccharide. After mixing evenly with a homogenizer, add 12 g of potassium dihydrogen phosphate, 4 g of potassium sulfate, 1 g of nano - silicon dioxide, 1 g of polyaspartic acid, and 2 g of dispersant sodium dodecylbenzenesulfonate. After stirring evenly, an amino acid water - soluble fertilizer is obtained.

[0079] Example 6

[0080] The difference between Example 6 and Example 1 is that for the compound amino acid used in Example 6, the proportion of water - soluble amino acid in fish scale protein is 65% and the proportion of water - soluble amino acid in bamboo shoot protein is 35%.

[0081] Example 7

[0082] The difference between Example 7 and Example 1 is that for the compound amino acid used in Example 7, the proportion of water - soluble amino acid in fish scale protein is 70% and the proportion of water - soluble amino acid in bamboo shoot protein is 30%.

[0083] Comparative Example 1

[0084] The difference between Comparative Example 1 and Example 1 is that for the compound amino acid used in Comparative Example 1, the proportion of water - soluble amino acid in fish scale protein is 50% and the proportion of water - soluble amino acid in bamboo shoot protein is 50%.

[0085] Comparative Example 2

[0086] The difference between Comparative Example 2 and Example 1 is that for the compound amino acid used in Comparative Example 2, the proportion of water - soluble amino acid in fish scale protein is 80% and the proportion of water - soluble amino acid in bamboo shoot protein is 20%.

[0087] Comparative Example 3

[0088] The difference between Comparative Example 3 and Example 1 is that the ultrafiltration membrane used in Comparative Example 3 is an ordinary unmodified PEEK ultrafiltration membrane.

[0089] Comparative Example 4

[0090] The difference between Comparative Example 4 and Example 1 is that the water - soluble amino acids of fish scale protein and bamboo shoot protein used in Comparative Example 4 are not treated with anti - fouling ultrafiltration membrane and nanofiltration membrane, that is, the molecular weight of the compound amino acid is not controlled to be 200 - 1000 Da.

[0091] Performance detection test

[0092] For the pot experiment, the tested crop was "Dashusheng" lettuce seedlings. Lettuce seedlings with a plant height of 4.5 - 5.0 cm were selected. The greenhouse temperature was set at 15 - 20 °C, sufficient light was provided, and the planting time was 45 days.

[0093] Experimental group: Urea was used as the base fertilizer, and the application rate was 0.1 g N / kg soil; then, the amino acid water-soluble fertilizers obtained in Examples 1 - 7 and Comparative Examples 1 - 4 (diluted with 800 times of clear water) were irrigated root by root every 10 days, 3 times during the whole growth period, and 12 mL was applied each time.

[0094] Blank control group: No fertilizer was applied, and clear water equal to the fertilization volume was provided.

[0095] Six pots of lettuce samples were provided for each group.

[0096] Test: Three pots of lettuce samples with similar growth trends were selected from each group for testing, and the average value was taken; a scale was used to measure the plant height, maximum leaf length, maximum leaf width, and root length of the lettuce, and a centesimal balance was used to measure the fresh weight of the lettuce.

[0097] The results are shown in Table 1.

[0098] The specific test results are as follows:

[0099] Table 1 Performance test results

[0100]

[0101]

[0102] It can be seen from the test results in Table 1 that the plant height, maximum leaf length, maximum leaf width, root length, and fresh weight of the lettuce treated with the amino acid water-soluble fertilizer provided in this application are all higher than those of the blank control group, indicating that the amino acid water-soluble fertilizer provided in this application can effectively promote the growth of crops.

[0103] It can be seen from the test results of Examples 1, 6, 7 and Comparative Examples 1, 2 that the preferred proportion of fish scale protein water-soluble amino acids in the composite amino acids of this application is 60 - 70%, and the proportion of bamboo shoot protein water-soluble amino acids is 30 - 40%.

[0104] It can be seen from the test results of Examples 1 - 5 and Comparative Examples 3, 4 that the anti-pollution ultrafiltration membrane provided in this application has a positive promoting effect on the growth of crops; when the anti-pollution ultrafiltration membrane and nanofiltration membrane are not used for treatment, the plant height, maximum leaf length, maximum leaf width, root length, and fresh weight of the lettuce all decrease significantly.

[0105] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. An amino acid water-soluble fertilizer, characterized in that: The raw materials include 35-45 parts by weight of compound amino acids, 8-12 parts of potassium dihydrogen phosphate, 3-4 parts of potassium sulfate, 1.5-2 parts of calcium disodium ethylene diamine tetraacetate, 1.2-1.8 parts of EDTA chelated magnesium, 0.3-0.7 parts of chelated zinc, 0.1-0.3 parts of zinc sulfate, 2-3 parts of citric acid-potassium dihydrogen phosphate buffer, 2-3 parts of seaweed polysaccharide, 0.5-1 part of mannitol, 2-4 parts of potassium fulvate, 1-2 parts of chitosan oligosaccharide, 0.5-1 part of nano-silica, 0.5-1 part of polyaspartic acid, and 1-2 parts of dispersant; The compound amino acid raw materials include 60-70% by mass of water-soluble amino acids of fish scale protein and 30-40% of water-soluble amino acids of bamboo shoot protein; The molecular weight of the compound amino acids is 200-1000 Da.

2. The amino acid water-soluble fertilizer according to claim 1, wherein: The molecular weight of the chitosan oligosaccharide is 1-5 kDa.

3. The amino acid water-soluble fertilizer according to claim 1, characterized in that: The preparation method of the compound amino acids includes the following steps: S1. Boil carp scales in pure water for 15-30 min, then crush them, filter out the water to make fish scale homogenate; add pure water to the fish scale homogenate, and then add compound protease A at an addition amount of 3000-5000 U / g, and perform water bath enzymatic hydrolysis for 4-8 h. After the enzymatic hydrolysis reaction is completed, perform water bath treatment at 90-95 °C for 10-15 min to inactivate the protease, and filter to obtain water-soluble amino acids of fish scale protein; S2. Wash the bamboo shoot processing waste, crush it, add pure water for cell wall breaking and pulping, and then add compound protease B at an addition amount of 5000-7000 U / g, and perform water bath enzymatic hydrolysis for 4-8 h. After the enzymatic hydrolysis reaction is completed, perform water bath treatment at 90-95 °C for 10-15 min to inactivate the protease, and filter to obtain water-soluble amino acids of bamboo shoot protein; S3. After the obtained water-soluble amino acids of fish scale protein and water-soluble amino acids of bamboo shoot protein are respectively treated by an anti-pollution ultrafiltration membrane and a nanofiltration membrane, mix the water-soluble amino acids of fish scale protein and water-soluble amino acids of bamboo shoot protein to obtain compound amino acids.

4. The amino acid water-soluble fertilizer according to claim 3, characterized in that: The compound protease A includes flavor protease and neutral protease; the mass ratio of the flavor protease to the neutral protease is 1:0.9-1.

1.

5. The amino acid water-soluble fertilizer according to claim 3, characterized in that: The compound protease B includes cellulase, pectinase, and acidic protease; the mass ratio of the cellulase, pectinase, and acidic protease is 1:0.8-1.2:1-1.

3.

6. The amino acid water-soluble fertilizer according to claim 3, characterized in that: The preparation method of the anti-pollution ultrafiltration membrane includes the following steps: Immerse the brominated polyether ether ketone ultrafiltration membrane in an aqueous solution of 2-[2-(dimethylamino)ethoxy]ethanol with a mass fraction of 10-15 wt%, and immerse it at room temperature for 20-24 h; after completion, take out the ultrafiltration membrane and repeatedly wash it with deionized water to remove the unreacted 2-[2-(dimethylamino)ethoxy]ethanol attached to the surface to obtain the anti-pollution ultrafiltration membrane.

7. The amino acid water-soluble fertilizer according to claim 6, wherein: The raw materials of the brominated polyether ether ketone ultrafiltration membrane are prepared from the following raw materials in parts by weight: 14-16 parts of PEEK-Br polymer, 2-4 parts of polyvinylpyrrolidone, and 80-90 parts of N-methylpyrrolidone.

8. The amino acid water-soluble fertilizer according to claim 7, characterized in that: The preparation method of the PEEK-Br polymer includes the following steps: S1. Mix 4 - 6 parts by weight of methylhydroquinone, 10 - 13 parts of 4,4'-dihydroxybenzophenone, 6 - 7 parts of anhydrous potassium carbonate, 40 - 50 parts of N,N-dimethylacetamide and 17 - 25 parts of toluene evenly, then slowly heat up to 140 - 150 °C to remove water for 4 - 5 h. After the water removal is completed, slowly heat up the system to 160 - 170 °C and separate the excess toluene. Then maintain the system at 160 - 170 °C for 8 - 10 h and then discharge. Crush the product with a crusher, wash it several times by refluxing with deionized water and several times by refluxing with ethanol, filter and vacuum dry at 60 - 70 °C for 8 - 10 h to obtain PEEK-CH3; S2. Add 8 - 10 parts of the obtained PEEK-CH3 to 250 - 300 parts of 1,1,2,2-tetrachloroethane, stir until dissolved, and continuously stir for 30 - 50 min in a nitrogen atmosphere to remove the oxygen in the solution; add 0.4 - 0.5 parts of benzoyl peroxide and 4 - 6 parts of N-bromosuccinimide to the system, continue to stir at room temperature for 20 - 30 min and then heat up to 80 - 90 °C, react for 5 - 7 h and then cool down to room temperature, and discharge; crush the product and ultrasonically wash it several times in absolute ethanol, filter and vacuum dry at 60 - 70 °C for 8 - 10 h to obtain the PEEK-Br polymer.

9. The amino acid water-soluble fertilizer according to claim 7, characterized in that: The preparation method of the brominated polyether ether ketone ultrafiltration membrane includes the following steps: Dissolve the PEEK-Br polymer, polyvinylpyrrolidone and N-methylpyrrolidone by magnetic stirring to obtain a casting solution; remove the bubbles from the casting solution at 45 - 55 °C, pour the degassed casting solution onto a clean glass plate, scrape it into a film with a scraper and let it stand in the air for 30 - 45 s, then quickly put it into a coagulation bath until the nascent film detaches from the glass plate; soak the nascent film in deionized water and change the deionized water every 6 - 8 h. Replace it multiple times to make the film form an asymmetric pore structure, that is, obtain the brominated polyether ether ketone ultrafiltration membrane.

10. The preparation process of an amino acid water-soluble fertilizer according to any one of claims 1-9, wherein: It includes the following steps: Add calcium disodium ethylene diamine tetraacetate, EDTA chelated magnesium, chelated zinc, zinc sulfate to the compound amino acids, add citric acid-potassium dihydrogen phosphate buffer solution, control the temperature at 40 - 50 °C, and carry out chelation reaction for 2 - 3 h; then add seaweed polysaccharide, mannitol, potassium fulvate, chitosan oligosaccharide, mix them evenly with a homogenizer, and then add potassium dihydrogen phosphate, potassium sulfate, nano-silica, polyaspartic acid, dispersant, stir evenly to obtain the amino acid water-soluble fertilizer.

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