Method for preparing animal-derived amino acid water-soluble fertilizer with stable quality
By concentrating, compounding, pH control and heating purification of the enzymatic waste liquid, a high stability of amino acid-containing water-soluble fertilizer was prepared, which solved the problem of insoluble precipitation in existing water-soluble fertilizers and achieved long-term stability and applicability of the product.
Patent Information
- Application Number
- CN202411679360.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-22
- Publication Date
- 2025-03-07
AI Technical Summary
The enzymatic waste liquid in existing water-soluble fertilizers is precipitated due to insoluble precipitation, resulting in blockage of the sprinkler system, causing trouble to the application.
By concentrating, compounding, heating and purification of the enzymatic waste liquid, a water-soluble fertilizer containing amino acids with stable quality and almost no precipitation was prepared.
It achieves long-term stability of the product, no deterioration, and no insoluble solids. It is suitable for use in drip irrigation or sprinkler systems, avoiding blockage and leakage of sprinkler systems.
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Abstract
Description
Technical Field
[0001] The invention relates to the field of biotechnology, and in particular to a method for preparing an animal-derived amino acid water-soluble fertilizer with stable quality. Background Art
[0002] Water-soluble fertilizer is a new type of liquid fertilizer in recent years. It is an efficient and environmentally friendly fertilizer. Its main features are small dosage, easy use, low cost, fast crop absorption, and high nutrient utilization rate. Because it can be completely dissolved in water, it is more conducive to direct absorption and utilization by crop roots and leaves. The specific methods of applying liquid fertilizers include foliar spraying, seed soaking, root dipping, injection, drench application, watering, sprinkler irrigation, drip irrigation, etc. The development of water-soluble fertilizers is the inevitable result of scientific fertilization and facility fertilization.
[0003] The industrial chain of water-soluble fertilizer industry consists of raw materials, production and application. The upstream is the raw material end, including basic fertilizers, macroelements, medium elements, trace elements, amino acids, humic acid organic matter, etc. At present, a new raw material is to enzymatically hydrolyze shrimp and crab shells, feathers or animal tissues, fully extract chitosan oligosaccharides, chitosan, mucopolysaccharides, etc., and recycle the enzymatic waste liquid to make water-soluble fertilizer. However, the quality of such products varies greatly, and the precipitation of insoluble precipitation is a common phenomenon, which makes this part of water-soluble fertilizer products more likely to cause blockage of the sprinkler system during use, causing great trouble to the users. Summary of the invention
[0004] The present invention overcomes the above technical deficiencies, concentrates, compounds, controls the pH process, raises the temperature, and purifies such enzymatic waste liquid to obtain a water-soluble amino acid fertilizer with stable quality and almost no precipitation, which is suitable for use in drip irrigation or sprinkler irrigation systems. The method of the present invention is simple to operate, pollution-free, and suitable for large-scale production. The product has an extremely low insoluble solid content, and has no precipitation or corruption after being placed for a long time.
[0005] The specific technical solution adopted by the present invention is as follows:
[0006] (1) Concentrating the above waste liquid to prepare amino acid mother liquor;
[0007] (2) According to the applicable scope of water-soluble fertilizer and crop requirements, the above amino acid mother solution is compounded, and salts of trace elements or medium elements required by plants are added, and stirred to dissolve;
[0008] (3) Heat the above solution to 40-60°C, maintain for 15-20 minutes, then heat to 90-96°C, continue stirring and heating for 50-60 minutes, and control the pH during the heating process to allow the protein and small peptide to be fully precipitated;
[0009] (4) Allow the above solution to stand and cool, and after it is fully precipitated, filter it by suction; adjust the pH of the filtrate and add water in proportion to obtain a water-soluble fertilizer containing amino acids.
[0010] Furthermore, the waste liquid is animal tissue enzymatic hydrolysis waste liquid, shrimp and crab shell enzymatic hydrolysis waste liquid, and animal feather enzymatic hydrolysis waste liquid.
[0011] Furthermore, the amino acid-containing mother liquor is concentrated to a free amino acid content of more than 110 g / L.
[0012] Furthermore, the secondary elements are one or two of calcium and magnesium, and the trace elements are one or more of copper, iron, manganese, zinc, boron, and molybdenum. The secondary elements are preferably calcium and magnesium, and the trace elements are preferably manganese, zinc, and boron.
[0013] Furthermore, salts of secondary elements and trace elements include but are not limited to calcium sulfate, calcium sugar alcohol, EDTA chelated calcium, calcium acetate, calcium nitrate, magnesium sulfate, potassium nitrate, magnesium sugar alcohol, EDTA chelated magnesium, magnesium acetate, magnesium nitrate, manganese sulfate, zinc sulfate, boric acid, ammonium heptamolybdate, ammonium molybdate, copper sulfate, humic acid, organic matter, amino acids, sodium nitrate, calcium nitrate, urea, ammonium chloride, ammonium sulfate, ammonium bicarbonate, ammonia water, calcium cyanammonium, monoammonium phosphate, diammonium and other inorganic salts.
[0014] Preferably, the salt of trace elements is one or more of ferrous sulfate, ammonium heptamolybdate, zinc sulfate, manganese sulfate, and boric acid, and the salt of medium elements is calcium nitrate and magnesium sulfate.
[0015] Furthermore, in step (3), the pH is 5.5-6.5.
[0016] Furthermore, in step (4), the standing time is 3 hours and the filtration membrane is 0.45 μm.
[0017] Furthermore, in step (4), the pH of the filtrate is adjusted to 3.0-5.0, and the amount of water added is determined according to the amino acid content of the mother liquor to ensure that the free amino acid is above 100 g / L.
[0018] Beneficial effects of the present invention:
[0019] The invention performs enzymatic hydrolysis and concentration on animal tissues, shrimp and crab shells and animal feathers, adds inorganic salts for compounding, maintains pH stability during temperature control, and adjusts the pH of the final product. This method does not destroy free amino acids, but can fully precipitate proteins and small peptides. The prepared animal-source amino acid water-soluble fertilizer can maintain a stable state after long-term storage, has no sour and smelly deterioration, and has no insoluble matter precipitated. This ensures that the sprinkler irrigation system is unblocked during actual use, avoids the occurrence of missed application, makes fertilizer application more uniform, and saves a lot of energy, manpower and material resources of the applicator. DETAILED DESCRIPTION
[0020] This aspect is further described below, but the present invention is not limited to the following embodiments.
[0021] Example 1: Preparation of amino acid-containing water-soluble fertilizer (medium element type) using animal tissue enzymatic wastewater
[0022] 30KG recycled waste liquid was concentrated under reduced pressure to obtain 1740g of amino acid mother liquor, and the free amino acid content was measured to be 145g / L. 580g of this mother liquor was taken, 112g of calcium nitrate tetrahydrate and 115g of magnesium sulfate hexahydrate were added, and heated to 40℃ after sufficient stirring. After heating for 15min, it was heated to 96℃ and continued to stir and heat for 60min. During the heating process, the pH value was adjusted to 6.0 with hydrochloric acid to make the precipitate fully precipitate. After heating, it was allowed to stand for 3h, and after cooling, it was filtered with a 0.45μm filter membrane to obtain 753g of filtrate, and the pH was adjusted to 3.5 with hydrochloric acid, and water was added to 812g. According to the method in GBT1429-2010, the free amino acid content was 105g / L, calcium 24g / L, and magnesium 12.5g / L. The product was tested for stability at 0℃, 55℃ and room temperature, and no precipitation was found. The sample was opened and placed without corruption and deterioration.
[0023] Example 2: Preparation of amino acid-containing water-soluble fertilizer (trace element type) using animal tissue enzymatic wastewater
[0024] 10KG recycled waste liquid was concentrated under reduced pressure to obtain 453g of amino acid mother liquor, and the free amino acid content was 170g / L. 17.5g of ferrous sulfate heptahydrate, 2.22g of ammonium heptamolybdate, and 1.55g of zinc sulfate heptahydrate were added to the mother liquor, and heated to 50°C after sufficient stirring. After heating for 20min, it was heated to 90°C and continued to stir and heat for 50min. During the heating process, the pH value was adjusted to 5.5 with hydrochloric acid to make the precipitate fully precipitate. After heating, it was allowed to stand for 3h, cooled and filtered with a 0.45μm filter membrane to obtain 459g of filtrate, and the pH was adjusted to 4.0 with hydrochloric acid, and water was added to 604g. At this time, the free amino acid content was detected to be 129g / L, iron 1.2g / L, molybdenum 5.0g / L, and zinc 17.0g / L. The product was tested for stability at 0°C, 55°C and room temperature, and no precipitation was found. The sample was opened and placed without corruption and deterioration.
[0025] Example 3: Preparation of amino acid-containing water-soluble fertilizer (medium element type) using shrimp and crab shell enzymatic wastewater
[0026] 10KG recycled waste liquid was concentrated under reduced pressure to obtain 530g of amino acid mother liquor, and the free amino acid content was measured to be 110g / L. 80g of calcium nitrate tetrahydrate and 82g of magnesium sulfate hexahydrate were added to the mother liquor, and heated to 60℃ after sufficient stirring. After heating for 18min, it was heated to 93℃ and continued to stir and heat for 55min. During the heating process, the pH value was adjusted to 6.5 with hydrochloric acid to make the precipitate fully precipitate. After heating, it was allowed to stand for 3h, cooled and filtered with a 0.45μm filter membrane to obtain 580g of filtrate, and the pH was adjusted to 3.5 with hydrochloric acid. At this time, the free amino acid content was detected to be 100.5g / L, calcium 24g / L, and magnesium 12.3g / L. The product was tested for stability at 0℃, 55℃ and room temperature, and no precipitation was found. The sample was opened and placed without corruption and deterioration.
[0027] Example 4: Preparation of amino acid-containing water-soluble fertilizer (trace element type) using animal feather enzymatic wastewater
[0028] 10KG recycled waste liquid was concentrated under reduced pressure to obtain 3100g of amino acid mother liquor, and the free amino acid content was 151g / L. 100.6g of monohydrate manganese sulfate, 293.9g of heptahydrate zinc sulfate, and 34.8g of boric acid were added to the mother liquor, and heated to 55°C after sufficient stirring. After heating for 15min, it was heated to 95°C and continued to stir and heat for 60min. During the heating process, the pH value was adjusted to 6.0 with hydrochloric acid to make the precipitate fully precipitate. After heating, it was allowed to stand for 3h, cooled and filtered with a 0.45μm filter membrane to obtain 3407.3g of filtrate, and the pH was adjusted to 5.0 with hydrochloric acid, and water was added to 3730.26g. At this time, the free amino acid content was detected to be 121g / L, manganese 6.5g / L, zinc 15.9g / L, and boron 1.2g / L. The product was tested for stability at 0°C, 55°C and room temperature, and no precipitation was found. The sample was opened and placed without corruption and deterioration.
[0029] Comparative Example 1: Preparation of amino acid-containing water-soluble fertilizer (medium element type) using animal tissue enzymatic wastewater
[0030] Take 580g of the mother liquor in Example 1, add 112g of calcium nitrate tetrahydrate and 115g of magnesium sulfate hexahydrate, stir well and heat to 50°C, heat for 20min, heat to 96°C, continue stirring and heating for 15min, adjust the pH value to 6.5 with hydrochloric acid during the heating process, make the precipitate fully precipitate, let stand for 3h after heating, cool and filter with 0.45μm filter membrane, get 768g of filtrate, adjust the pH to 3.5 with hydrochloric acid, add water to 812g, and then detect the free amino acid content of 105g / L, calcium 24g / L, and magnesium 12.5g / L. The product was tested for stability at 0°C for 15 days, and a small amount of precipitation began to appear from the 5th day, and there was a slight sour smell after opening, which became increasingly severe; the product was tested for stability at 55°C for 15 days, and a small amount of precipitation began to appear from the 5th day, and there was a slight sour smell after opening, which became increasingly severe; the product was tested for stability at room temperature for 9 months, and a small amount of precipitation began to appear from one month, and there was a slight sour smell after opening, which became increasingly severe.
[0031] Comparative Example 2: Preparation of amino acid-containing water-soluble fertilizer (medium element type) using animal tissue enzymatic wastewater
[0032] Take 580g of the mother liquor in Example 1, add 112g of calcium nitrate tetrahydrate and 115g of magnesium sulfate hexahydrate, stir well and heat to 60°C, heat for 15min, heat to 96°C, continue stirring and heating for 30min, adjust the pH value to 6.5 with hydrochloric acid, make the precipitate fully precipitate, let stand for 3h after heating, cool and filter with 0.45μm filter membrane, get 759g of filtrate, adjust the pH to 4.0 with hydrochloric acid, add water to 812g, and detect the free amino acid content of 105g / L, calcium 24g / L, and magnesium 12.5g / L at this time. The product was tested for stability at 0°C for 15 days, and a small amount of precipitation began to appear from the 5th day, and there was a slight sour smell after opening, which became increasingly severe; the product was tested for stability at 55°C for 15 days, and a small amount of precipitation began to appear from the 5th day, and there was a slight sour smell after opening, which became increasingly severe; the product was tested for stability at room temperature for 9 months, and a small amount of precipitation began to appear from one month, and there was a slight sour smell after opening, which became increasingly severe.
[0033] Comparative Example 3: Preparation of amino acid-containing water-soluble fertilizer (medium element type) using animal tissue enzymatic wastewater
[0034] Take 580g of the mother liquor in Example 1, add 112g of calcium nitrate tetrahydrate and 115g of magnesium sulfate hexahydrate, stir thoroughly and heat to 96°C, continue stirring and heating for 60min, during the heating process, adjust the pH value to 6.5 with hydrochloric acid to make the precipitate fully precipitate, let stand for 3h after heating, cool and filter with 0.45μm filter membrane to obtain 759g of filtrate, adjust the pH to 4.5 with hydrochloric acid, add water to 812g, at this time, the free amino acid content is 105g / L, calcium is 24g / L, and magnesium is 12.5g / L. The product was tested for stability at 0°C for 15 days. Trace precipitation began to appear on the 5th day and became increasingly severe. There was no sour odor after opening, but a slight sour odor appeared on the 15th day. The product was tested for stability at 55°C for 15 days. Trace precipitation began to appear on the 5th day and became increasingly severe. There was no sour odor after opening, but a slight sour odor appeared on the 15th day. The product was tested for stability at room temperature for 9 months. Trace precipitation began to appear on the 1st month and became increasingly severe. There was no sour odor after opening, but a slight sour odor appeared on the 3rd month and became increasingly severe.
[0035] Comparative Example 4: Preparation of amino acid-containing water-soluble fertilizer (medium element type) using animal tissue enzymatic wastewater
[0036] Take 580g of the mother liquor in Example 1, add 112g of calcium nitrate tetrahydrate and 115g of magnesium sulfate hexahydrate, stir thoroughly and heat to 60°C, heat for 15min, heat to 96°C, continue stirring and heating for 60min to allow the precipitate to fully precipitate, let stand for 3h after heating, cool and filter with a 0.45μm filter membrane to obtain 759g of filtrate, adjust pH to 3.5 with hydrochloric acid, add water to 812g, and the free amino acid content is 105g / L, calcium is 24g / L, and magnesium is 12.5g / L. The product was tested for stability at 0°C for 15 days. Trace precipitation began to appear on the 5th day and became increasingly severe. There was no sour odor after opening, but a slight sour odor appeared on the 15th day. The product was tested for stability at 55°C for 15 days. Trace precipitation began to appear on the 5th day and became increasingly severe. There was no sour odor after opening, but a slight sour odor appeared on the 15th day. The product was tested for stability at room temperature for 9 months. Trace precipitation began to appear on the 1st month and became increasingly severe. There was no sour odor after opening, but a slight sour odor appeared on the 3rd month and became increasingly severe.
[0037] The products obtained in the above Examples 1-4 and Comparative Examples 1-4 were placed at room temperature and at 0°C and 55°C for a long time to investigate their stability. The properties of the products are shown in Table 1-3:
[0038] Table 1 Results of accelerated placement of water-soluble fertilizer at 0°C in the examples and comparative examples
[0039]
[0040] Table 2 Results of accelerated placement of water-soluble fertilizer at 55°C in the examples and comparative examples
[0041]
[0042] Table 3 Results of long-term placement of water-soluble fertilizer at room temperature in the examples and comparative examples
[0043]
[0044] Precipitation-: no precipitation; Precipitation+: trace precipitation; Precipitation++: small amount of precipitation; Precipitation+++: medium amount of precipitation; Precipitation++++: large amount of precipitation.
[0045] Sour smell -: no sour smell; Sour smell +: slight sour smell; Sour smell ++: moderate sour smell; Sour smell +++: severe sour smell.
Claims
1. A method for preparing a water-soluble amino acid fertilizer of animal origin with stable quality, comprising the following steps: (1) Concentrating the waste liquid to produce mother liquor; (2) Add salts of trace elements or medium elements required by plants and stir to dissolve; (3) Heat to 40-60°C for 15-20 minutes, then heat to 90-96°C, continue stirring and heating for 50-60 minutes, and control the pH during the heating process; (4) After standing and cooling, filter, adjust the pH, and add water to obtain water-soluble fertilizer.
2. The method according to claim 1, characterized in that The waste liquid is animal tissue enzymatic hydrolysis waste liquid, shrimp and crab shell enzymatic hydrolysis waste liquid, and animal feather enzymatic hydrolysis waste liquid.
3. The method according to claim 2, characterized in that The amino acid content of the mother liquor is above 110 g / L.
4. The method according to claim 3, characterized in that The intermediate elements are one or two of calcium and magnesium, and the trace elements are one or more of copper, iron, manganese, zinc, boron and molybdenum. The intermediate elements are preferably calcium and magnesium, and the trace elements are preferably manganese, zinc and boron.
5. The method according to claim 4, characterized in that The salts include, but are not limited to, calcium sulfate, calcium sugar alcohol, EDTA chelated calcium, calcium acetate, calcium nitrate, magnesium sulfate, potassium nitrate, magnesium sugar alcohol, EDTA chelated magnesium, magnesium acetate, magnesium nitrate, manganese sulfate, zinc sulfate, boric acid, ammonium heptamolybdate, ammonium molybdate, copper sulfate, humic acid, organic matter, amino acids, sodium nitrate, calcium nitrate, urea, ammonium chloride, ammonium sulfate, ammonium bicarbonate, ammonia water, calcium cyanammonium, monoammonium phosphate, and diammonium phosphate.
6. The method according to claim 5, characterized in that The salts of the trace elements are one or more of ferrous sulfate, ammonium heptamolybdate, zinc sulfate, manganese sulfate, and boric acid, and the salts of the medium elements are calcium nitrate and magnesium sulfate.
7. The method according to claim 1, characterized in that In step (3), the pH is 5.5-6.
5.
8. The method according to claim 1, characterized in that In step (4), the standing time is 2-4 hours, and the product is filtered using a 0.45 μm filter membrane.
9. The method according to claim 1, characterized in that: In step (4), the pH is 3.0-5.0, and the amount of water added is determined according to the amino acid content of the mother liquor so that the free amino acid is above 100 g / L.