Method for preparing amino acid water-soluble fertilizer from heparin sodium enzymatic hydrolysate wastewater

Abstract

The invention relates to the technical field of fertilizer preparation, in particular to a method for preparing an amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater, which comprises the following steps: S1, pretreatment: filtering the collected heparin sodium enzymatic hydrolysate wastewater to remove solid impurities, then carrying out centrifugal separation, and filtering the separated liquid through a microporous filter membrane to obtain a filtrate; pre-treated wastewater is obtained; s2, deep treatment: adding a compound enzyme preparation into the pretreated wastewater to carry out an enzymolysis reaction, adding a flocculant after the reaction is finished, uniformly stirring, standing and precipitating, and removing a precipitate to obtain a purified enzymatic hydrolysate. According to the method, the problem of discharge of the heparin sodium enzymatic hydrolysate wastewater is solved, environmental pollution caused by the heparin sodium enzymatic hydrolysate wastewater is avoided, discharge of pollutants such as chemical oxygen demand and ammonia nitrogen is reduced, the ecological environment is protected, organic substances and nutritional ingredients in the wastewater are converted into the amino acid water-soluble fertilizer with economic value, and the resource utilization rate is increased.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fertilizer preparation, in particular to a method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater. BACKGROUND

[0002] Heparin sodium is an important anticoagulant drug and is widely used in the medical field. At present, the enzyme hydrolysis method is often used in industry to extract heparin sodium from pig small intestinal mucosa and other raw materials. This process will produce a large amount of enzymatic hydrolysate wastewater. These wastewaters are rich in nutrients such as proteins, polypeptides, amino acids, and various mineral elements. If they are directly discharged, not only will it cause waste of resources, but also will cause serious pollution to the environment, leading to water eutrophication and other problems.

[0003] At the same time, the demand for high-quality water-soluble fertilizers in agricultural production is increasing. Amino acid water-soluble fertilizer, as a new type of efficient and environmentally friendly fertilizer, can provide comprehensive nutrition for plants, promote the growth and development of plants, improve the yield and quality of crops, and enhance the stress resistance of crops. However, the existing preparation method of amino acid water-soluble fertilizer often needs to use a large amount of raw materials and complex processes, which has a high cost. Therefore, how to effectively utilize heparin sodium enzymatic hydrolysate wastewater to prepare amino acid water-soluble fertilizer and realize resource recycling and environmental protection has important practical significance. SUMMARY

[0004] To achieve the above-mentioned purpose, the present application provides the following technical scheme: a method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater, comprising the following steps: S1, pretreatment: filtering the collected heparin sodium enzymatic hydrolysate wastewater to remove solid impurities, then centrifuging, and filtering the separated liquid through a microporous filter membrane to obtain pretreated wastewater; S2, deep treatment: adding a composite enzyme preparation to the pretreated wastewater for enzymatic hydrolysis reaction, adding a flocculating agent after the reaction is completed, stirring uniformly, and then standing and precipitating to remove the precipitate to obtain purified enzymatic hydrolysate; S3, nutrient content adjustment: detecting the nutrient content of the purified enzymatic hydrolysate, adding macroelement fertilizer and microelement fertilizer according to a preset standard to obtain a nutrient adjustment solution; S4, stability adjustment: adding a stabilizer to the nutrient adjustment solution and adjusting the pH value to obtain a fertilizer solution; S5, product processing: sterilizing the fertilizer solution at high temperature, filling after cooling, and obtaining an amino acid water-soluble fertilizer product.

[0005] Preferably, in step S1, the centrifugation speed is 3000-5000 r / min, and the centrifugation time is 10-20 minutes.

[0006] Preferably, in the step S1, the pore size of the microporous filter membrane is 0.2-0.5 μm.

[0007] Preferably, in the step S2, the complex enzyme preparation comprises protease, amylase and lipase, and the adding amount of the protease, the amylase and the lipase is 0.2-0.5%, 0.1-0.3% and 0.1-0.2% of the mass of the enzymatic hydrolysate wastewater, respectively.

[0008] Preferably, in the step S2, the enzyme reaction is carried out under the conditions of temperature 40-50℃, pH value 6.5-7.5 and reaction time 3-5 hours.

[0009] Preferably, in the step S2, the adding amount of the flocculating agent is 3-5% by mass, and the standing time for precipitation is 1-2 hours.

[0010] Preferably, in the step S3, the macroelement fertilizer comprises nitrogen, phosphorus and potassium, and the medium and trace element fertilizer comprises calcium, magnesium, zinc and boron, and the adding amount satisfies the conditions that the total content of nitrogen, phosphorus and potassium in the final product is not less than 20%, the content of amino acid is not less than 10%, and the total content of medium and trace elements is not less than 2%.

[0011] Preferably, in the step S4, the adding amount of the stabilizer is 0.5-1% by mass, and the adjusted pH value is 5.5-7.0.

[0012] Preferably, in the step S5, the temperature of the high-temperature sterilization treatment is 120-130℃, and the holding time is 15-20 minutes.

[0013] Compared with the prior art, the present application has the following beneficial effects: (1) The present application effectively solves the problem of the discharge of the heparin sodium enzymatic hydrolysate wastewater, avoids the pollution of the environment, reduces the discharge of the chemical oxygen demand, ammonia nitrogen and other pollutants, protects the ecological environment, converts the organic matter and the nutrient components in the wastewater into the amino acid water-soluble fertilizer with economic value, realizes the recycling of the resources, improves the resource utilization rate, reduces the dependence on new raw materials, uses the discarded enzymatic hydrolysate wastewater as the raw material, reduces the production cost of the amino acid water-soluble fertilizer, and improves the market competitiveness of the product; (2) The present application adopts the complex enzyme preparation technology of protease+amylase+lipase in the advanced treatment stage, carries out secondary directional enzyme hydrolysis on the residual macromolecular proteins, polysaccharides and fats and other difficult-to-absorb substances in the wastewater, converts them into small-molecule amino acids, monosaccharides and fatty acids which are easily absorbed and utilized by plants, this treatment mode significantly improves the biological activity and the nutrient utilization rate of the fertilizer, and can more effectively promote the growth of crops, improve the quality and the stress resistance of crops; (3) The present application removes the suspended solids, un-enzymolysis tissue fragments and colloidal impurities in the wastewater through the pretreatment and deep treatment process combining physical filtration, centrifugal separation and chemical flocculation, significantly reduces the color and turbidity of the liquid, in addition, through adding stabilizer and adjusting pH value, effectively solves the problems of precipitation, delamination and deterioration of the liquid fertilizer during storage, prolongs the shelf life of the product. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 It is a schematic diagram of the step flow of the overall method in an embodiment of the present application. DETAILED DESCRIPTION

[0015] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0016] In one aspect, as shown in the figure, a method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater, comprising the following steps: Figure 1 S1, pretreatment: filtering the collected heparin sodium enzymatic hydrolysate wastewater to remove solid impurities, then centrifugal separation, and filtering the separated liquid through a microporous filter membrane to obtain pretreated wastewater; S2, deep treatment: adding a composite enzyme preparation to the pretreated wastewater for enzymatic reaction, adding a flocculating agent after the reaction is completed, stirring uniformly, and then standing and precipitating to remove the precipitate to obtain purified enzymatic hydrolysate; S3, nutrient component blending: detecting the nutrient component content of the purified enzymatic hydrolysate, adding macroelement fertilizer and microelement fertilizer according to the preset standard to obtain a nutrient blending solution; S4, stability adjustment: adding a stabilizer to the nutrient blending solution and adjusting the pH value to obtain a fertilizer solution; S5, product processing: sterilizing the fertilizer solution at high temperature, filling after cooling, and obtaining an amino acid water-soluble fertilizer product. In an optional embodiment, in step S1, the centrifugal separation speed is 3000-5000 r / min, and the centrifugal time is 10-20 minutes.

[0017] In an optional embodiment, in step S1, the pore size of the microporous filter membrane is 0.2-0.5 μm.

[0018]

[0019] ​In an alternative embodiment, in step S2, the complex enzyme preparation comprises protease, amylase and lipase; and the added amounts are 0.2-0.5%, 0.1-0.3% and 0.1-0.2% of the mass of the enzymatic hydrolysate wastewater, respectively.

[0020] In an alternative embodiment, in step S2, the enzymatic hydrolysis reaction is carried out under the following conditions: temperature 40-50℃, pH value 6.5-7.5, and reaction time 3-5 hours.

[0021] In an alternative embodiment, in step S2, the added amount of the flocculating agent is 3-5% by mass; and the standing and precipitation time is 1-2 hours.

[0022] In an alternative embodiment, in step S3, the macroelement fertilizer comprises nitrogen, phosphorus and potassium; and the microelement fertilizer comprises calcium, magnesium, zinc and boron; and the added amounts are required to meet the following conditions: the total content of nitrogen, phosphorus and potassium in the final product is not less than 20%, the content of amino acid is not less than 10%, and the total content of microelements is not less than 2%.

[0023] In an alternative embodiment, in step S4, the added amount of the stabilizer is 0.5-1% by mass; and the adjusted pH value is 5.5-7.0.

[0024] In an alternative embodiment, in step S5, the high-temperature sterilization treatment is carried out at a temperature of 120-130℃ for 15-20 minutes.

[0025] In order to further illustrate the present application, the technical solutions provided by the present application are described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0026] The production process, experimental method or detection method involved in the embodiments of the present application are all conventional methods in the prior art without specific description, and the name and / or abbreviation thereof all belong to the conventional name in the art and are very clear and explicit in the related application field, and the person skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the name, and implement it under the conventional conditions or the conditions recommended by the manufacturer.

[0027] The various instruments, equipment, raw materials or reagents used in the embodiments of the present application do not have special restrictions on the source, and are all conventional products that can be purchased through normal commercial channels, or can be prepared according to the conventional method well known to the person skilled in the art.

[0028] Example 1: A method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater, comprising the following steps: S1. Pretreatment: The collected 1000 kg of heparin sodium hydrolysate wastewater was coarsely filtered to remove solid impurities, and then placed in a centrifuge. The centrifugation speed was set to 3000 r / min and the centrifugation time was 10 minutes. The supernatant was separated and filtered through a microporous membrane with a pore size of 0.5 μm to obtain clear pretreated wastewater. S2. Advanced Treatment: Add a compound enzyme preparation to the pretreated wastewater; wherein, the amount of protease added is 0.2%, the amount of amylase added is 0.1%, and the amount of lipase added is 0.1%; adjust the temperature to 40℃, adjust the pH value to 6.5, and carry out the enzymatic hydrolysis reaction for 3 hours; after the reaction is completed, add 3% by mass of flocculant, the flocculant is polyaluminum chloride, stir evenly, and let it stand for 1 hour to remove the bottom precipitate to obtain the purified enzymatic hydrolysate; S3. Nutrient Component Blending: After testing the components of the enzymatic hydrolysate, fertilizers such as urea, potassium dihydrogen phosphate, and zinc sulfate were added to blend and obtain a nutrient blending solution, so that the total nitrogen, phosphorus, and potassium content in the final product is 20.5%, the amino acid content is 10.2%, and the total content of trace elements is 2.1%. S4. Stability adjustment: Add 0.5% xanthan gum by mass to the prepared solution as a stabilizer, and adjust the pH of the solution to 5.5 using potassium hydroxide / citric acid; S5. Finished product processing: The solution is sent into a high-temperature sterilization device and kept at 120°C for 15 minutes. After cooling to room temperature, it is aseptically filled to obtain the amino acid water-soluble fertilizer product.

[0029] Example 2: A method for preparing amino acid water-soluble fertilizer using heparin sodium enzymatic hydrolysis wastewater, comprising the following steps: A method for preparing amino acid water-soluble fertilizer using wastewater from heparin sodium enzymatic hydrolysis includes the following steps: S1. Pretreatment: The collected 1000 kg of heparin sodium hydrolysate wastewater was filtered to remove impurities, and then centrifuged at a speed of 4000 r / min for 15 minutes. The separated liquid was filtered through a microporous membrane with a pore size of 0.3 μm to obtain pretreated wastewater. S2. Advanced Treatment: Add a compound enzyme preparation to the pretreated wastewater; the amount of protease added is 0.35%, the amount of amylase added is 0.2%, and the amount of lipase added is 0.15%; adjust the temperature to 45℃, adjust the pH value to 7.0, and carry out the enzymatic hydrolysis reaction for 4 hours; after the reaction is completed, add 4% by mass of flocculant, the flocculant is polyaluminum chloride, stir and let it stand for 1.5 hours to remove the bottom precipitate to obtain the purified enzymatic hydrolysate; S3. Nutrient Component Blending: After testing the components of the enzymatic hydrolysate, fertilizers such as urea, potassium dihydrogen phosphate, and zinc sulfate are added to blend and obtain a nutrient blending solution, so that the total nitrogen, phosphorus, and potassium content in the final product is 25%, the amino acid content is 12%, and the total content of trace elements is 2.5%. S4. Stability adjustment: Add 0.8% xanthan gum by mass to the prepared solution as a stabilizer, and adjust the pH of the solution to 6.5 using potassium hydroxide / citric acid; S5. Finished product processing: The solution is sent into a high-temperature sterilization device and kept at 125°C for 18 minutes. After cooling to room temperature, it is aseptically filled to obtain the amino acid water-soluble fertilizer product.

[0030] Example 3: A method for preparing amino acid water-soluble fertilizer using heparin sodium enzymatic hydrolysis wastewater, comprising the following steps: S1. Pretreatment: The collected 1000 kg of heparin sodium hydrolysate wastewater was coarsely filtered to remove solid impurities, and then placed in a centrifuge. The centrifugation speed was set to 5000 r / min and the centrifugation time was 20 minutes. The supernatant was separated and filtered through a microporous membrane with a pore size of 0.2 μm to obtain clear pretreated wastewater. S2. Advanced Treatment: Add a compound enzyme preparation to the pretreated wastewater; wherein, the amount of protease added is 0.5%, the amount of amylase added is 0.3%, and the amount of lipase added is 0.2%; adjust the temperature to 50℃, adjust the pH value to 7.5, and carry out the enzymatic hydrolysis reaction for 5 hours; after the reaction is completed, add 5% by mass of flocculant, the flocculant is polyaluminum chloride, stir evenly, and let it stand for 2 hours to remove the bottom precipitate to obtain the purified enzymatic hydrolysate; S3. Nutrient Component Blending: After testing the components of the enzymatic hydrolysate, fertilizers such as urea, potassium dihydrogen phosphate, and zinc sulfate are added to blend and obtain a nutrient blending solution, so that the total nitrogen, phosphorus, and potassium content in the final product is 28%, the amino acid content is 15%, and the total content of trace elements is 3.0%. S4. Stability adjustment: Add 1.0% xanthan gum by mass to the prepared solution as a stabilizer, and adjust the pH of the solution to 7.0 using potassium hydroxide / citric acid; S5. Finished product processing: The solution is sent into a high-temperature sterilization device and kept at 130°C for 20 minutes. After cooling to room temperature, it is aseptically filled to obtain the amino acid water-soluble fertilizer product.

[0031] Comparative Example 1 The only difference from Example 2 is: In step S2, only 0.7% of protease was added, and no amylase or lipase was added. The remaining steps and parameters were exactly the same as in Example 2.

[0032] Comparative Example 2 The only difference from Example 2 is: In step S1, only preliminary filtration was performed, without centrifugation and microporous membrane filtration. The process proceeds directly to step S2, and the remaining steps and parameters are exactly the same as in Example 2.

[0033] The amino acid fertilizers prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were subjected to performance testing. The testing was conducted in accordance with the "Determination of Amino Acid Content in Water-Soluble Fertilizers" (NY / T 1429-2010) and relevant industry standards. The comparative results are shown in Table 1. Table 1: Performance Test Results of Each Example and Comparative Example Test item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 National standard / industry reference Appearance Brown and clear, no precipitate Dark brown and uniform, no precipitate Dark brown and uniform, no precipitate Hazy, with a small amount of flocculation Obvious precipitate at the bottom Uniform liquid pH value 5.5 6.5 7.0 6.5 6.5 3.0-8.0 Amino acid content (g / L) 102 120 150 85 118 ≥100 Total N+P+K content (g / L) 205 250 280 248 250 ≥200 Water-insoluble content (%) 0.8% 0.5% 0.2% 2.5% 3.8% ≤2.0% Stability (3 months at room temperature) No precipitate No precipitate No precipitate Layering occurred Large amount of precipitate - As shown in Table 1, the products prepared in Examples 1 to 3 all exceeded the national standards in various indicators and exhibited good stability. In Comparative Example 1, due to the lack of a combined enzymatic hydrolysis technology of protease + amylase + lipase, some lipids and polysaccharides in the wastewater were not decomposed, resulting in a low amino acid conversion rate and affecting the clarity of the liquid. In Comparative Example 2, due to the lack of centrifugation and microfiltration in the pretreatment stage, the content of water-insoluble matter in the finished product seriously exceeded the standard, and a large amount of sediment was easily generated during the storage process, resulting in poor stability. This fully demonstrates the necessity and technical advantages of combining the pretreatment fine filtration with the combined enzymatic hydrolysis step in this invention.

[0034] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited thereto. Various changes can be made within the scope of knowledge possessed by those skilled in the art without departing from the spirit of the present invention.

Claims

1. A method for preparing amino acid water-soluble fertilizer using wastewater from heparin sodium enzymatic hydrolysis solution, characterized in that, The method comprises the following steps: S1, pretreatment: filtering the collected heparin sodium enzymatic hydrolysate wastewater to remove solid impurities, then centrifuging and separating, and filtering the separated liquid through a microporous filter membrane to obtain pretreated wastewater; S2, deep treatment: adding a composite enzyme preparation to the pretreated wastewater for enzymatic hydrolysis, adding a flocculating agent after the reaction is completed, stirring uniformly, and then standing and precipitating to remove the precipitate to obtain purified enzymatic hydrolysate; S3, nutrient component dispensing: detecting the nutrient component content of the purified enzymatic hydrolysate, adding macroelement fertilizer and microelement fertilizer according to a preset standard to obtain a nutrient dispensing liquid; S4, stability adjustment: adding a stabilizer to the nutrient dispensing liquid and adjusting the pH value to obtain a fertilizer solution; S5, product processing: sterilizing the fertilizer solution at high temperature, filling after cooling, and obtaining an amino acid water-soluble fertilizer product.

2. The method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater according to claim 1, characterized in that, In the step S1, the centrifugal speed is 3000-5000 r / min, and the centrifugal time is 10-20 minutes.

3. The method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater according to claim 1, characterized in that, In the step S1, the pore size of the microporous filter membrane is 0.2-0.5 μm.

4. The method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater according to claim 1, characterized in that, In the step S2, the composite enzyme preparation comprises protease, amylase and lipase, and the addition amounts are 0.2-0.5%, 0.1-0.3% and 0.1-0.2% of the mass of the enzymatic hydrolysate wastewater, respectively.

5. The method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater according to claim 1, characterized in that, In the step S2, the enzymatic hydrolysis conditions are as follows: temperature 40-50℃, pH value 6.5-7.5, and reaction time 3-5 hours.

6. The method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater according to claim 1, characterized in that, In the step S2, the addition amount of the flocculating agent is 3-5% by mass, and the standing and precipitating time is 1-2 hours.

7. The method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater according to claim 1, characterized in that, In the step S3, the macroelement fertilizer comprises nitrogen, phosphorus and potassium, and the microelement fertilizer comprises calcium, magnesium, zinc and boron; the addition amounts meet the requirements that the total content of nitrogen, phosphorus and potassium in the final product is not less than 20%, the amino acid content is not less than 10%, and the total content of microelements is not less than 2%. 8.The method of claim 1, wherein the method further comprises: adding a catalyst to the hydrolysate of heparin sodium to produce a product; and adding a chelating agent to the product to produce the amino acid water-soluble fertilizer. In the step S4, the addition amount of the stabilizer is 0.5-1% by mass, and the adjusted pH value is 5.5-7.

0.

9. The method for preparing amino acid water-soluble fertilizer by using heparin sodium enzymatic hydrolysate wastewater according to claim 1, characterized in that, In the step S5, the high-temperature sterilization temperature is 120-130℃, and the holding time is 15-20 minutes.

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