Antibiotic mushroom dreg and phosphoric acid integrated fertilizer synergistic carrier as well as preparation method and application thereof

Abstract

The invention relates to an antibiotic mushroom dreg and phosphoric acid integrated fertilizer synergistic carrier as well as a preparation method and application thereof, and belongs to the field of compound fertilizers. Penicillin mycelium residues and wet-process phosphoric acid are adopted as raw materials, a liquid-phase synergistic carrier is obtained through hydrothermal acidolysis, insoluble residues are subjected to alkali-sulfite synergistic treatment to prepare a full-water-soluble solid-phase synergistic carrier, and finally the antibiotic mushroom residue and phosphoric acid integrated fertilizer synergistic carrier is prepared. According to the technology, residual antibiotics and resistance genes in the mushroom residues are removed, amino acid and polypeptide active substances are generated in situ, the phosphorus utilization rate is remarkably increased, full-amount recycling of the mushroom residues is achieved, and the technology can flexibly adapt to various fertilizer systems. The invention provides an innovative solution for antibiotic mushroom dreg resourceful treatment and environment-friendly fertilizer development.

Description

Technical Field

[0001] The present invention belongs to the technical field of compound fertilizers, and particularly relates to an antibiotic residue phosphoric acid integrated fertilizer synergistic carrier, a preparation method thereof, and an application thereof. Background Art

[0002] Antibiotic residue is a kind of biological waste generated in the production process of fermentation antibiotics, containing a large amount of nutrients such as nitrogen, phosphorus, and organic matter, but also containing residual antibiotics and their metabolites. Due to its high moisture content, complex composition, and antibiotic residues, the treatment and resource utilization of antibiotic residue face many technical challenges. The antibiotic residues in antibiotic residue may pose potential risks to the environment. In particular, antibiotic resistance genes may spread into the ecosystem through soil, water bodies and other channels, thus affecting human health.

[0003] At present, the traditional treatment methods of antibiotic residue mainly include incineration, direct pyrolysis, anaerobic digestion, aerobic composting, etc. Among them, although incineration and direct pyrolysis can completely remove the residual antibiotics and resistance genes in the residue, due to their high moisture content and high nitrogen content, these two treatment methods have high energy consumption, high cost, a large amount of nitrogen oxide emissions causing secondary pollution, and serious waste of resources. Although anaerobic digestion can effectively degrade antibiotics and produce biogas, its reaction cycle is long, the subsequent treatment of the digestion liquid is complex, and the digestion liquid may contain pathogenic bacteria and resistance genes, which greatly increases the environmental risk. In contrast, although aerobic composting can degrade antibiotics and prepare organic fertilizers in a relatively short time, the existence of resistance genes in the process and the safety assessment of the compost products are still important reasons why this method is difficult to be actually applied at present. Therefore, how to achieve the efficient and environmental protection treatment of fermentation antibiotic residue without increasing secondary pollution is of great significance for the development of the pharmaceutical industry, environmental protection, and efficient utilization of resources.

[0004] Phosphorus resources are finite resources that are non-renewable and irreplaceable in the short term. Phosphorus is one of the essential nutrients for crop growth and is involved in a series of processes such as photosynthesis, respiration, energy generation, and nucleic acid biosynthesis. The effectiveness of phosphate fertilizers is related to the composition of the fertilizers themselves, the form of phosphorus, and the characteristics of the soil into which they are applied. However, traditional inorganic phosphate fertilizers currently available have poor mobility in the soil and are easily chemically fixed and adsorbed by the soil, resulting in a utilization rate of only 10-15% in the current season. Moreover, if only the amount of phosphate fertilizer is blindly increased, due to the antagonistic effect between phosphorus and metal ions such as zinc, calcium, and magnesium, it will lead to a decrease in land productivity, exacerbate soil salinization, and the phosphorus fixed in the soil will be lost through processes such as soil leaching, erosion, and surface runoff, causing serious waste of phosphorus resources and ecological and environmental problems such as water eutrophication. Therefore, guided by agricultural needs, developing and preparing cheap, efficient, and green phosphorus-based new fertilizer synergistic carriers to improve the phosphorus utilization rate and reduce the total amount of phosphate fertilizer used is an urgent problem in the field of resources and the environment. Summary of the Invention

[0005] In view of the above-mentioned prior art, the present invention provides an antibiotic residue-phosphoric acid integrated fertilizer synergistic carrier, its preparation method, and application to solve the technical problems of difficult treatment of antibiotic residues and low phosphorus utilization rate.

[0006] To achieve the above object, the technical solution adopted by the present invention is to provide a preparation method of an antibiotic residue-phosphoric acid integrated fertilizer synergistic carrier, which includes the following steps:

[0007] S1: Mix antibiotic residues with wet-process phosphoric acid, and then carry out hydrothermal reaction; after the reaction is completed, filter and collect the filtrate to obtain a liquid-phase synergistic carrier;

[0008] S2: Disperse the solid residue obtained by filtration, alkali, and sulfite in water, heat to 55-85°C under closed conditions, and keep stirring for 30-120 minutes to obtain an impregnation system;

[0009] S3: Evaporate the impregnation system to dryness to obtain a solid-phase synergistic carrier;

[0010] S4: Add the solid-phase synergistic carrier to the liquid-phase synergistic carrier and stir evenly to obtain the product.

[0011] On the basis of the above technical solution, the present invention can also be improved as follows.

[0012] Further, the content of phosphoric acid in the wet-process phosphoric acid is 30-46 wt% (calculated as P2O5%).

[0013] Further, the mass ratio of antibiotic residues to wet-process phosphoric acid is 1:10-20.

[0014] Furthermore, the temperature of the hydrothermal reaction is 100~160 °C, and the hydrothermal reaction time is 1~6 h.

[0015] Furthermore, the base is potassium hydroxide; the sulfite is at least one of potassium sulfite, ammonium sulfite, potassium bisulfite, and ammonium bisulfite.

[0016] Furthermore, the mass ratio of the solid residue, base, sulfite, and water in S2 is 80~200:80~170:60~150:500~1800.

[0017] Furthermore, the final temperature of the temperature rise in S2 is 80 °C, and the holding and stirring time is 120 min.

[0018] Furthermore, the evaporation-to-dryness temperature in S3 is 100~150 °C.

[0019] The present invention also discloses an antibiotic residue phosphoric acid integrated fertilizer synergistic carrier, which is prepared by the above preparation method.

[0020] The present invention also discloses the application of the above antibiotic residue phosphoric acid integrated fertilizer synergistic carrier in the preparation of water-soluble fertilizers.

[0021] The beneficial effects of the present invention are as follows:

[0022] 1. The present invention uses penicillin mycelium residue (antibiotic residue) as the raw material, and through the hydrothermal method of wet-process phosphoric acid, with the synergistic effect of high temperature and acidic conditions, effectively removes the antibiotic residues and potential resistance genes in the residue, destroys the genetic material of the resistance genes, solves the risk of the spread and transfer of resistance genes in the environment causing drug resistance, and provides a feasible solution for solving the problem of antibiotic resistance.

[0023] 2. The present invention can efficiently decompose a large amount of crude protein in the residue into fertilizer synergistic substances such as amino acids and polypeptides by hydrothermal acidolysis of the antibiotic residue with phosphoric acid. This method in-situ introduces 18 kinds of amino acids into the liquid-phase synergistic carrier by chemical methods, effectively improving the biological availability of phosphorus. It not only greatly reduces the cost of exogenous synergistic substances in fertilizers, but also significantly improves the resource utilization efficiency of penicillin residue, which has important environmental and economic significance.

[0024] 3. The present invention conducts secondary treatment on the insoluble solid residue after hydrothermal acidolysis of wet-process phosphoric acid, makes it transform into a fully water-soluble solid-phase synergistic carrier under mild conditions, and then adds the fully water-soluble solid-phase synergistic carrier into the liquid-phase synergistic carrier. The obtained antibiotic residue phosphoric acid integrated fertilizer synergistic carrier truly realizes the full utilization of penicillin residue.

[0025] 4. During the preparation of the integrated phosphate fertilizer synergistic carrier from antibiotic bacterial residues of the present invention, nitrogen-containing or potassium-containing sulfites can be selected according to the requirements of the target fertilizer. When applied to solid fertilizers (such as monoammonium phosphate, potassium dihydrogen phosphate, etc.), it can improve the water solubility of the fertilizer itself and introduce active substances such as amino acids and polypeptides at low cost; when applied to liquid fertilizers (such as NPK suspension fertilizers), due to the solid-phase carrier containing lignosulfonate, it can be used instead of the suspension fertilizer dispersant (such as common sodium lignosulfonate), simultaneously improving the fertilizer efficiency and reducing the production cost. This technology realizes the precise adaptation of solid / liquid fertilizer systems through raw material compatibility regulation. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is the antibiotic content in penicillin bacterial residues and the integrated phosphate fertilizer synergistic carrier of antibiotic bacterial residues;

[0027] Figure 2 is the amino acid content in the monoammonium phosphate obtained in Example 1 and Comparative Example 1;

[0028] Figure 3 is the infrared spectrogram of the monoammonium phosphate obtained in Example 1 and Comparative Example 1;

[0029] Figure 4 is the content of 18 amino acids in Example 2, Example 3, Comparative Example 2, and Comparative Example 3;

[0030] Figure 5 is the effect diagram after the suspension fertilizer products in Example 3 and Comparative Example 3 are left standing for 30 days. DETAILED DESCRIPTION OF THE INVENTION

[0031] The following detailed description of the specific embodiments of the present invention is given in conjunction with the examples.

[0032] Example 1

[0033] An integrated phosphate fertilizer synergistic carrier of antibiotic bacterial residues is prepared through the following steps:

[0034] S1: Add penicillin bacterial residues (dry basis) and wet-process phosphoric acid (concentration in terms of P2O5% is 35 wt%) in a mass ratio of 1:20 to a 100 ml polytetrafluoroethylene inner liner, and stir at room temperature for 0.5 h;

[0035] S2: Place the inner liner into a hydrothermal reaction kettle, seal it, and carry out hydrothermal reaction at 150 °C for 120 min. After the reaction is completed, cool it to room temperature, filter the reaction solution to obtain the liquid-phase synergistic carrier;

[0036] S3: Disperse the filtered solid residue, potassium hydroxide, and ammonium bisulfite in water, heat up to 80 °C under sealed conditions, and keep stirring for 120 min to obtain an impregnation system; the mass ratio of the solid residue, potassium hydroxide, ammonium bisulfite, and water is 100:110:110:1000.

[0037] S4: Evaporate the impregnation system to dryness at 120 °C to obtain a solid-phase synergistic carrier;

[0038] S5: Add the solid-phase synergistic carrier to the liquid-phase synergistic carrier and stir evenly to obtain the product.

[0039] To prepare water-soluble monoammonium phosphate using the fertilizer synergistic carrier in this example, the specific steps are as follows:

[0040] (1) Add ammonia water to the antibiotic residue phosphoric acid integrated fertilizer synergistic carrier until the solution pH = 4.5 to obtain a monoammonium phosphate slurry;

[0041] (2) Spray-dry the monoammonium phosphate slurry at 210 °C to obtain a monoammonium phosphate product containing the antibiotic residue phosphoric acid integrated synergistic carrier.

[0042] Example 2

[0043] An antibiotic residue phosphoric acid integrated fertilizer synergistic carrier is prepared through the following steps:

[0044] S1: Add penicillin residue (dry basis) and wet-process phosphoric acid (concentration is 40 wt% in terms of P2O5%) at a mass ratio of 1:15 to a 100 ml polytetrafluoroethylene inner liner, and stir at room temperature for 0.5 h;

[0045] S2: Place the inner liner into a hydrothermal reaction kettle, seal it, and carry out hydrothermal reaction at 160 °C for 1 h. After the reaction, cool it to room temperature, filter the reaction solution to obtain a liquid-phase synergistic carrier;

[0046] S3: Disperse the filtered solid residue, potassium hydroxide, and potassium sulfite in water, heat up to 85 °C under sealed conditions, and keep stirring for 30 min to obtain an impregnation system; the mass ratio of the solid residue, potassium hydroxide, potassium sulfite, and water is 80:80:60:500.

[0047] S4: Evaporate the impregnation system to dryness at 150 °C to obtain a solid-phase synergistic carrier;

[0048] S5: Add the solid-phase synergistic carrier to the liquid-phase synergistic carrier and stir evenly to obtain the product.

[0049] To prepare water-soluble potassium dihydrogen phosphate using the fertilizer synergistic carrier in this example, the specific steps are as follows:

[0050] (1) Slowly add 50% potassium hydroxide solution to the antibiotic residue integrated phosphorus fertilizer synergistic carrier to obtain potassium dihydrogen phosphate slurry; the mass ratio of the potassium hydroxide solution to the antibiotic residue integrated phosphorus fertilizer synergistic carrier is 550:480;

[0051] (2) Spray-dry the potassium dihydrogen phosphate slurry at 220 °C to obtain a potassium dihydrogen phosphate product containing the antibiotic residue integrated phosphorus synergistic carrier.

[0052] Example 3

[0053] An antibiotic residue integrated phosphorus fertilizer synergistic carrier is prepared through the following steps:

[0054] S1: Add penicillin residue (dry basis) and wet-process phosphoric acid (concentration is 46 wt% in terms of P2O5%) to a 100 ml polytetrafluoroethylene liner in a mass ratio of 1:10, and stir at room temperature for 0.5 h;

[0055] S2: Put the liner into a hydrothermal reaction kettle, seal it, and carry out hydrothermal reaction at 100 °C for 2 h. After the reaction is completed, cool it to room temperature, filter the reaction solution to obtain a liquid-phase synergistic carrier;

[0056] S3: Disperse the filtered solid residue, potassium hydroxide, and potassium bisulfite in water, heat it up to 55 °C under a closed condition, and keep stirring for 120 min to obtain an impregnation system; the mass ratio of the solid residue, potassium hydroxide, potassium bisulfite, and water is 200:170:150:1800.

[0057] S4: Evaporate the impregnation system to dryness at 100 °C to obtain a solid-phase synergistic carrier;

[0058] S5: Add the solid-phase synergistic carrier to the liquid-phase synergistic carrier and stir evenly to obtain it.

[0059] Using the fertilizer synergistic carrier in this example to prepare a water-soluble nitrogen, phosphorus, and potassium suspension fertilizer, which specifically includes the following steps:

[0060] Add urea, potassium chloride, and xanthan gum to the antibiotic residue integrated phosphorus synergistic carrier in sequence, and then add the mixture to a sand mill and sand mill it at a speed of 3000 rpm for 15 min to obtain a nitrogen, phosphorus, and potassium suspension fertilizer containing the antibiotic residue integrated phosphorus synergistic carrier; the mass ratio of the antibiotic residue integrated phosphorus synergistic carrier, urea, potassium chloride, and xanthan gum is 500:800:100:2.

[0061] Comparative Example 1

[0062] A monoammonium phosphate containing amino acids is prepared through the following steps:

[0063] S1: Add ammonia water to wet-process phosphoric acid (with a concentration of 35 wt% in terms of P2O5%) until the pH of the solution reaches 4.5 to obtain monoammonium phosphate slurry;

[0064] S2: Mix amino acid raw powder with monoammonium phosphate slurry at a mass ratio of 1:20 to obtain amino acid-containing monoammonium phosphate slurry;

[0065] S3: Spray-dry the amino acid-containing monoammonium phosphate slurry at 210 °C to obtain amino acid-containing monoammonium phosphate product.

[0066] Comparative Example 2

[0067] A kind of potassium dihydrogen phosphate containing amino acids is prepared through the following steps:

[0068] S1: Slowly drop 50% potassium hydroxide solution into wet-process phosphoric acid (with a concentration of 40 wt% in terms of P2O5%) to obtain potassium dihydrogen phosphate slurry; the mass ratio of potassium hydroxide solution to wet-process phosphoric acid is 550:480;

[0069] S2: Mix amino acid raw powder with potassium dihydrogen phosphate slurry at a mass ratio of 1:20 to obtain amino acid-containing potassium dihydrogen phosphate slurry;

[0070] S3: Spray-dry the potassium dihydrogen phosphate slurry at 220 °C to obtain amino acid-containing potassium dihydrogen phosphate product.

[0071] In the preparation method of the potassium dihydrogen phosphate containing amino acids in this comparative example, the raw materials used are as follows by mass parts:

[0072] 550 parts of 50% potassium hydroxide solution and 480 parts of wet-process phosphoric acid.

[0073] Comparative Example 3

[0074] A kind of amino acid-containing nitrogen, phosphorus and potassium suspension fertilizer is prepared through the following steps:

[0075] S1: Add urea, potassium chloride, amino acid raw powder and sodium lignosulfonate to wet-process phosphoric acid (with a concentration of 46 wt% in terms of P2O5%) in sequence, and use a shear emulsifier to conduct rough crushing at a shear rate of 4000 rpm for 30 min;

[0076] S2: Add xanthan gum to the roughly crushed suspension, and add it to a sand mill at 3000 rpm for sand milling for 15 min to obtain amino acid-containing nitrogen, phosphorus and potassium suspension fertilizer;

[0077] In the preparation method of the amino acid-containing nitrogen, phosphorus and potassium suspension fertilizer in this comparative example, the raw materials used are as follows by mass parts:

[0078] 500 parts of wet-process phosphoric acid, 800 parts of urea, 100 parts of potassium chloride, 35 parts of amino acid raw powder, 15 parts of sodium lignosulfonate, 2 parts of xanthan gum.

[0079] Experimental Example 1: Antibiotic Residue and Resistance Gene Content in the Phosphorus-integrated Synergistic Carrier of Untreated Penicillin Bacterial Residue and Antibiotic Bacterial Residue

[0080] The residues of antibiotics such as tetracycline, oxytetracycline, and penicillin in the untreated antibiotic bacterial residue and the phosphorus-integrated synergistic carrier of antibiotic bacterial residue prepared in Example 1 were detected, and the results are as Figure 1 shown. It can be seen from Figure 1 that tetracycline, oxytetracycline, and chlortetracycline were not detected in the synergistic carrier, while the contents of penicillin and doxycycline were only 1.88 and 0.38 μg / kg respectively, and the total elimination rate of antibiotics was higher than 99%. According to the national standard requirements of "Fertilizer Classification and Requirements", the total antibiotic (the sum of tetracycline, oxytetracycline, chlortetracycline, and doxycycline) content in ecological organic fertilizers should be less than 3.25 mg / kg, while the total antibiotic content in the synergistic carrier was only 0.00038 mg / kg, far lower than the required value, indicating that the phosphorus-integrated synergistic carrier of antibiotic bacterial residue prepared in Examples 1 to 3 meets the basic requirements for the subsequent preparation of different fertilizers.

[0081] Furthermore, the resistance genes in the penicillin bacterial residue and the phosphorus-integrated synergistic carrier of antibiotic bacterial residue prepared in Example 1 were detected respectively. Samples obtained from 3 different experiments were taken to ensure the accuracy of the detection results. The results are shown in Table 1. The total amount of resistance genes in the synergistic carrier decreased by 2 to 3 orders of magnitude, proving that the resistance genes in the penicillin bacterial residue can be effectively destroyed by the methods in Examples 1 to 3, providing an important environmental safety guarantee and laying a scientific foundation for the subsequent preparation of different fertilizers, and at the same time providing a feasible technical approach for the resource-efficient utilization of fermented antibiotic bacterial residue.

[0082] Table 1 Total Amount of Resistance Genes in Penicillin Bacterial Residue and Organic Phosphoric Acid

[0083] Sample Name Concentration (ng / μl) Total Amount (μg) Bacterial Residue - 1 37.8 2.65 Bacterial Residue - 2 36.4 2.55 Bacterial Residue - 3 38.4 2.69 Synergistic Carrier - 1 0.05 0.004 Synergistic Carrier - 2 0.01 0.001 Synergistic Carrier - 3 0.01 0.001

[0084] Experimental Example 2: Determination of Water-insoluble Matter and Sulfonation Degree of the Solid-phase Synergistic Carrier in Examples 1 to 3

[0085] The water-insoluble matter was determined with reference to the standard of NY / T 1973-2021;

[0086] Determination of sulfonation degree: Add the solid-phase synergistic carrier to deionized water, adjust the pH of the solution to 5.5, take 10 ml of the above solution into a 20-ml volumetric flask, add different volumes of cetyltrimethylammonium bromide solution to the volumetric flask, shake well and let stand for 15 min. Centrifuge each mixture at 10,000 rpm for 5 min, take the supernatant and dilute it by the same multiple, measure the absorbance at 280 nm, and record the volume value of the cetyltrimethylammonium bromide solution corresponding to the minimum absorbance, which is the sulfonation degree of the solid-phase synergistic carrier.

[0087] Table 2 Water-insoluble substances and sulfonation degree of the solid-phase synergistic carrier

[0088] Sample Name Insoluble Matter in Water (G1) / % <![CDATA[Sulfonation degree / mmol·g -1 <!-- 5 -->]]> Example 1 0 0.7 Example 2 0 0.8 Example 3 0 0.7

[0089] The results in Table 2 show that the solid-phase synergistic carrier obtained from the treated insoluble solid residue is completely water-soluble, and the sulfonation degree can reach 0.7 - 0.8 mmol·g -1 。

[0090] Experimental Example 3: Determination of water-insoluble substances, turbidity, water-soluble phosphorus, available phosphorus, total phosphorus, amino acids and polypeptides in monoammonium phosphate in Example 1 and Comparative Example 1, and economic analysis

[0091] The water-insoluble substances were determined according to the NY / T 1973-2021 standard;

[0092] Turbidity determination: After dissolving monoammonium phosphate and water in a ratio of 1:30, measure it using a turbidimeter;

[0093] The water-soluble phosphorus, available phosphorus and total phosphorus were determined according to the GB / T 8573-2017 standard;

[0094] The contents of amino acids and polypeptides were determined using an amino acid analyzer.

[0095] Table 3 Water-insoluble substances, turbidity, water-soluble phosphorus, available phosphorus, total phosphorus and polypeptides in monoammonium phosphate in Example 1 and Comparative Example 1

[0096] Sample Name Insoluble Matter in Water (G4) / % Turbidity / NTU Water - soluble Phosphorus / % Available Phosphorus / % Water Ratio Total Phosphorus / % Polypeptide / % Example 1 9.34 1257 51.50 54.65 0.94 54.94 0.81 Comparative Example 1 18.19 2213 47.32 52.28 0.90 54.81 0

[0097] It can be concluded from Table 3 that the monoammonium phosphate product of the antibiotic-containing bacterial residue phosphoric acid integrated synergistic carrier obtained in Example 1 has a 48% decrease in water-insoluble substances and a 43% decrease in turbidity compared with the monoammonium phosphate with exogenous addition of amino acid powder. The ratio of water-soluble phosphorus to available phosphorus has increased slightly. This is because after in-situ introduction of amino acids by the chemical method, on the one hand, amino acids can chelate metal ions in wet-process phosphoric acid to reduce precipitation during the pH increase, and on the other hand, the formation of phosphoester bonds ( Figure 3 ) can improve the utilization rate of phosphorus.

[0098] In addition, the monoammonium phosphate product containing the antibiotic bacterial residue phosphoric acid integrated synergistic carrier obtained in Example 1 contains 0.992% amino acids and 0.813% polypeptides, effectively reducing the cost of adding exogenous amino acids and polypeptides.

[0099] Experimental Example 4: Determination of water-insoluble substances, turbidity, amino acids and polypeptides in potassium dihydrogen phosphate and NPK suspension fertilizers in Example 2, Example 3, Comparative Example 2 and Comparative Example 3, and analysis of the stability of the suspension fertilizers

[0100] As can be seen from Table 4, the water-insoluble substances and turbidity in Example 2 and Example 3 both decreased significantly, and the fertilizer contains about 1% amino acids ( Figure 4 ) and polypeptides.

[0101] Table 4 Water-insoluble substances, turbidity, water-soluble phosphorus, available phosphorus and total phosphorus

[0102] Sample Name Insoluble Matter in Water (G4) / % Turbidity / NTU Polypeptide / % Example 2 7.52 985 0.96 Comparative Example 2 15.46 1499 0 Example 3 1.53 268 1.01 Comparative Example 3 3.67 675 0

[0103] Example 3 and Comparative Example 3 were left standing at room temperature for 30 days to observe the water separation and stratification conditions. The results showed that even without adding sodium lignosulfonate as a dispersant, Example 3 could still remain stable without water separation and stratification ( Figure 5 ), providing reliable technical support for its practical application.

[0104] Although the specific implementation manners of the present invention have been described in detail in conjunction with the embodiments, it should not be construed as a limitation on the protection scope of this patent. Within the scope described in the claims, various modifications and deformations that can be made by those skilled in the art without creative labor still fall within the protection scope of this patent.

Claims

1. A method for preparing an antibiotic bacterial residue phosphate integrated fertilizer synergistic carrier, characterized in that: The following steps are involved: S1: Mixing antibiotic bacterial residue with wet-process phosphoric acid, and then subjecting it to a hydrothermal reaction; filtering after the reaction is completed, collecting the filtrate, and obtaining a liquid-phase synergistic carrier; S2: Disperse the filtered solid residue, alkali and sulfite in water, heat to 55-85°C under closed conditions, and stir for 30-120 minutes to obtain an impregnation system; S3: evaporating the impregnation system to dryness to obtain a solid phase synergistic carrier; S4: Add the solid phase synergistic carrier into the liquid phase synergistic carrier and stir evenly to obtain.

2. The method for preparing the antibiotic bacterial residue phosphate integrated fertilizer synergistic carrier according to claim 1, characterized in that: The content of phosphoric acid in the wet-process phosphoric acid is 30-46 wt %.

3. The method for preparing the antibiotic bacterial residue phosphate integrated fertilizer synergistic carrier according to claim 2, characterized in that: The mass ratio of the antibiotic bacterial residue to the wet-process phosphoric acid is 1:10-20.

4. The method for preparing the antibiotic bacterial residue phosphate integrated fertilizer synergistic carrier according to claim 1, characterized in that: The temperature of the hydrothermal reaction is 100~160℃, and the hydrothermal reaction time is 1~6h.

5. The method for preparing the antibiotic bacterial residue phosphate integrated fertilizer synergistic carrier according to claim 1, characterized in that: The alkali is potassium hydroxide; the sulfite is at least one of potassium sulfite, ammonium sulfite, potassium bisulfite and ammonium bisulfite.

6. The method for preparing the antibiotic bacterial residue phosphate integrated fertilizer synergistic carrier according to claim 5, characterized in that: The mass ratio of solid residue, alkali, sulfite and water in S2 is 80~200:80~170:60~150:500~1800.

7. The method for preparing the antibiotic bacterial residue phosphate integrated fertilizer synergistic carrier according to claim 6, characterized in that: The final temperature of the heating in S2 is 80°C, and the insulation stirring time is 120 minutes.

8. The method for preparing the antibiotic bacterial residue phosphate integrated fertilizer synergistic carrier according to claim 6, characterized in that: The evaporation temperature in S3 is 100~150℃.

9. The antibiotic bacterial residue phosphate integrated fertilizer synergistic carrier prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the antibiotic bacterial residue phosphate integrated fertilizer synergistic carrier according to claim 9 in the preparation of water-soluble fertilizer.

Images