Azoxystrobin and mesnigicin fermented bacterial residue-containing pesticide fertilizer granules and application thereof

Abstract

The present application provides a kind of azoxystrobin and mesn fermentation residue containing fungicide fertilizer granules. By preparing 3-6% mesn fermentation residue containing, and adding azoxystrobin, so that mesn and azoxystrobin are used in combination, the generation of disease resistance is slowed down; At the same time, the fertilizer component is added to prepare the medicine fertilizer granules, so that the formula system is weakly acidic, ensuring the stability of mesn, which can fully utilize the nutrient components in the residue, and improve the control effect of soil-borne disease on the preparation, medicine and fertilizer are applied together, improve the efficacy, realize the full use of mesn fermentation product, meet the requirements of green pesticide development.

Description

Technical Field

[0001] This invention relates to the technical field of preparing medicated fertilizer by combining nutrients in fermentation residue of biological pesticides with chemical pesticides, specifically to a medicated fertilizer composition containing pyraclostrobin and streptomycin fermentation residue and its application. Background Technology

[0002] Streptomycin is a novel agricultural antibiotic developed by the Institute of Biological Control, Chinese Academy of Agricultural Sciences. It is produced by *Streptomyces lilacinus* var. *hainanensis* and belongs to the N-glycoside class of alkaline, water-soluble substances. It has a broad antibacterial spectrum, effective against Gram-positive and Gram-negative bacteria, mycobacteria, yeasts, and filamentous fungi. It exhibits significant antibacterial activity against pathogenic fungi of crops such as *Streptomyces cerevisiae* (causing soft rot in cabbage), *Streptomyces cerevisiae* (causing ginger wilt), *Streptomyces angularis* (causing cucumber angular leaf spot), *Streptomyces cerevisiae* (causing rice bacterial blight), *Streptomyces cerevisiae* (causing apple ring rot), and *Streptomyces fusarium* (causing wheat scab). It can stimulate the production of phytoalexins and lignin precursors in plants, thereby enhancing their disease resistance. However, the fermentation residue of Streptomycin is classified as hazardous solid waste; if not effectively utilized, it will cause environmental pollution or resource waste.

[0003] Chinese patent application No. 201210515430.8 discloses a method for producing raw powder of kasugamycin. The process involves preliminary water separation of the kasugamycin fermentation broth, followed by secondary addition of mycelia separated by a ceramic membrane to a concentrated liquid for spray drying. The product has a high water-insoluble content, ranging from 12% to 24%, and does not generate solid hazardous waste, but the content is low. The use of evaporation and concentration results in a low yield, and the product has a dark color and poor quality.

[0004] Chinese patent application No. 202011030686.0 discloses a method for preparing high-purity kasugamycin mother drug. The preparation process is relatively complex, involving sequential steps of plate and frame separation, resin adsorption separation, nanofiltration concentration, activated carbon treatment, plate and frame filtration, and spray drying. The resulting kasugamycin mother powder has a content of more than 40%, but the actual production yield is less than 70%, and it also generates solid hazardous waste, which is not conducive to environmental control.

[0005] Chinese patent application No. 202111073835.6 discloses a ceramic membrane filtration method in which the clarified liquid is concentrated by nanofiltration and then spray-dried to form a soluble active ingredient product. The concentrated material is flash-dried to obtain an insoluble granular formulation or powder product, realizing the integrated production of different dosage forms. Although this method improves the production yield and solves the problem of green and environmentally friendly production, the nutrient content of the granular or powder products prepared from the concentrated material is far below the concentration that crops can utilize, resulting in resource waste.

[0006] Therefore, if the existing fermentation process for streptomycin does not generate solid hazardous waste (fermentation residue), the quality of the resulting streptomycin product is not high. If the fermentation process generates solid hazardous waste that is difficult to utilize, it is detrimental to environmental protection and also results in resource waste.

[0007] Azoxystrobin, the first commercially available methoxyacrylate fungicide, quickly gained global acceptance among farmers after its market launch in 1996 due to its safe, highly effective, broad-spectrum, and systemic fungicidal properties, as well as its growth-promoting effects on crops. As a representative member of the methoxyacrylate fungicide class, azoxystrobin's active group is methoxyacrylate (ester / amide). Its action site is the Cyt b low-potential heme binding inhibitor at the Qo site on the outer wall of the inner mitochondrial membrane. By inhibiting ATP synthesis and interfering with fungal cell respiration, it inhibits the growth of target pathogens or kills them. Azoxystrobin possesses extremely strong systemic penetration, allowing it to quickly penetrate the crop after application to the crop surface and be translocated upwards through the xylem to the entire plant. It exhibits excellent broad-spectrum protection and fungicidal / curative effects against diseases caused by oomycetes such as downy mildew and late blight; diseases caused by deuteromycetes such as rice blast and sheath blight; diseases caused by basidiomycetes such as rust and smut; and diseases caused by ascomycetes such as powdery mildew, leaf spot, and sclerotinia rot. Simultaneously, crops treated with azoxystrobin, especially fruit and vegetable crops, show significantly enhanced resistance to adverse conditions and senescence, greatly improved nitrogen fertilizer utilization and photosynthetic efficiency, resulting in a higher yield of beautiful and high-quality fruit. In China, as of now, the China Pesticide Information Network shows 639 registered azoxystrobin products, including 74 technical grade products, 208 single-agent products, and 357 mixtures with other ingredients. All these products, whether through stem and leaf treatment, seed treatment, or soil treatment, have increased crop yields by more than 260 million tons across more than 10 billion mu (approximately 6.67 million hectares).

[0008] However, long-term and excessive use of a single pesticide can easily lead to drug resistance in pathogens. Increasing the dosage will increase the cost of pesticide use and increase environmental pollution. Summary of the Invention

[0009] To address the aforementioned technical problems, this invention, after extensive scientific formula screening and outdoor bioassay experiments, combines kasugamycin fermentation residue with azoxystrobin to prepare a granular fertilizer-pesticide mixture. On one hand, the fermentation residue contains a small amount of kasugamycin, which, when combined with azoxystrobin, produces a synergistic effect, reducing the amount of azoxystrobin needed, decreasing usage costs and environmental pollution, and delaying the development of pathogen resistance. On the other hand, the kasugamycin fermentation residue also contains a certain amount of nutrients, which can supplement fertilizer components as needed, facilitating crop absorption and utilization.

[0010] The technical solution of the present invention is as follows:

[0011] A fertilizer granule containing pyraclostrobin and kasugamycin fermentation residue comprises the following components in weight percentage: 3-70% kasugamycin fermentation residue, 0.1-4% pyraclostrobin, 8% adjuvants, and fertilizer carrier to bring the total to 100%. Preferably, the kasugamycin fermentation residue comprises 5-65% and 8-60%. The kasugamycin content in the fermentation residue is 3-6%.

[0012] In a preferred embodiment of the present invention, the fermentation residue of the kasugamycin is prepared according to the following method:

[0013] (1) The fermentation broth of kasugamycin is filtered through a rotary ceramic membrane without the need for water replenishment and washing of the bacterial residue. The circulation rate of the equipment is controlled to press the volume of the concentrated material above the membrane to the lowest liquid level. The clear liquid is collected for the preparation of kasugamycin products and ceramic membrane concentrate is obtained.

[0014] (2) The ceramic membrane concentrate is filtered by a continuous feed centrifuge or a tubular centrifuge to achieve a concentration ratio of 2.5-3.0 times. The volume is compressed, the clear liquid is collected for the preparation of kasugamycin products, and the concentrated residue is pumped into a pulping tank.

[0015] (3) The ceramic membrane concentrate from step (1) or the centrifuged concentrate from step (2) is flash-dried to obtain fermentation residue with a kasugamycin content of 3-6%.

[0016] As a preferred embodiment of the present invention, the content of pure kasugamycin and azoxystrobin in the granulated fertilizer is 0.5%. For example, to prepare 100g of granulated fertilizer, 10g of fermentation residue with a kasugamycin content of 5% is used.

[0017] In a preferred embodiment of the present invention, the adjuvant in the fertilizer granules is 6% alkylphenol polyoxyethylene ether polyoxypropylene ether and 2% chelating agent EDTA.

[0018] In a preferred embodiment of the present invention, the fertilizer carrier is one or more of potassium nitrate, urea, ammonium sulfate, potassium dihydrogen phosphate, potassium pyrophosphate, potassium phosphite, potassium sulfate, and potassium chloride.

[0019] In a preferred embodiment of the present invention, the method for preparing the granulated fertilizer includes the following steps:

[0020] (1) Mechanically pulverize each component to about 100 mesh, and mix them evenly according to the ratio for later use;

[0021] (2) After all components are mixed evenly, add them to an extrusion granulator, add water to granulate, and the particle size is 1-5 mm.

[0022] (3) After granulation, the granules are dried in a fluidized bed at 70°C until the moisture content is ≤3%, then sieved to finally obtain the fertilizer granules.

[0023] In a preferred embodiment of the present invention, the fertilizer granules are used to prevent and control crop diseases.

[0024] In a preferred embodiment of the present invention, the crop disease controlled by the granular pesticide is a soil-borne disease, mainly damping-off of pepper.

[0025] The beneficial effects of this invention are as follows:

[0026] This invention solves the green process problem in the production of streptomycin, realizes the full utilization of the fermentation products of streptomycin, eliminates the generation of solid waste and hazardous waste in the entire production process, reduces the risks and costs of solid waste and hazardous waste treatment, improves production efficiency, effectively reduces production costs, and achieves the green process goal of high-quality and clean production of streptomycin.

[0027] The fermentation broth containing 3-6% kasugamycin is filtered through a rotary ceramic membrane without the need for water replenishment or washing of the residue. After centrifugation, the volume of the concentrated liquid is forcibly reduced to prepare fermentation residue containing 3-6% kasugamycin.

[0028] By adding azoxystrobin to the fermentation residue of kasugamycin, the combined use of kasugamycin and azoxystrobin achieves synergistic effects and slows down the development of disease resistance. At the same time, the addition of fertilizer components to produce granular pesticide-fertilizer formulations makes the formula system weakly acidic, ensuring the stability of kasugamycin. This not only makes full use of the nutrients in the fermentation residue but also enhances the control effect of the formulation on soil-borne diseases. The simultaneous application of pesticide and fertilizer enhances the efficacy of the pesticide, which meets the requirements for the development of green pesticides. Attached Figure Description

[0029] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0030] Figure 1 To show the rooting of wheat after applying the fertilizer granules of Example 1 and Control Example 3 of the present invention, the left side of each picture shows the application of Example 1, and the right side shows the application of Control Example 3. Detailed Implementation

[0031] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] The present invention will be further explained below with reference to specific embodiments.

[0033] Unless otherwise stated, all "%" refers to "weight percentage".

[0034] The method for preparing fermentation residue of kasugamycin includes the following steps:

[0035] (1) The fermentation broth of kasugamycin is filtered through a rotary ceramic membrane without the need for water replenishment and washing of the bacterial residue. The circulation rate of the equipment is controlled to press the volume of the concentrated material above the membrane to the lowest liquid level. The clear liquid is collected for the preparation of kasugamycin products and ceramic membrane concentrate is obtained.

[0036] (2) The ceramic membrane concentrate is filtered by a continuous feed centrifuge or a tubular centrifuge to achieve a concentration ratio of 2.5-3.0 times. The volume is compressed, the clear liquid is collected for the preparation of kasugamycin products, and the concentrated residue is pumped into a pulping tank.

[0037] (3) The ceramic membrane concentrate from step (1) or the centrifuged concentrate from step (2) is flash-dried to obtain fermentation residue with a kasugamycin content of 3-6%.

[0038] Example 1: Preparation of granular fertilizer containing kasugamycin and azoxystrobin

[0039] Weigh the components according to the following weight percentages:

[0040]

[0041] The preparation method includes the following steps:

[0042] (1) Mechanically pulverize each component to about 100 mesh, stir evenly and set aside;

[0043] (2) After the pulverized sample is mixed evenly, it is added to the extrusion granulator, water is added for granulation, and the particle size is 1-5mm.

[0044] (3) After granulation, the sample is collected and dried in a fluidized bed at 70°C until the moisture content is ≤3%. The sample is then sieved to obtain the final granules of the fertilizer.

[0045] The quality indicators are as follows:

[0046] kasugamycin mass fraction, % Within the acceptable range % of azoxystrobin by mass Within the acceptable range Moisture,%≤ 3 pH range 4.0-7.0 Particle size range (1-5mm), % ≥ 90

[0047] Refer to GB / T 34771-2017

[0048] Comparative Example 1: 0.5% azoxystrobin fertilizer granules

[0049] Prepared according to the formula and preparation method of Example 1, except that the fermentation residue of kasugamycin is not used.

[0050] Comparative Example 2: 0.5% Kasugamycin fertilizer granules

[0051] Prepared according to the formulation and preparation method of Example 1, except that pyraclostrobin is not used.

[0052] Control Example 3: 0.5% Kasugamycin + 0.5% Azoxystrobin fertilizer granules

[0053] Prepared according to the formulation and preparation method of Example 1, the difference being that purified kasugamycin product was used.

[0054] Example 2: Determination of the antibacterial effect of fertilizer-medicine granules on Rhizoctonia solani in the laboratory. Test reagent: Fertilizer-medicine granules from Example 1;

[0055] Control agent: The fertilizer granules of control examples 1-3.

[0056] The mycelial growth rate method was used. The experimental and control solutions were mixed with melted and cooled PDA medium (45-50℃), poured into plates, and used as a control. A 6mm diameter pathogenic fungal disc was inoculated in the center of each plate. The plates were incubated at 25℃, and the colony diameter was observed daily. When the control colony diameter reached 3 / 4 of the plate, the colony diameter of both the control and treatment groups was measured using the cross-sectional method to calculate the inhibition rate. Each treatment was replicated in triplicate. The results are shown in Table 1 below.

[0057] Table 1. Antibacterial effect of Rhizoctonia solani.

[0058] Example 1 200 times 80.3 Compare with Example 1 200 times 55.7 Compare with Example 2 200 times 68.5 Compare with Example 3 200 times 70.5 Blank control (CK) / 0

[0059] Example 3: Determination of the antibacterial effect of fertilizer-pesticide granules on indoor tomato gray mold. Test agent: Example 1 fertilizer-pesticide granules;

[0060] Control agent: The fertilizer granules of control examples 1-3.

[0061] The experimental method was the same as that in Example 2, and the results are shown in Table 2 below.

[0062] Table 2. Antifungal effect against gray mold in tomatoes

[0063]

[0064]

[0065] Example 4: Determination of the antibacterial effect of fertilizer-pesticide granules on early blight pathogens of indoor tomatoes. Test agent: Fertilizer-pesticide granules from Example 1;

[0066] Control agent: The fertilizer granules of control examples 1-3.

[0067] The experimental method was the same as that in Example 2, and the results are shown in Table 3 below.

[0068] Table 3. Antibacterial effect against early blight in tomatoes

[0069] Example 1 200 times 77.3 Compare with Example 1 200 times 54.2 Compare with Example 2 200 times 28.2 Compare with Example 3 200 times 73.4 Blank control (CK) / 0

[0070] Example 5: Determination of the antibacterial effect of fertilizer-pesticide granules on indoor cotton wilt pathogens. Test agent: Example 1 fertilizer-pesticide granules;

[0071] Control agent: The fertilizer granules of control examples 1-3.

[0072] The experimental method was the same as that in Example 2, and the results are shown in Table 4 below.

[0073] Table 4. Antifungal effect on cotton wilt disease

[0074] Example 1 1000 times 68.3 Compare with Example 1 1000 times 48.2 Compare with Example 2 1000 times 61.2 Compare with Example 3 1000 times 63.4 Blank control (CK) / 0

[0075] Example 6: Determination of the control effect of fertilizer-pesticide granules on damping-off disease of Shouguang peppers. Test agent: Example 1 fertilizer-pesticide granules;

[0076] Control agent: The fertilizer granules of control examples 1-3.

[0077] Field trials were conducted at the early stage of damping-off disease in peppers. The experimental agent, control agent, and blank control were applied in randomized block design, with each plot measuring 50 square meters and replicated three times. Seven days after application, a random five-point sampling method was used for investigation. The results are shown in Table 5 below.

[0078] Table 5. Field control effect of damping-off disease on peppers

[0079] Example 1 5000 grams / mu 86.07 Compare with Example 1 5000 grams / mu 50.24 Compare with Example 2 5000 grams / mu 59.87 Compare with Example 3 5000 grams / mu 72.53 Blank control (CK) / 0

[0080] The experimental data from Examples 2-6 show that, for indoor antibacterial experiments or field disease control of common pathogens of different crops, the fertilizer-pesticide granules of Example 1 of this invention are significantly more effective than the control fertilizer-pesticide granules. This is especially evident in the comparison between Example 1 and Control Example 3. Example 1 used kasugamycin fermentation residue, while Control Example 3 used purified kasugamycin product. Both had the same content of kasugamycin and azoxystrobin, and theoretically, their inhibitory effects on pathogens should be the same. However, in practice, Example 1 was significantly superior to Control Example 3. Without being bound by any theory, the inventors believe that the kasugamycin fermentation residue also contains a large amount of protein, cellulose, minerals, and polysaccharides, which can provide additional nutrition, promote robust crop growth, resist pathogen invasion, and may also contain unknown antibacterial substances that provide additional inhibition against pathogens.

[0081] Example 7: Determination of the effect of the agent on indoor wheat rooting test

[0082] Test crop: wheat;

[0083] Test reagent: Example 1 fertilizer granules

[0084] Control agent: Control Example 3, fertilizer granules.

[0085] Test method:

[0086] 1. Soaking seeds

[0087] Soak wheat seeds for 8 hours to allow them to fully absorb water and promote germination;

[0088] 2. Breeding

[0089] Place the soaked wheat seeds in a dark environment at around 25°C, keeping them moist (you can cover them with plastic wrap) to promote germination.

[0090] 3. Preparation of culture flasks

[0091] A transparent container was filled with a 300-fold diluted aqueous solution of Example 1 and Control Example 3, with the water level 2 cm from the rim. A single layer of non-woven fabric was secured to the rim of the container with a rubber band, the fabric recessed to ensure it was flush with the water surface. Only one layer of non-woven fabric was used; otherwise, it would obstruct root penetration.

[0092] 4. Seedling raising

[0093] When the wheat seeds have germinated to a root length of about 0.3-0.5 cm (approximately 12-16 hours), select 30 uniformly developed wheat seeds and place them evenly on the bottom layer of a non-woven fabric. Continue the dark and moisturizing treatment.

[0094] Once the white roots of the wheat seeds have penetrated through the non-woven fabric and the upper buds have grown to about 1 cm, they can be exposed to light.

[0095] 5. Cultivate

[0096] The treated culture flasks were placed at a temperature slightly below room temperature (18-22℃) for incubation; results were observed 4 and 11 days after drug administration. See appendix. Figure 1 The results showed that for wheat crops, Example 1 showed significantly better root length and root quantity than Control Example 3 4 and 11 days after application, indicating a significant health-promoting effect on the crop.

[0097] Unbound by any theoretical constraints, this further illustrates that the fermentation residue of kasugamycin contains a large amount of nutrients and may also contain other substances that stimulate plant growth, thus promoting crop growth more effectively than Control Example 3, which only contains conventional fertilizers (potassium dihydrogen phosphate and ammonium sulfate).

[0098] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A granular fertilizer containing azoxystrobin and kasugamycin fermentation residue, characterized in that... The product comprises the following components by weight percentage: 3-70% kasugamycin fermentation residue, 0.1-4% azoxystrobin, 6% alkylphenol polyoxyethylene ether polyoxypropylene ether, 2% chelating agent EDTA, and fertilizer carrier to bring the total to 100%, wherein the kasugamycin fermentation residue contains 3% kasugamycin. 6%; The fermentation residue of the kasugamycin is prepared according to the following method: (1) The fermentation broth of kasugamycin is filtered through a rotary ceramic membrane without the need for water replenishment and washing of the bacterial residue. The circulation rate of the equipment is controlled to press the volume of the concentrated material above the membrane to the lowest liquid level. The clear liquid is collected for the preparation of kasugamycin products and ceramic membrane concentrate is obtained. (2) The ceramic membrane concentrate is filtered by a continuous feed centrifuge or a tubular centrifuge to achieve a concentration ratio of 2.5-3.0 times. The volume is compressed, the clear liquid is collected for the preparation of kasugamycin products, and the concentrated residue is pumped into a pulping tank. (3) The ceramic membrane concentrate from step (1) or the centrifuged concentrate from step (2) is flash-dried to obtain fermentation residue with a kasugamycin content of 3-6%.

2. The granular fertilizer containing azoxystrobin and kasugamycin fermentation residue according to claim 1, characterized in that, The granules contain 10% fermentation residue with 5% kasugamycin content and 0.5% azoxystrobin.

3. The granular fertilizer-pesticide mixture containing azoxystrobin and kasugamycin fermentation residue according to claim 1, characterized in that, The fertilizer carrier is one or more of potassium nitrate, urea, ammonium sulfate, potassium dihydrogen phosphate, potassium pyrophosphate, potassium phosphite, potassium sulfate, and potassium chloride.

4. The method for preparing granules of azoxystrobin and kasugamycin-containing fermentation residue as described in any one of claims 1-3, characterized in that, (1) Crush each component into a fine powder to about 100 mesh and mix them evenly according to the ratio for later use; (2) All the components after being mixed evenly are added to an extrusion granulator for granulation, with a particle size of 1-5 mm; (3) After granulation, the granules are dried in a fluidized bed at 70°C until the moisture content is ≤3%, and finally the granules are obtained.

5. The granular fertilizer containing pyraclostrobin and streptomycin fermentation residue as described in any one of claims 1-3 is used for preventing and controlling crop diseases and promoting crop growth.

6. The granular fertilizer containing azoxystrobin and kasugamycin fermentation residue as described in claim 5, used for preventing and controlling crop diseases and promoting crop growth, is characterized in that... The crop disease mentioned is a soil-borne disease.

7. The granular fertilizer containing azoxystrobin and kasugamycin fermentation residue as described in claim 6, used for preventing crop diseases and promoting crop growth, is characterized in that... The soil-borne disease mentioned is damping-off of chili peppers.

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