Formula of endowed netting loss-control pesticide fertilizer based on synthetic biotechnology and preparation process of endowed netting loss-control pesticide fertilizer

Abstract

The invention discloses a formula and a preparation process of a synthetic biotechnology-based endowed netting loss-control pesticide fertilizer, and relates to the technical field of fertilizers, the loss-control pesticide fertilizer is prepared from the following components by weight: 60-80 parts of a compound fertilizer, 10-20 parts of diammonium phosphate, 2-10 parts of trace elements, 2-8 parts of modified attapulgite, 1-4 parts of an insecticide, 0.5-3 parts of polyglutamic acid, and 1-5 parts of polyvinyl alcohol; according to the invention, a high-efficiency netting loss control system is formed through the energization of polyglutamic acid and the synergistic effect of multiple components, so that not only are the problems of easy nutrient loss and poor pesticide stability in the traditional pesticide fertilizer solved, but also the synergistic slow release of nutrients and pesticide is realized, the utilization rate of the fertilizer is remarkably increased, the control period of the pesticide is remarkably prolonged, and the application value is good.

Description

Technical Field

[0001] The present invention relates to the technical field of fertilizers, and in particular to a formula of a fertilizer for controlling drug loss based on synthetic biology and its preparation process. Background Art

[0002] Fertilizer is the basic condition for crop growth and an important factor restricting the sustainable development of my country's agriculture. At present, my country is a major agricultural country and ranks first in the world in fertilizer application, but the fertilizer utilization efficiency is generally low. A large amount of unused fertilizer enters water bodies through surface runoff, groundwater infiltration and other channels, causing serious non-point source pollution problems.

[0003] To solve the problem of low fertilizer utilization efficiency, two main technical routes are currently used: slow-release fertilizer and controlled-loss fertilizer. Slow-release fertilizer is a new type of fertilizer. Its core is to control the release rate and time of fertilizer nutrients through coating, resin coating and other technologies, so that the nutrient release process matches the growth needs of crops. However, this type of fertilizer has the following problems: 1) The nutrient release pattern is relatively fixed and it is difficult to dynamically adjust according to the fertilizer needs of crops; 2) Existing coating materials such as sulfur, resin, paraffin, polyethylene, etc. are difficult to degrade in the soil and easily cause environmental pollution; 3) The production cost is high, which is not conducive to large-scale promotion and application.

[0004] Loss-control fertilizers use different technical principles, mainly by adding special loss-control agents to form a protective structure in the soil. Loss-control materials, represented by attapulgite, can fix nutrients through chemical and physical adsorption by using their nanoporous structure, high specific surface area and ion exchange capacity. This method can effectively reduce nutrient loss and has relatively low production costs.

[0005] As a new type of preparation that combines fertilizers and pesticides, medicated fertilizers can achieve the goal of "fertilizers with pesticides" and prevent and control pests while providing nutrients. It is an important direction for the development of modern agriculture. However, there are still many technical bottlenecks in the medicated fertilizer products on the market: first, physical and chemical reactions are prone to occur between fertilizers and pesticides, affecting their respective efficacy; second, due to the lack of effective carriers and stabilization systems, the active ingredients of pesticides are easily degraded and lost; third, the release rates of nutrients and pesticides are difficult to coordinate and match, and it is impossible to achieve a sustained and stable prevention effect.

[0006] Although the common compound fertilizers on the market can provide multiple nutrients, they lack effective synergy between their components and release nutrients unevenly, making it difficult to meet the nutritional needs of crop growth. At the same time, the single application of compound fertilizers often requires additional supplementation of quick-acting fertilizers such as diammonium phosphate, which increases fertilization costs and labor intensity.

[0007] CN117658733A discloses a special compound fertilizer for controlling loss of corn and a preparation method thereof, belonging to the technical field of fertilizers. The invention discloses a special compound fertilizer for controlling loss of corn, comprising the following raw materials in parts by weight: 30-50 parts of urea, 5-10 parts of diammonium hydrogen phosphate, 15-20 parts of superphosphate, 10-15 parts of potassium chloride, 2-6 parts of zinc sulfate, 2-5 parts of organic acid, and 1-5 parts of a control agent.

[0008] The research and development of new fertilizers is moving towards the direction of high nutrient efficiency and diversified functions. Studies have shown that by using new materials and new processes to improve traditional fertilizers, their nutritional functions can be significantly improved or given new characteristics. Among them, functional polymer materials have shown good application prospects in improving fertilizer utilization efficiency due to their unique structural characteristics and performance advantages. This type of material mainly includes three categories: synthetic polymers, natural polymers and modified natural polymers. Among them, modified natural polymers have both excellent functionality and maintain low cost advantages.

[0009] In the context of increasingly serious agricultural non-point source pollution in my country, it is urgent to develop a high-efficiency loss-control fertilizer that can not only meet the needs of crop growth, but also effectively control nutrient loss, and is environmentally friendly, economical and practical. This is of great significance to improving fertilizer utilization efficiency, reducing agricultural non-point source pollution, and promoting sustainable agricultural development. Summary of the invention

[0010] In order to solve the shortcomings of the prior art, the purpose of the present invention is to provide a formula of a net-catching and loss-control fertilizer based on synthetic biology empowerment and a preparation process thereof, which forms an efficient net-catching and loss-control system through polyglutamic acid empowerment and multi-component synergy, which not only solves the problems of easy nutrient loss and poor stability of pesticides in traditional fertilizers, but also realizes the synergistic slow release of nutrients and pesticides, significantly improves the fertilizer utilization rate and the pesticide protection period, and has good application value.

[0011] In order to achieve the above object, the present invention adopts the following technical solution:

[0012] A formula of a synthetic biology-enabled net capture and control fertilizer for pesticide loss, which is made of the following components in parts by weight: 60-80 parts of compound fertilizer, 10-20 parts of diammonium phosphate, 2-10 parts of trace elements, 2-8 parts of modified attapulgite, 1-4 parts of pesticide, 0.5-3 parts of polyglutamic acid, and 1-5 parts of polyvinyl alcohol.

[0013] Preferably, the method for preparing the modified attapulgite comprises the following steps:

[0014] (1) dispersing attapulgite in a methanol / water mixture, ultrasonically treating, adjusting the pH of the dispersion, adding KH570, heating the mixture for reaction, centrifuging, washing, and drying the product to obtain pretreated attapulgite;

[0015] Silylation modification: The methoxyl groups of KH570 are hydrolyzed under acidic conditions to generate silanol groups (-Si-OH), which react with the hydroxyl groups (-OH) on the surface of attapulgite to form stable Si-O-Si covalent bonds. At the same time, the double bond groups in the KH570 molecules are exposed on the surface of attapulgite, providing active sites for subsequent grafting reactions. This step realizes the organic modification of the surface of attapulgite and increases its compatibility with organic monomers.

[0016] Preferably, in step (1), the particle size of the attapulgite is 200-400 mesh.

[0017] Preferably, in step (1), the volume ratio of methanol to deionized water in the methanol / water mixture is 7-9:3-1; the dosage ratio of attapulgite, methanol / water mixture, and KH570 is 10 g:80-150 mL:0.3-1 g.

[0018] Preferably, in step (1), ultrasonic treatment is performed for 15 to 30 minutes, and the pH value of the dispersion is adjusted to 4 to 5 with glacial acetic acid; the temperature reaction conditions are heating to 60 to 75° C. and reacting at 400 to 600 r / min for 12 to 18 hours.

[0019] (2) dispersing the pretreated attapulgite in deionized water, ultrasonically treating it, adding L-allylglycine, introducing nitrogen gas and adding ammonium persulfate, stirring the reaction, centrifuging, washing, and drying the product to obtain grafted attapulgite;

[0020] Free radical grafting polymerization: Ammonium persulfate decomposes under heating conditions to produce free radicals, which trigger free radical polymerization of the double bonds introduced in the first step. The double bonds in the L-allylglycine molecule are activated and gradually grow through the free radical addition mechanism to form grafted polymer chains on the surface of attapulgite. The amino groups on the polymer chains act as active groups, providing reaction sites for subsequent modifications. Nitrogen protection prevents oxygen from inhibiting the free radical polymerization process.

[0021] Preferably, in step (2), the dosage ratio of pretreated attapulgite, deionized water, L-allylglycine and ammonium persulfate is 10 g: 80-150 mL: 1-2 g: 0.02-0.1 g.

[0022] Preferably, in step (2), ultrasonic treatment is performed for 15 to 30 minutes; the stirring reaction conditions are 55 to 70° C. and 300 to 400 r / min for 4 to 8 hours; and washing is performed with 70 to 90° C. warm water for 3 to 4 times.

[0023] (3) The grafted attapulgite is dispersed in DMF, ultrasonically treated, 2-hydroxyphosphonoacetic acid is added, EDC and NHS are added under light-shielding conditions, the reaction is stirred, the product is centrifuged, washed, and dried to obtain modified attapulgite.

[0024] Amidation reaction: EDC first reacts with the carboxyl group of 2-hydroxyphosphonoacetic acid to form an O-acylurea intermediate, and NHS then reacts with the intermediate to form an active ester intermediate. This active ester intermediate can undergo a nucleophilic substitution reaction with the amino group introduced in the second step to form a stable amide bond, covalently connecting the phosphorus-containing group to the surface of attapulgite.

[0025] Preferably, in step (3), the ratio of grafted attapulgite, DMF, 2-hydroxyphosphonoacetic acid, EDC, and NHS is 10 g: 80-150 mL: 0.6-1.5 g: 0.8-1.2 g: 0.4-0.6 g.

[0026] Preferably, in step (3), the stirring reaction conditions are 20-30° C. and 200-300 r / min for 12-24 h; and washing with DMF, anhydrous ethanol, and deionized water in sequence.

[0027] Preferably, in the compound fertilizer, the content ratio of nitrogen fertilizer, phosphate fertilizer and potassium fertilizer is 12~16:12~16:12~16; the content of the nitrogen fertilizer is calculated as the nitrogen element in the nitrogen fertilizer, the content of the phosphate fertilizer is calculated as phosphorus pentoxide, and the content of the potassium fertilizer is calculated as potassium oxide; the trace elements are chelated ferrous iron, chelated copper and chelated zinc mixed in a weight ratio of 1:0.4~0.6:0.8~1.2.

[0028] Preferably, the nitrogen fertilizer is one or more of urea, ammonium sulfate, ammonium bicarbonate, ammonium nitrate, ammonium chloride, sodium nitrate, calcium nitrate, and ammonium sulfate nitrate; the phosphate fertilizer is one or more of monoammonium phosphate, diammonium phosphate, calcium magnesium phosphate, superphosphate, double superphosphate, sodium phosphate, rich superphosphate, and ammonium phosphate; and the potassium fertilizer is one or more of potassium sulfate, potassium chloride, potassium nitrate, and potassium dihydrogen sulfate.

[0029] Preferably, the trace elements are ferrous sulfate, copper sulfate and zinc sulfate mixed in a weight ratio of 1:0.4~0.6:0.8~1.2.

[0030] Preferably, the molecular weight of the polyvinyl alcohol is 3500-7000.

[0031] Preferably, the preparation method of the insecticide comprises the following steps: dispersing mesoporous silica in a 5-20 mg / L pesticide ethanol solution, oscillating in a constant temperature water bath oscillator at 25-40°C for 18-24 hours, filtering the product with a sand core, washing with deionized water, and vacuum drying to obtain the insecticide; the pesticide is one or more of chlorfenapyr, clothianidin, dinotefuran, myclobutanil, prothioconazole, and thiophanate-methyl; the dosage ratio of the mesoporous silica to the pesticide ethanol solution is 8-14 g:10 mL.

[0032] The present invention also claims protection for a preparation process of the net-catching and drug-lost-control fertilizer based on synthetic biology, comprising the following steps: mixing compound fertilizer, diammonium phosphate, trace elements, modified attapulgite, pesticide, and polyglutamic acid, stirring for 10 to 20 minutes, grinding through a 40 to 60 mesh sieve, adding polyvinyl alcohol, stirring for 10 to 30 minutes, and granulating to obtain the net-catching and drug-lost-control fertilizer.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. The present invention provides a polyglutamic acid-enabled net-catching fertilizer for controlling pesticide loss. The abundant carboxyl functional groups on the polyglutamic acid molecular chain have excellent chelating ability and can form stable complexes with nutrient ions. Its mesh structure forms an interpenetrating network with modified attapulgite, which enhances the coating effect on nutrients and pesticides. The attapulgite modified in three steps has excellent organic compatibility and dispersibility. Its large specific surface area and the introduction of functional groups improve the nutrient loading capacity. Mesoporous silica is used as a pesticide carrier, and directional loading is achieved through a porous structure to improve stability. The ratio of compound fertilizer to diammonium phosphate is optimized to achieve a reasonable ratio of fast-acting and long-acting nutrients. Chelated trace elements form secondary chelation with polyglutamic acid to improve biological effectiveness. Polyvinyl alcohol acts as a film-forming agent and synergistically with polyglutamic acid to form a dense coating layer. Through these designs, the present invention realizes the integration of medicine and fertilizer, efficient utilization of nutrients, and synergistic release of nutrients and pesticides, and has good processing performance and product stability.

[0035] 2. The present invention provides a modified attapulgite. First, natural attapulgite is selected as a carrier. Its unique layered chain structure, large specific surface area and excellent adsorption performance provide a good basis for nutrient controlled release. The silicon-oxygen bond (Si-O-Si) introduced on the surface of KH570 provides a stable organic modification interface, which enhances the grafting stability of subsequent functional groups. Secondly, L-allylglycine grafted by free radical polymerization has a large amount of negative charge on the carboxyl group of its molecular chain, which can form a complex with metal cations such as calcium, magnesium and iron, which not only reduces the probability of anions and cations combining with each other to produce insoluble substances, but also protects and activates phosphate ions, thereby improving the biological effectiveness of nutrients. The carboxyl and amino groups on its molecular chain also have good water absorption and water retention properties. In the later stage of crop growth, the fixed nutrients can be activated to achieve slow release, avoiding premature aging and fertilizer loss. Finally, the phosphoryl group introduced by the amidation reaction has a strong coordination ability, forming a dual coordination effect with the carboxyl group on the polymer chain, and can form a stable complex with the metal ions in the soil. This complexation reduces the fixation of phosphate by metal ions on the one hand, improving the utilization rate of phosphorus. On the other hand, the reversible complex formed can temporarily fix nutrients to prevent loss, and can be gradually released according to crop needs. At the same time, it can also improve the cation exchange capacity and aggregate structure of the soil, creating a good soil environment for crop growth. This layer-by-layer structural design enables the modified attapulgite to form a flocculent network structure in the soil, which can effectively encapsulate and control the release of nutrients without affecting the crop's absorption of fertilizers, significantly improving the fertilizer utilization efficiency, reducing the pollution of soil and water bodies by nutrients such as nitrogen and phosphorus, and achieving the dual goals of increasing production and efficiency and being environmentally friendly. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical solution and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiments. Of course, the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention.

[0037] Unless otherwise specified, the chemical reagents and materials in the present invention are purchased from commercial sources or synthesized from raw materials purchased from commercial sources.

[0038] Attapulgite was purchased from Xingzhou Mineral Products Processing Plant in Lingshou County;

[0039] Mesoporous silica was purchased from Nanjing Xianfeng Nanomaterials Technology Co., Ltd. Model: XFF29, with a specific surface area of ​​133.3 m 2 / g, diameter is 70nm~90nm;

[0040] Polyglutamic acid has a molecular weight of 700,000 to 2,000,000 Da and was purchased from Shandong Qianfeng Agricultural Technology Co., Ltd.;

[0041] Polyvinyl alcohol was purchased from Hai'an Petrochemical Plant in Jiangsu Province with the brand name PVA-4000.

[0042] A preparation process of a fertilizer for capturing and controlling drug loss based on synthetic biology technology, comprising the following steps:

[0043] (1) Disperse 10 g of attapulgite into 80-150 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 7-9:3-1), perform ultrasonic treatment for 15-30 min, adjust the pH of the dispersion to 4-5 with glacial acetic acid, add 0.3-1 g of KH570, heat to 60-75 °C, react at 400-600 r / min for 12-18 h, centrifuge, wash, and dry the product to obtain pretreated attapulgite;

[0044] (2) Disperse 10 g of pretreated attapulgite in 80-150 mL of deionized water, perform ultrasonic treatment for 15-30 min, add 1-2 g of L-allylglycine, introduce nitrogen and add 0.02-0.1 g of ammonium persulfate, react at 55-70 °C and 300-400 r / min for 4-8 h, centrifuge the product, wash it with 70-90 °C warm water for 3-4 times, and dry it to obtain grafted attapulgite;

[0045] (3) Disperse 10 g of grafted attapulgite in 80-150 mL of DMF, treat with ultrasound, add 0.6-1.5 g of 2-hydroxyphosphonoacetic acid, add 0.8-1.2 g of EDC and 0.4-0.6 g of NHS under light protection, stir and react at 20-30 ° C and 200-300 r / min for 12-24 h, centrifuge the product, wash with DMF, anhydrous ethanol, and deionized water in sequence, and dry to obtain modified attapulgite;

[0046] (4) dispersing 8-14 g of mesoporous silica in 10 mL of 5-20 mg / L pesticide ethanol solution, oscillating in a constant temperature water bath oscillator at 25-40° C. for 18-24 h, filtering the product with a sand core, washing with deionized water, and vacuum drying to obtain the pesticide; the pesticide is one or more of chlorantraniliprole, clothianidin, dinotefuran, myclobutanil, prothioconazole, and thiofuran;

[0047] (5) 60-80 parts of compound fertilizer, 10-20 parts of diammonium phosphate, 2-10 parts of trace elements (chelated ferrous iron, chelated copper, and chelated zinc are mixed in a weight ratio of 1:0.4-0.6:0.8-1.2), 2-8 parts of modified attapulgite, 1-4 parts of insecticide, and 0.5-3 parts of polyglutamic acid are mixed, stirred for 10-20 minutes, ground through a 40-60 mesh sieve, added with 1-5 parts of polyvinyl alcohol, stirred for 10-30 minutes, and granulated to obtain the net-catching and loss-control fertilizer.

[0048] In the compound fertilizer, the content ratio of nitrogen fertilizer, phosphorus fertilizer and potassium fertilizer is 12-16:12-16:12-16; the content of the nitrogen fertilizer is calculated as the nitrogen element in the nitrogen fertilizer, the content of the phosphorus fertilizer is calculated as phosphorus pentoxide, and the content of the potassium fertilizer is calculated as potassium oxide.

[0049] The present invention will be further described below through specific embodiments.

[0050] Example 1

[0051] A preparation process of a fertilizer for capturing and controlling drug loss based on synthetic biology technology, comprising the following steps:

[0052] (1) Disperse 10 g of attapulgite into 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), ultrasonically treat for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 1 g of KH570, heat to 75 °C, and react at 500 r / min for 12 h. Centrifuge, wash, and dry the product to obtain pretreated attapulgite.

[0053] (2) Disperse 10 g of pretreated attapulgite in 100 mL of deionized water, ultrasonicate for 20 min, add 2 g of L-allylglycine, introduce nitrogen and add 0.1 g of ammonium persulfate, react at 70 °C and 350 r / min for 4 h, centrifuge the product, wash it three times with 80 °C warm water, and dry it to obtain grafted attapulgite;

[0054] (3) Disperse 10 g of grafted attapulgite in 100 mL of DMF, treat with ultrasound, add 1.5 g of 2-hydroxyphosphonoacetic acid, add 1.2 g of EDC and 0.6 g of NHS under light protection, stir and react at 30 ° C and 250 r / min for 12 h, centrifuge the product, wash with DMF, anhydrous ethanol, and deionized water in sequence, and dry to obtain modified attapulgite;

[0055] (4) dispersing 10 g of mesoporous silica in 10 mL of a 10 mg / L dinotefuran ethanol solution, oscillating the mixture in a constant temperature water bath oscillator at 35° C. for 20 h, filtering the product with a sand core, washing with deionized water, and vacuum drying to obtain the insecticide;

[0056] (5) 800 g of compound fertilizer (prepared by mixing urea, sodium phosphate and potassium sulfate in an effective content ratio of 16:12:15), 200 g of diammonium phosphate, 100 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate and zinc sulfate in a weight ratio of 1:0.5:1), 80 g of modified attapulgite, 40 g of insecticide and 30 g of polyglutamic acid were mixed, stirred for 15 min, ground through a 50-mesh sieve, 50 g of polyvinyl alcohol was added, stirred for 20 min, and granulated to obtain the net-catching and loss-control fertilizer.

[0057] Example 2

[0058] A preparation process of a fertilizer for capturing and controlling drug loss based on synthetic biology technology, comprising the following steps:

[0059] (1) Disperse 10 g of attapulgite into 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), ultrasonically treat for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 0.8 g of KH570, heat to 70 °C, and react at 500 r / min for 14 h. Centrifuge, wash, and dry the product to obtain pretreated attapulgite.

[0060] (2) Disperse 10 g of pretreated attapulgite in 100 mL of deionized water, ultrasonicate for 20 min, add 1.6 g of L-allylglycine, introduce nitrogen and add 0.08 g of ammonium persulfate, react at 65 °C and 350 r / min for 5 h, centrifuge the product, wash it three times with 80 °C warm water, and dry it to obtain grafted attapulgite;

[0061] (3) Disperse 10 g of grafted attapulgite in 100 mL of DMF, treat with ultrasound, add 1.2 g of 2-hydroxyphosphonoacetic acid, add 1.0 g of EDC and 0.5 g of NHS in a dark environment, stir and react at 28 ° C and 250 r / min for 16 h, centrifuge the product, wash with DMF, anhydrous ethanol, and deionized water in sequence, and dry to obtain modified attapulgite;

[0062] (4) dispersing 10 g of mesoporous silica in 10 mL of a 10 mg / L dinotefuran ethanol solution, oscillating the mixture in a constant temperature water bath oscillator at 35° C. for 20 h, filtering the product with a sand core, washing with deionized water, and vacuum drying to obtain the insecticide;

[0063] (5) 720 g of compound fertilizer (prepared by mixing urea, sodium phosphate and potassium sulfate in an effective content ratio of 16:12:15), 180 g of diammonium phosphate, 80 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate and zinc sulfate in a weight ratio of 1:0.5:1), 60 g of modified attapulgite, 30 g of insecticide and 25 g of polyglutamic acid were mixed, stirred for 15 min, ground through a 50-mesh sieve, 40 g of polyvinyl alcohol was added, stirred for 20 min, and granulated to obtain the net-catching and loss-control fertilizer.

[0064] Example 3

[0065] A preparation process of a fertilizer for capturing and controlling drug loss based on synthetic biology technology, comprising the following steps:

[0066] (1) Disperse 10 g of attapulgite into 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), ultrasonically treat for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 0.5 g of KH570, heat to 65 °C, and react at 500 r / min for 16 h. Centrifuge, wash, and dry the product to obtain pretreated attapulgite.

[0067] (2) Disperse 10 g of pretreated attapulgite in 100 mL of deionized water, ultrasonicate for 20 min, add 1.5 g of L-allylglycine, introduce nitrogen and add 0.05 g of ammonium persulfate, react at 60 °C and 350 r / min for 7 h, centrifuge the product, wash it three times with 80 °C warm water, and dry it to obtain grafted attapulgite;

[0068] (3) Disperse 10 g of grafted attapulgite in 100 mL of DMF, treat with ultrasound, add 1 g of 2-hydroxyphosphonoacetic acid, add 1 g of EDC and 0.5 g of NHS in a dark environment, stir and react at 24 °C and 250 r / min for 20 h, centrifuge the product, wash with DMF, anhydrous ethanol, and deionized water in sequence, and dry to obtain modified attapulgite;

[0069] (4) dispersing 10 g of mesoporous silica in 10 mL of a 10 mg / L dinotefuran ethanol solution, oscillating the mixture in a constant temperature water bath oscillator at 35° C. for 20 h, filtering the product with a sand core, washing with deionized water, and vacuum drying to obtain the insecticide;

[0070] (5) 640 g of compound fertilizer (prepared by mixing urea, sodium phosphate and potassium sulfate in an effective content ratio of 16:12:15), 140 g of diammonium phosphate, 50 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate and zinc sulfate in a weight ratio of 1:0.5:1), 40 g of modified attapulgite, 20 g of insecticide and 15 g of polyglutamic acid were mixed, stirred for 15 min, ground through a 50-mesh sieve, 30 g of polyvinyl alcohol was added, stirred for 20 min, and granulated to obtain the net-catching fertilizer for controlling drug loss.

[0071] Example 4

[0072] A preparation process of a fertilizer for capturing and controlling drug loss based on synthetic biology technology, comprising the following steps:

[0073] (1) Disperse 10 g of attapulgite into 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), ultrasonically treat for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 0.3 g of KH570, heat to 60 °C, and react at 500 r / min for 18 h. Centrifuge, wash, and dry the product to obtain pretreated attapulgite.

[0074] (2) Disperse 10 g of pretreated attapulgite in 100 mL of deionized water, ultrasonicate for 20 min, add 1 g of L-allylglycine, introduce nitrogen and add 0.02 g of ammonium persulfate, react at 55 °C and 350 r / min for 8 h, centrifuge the product, wash it three times with 80 °C warm water, and dry it to obtain grafted attapulgite;

[0075] (3) Disperse 10 g of grafted attapulgite in 100 mL of DMF, treat with ultrasound, add 0.6 g of 2-hydroxyphosphonoacetic acid, add 0.8 g of EDC and 0.4 g of NHS in a dark environment, stir and react at 20 °C and 250 r / min for 24 h, centrifuge the product, wash with DMF, anhydrous ethanol, and deionized water in sequence, and dry to obtain modified attapulgite;

[0076] (4) dispersing 10 g of mesoporous silica in 10 mL of a 10 mg / L dinotefuran ethanol solution, oscillating the mixture in a constant temperature water bath oscillator at 35° C. for 20 h, filtering the product with a sand core, washing with deionized water, and vacuum drying to obtain the insecticide;

[0077] (5) 600 g of compound fertilizer (prepared by mixing urea, sodium phosphate and potassium sulfate in an effective content ratio of 16:12:15), 100 g of diammonium phosphate, 20 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate and zinc sulfate in a weight ratio of 1:0.5:1), 20 g of modified attapulgite, 10 g of insecticide and 5 g of polyglutamic acid were mixed, stirred for 15 min, ground through a 50-mesh sieve, 10 g of polyvinyl alcohol was added, stirred for 20 min, and granulated to obtain the net-catching and loss-control fertilizer.

[0078] Comparative Example 1

[0079] A preparation process of a controlled-loss fertilizer comprises the following steps:

[0080] (1) Disperse 10 g of attapulgite into 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), ultrasonically treat for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 1 g of KH570, heat to 75 °C, and react at 500 r / min for 12 h. Centrifuge, wash, and dry the product to obtain pretreated attapulgite.

[0081] (2) Disperse 10 g of pretreated attapulgite in 100 mL of deionized water, ultrasonicate for 20 min, add 2 g of L-allylglycine, introduce nitrogen and add 0.1 g of ammonium persulfate, react at 70 °C and 350 r / min for 4 h, centrifuge the product, wash it three times with 80 °C warm water, and dry it to obtain grafted attapulgite;

[0082] (3) 800 g of compound fertilizer (prepared by mixing urea, sodium phosphate and potassium sulfate in an effective content ratio of 16:12:15), 200 g of diammonium phosphate, 100 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate and zinc sulfate in a weight ratio of 1:0.5:1), 80 g of grafted attapulgite, 40 g of insecticide and 30 g of polyglutamic acid were mixed, stirred for 15 min, ground through a 50-mesh sieve, 50 g of polyvinyl alcohol was added, stirred for 20 min, and granulated to obtain the controlled-loss fertilizer.

[0083] Comparative Example 2

[0084] A preparation process of a controlled-loss fertilizer comprises the following steps:

[0085] (1) Disperse 10 g of attapulgite into 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), ultrasonically treat for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 1 g of KH570, heat to 75 °C, and react at 500 r / min for 12 h. Centrifuge, wash, and dry the product to obtain pretreated attapulgite.

[0086] (2) 800 g of compound fertilizer (prepared by mixing urea, sodium phosphate and potassium sulfate in an effective content ratio of 16:12:15), 200 g of diammonium phosphate, 100 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate and zinc sulfate in a weight ratio of 1:0.5:1), 80 g of pretreated attapulgite, 40 g of insecticide and 30 g of polyglutamic acid were mixed, stirred for 15 min, ground through a 50-mesh sieve, 50 g of polyvinyl alcohol was added, stirred for 20 min, and granulated to obtain the controlled loss fertilizer.

[0087] The modified attapulgite prepared in Examples 1 to 4, the grafted attapulgite prepared in Comparative Example 1, and the pretreated attapulgite prepared in Comparative Example 2 were tested for water absorption rate. The sample W0 was weighed and placed in a 400-mesh nylon bag, placed in 1000 mL of deionized water, and fully swelled by water. After the sample was balanced with water absorption and swelling, the water-saturated sample mass W1 was weighed, and the sample water absorption rate S was obtained according to the formula:

[0088] S = (W1-W0) / W0×100%;

[0089] In the same way, physiological saline was used instead of deionized water to measure the saline absorption rate of the samples. The specific data are shown in Table 1.

[0090] Table 1 Water absorption rate of samples

[0091]

[0092] The performance of the controlled-release fertilizers prepared in Examples 1 to 4 and Comparative Examples 1 to 2 was tested. The 24-hour release rate of the fertilizer, the 7-day cumulative release rate of the fertilizer, the 28-day cumulative release rate of the fertilizer, and the time required for 80% release of the fertilizer were tested in accordance with GB / T 23348-2009 "Slow-release Fertilizers"; the water retention in the soil was measured using the soil column method to determine the effect of the fertilizer on the infiltration amount at the same infiltration distance, and the infiltration amount was based on the height (cm) of the water level drop in the Malchow flask; the specific test results are shown in Table 2.

[0093] Table 2 Test results of fertilizer loss control performance

[0094]

[0095] The loss-control fertilizer prepared in Examples 1-4 and Comparative Examples 1-2 was used in a rice experiment in a plot, each plot was 10 m long and 4 m wide, with protective rows set around it, and the fertilizer dosage was 40 kg / mu for basal application. The rice growth and yield are shown in Table 3.

[0096] Table 3 Effects of controlled fertilizer loss on rice growth and yield

[0097]

[0098] The insecticide prepared in the embodiment of the present invention was subjected to a primary insecticidal efficiency and a secondary insecticidal efficiency determination experiment. The specific experimental steps were as follows: unpolluted agricultural land surface soil (20-40 cm) was collected, naturally air-dried for several days, and ground through a 60-mesh sieve after removing debris to obtain test soil, and the insecticide prepared in Examples 1-4 and pure dinotefuran pesticide were added to the test soil at 0.2 g / kg to obtain experimental soil and control soil, and cabbage worms of the same age were selected and randomly placed in the experimental soil and the control soil. After 48 hours, the number of cabbage worms surviving in the soil was counted, and the insecticidal rate was calculated to obtain the primary insecticidal rate; the soil matrix containing pure pesticides and insecticides in the primary insecticidal stage was washed with deionized water, and cabbage worms were placed again after drying, and the secondary insecticidal rate was calculated after 72 hours. Specific data are shown in Table 4.

[0099] Insecticidal rate (%) = (N1-N0) / N1×100%;

[0100] N1 is the number of cabbage loopers placed in the soil before the test; N0 is the number of surviving cabbage loopers in the soil after the test.

[0101] Table 4 Insecticide killing rate results

[0102]

[0103] The data in Table 4 show that the insecticide of the present invention can prolong the effective period of the pesticide and improve the utilization rate of the pesticide.

[0104] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A formula of a fertilizer for net-catching and controlling drug loss based on synthetic biology technology, characterized in that: The invention is prepared from the following components by weight: 60-80 parts of compound fertilizer, 10-20 parts of diammonium phosphate, 2-10 parts of trace elements, 2-8 parts of modified attapulgite, 1-4 parts of pesticide, 0.5-3 parts of polyglutamic acid and 1-5 parts of polyvinyl alcohol.

2. The formula of the net-catching and drug-loss-control fertilizer according to claim 1, characterized in that: The preparation method of the modified attapulgite comprises the following steps: (1) dispersing attapulgite in a methanol / water mixture, ultrasonically treating, adjusting the pH of the dispersion, adding KH570, heating the mixture for reaction, centrifuging, washing, and drying the product to obtain pretreated attapulgite; (2) dispersing the pretreated attapulgite in deionized water, ultrasonically treating it, adding L-allylglycine, introducing nitrogen gas and adding ammonium persulfate, stirring the reaction, centrifuging, washing, and drying the product to obtain grafted attapulgite; (3) The grafted attapulgite is dispersed in DMF, ultrasonically treated, 2-hydroxyphosphonoacetic acid is added, EDC and NHS are added under light-shielding conditions, the reaction is stirred, the product is centrifuged, washed, and dried to obtain modified attapulgite.

3. The formula of the net-catching and loss-control fertilizer according to claim 2, characterized in that: In step (1), the volume ratio of methanol to deionized water in the methanol / water mixture is 7-9:3-1; the dosage ratio of attapulgite, methanol / water mixture, and KH570 is 10 g:80-150 mL:0.3-1 g.

4. The formula of the net-catching and loss-control fertilizer according to claim 2, characterized in that: In step (1), ultrasonic treatment is performed for 15 to 30 minutes, and the pH value of the dispersion is adjusted to 4 to 5 with glacial acetic acid; the temperature reaction conditions are heating to 60 to 75° C. and reacting at 400 to 600 r / min for 12 to 18 hours.

5. The formula of the net-catching and loss-control fertilizer according to claim 2, characterized in that: In step (2), the dosage ratio of pretreated attapulgite, deionized water, L-allylglycine, and ammonium persulfate is 10 g: 80-150 mL: 1-2 g: 0.02-0.1 g.

6. The formula of the net-catching and loss-control fertilizer according to claim 2, characterized in that: In step (2), ultrasonic treatment is performed for 15 to 30 minutes; the stirring reaction conditions are 55 to 70° C. and 300 to 400 r / min for 4 to 8 hours; and washing is performed with 70 to 90° C. warm water for 3 to 4 times.

7. The formula of the net-catching and drug-loss-control fertilizer according to claim 2, characterized in that: In step (3), the ratio of grafted attapulgite, DMF, 2-hydroxyphosphonoacetic acid, EDC and NHS is 10 g: 80-150 mL: 0.6-1.5 g: 0.8-1.2 g: 0.4-0.6 g; the stirring reaction conditions are 20-30° C. and 200-300 r / min for 12-24 h; and the mixture is washed with DMF, anhydrous ethanol and deionized water in turn.

8. The formula of the net-catching and drug-loss-control fertilizer according to claim 1, characterized in that: The preparation method of the insecticide comprises the following steps: dispersing mesoporous silica in a 5-20 mg / L pesticide ethanol solution, oscillating in a constant temperature water bath oscillator at 25-40° C. for 18-24 hours, filtering the product with a sand core, washing with deionized water, and vacuum drying to obtain the insecticide; the pesticide is one or more of chlorfenapyr, clothianidin, dinotefuran, myclobutanil, prothioconazole, and thiofuran; the usage ratio of the mesoporous silica to the pesticide ethanol solution is 8-14 g:10 mL.

9. The formula of the net-catching and loss-control fertilizer according to claim 1, characterized in that: In the compound fertilizer, the content ratio of nitrogen fertilizer, phosphorus fertilizer and potassium fertilizer is 12-16:12-16:12-16; the content of the nitrogen fertilizer is calculated as the nitrogen element in the nitrogen fertilizer, the content of the phosphorus fertilizer is calculated as phosphorus pentoxide, and the content of the potassium fertilizer is calculated as potassium oxide; the trace elements are chelated ferrous iron, chelated copper and chelated zinc mixed in a weight ratio of 1:0.4-0.6:0.8-1.

2.

10. A preparation process for a fertilizer formula for controlling drug loss based on synthetic biology technology, characterized in that: The method comprises the following steps: mixing compound fertilizer, diammonium phosphate, trace elements, modified attapulgite, insecticide and polyglutamic acid, stirring for 10-20 minutes, grinding through a 40-60 mesh sieve, adding polyvinyl alcohol, stirring for 10-30 minutes, and granulating to obtain the net-catching and loss-controlling fertilizer.

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