Infinitesimal bio-enzyme fertilizer for degrading pesticide residues of crops as well as preparation method and application thereof

Abstract

The invention discloses an infinitesimal bio-enzyme fertilizer capable of degrading pesticide residues of crops as well as a preparation method and application of the infinitesimal bio-enzyme fertilizer, and belongs to the technical field of bio-fertilizers. The infinitesimal biological enzyme fertilizer is prepared from the following components in parts by weight: 600 to 700 parts of water, 100 to 150 parts of immobilized beneficial microorganism bacterial material, 80 to 120 parts of activated carbon, 31 to 62 parts of amino acid material, 55 to 65 parts of organic material, 35 to 50 parts of mineral material, 32 to 64 parts of enzyme-containing base material, 1 to 5 parts of vitamin B material, 1 to 2 parts of vitamin C, 5 to 10 parts of acid-base balancing agent, 1 to 2 parts of plant growth regulator and 0.1 to 0.5 part of modified nano-selenium, the modified nano-selenium is prepared from zinc selenite, potassium selenite, sodium selenite and calcium selenite through reduction modification; the immobilized beneficial microbial material is prepared by beneficial microbial fermentation, immobilization and reinforcement. The infinitesimal biological enzyme fertilizer provided by the invention can improve the pesticide degradation rate.

Description

Technical Field

[0001] The invention belongs to the technical field of biological fertilizers, and in particular relates to a micro-element biological enzyme fertilizer for degrading pesticide residues of crops, and a preparation method and application thereof. Background Art

[0002] In the process of modern agricultural planting practice, although the large-scale application of pesticides and fertilizers has maintained the scale of crop production to a certain extent, the excessive pesticide residues in agricultural products caused by this is extremely serious, posing a potential risk to the health and safety of consumers. With the continuous deepening of the public's health concept, the expectations and demands for the quality of agricultural products have also shown a significant upward trend. Therefore, the effective resolution of the problem of pesticide residues in agricultural products has become a key core task that urgently needs to be broken through in the agricultural field at this stage. It is not only closely related to the dietary health rights and interests of consumers, but also a key transformation node and core driving factor for the agricultural industry to move from a simple output orientation to a new paradigm of quality and safety, green and sustainable development.

[0003] As an indispensable key trace element for the human body, selenium has shown diverse and positive physiological effects in maintaining human health. According to its chemical form differences, selenium can be subdivided into inorganic selenium (typical representatives such as sodium selenite, sodium selenate, etc.), organic selenium (such as selenomethionine, selenomethionine, etc.) and zero-valent selenium (i.e., elemental selenium form). Among them, when the particle size of zero-valent selenium is at the nanometer level, it appears red, which is nano-selenium. Nano-selenium has excellent stability, high biological activity, good water solubility and low toxicity. At the same time, it shows stronger antioxidant properties and higher bioavailability. It contains broad application potential and value space in many fields such as medical health, health protection, health care and agricultural production practice. Among all kinds of selenium forms, organic selenium has attracted much attention because of its better human absorption characteristics. Therefore, increasing the level of organic selenium in agricultural products through effective means and simultaneously achieving deep degradation of pesticide residues in agricultural products constitutes the core path and key strategy for improving the nutritional value of agricultural products and ensuring food safety. However, looking back at the existing relevant functional products and technical solution systems in the current market, they generally have significant limitations and shortcomings. Most of them only focus on the single dimension of improving the selenium content of agricultural products, but have insufficient achievements in the effective elimination of pesticide residues, making it difficult to effectively meet the ardent expectations and practical demands of modern consumers for green, healthy, and high-quality agricultural products without pesticide residues. Therefore, the present invention develops a micro-element bioenzyme fertilizer for degrading pesticide residues in crops and its preparation method and application, which are used to solve the technical problems of low degradation rate of pesticides by fertilizers in the prior art and lack of high oxidizing, high catalytic and slow-release components in fertilizers. Summary of the invention

[0004] The object of the present invention is to provide a microelement biological enzyme fertilizer for degrading pesticide residues in crops, its preparation method and application, aiming to solve the technical problems in the prior art that the degradation rate of pesticides by fertilizers is low, and the fertilizers lack components with high oxidation, high catalysis and slow-release effects.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] The microelement biological enzyme fertilizer for degrading pesticide residues in crops is composed of the following components in parts by weight: 600 - 700 parts of water, 100 - 150 parts of immobilized beneficial microbial bacteria, 80 - 120 parts of activated carbon, 31 - 62 parts of amino acid materials, 55 - 65 parts of organic materials, 35 - 50 parts of mineral materials, 32 - 64 parts of enzyme-containing materials, 1 - 5 parts of vitamin B materials, 1 - 2 parts of vitamin C, 5 - 10 parts of acid-base balance agents, 1 - 2 parts of plant growth regulators and 0.1 - 0.5 parts of modified nano-selenium; the modified nano-selenium is prepared by reduction modification of zinc selenite, potassium selenite, sodium selenite and calcium selenite; the immobilized beneficial microbial bacteria are obtained by fermentation, immobilization and reinforcement of beneficial microorganisms.

[0007] The amino acid materials are obtained by mixing glutamic acid, alanine, aspartic acid, lysine, methionine and cysteine in a mass ratio of 1:1:1.2:2:0.5:0.5; the organic materials are obtained by mixing peptone, brown sugar, glucose and honey in a ratio of 0.5:1 - 2:2:2; the mineral materials are obtained by mixing boric acid, calcium chloride and magnesium sulfate in a mass ratio of 1:1.5 - 2:1 - 2; the enzyme-containing materials are obtained by mixing rosa roxburghii tratt enzyme, blueberry enzyme and kiwifruit enzyme in a mass ratio of 1.2:1:1; the vitamin B materials are obtained by mixing vitamin B1, vitamin B6 and vitamin B12 in a mass ratio of 1 - 2:1 - 2:1 - 2; the acid-base balance agents are an equal mixture of monopotassium phosphate and dipotassium phosphate; the plant growth regulators are an equal mixture of sodium alginate and potassium fulvate.

[0008] The preparation method of the modified nano-selenium includes the following steps:

[0009] S1. Dissolution: Dissolve zinc selenite, potassium selenite and sodium selenite in water respectively, dissolve calcium selenite in dilute hydrochloric acid, mix the dissolved solutions evenly, and adjust the pH to 6 - 8 to obtain a selenite solution;

[0010] S2. Reduction: Heat the selenite solution, add a reducing agent, stir and react, after completion, filter, wash and dry to obtain dry nano-selenium powder;

[0011] S3. Modification: Disperse the dried nano-selenium powder in deionized water to obtain a uniform suspension. Add polyethylene glycol to the nano-selenium suspension, stir and react, then filter, wash, and dry to obtain the modified nano-selenium powder.

[0012] Further, in S1, the mass ratio of zinc selenite, calcium selenite, potassium selenite, and sodium selenite is 2:1:1:1, the dissolution temperature is 60 - 65 °C, the concentration of dilute hydrochloric acid is 0.1 - 0.5 M, the pH is adjusted to 6 - 8 with 2 M sodium hydroxide solution, and the mass concentration of the selenite solution is 2.5 - 5 wt%; in S2, the reducing agent is sodium borohydride, the mass ratio of sodium borohydride to selenite is 0.1 - 0.5:1, heated to 30 - 50 °C, the reaction time is 1 - 4 hours, washed 3 - 5 times with deionized water, and the drying temperature is 50 - 80 °C; in S3, the mass-volume ratio of the dried nano-selenium powder to deionized water is 1 - 5:100 g / mL, the mass ratio of polyethylene glycol to the dried nano-selenium powder is 0.01 - 0.05:1, the polyethylene glycol is PEG2000, the stirring reaction time is 30 - 60 minutes, washed 3 - 5 times with deionized water, and the drying temperature is 50 - 80 °C.

[0013] The preparation method of the immobilized beneficial microorganism bacterial agent includes the following steps:

[0014] Q1. Dissolve nutrients: Dissolve the nutrients in a phosphate buffer solution to obtain a nutrient solution, then add the beneficial microorganisms to the nutrient solution, stir evenly, ferment, and after completion, obtain the beneficial microorganism liquid;

[0015] Q2. Immobilization: Mix the beneficial microorganism liquid evenly with the sodium alginate solution, and then drop it into the calcium chloride solution to obtain the beneficial microorganism microcapsules;

[0016] Q3. Reinforcement: Take out the beneficial microorganism microcapsules from the calcium chloride solution, soak them in the sodium carboxymethyl cellulose solution, after completion, filter, wash, and dry to obtain the immobilized beneficial microorganism bacterial agent.

[0017] Furthermore, the nutrients in Q1 are a mixture of peptone, glucose, brown sugar, magnesium sulfate, ferrous sulfate and yeast extract, the mass ratio of peptone, glucose, brown sugar, magnesium sulfate, ferrous sulfate, yeast extract and phosphate buffer is 2-3:8-10:4-8:0.05-0.1:0.02-0.05:0.5-1:1000, the beneficial microorganisms are a mixture of nitrogen-fixing bacteria, phosphate-solubilizing bacteria, potassium-solubilizing bacteria, lactic acid bacteria and yeast, the mass ratio of nitrogen-fixing bacteria, phosphate-solubilizing bacteria, potassium-solubilizing bacteria, lactic acid bacteria, yeast and phosphate buffer is 2-4:2-4:2-4:2-4:2-5:1000, the fermentation temperature is 35-40°C, the fermentation time is 6-12 hours, the fermentation is stirred 1-2 times per hour for 1-2 minutes each time, and the microbial concentration of the beneficial microbial liquid reaches 10 8 -10 9 CFU / mL; the mass concentration of the sodium alginate solution in Q2 is 2-3wt%, the volume ratio of the sodium alginate solution to the beneficial microorganism solution is 10-12:1, the mass concentration of the calcium chloride solution is 1-1.2wt%, and the volume ratio of the calcium chloride solution to the sodium alginate solution is 1:2; the mass concentration of the sodium carboxymethyl cellulose solution in Q3 is 0.5-0.6wt%, and the volume ratio of the sodium carboxymethyl cellulose solution to the beneficial microorganism microcapsule is 2-3:1, the soaking time is 10-15 minutes, the solution is washed with deionized water 2-3 times, the drying temperature is 40-50°C, and the drying time is 20-24 hours.

[0018] The preparation method of micro-element bio-enzyme fertilizer for degrading pesticide residues in crops comprises the following steps:

[0019] (1) Adsorption: The activated carbon is cleaned and dried, and the amino acid material, the enzyme-containing base material and the plant growth regulator are wetted by spraying water to obtain the flowable amino acid material and the plant growth regulator, which are then mixed with the activated carbon, stirred and dried to obtain the adsorbent;

[0020] (2) Mixing: Putting the immobilized beneficial microorganism material, organic material, mineral material, vitamin B material, vitamin C, modified nano-selenium and water into a stainless steel reactor, stirring and mixing them thoroughly to obtain a micro-element bio-enzyme fertilizer mixture;

[0021] (3) Fermentation and pH adjustment: adding an acid-base balance agent to adjust the pH value of the micro-element bio-enzyme fertilizer mixture to 5.8-7, and fermenting to obtain a micro-element bio-enzyme fertilizer that degrades pesticide residues in crops.

[0022] Furthermore, in step (1), the mass of the water sprayed is 2-3 times the total mass of the amino acid material, the enzyme-containing base material and the plant growth regulator, the stirring speed is 20-30 rpm, the stirring time is 4-6 hours, the drying temperature is 60-80° C., and the drying time is 2-4 hours; in step (2), the stirring speed is 30-50 rpm, and the stirring time is 2-3 hours; in step (3), the fermentation temperature is 16-32° C., and the fermentation time is 15-25 days. During the fermentation period, the lid is opened every 5 days, and the mixture is fully stirred to ensure uniform fermentation. The fermentation is terminated when the mixture becomes brick red with a slightly sour taste.

[0023] The invention also provides application of micro-element bio-enzyme fertilizer for degrading pesticide residues of crops in degrading pesticide residues of crops.

[0024] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0025] 1. The present invention improves the degradation rate of pesticides through the antioxidant and catalytic effects of modified nano-selenium, especially for difficult-to-degrade pesticide residues. The immobilized beneficial microorganisms can continuously release beneficial metabolites and participate in the degradation process of pesticide residues. The modified nano-selenium and immobilized beneficial microorganisms in the micro-element bio-enzyme fertilizer work synergistically to jointly degrade the pesticide residues on the surface of crops. Activated carbon, amino acid materials, enzyme-based materials and other ingredients provide a good adsorption and catalytic environment, which helps to accelerate the degradation process. Vitamin B materials, vitamin C, acid-base balance agents and plant growth regulators can regulate the soil environment and promote the growth and development of crops.

[0026] 2. The present invention converts zinc selenite, potassium selenite, sodium selenite and calcium selenite into modified nano-selenium through three steps of dissolution, reduction and modification. After the nano-selenium is modified by PEG2000, it has better dispersibility and stability and can play a role in the soil for a long time. The modified nano-selenium has excellent antioxidant and catalytic properties, can participate in the redox reaction in crops, and help degrade pesticide residues. At the same time, the tiny size of nano-selenium makes it easier to be absorbed and utilized by crops, thereby exerting better biological effects.

[0027] 3. The present invention achieves degradation of pesticide residues by immobilizing beneficial microbial materials, such as nitrogen-fixing bacteria, phosphate-solubilizing bacteria, potassium-solubilizing bacteria, lactic acid bacteria and yeast. The microorganisms can secrete oxidase and hydrolase to directly decompose harmful components in pesticide molecules and convert them into harmless or low-toxic substances. At the same time, the protective effect of the microcapsules enables the beneficial microorganisms to survive and reproduce stably in the soil, thereby continuously exerting a degradation effect. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0029] Embodiment 1:

[0030] This embodiment discloses a microbial enzyme fertilizer for degrading pesticide residues in crops, which is composed of the following components by weight: 600 kg of water, 100 kg of immobilized beneficial microbial bacteria, 80 kg of activated carbon, 31 kg of amino acid material, 55 kg of organic material, 35 kg of mineral material, 32 kg of enzyme-containing material, 1 kg of vitamin B material, 1 kg of vitamin C, 2.5 kg of monopotassium phosphate, 2.5 kg of dipotassium phosphate, 0.5 kg of sodium alginate, 0.5 kg of potassium fulvate, and 0.1 kg of modified nano selenium.

[0031] The amino acid material is obtained by mixing glutamic acid, alanine, aspartic acid, lysine, methionine, and cysteine in a mass ratio of 1:1:1.2:2:0.5:0.5; the organic material is obtained by mixing peptone, brown sugar, glucose, and honey in a ratio of 0.5:1:2:2; the mineral material is obtained by mixing boric acid, calcium chloride, and magnesium sulfate in a mass ratio of 1:1.5:1; the enzyme-containing material is obtained by mixing rose hip enzyme, blueberry enzyme, and kiwifruit enzyme in a mass ratio of 1.2:1:1; the vitamin B material is obtained by mixing vitamin B1, vitamin B6, and vitamin B12 in a mass ratio of 1:1:1.

[0032] The preparation method of the modified nano selenium includes the following steps:

[0033] S1. Dissolution: 200 g of zinc selenite, 100 g of potassium selenite, and 100 g of sodium selenite are respectively dissolved in water at a dissolution temperature of 60°C. 100 g of calcium selenite is dissolved in 0.1 M dilute hydrochloric acid. The dissolved solutions are mixed evenly, and the pH is adjusted to 6 with 2 M sodium hydroxide solution to obtain a 2.5 wt% selenite solution.

[0034] S2. Reduction: The selenite solution is heated to 30°C, 50 g of sodium borohydride is added, and the mixture is stirred and reacted for 1 hour. After filtration, it is washed 3 times with deionized water and dried at a drying temperature of 50°C to obtain dry nano selenium powder.

[0035] S3, modification: 10g of dry nano-selenium powder was dispersed in 1L of deionized water to obtain a uniform suspension, 0.1g of PEG2000 was added to the nano-selenium suspension, and the mixture was stirred for reaction for 30 minutes, then filtered, washed with deionized water for 3 times, and dried at 50°C to obtain modified nano-selenium powder.

[0036] The method for preparing the immobilized beneficial microbial material comprises the following steps:

[0037] Q1. Dissolve nutrients: Dissolve 2g of peptone, 8g of glucose, 4g of brown sugar, 0.05g of magnesium sulfate, 0.02g of ferrous sulfate and 0.5g of yeast extract in 1L of phosphate buffer to obtain a nutrient solution. Then add 2g of nitrogen-fixing bacteria, 2g of phosphate-solubilizing bacteria, 2g of potassium-solubilizing bacteria, 2g of lactic acid bacteria and 25g of yeast to the nutrient solution, stir evenly and ferment. The fermentation temperature is 35°C and the fermentation time is 6 hours. Stir once every hour for 1 minute each time during the fermentation. After the end, the concentration reaches 10 8 CFU / mL of beneficial microbial liquid;

[0038] Q2, immobilization: 100mL of beneficial microbial liquid was mixed evenly with 1L of 2wt% sodium alginate solution, and then dripped into 500mL of 1wt% calcium chloride solution to obtain beneficial microbial microcapsules;

[0039] Q3. Reinforcement: Take out the beneficial microorganism microcapsules from the calcium chloride solution, soak them in 200 mL of 0.5 wt% sodium carboxymethyl cellulose solution for 10 minutes, filter them, wash them twice with deionized water, and dry them at 40°C for 20 hours to obtain immobilized beneficial microorganisms.

[0040] The preparation method of micro-element bio-enzyme fertilizer for degrading pesticide residues in crops comprises the following steps:

[0041] (1) Adsorption: The activated carbon is cleaned and dried, and the amino acid material, the enzyme-containing base material and the plant growth regulator are soaked with water, the mass of the water sprayed is twice the total mass of the amino acid material, the enzyme-containing base material and the plant growth regulator, to obtain a fluid amino acid material and a plant growth regulator, which are mixed with the activated carbon, stirred at a speed of 20 rpm for 4 hours, and dried at a drying temperature of 60° C. for 2 hours to obtain an adsorbent;

[0042] (2) Mixing: Put the immobilized beneficial microorganism material, organic material, mineral material, vitamin B material, vitamin C, modified nano-selenium and water into a stainless steel reactor, stir and mix them thoroughly, the stirring speed is 30 rpm, and the stirring time is 2 hours to obtain a micro-element bio-enzyme fertilizer mixture;

[0043] (3) Fermentation and pH adjustment: Add acid-base balance agent to adjust the pH value of the microbial enzyme fertilizer mixture to 5.8, and ferment. The fermentation temperature is 16 °C and the fermentation time is 15 days. During fermentation, open the lid every 5 days and fully stir the mixture to ensure uniform fermentation. Stop fermentation until the mixture shows brick red color and has a slight sour taste, obtaining the microbial enzyme fertilizer for degrading agricultural pesticide residues.

[0044] Example 2:

[0045] The microbial enzyme fertilizer for degrading agricultural pesticide residues disclosed in this example is composed of the following components by weight: 650 kg of water, 130 kg of immobilized beneficial microbial bacteria material, 100 kg of activated carbon, 31 kg of amino acid material, 65 kg of organic material, 40 kg of mineral material, 64 kg of enzyme-containing material, 2.5 kg of vitamin B material, 1.5 kg of vitamin C, 3 kg of monopotassium phosphate, 3 kg of dipotassium phosphate, 0.8 kg of sodium alginate, 0.8 kg of potassium fulvate, and 0.3 kg of modified nano selenium.

[0046] The amino acid material is obtained by mixing glutamic acid, alanine, aspartic acid, lysine, methionine, and cysteine according to a mass ratio of 1:1:1.2:2:0.5:0.5; the organic material is obtained by mixing peptone, brown sugar, glucose, and honey according to 0.5:1:2:2; the mineral material is obtained by mixing boric acid, calcium chloride, and magnesium sulfate according to a mass ratio of 1:1.5:1; the enzyme-containing material is obtained by mixing rosa roxburghii tratt enzyme, blueberry enzyme, and kiwifruit enzyme according to a mass ratio of 1.2:1:1; the vitamin B material is obtained by mixing vitamin B1, vitamin B6, and vitamin B12 according to a mass ratio of 1:1:1.

[0047] The preparation method of the modified nano selenium includes the following steps:

[0048] S1. Dissolution: Dissolve 200 g of zinc selenite, 100 g of potassium selenite, and 100 g of sodium selenite in water respectively. The dissolution temperature is 63 °C. Dissolve 100 g of calcium selenite in 0.3 M dilute hydrochloric acid. Mix the dissolved solutions evenly and adjust the pH to 6 with 2 M sodium hydroxide solution to obtain a 2.3 wt% selenite solution.

[0049] S2. Reduction: Heat the selenite solution to 40 °C, add 100 g of sodium borohydride, stir and react for 3 hours, filter, wash 4 times with deionized water, and dry at a temperature of 60 °C to obtain dry nano selenium powder.

[0050] S3. Modification: Disperse 40 g of dry nano-selenium powder in 1 L of deionized water to obtain a uniform suspension. Add 0.4 g of PEG2000 to the nano-selenium suspension, stir and react for 50 minutes, then filter, wash 4 times with deionized water, and dry at a temperature of 60 °C to obtain modified nano-selenium powder.

[0051] The preparation method of the immobilized beneficial microorganism bacterial agent comprises the following steps:

[0052] Q1. Dissolve nutrients: Dissolve 2.5 g of peptone, 9 g of glucose, 6 g of brown sugar, 0.08 g of magnesium sulfate, 0.04 g of ferrous sulfate, and 0.8 g of yeast extract in 1 L of phosphate buffer to obtain a nutrient solution. Then add 3 g of nitrogen-fixing bacteria, 3 g of phosphate-solubilizing bacteria, 3 g of potassium-solubilizing bacteria, 3 g of lactic acid bacteria, and 3 g of yeast to the nutrient solution, stir evenly, ferment at a temperature of 37 °C for 8 hours, stir once per hour during fermentation, each time for 1.5 minutes. After completion, obtain a beneficial microorganism liquid with a concentration reaching 10 8 CFU / mL;

[0053] Q2. Immobilization: Mix 100 mL of the beneficial microorganism bacterial liquid evenly with 1.1 L of 2.5 wt% sodium alginate solution, and then drop it into 550 mL of 1.1 wt% calcium chloride solution to obtain beneficial microorganism microcapsules;

[0054] Q3. Reinforcement: Take out the beneficial microorganism microcapsules from the calcium chloride solution, soak them in 250 mL of 0.55 wt% sodium carboxymethylcellulose solution for 13 minutes. After completion, filter, wash 3 times with deionized water, and dry at a temperature of 45 °C for 22 hours to obtain the immobilized beneficial microorganism bacterial agent.

[0055] The preparation method of the microbial enzyme fertilizer for degrading agricultural pesticide residues in crops comprises the following steps:

[0056] (1) Adsorption: Clean and dry the activated carbon. Spray water on the amino acid material, the enzyme-containing material, and the plant growth regulator until they are wet. The mass of the sprayed water is 2 times the total mass of the amino acid material, the enzyme-containing material, and the plant growth regulator to obtain a flowing amino acid material and plant growth regulator. Mix it with the activated carbon and stir at a speed of 25 rpm for 5 hours, then dry at a temperature of 70 °C for 3 hours to obtain an adsorption material;

[0057] (2) Mixing: Put the immobilized beneficial microorganism material, organic material, mineral material, vitamin B material, vitamin C, modified nano-selenium and water into a stainless steel reactor, stir and mix them thoroughly, the stirring speed is 40 rpm, and the stirring time is 2 hours to obtain a micro-element bio-enzyme fertilizer mixture;

[0058] (3) Fermentation and pH adjustment: an acid-base balancer was added to adjust the pH value of the micro-element bio-enzyme fertilizer mixture to 6.3, and fermentation was performed at a temperature of 25° C. for 20 days. During the fermentation period, the lid was opened every 5 days and the mixture was fully stirred to ensure uniform fermentation. The fermentation was terminated when the mixture was brick red with a slightly sour taste, thereby obtaining a micro-element bio-enzyme fertilizer capable of degrading pesticide residues in crops.

[0059] Embodiment 3:

[0060] The present embodiment discloses a micro-element bio-enzyme fertilizer for degrading pesticide residues in crops, which is composed of the following ingredients by weight: 700 kg of water, 150 kg of immobilized beneficial microbial bacteria, 120 kg of activated carbon, 62 kg of amino acid material, 65 kg of organic material, 50 kg of mineral material, 64 kg of enzyme-based material, 5 kg of vitamin B material, 2 kg of vitamin C, 5 kg of monopotassium phosphate, 5 kg of dipotassium phosphate, 1 kg of sodium alginate, 1 kg of potassium humate and 0.5 kg of modified nano-selenium.

[0061] The amino acid material is obtained by mixing glutamic acid, alanine, aspartic acid, lysine, methionine and cysteine ​​in a mass ratio of 1:1:1.2:2:0.5:0.5; the organic material is obtained by mixing peptone, brown sugar, glucose and honey in a mass ratio of 0.5:2:2:2; the mineral material is obtained by mixing boric acid, calcium chloride and magnesium sulfate in a mass ratio of 1:2:2; the enzyme-containing base material is obtained by mixing sea buckthorn enzyme, blueberry enzyme and kiwi enzyme in a mass ratio of 1.2:1:1; the vitamin B material is obtained by mixing vitamin B1, vitamin B6 and vitamin B12 in a mass ratio of 2:2:2.

[0062] The preparation method of the modified nano-selenium comprises the following steps:

[0063] S1, dissolving: 200g zinc selenite, 100g potassium selenite and 100g sodium selenite were dissolved in water at 65°C, 100g calcium selenite was dissolved in 0.5M dilute hydrochloric acid, the dissolved solutions were mixed evenly, and the pH was adjusted to 8 with 2M sodium hydroxide solution to obtain a 5wt% selenite solution;

[0064] S2. Reduction: Heat the selenite solution to 50°C, add 250 g of sodium borohydride, stir and react for 4 hours, filter, wash 5 times with deionized water, and dry at a temperature of 80°C to obtain dry nano-selenium powder;

[0065] S3. Modification: Disperse 50 g of dry nano-selenium powder in 1 L of deionized water to obtain a uniform suspension. Add 0.5 g of PEG2000 to the nano-selenium suspension, stir and react for 60 minutes, then filter, wash 5 times with deionized water, and dry at a temperature of 80°C to obtain modified nano-selenium powder.

[0066] The preparation method of the immobilized beneficial microorganism bacterial material includes the following steps:

[0067] Q1. Dissolve nutrients: Dissolve 3 g of peptone, 10 g of glucose, 8 g of brown sugar, 0.1 g of magnesium sulfate, 0.05 g of ferrous sulfate, and 1 g of yeast extract in 1 L of phosphate buffer to obtain a nutrient solution. Then add 4 g of nitrogen-fixing bacteria, 4 g of phosphate-solubilizing bacteria, 4 g of potassium-solubilizing bacteria, 4 g of lactic acid bacteria, and 5 g of yeast to the nutrient solution, stir evenly, ferment at a temperature of -40°C for 12 hours, stir 2 times per hour for 2 minutes each time. After completion, obtain a beneficial microorganism liquid with a concentration reaching 10 9 CFU / mL;

[0068] Q2. Immobilization: Mix 100 mL of the beneficial microorganism bacterial liquid evenly with 1.2 L of 3 wt% sodium alginate solution, and then drop it into 600 mL of 1.2 wt% calcium chloride solution to obtain beneficial microorganism microcapsules;

[0069] Q3. Reinforcement: Take out the beneficial microorganism microcapsules from the calcium chloride solution, soak them in 300 mL of 0.6 wt% sodium carboxymethylcellulose solution for 15 minutes. After completion, filter, wash 3 times with deionized water, and dry at a temperature of 50°C for 24 hours to obtain the immobilized beneficial microorganism bacterial material.

[0070] The preparation method of the microbial enzyme fertilizer for degrading crop pesticide residues includes the following steps:

[0071] (1) Adsorption: Clean and dry the activated carbon, spray water on the amino acid material, enzyme-containing material, and plant growth regulator until wet. The mass of the sprayed water is 3 times the total mass of the amino acid material, enzyme-containing material, and plant growth regulator to obtain a fluid amino acid material and plant growth regulator. Mix it with the activated carbon, stir at a speed of 30 rpm for 6 hours, and dry at a temperature of 80°C for 4 hours to obtain an adsorption material;

[0072] (2) Mixing: Put the immobilized beneficial microbial material, organic material, mineral material, vitamin B material, vitamin C, modified nano-selenium and water into a stainless-steel reactor, stir and mix thoroughly. The stirring speed is 50 rpm and the stirring time is 3 hours to obtain a micro-element biological enzyme fertilizer mixture.

[0073] (3) Fermentation and pH adjustment: Add an acid-base balance agent to adjust the pH value of the micro-element biological enzyme fertilizer mixture to 7, and ferment. The fermentation temperature is 32 °C and the fermentation time is 25 days. During the fermentation period, open the lid every 5 days and stir the mixture thoroughly to ensure uniform fermentation. Terminate the fermentation when the mixture shows a brick-red color and has a slight sour smell to obtain a micro-element biological enzyme fertilizer for degrading agricultural pesticide residues.

[0074] Comparative Example 1:

[0075] Compared with Example 3, in the preparation process of the micro-element biological enzyme fertilizer in Comparative Example 2, modified nano-selenium is not added, and other conditions remain unchanged.

[0076] Comparative Example 2:

[0077] Compared with Example 3, in the preparation process of the micro-element biological enzyme fertilizer in Comparative Example 2, the immobilized beneficial microbial material is not added, and other conditions remain unchanged.

[0078] Experimental Example

[0079] Perform the following pesticide residue detections on the micro-element biological enzyme fertilizers prepared in Examples 1 - 3 and Comparative Examples 1 - 2: Through the experiment of spraying the micro-element biological enzyme fertilizers prepared in Examples 1 - 3 and Comparative Examples 1 - 2 on the leaves and fruits of planted apples in a mist form. Dilute the nano-selenium micro-element biological enzyme with water by 30 times, and perform mist spraying on the leaves and fruits respectively at the young fruit stage, the fruit swelling stage, and 15 - 20 days before picking, for a total of 3 times. The dosage per mu each time is 2 kg. The results of pesticide detections by CTI Testing are shown in Table 1:

[0080] Table 1

[0081] Group Dichlorvos Acetamiprid Chlorpyrifos Phorate Carbofuran Dicofol Omethoate Example 1 Not detected Not detected Not detected Not detected Not detected Not detected Not detected Example 2 Not detected Not detected Not detected Not detected Not detected Not detected Not detected Example 3 Not detected Not detected Not detected Not detected Not detected Not detected Not detected Comparative Example 1 Not detected Not detected Not detected Detected Not detected Not detected Detected Comparative Example 2 Detected Not detected Not detected Detected Not detected Detected Not detected

[0082] The selenium-rich apples produced using the micro-element biological enzyme fertilizers prepared in Examples 1 - 3 have an increase of 2 - 3 degrees in soluble solids, a strong fruity aroma, large fruits, beautiful appearance, good taste, and a long shelf life during storage.

[0083] According to the detection results in Table 1, it can be seen that no agricultural pesticide residues were detected in Examples 1 - 3. In Comparative Example 1, phorate and omethoate were detected, and in Comparative Example 2, phorate, dichlorvos, and dicofol were detected. By comparing Examples 1 - 3 and Comparative Examples 1 - 2, it can be known that adding modified nano-selenium and immobilized beneficial microbial material can significantly improve the rate of pesticide degradation.

[0084] As described above, it is only the preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes, shall be covered by the protection scope of the present invention.

[0085] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the present invention to only the specific embodiments. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principle and practical application of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A micro-element bio-enzyme fertilizer for degrading pesticide residues in crops, characterized in that: The invention is composed of the following ingredients in parts by weight: 600-700 parts of water, 100-150 parts of immobilized beneficial microorganism material, 80-120 parts of activated carbon, 31-62 parts of amino acid material, 55-65 parts of organic material, 35-50 parts of mineral material, 32-64 parts of enzyme-containing base material, 1-5 parts of vitamin B material, 1-2 parts of vitamin C, 5-10 parts of acid-base balance agent, 1-2 parts of plant growth regulator and 0.1-0.5 parts of modified nano-selenium; the modified nano-selenium is prepared by reduction modification of zinc selenite, potassium selenite, sodium selenite and calcium selenite; the immobilized beneficial microorganism material is prepared by fermentation, immobilization and reinforcement of beneficial microorganisms.

2. The micro-element bio-enzyme fertilizer for degrading pesticide residues in crops according to claim 1, characterized in that: The amino acid material is obtained by mixing glutamic acid, alanine, aspartic acid, lysine, methionine and cysteine ​​in a mass ratio of 1:1:1.2:2:0.5:0.5; the organic material is obtained by mixing peptone, brown sugar, glucose and honey in a mass ratio of 0.5:1-2:2:2; the mineral material is obtained by mixing boric acid, calcium chloride and magnesium sulfate in a mass ratio of 1:1.5-2:1-2; the enzyme-containing base material is obtained by mixing roxburghii enzyme, blueberry enzyme and kiwi enzyme in a mass ratio of 1.2:1:1; the vitamin B material is obtained by mixing vitamin B1, vitamin B6 and vitamin B12 in a mass ratio of 1-2:1-2:1-2; the acid-base balancer is an equal mixture of monopotassium phosphate and dipotassium phosphate; and the plant growth regulator is an equal mixture of sodium alginate and potassium humate.

3. The micro-element bio-enzyme fertilizer for degrading pesticide residues in crops according to claim 1, characterized in that: The preparation method of the modified nano-selenium comprises the following steps: S1. Dissolving: Dissolve zinc selenite, potassium selenite and sodium selenite in water respectively, dissolve calcium selenite in dilute hydrochloric acid, mix the dissolved solutions evenly, and adjust the pH to 6-8 to obtain a selenite solution; S2, reduction: heating the selenite solution, adding a reducing agent, stirring the reaction, filtering, washing, and drying after the reaction is completed to obtain dry nano-selenium powder; S3, modification: disperse the dried nano-selenium powder in deionized water to obtain a uniform suspension, add polyethylene glycol to the nano-selenium suspension, stir to react, then filter, wash and dry to obtain modified nano-selenium powder.

4. The micro-element bio-enzyme fertilizer for degrading pesticide residues in crops according to claim 3, characterized in that: The mass ratio of zinc selenite, calcium selenite, potassium selenite and sodium selenite in S1 is 2:1:1:1, the dissolution temperature is 60-65°C, the concentration of dilute hydrochloric acid is 0.1-0.5M, the pH is adjusted to 6-8 with 2M sodium hydroxide solution, and the mass concentration of the selenite solution is 2.5-5wt%.

5. The micro-element bio-enzyme fertilizer for degrading pesticide residues in crops according to claim 3, characterized in that: The reducing agent in S2 is sodium borohydride, the mass ratio of sodium borohydride to selenite is 0.1-0.5:1, the mixture is heated to 30-50°C, and the reaction time is 1-4 hours; the mass volume ratio of the dried nano-selenium powder to deionized water in S3 is 1-5:100 g / mL, the mass ratio of polyethylene glycol to the dried nano-selenium powder is 0.01-0.05:1, and the polyethylene glycol is PEG2000.

6. The micro-element bio-enzyme fertilizer for degrading pesticide residues in crops according to claim 1, characterized in that: The method for preparing the immobilized beneficial microbial material comprises the following steps: Q1. Dissolve nutrients: dissolve nutrients in phosphate buffer to obtain nutrient solution, then add beneficial microorganisms into the nutrient solution, stir evenly, and ferment to obtain beneficial microorganism solution; Q2. Immobilization: Mix the beneficial microbial liquid with the sodium alginate solution evenly, and then drop it into the calcium chloride solution to obtain beneficial microbial microcapsules; Q3. Reinforcement: Take out the beneficial microorganism microcapsules from the calcium chloride solution and soak them in a sodium carboxymethyl cellulose solution. After the soaking, filter, wash and dry to obtain the immobilized beneficial microorganism material.

7. The micro-element bio-enzyme fertilizer for degrading pesticide residues in crops according to claim 6, characterized in that: The nutrients in Q1 are a mixture of peptone, glucose, brown sugar, magnesium sulfate, ferrous sulfate and yeast extract. The mass ratio of peptone, glucose, brown sugar, magnesium sulfate, ferrous sulfate, yeast extract and phosphate buffer is 2-3:8-10:4-8:0.05-0.1:0.02-0.05:0.5-1:1000. The beneficial microorganisms are a mixture of nitrogen-fixing bacteria, phosphate-solubilizing bacteria, potassium-solubilizing bacteria, lactic acid bacteria and yeast. The mass ratio of nitrogen-fixing bacteria, phosphate-solubilizing bacteria, potassium-solubilizing bacteria, lactic acid bacteria, yeast and phosphate buffer is 2-4:2 -4:2-4:2-4:2-5:1000; the mass concentration of the sodium alginate solution in Q2 is 2-3wt%, the volume ratio of the sodium alginate solution to the beneficial microorganism solution is 10-12:1, the mass concentration of the calcium chloride solution is 1-1.2wt%, and the volume ratio of the calcium chloride solution to the sodium alginate solution is 1:2; the mass concentration of the sodium carboxymethyl cellulose solution in Q3 is 0.5-0.6wt%, the volume ratio of the sodium carboxymethyl cellulose solution to the beneficial microorganism microcapsule is 2-3:1, and the immersion time is 10-15 minutes.

8. A method for preparing a micro-element bio-enzyme fertilizer for degrading pesticide residues in crops, characterized in that: The following steps are involved: (1) Adsorption: The activated carbon is cleaned and dried, and the amino acid material, the enzyme-containing base material and the plant growth regulator are wetted by spraying water to obtain the flowable amino acid material and the plant growth regulator, which are then mixed with the activated carbon, stirred and dried to obtain the adsorbent; (2) Mixing: Putting the immobilized beneficial microorganism material, organic material, mineral material, vitamin B material, vitamin C, modified nano-selenium and water into a stainless steel reactor, stirring and mixing them thoroughly to obtain a micro-element bio-enzyme fertilizer mixture; (3) Fermentation and pH adjustment: adding an acid-base balance agent to adjust the pH value of the micro-element bio-enzyme fertilizer mixture to 5.8-7, and fermenting to obtain a micro-element bio-enzyme fertilizer that degrades pesticide residues in crops.

9. The micro-element bio-enzyme fertilizer for degrading pesticide residues in crops according to claim 8, characterized in that: The mass of the water sprayed in step (1) is 2-3 times the total mass of the amino acid material, the enzyme-containing base material and the plant growth regulator.

10. Use of the micro-element bio-enzyme fertilizer for degrading pesticide residues in crops according to any one of claims 1 to 9 in degrading pesticide residues in crops.