Fertilizer containing biological agent and preparation method thereof

Abstract

The invention discloses a fertilizer containing a biological agent and a preparation method thereof. The fertilizer containing the biological agent sequentially comprises inorganic fertilizer particles, a resin coating layer, a microbial agent coating layer and an anti-caking protection layer from inside to outside, wherein the resin coating layer is formed by reaction of resin coating layer raw material liquid under catalysis of acid liquor; based on 100 parts by weight of the fertilizer containing the biological agent, the inorganic fertilizer particle core accounts for 95.5-99 parts by weight, and the acid solution accounts for 0.2-1 part by weight; the weight part of the resin coating layer is 0.5-2; the weight part of the microbial agent coating layer is 0.1 to 0.5; and the weight part of the anti-caking protective layer is 0.2-1. The fertilizer containing the biological agent is high in viable bacteria retention rate, high in overall efficiency, long in nutrient release period and long in shelf life, has a slow release function, is suitable for being widely popularized in agricultural production, and is wide in application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of biological fertilizers, and in particular relates to a fertilizer containing a biological bacterial agent and a preparation method thereof. Background Art

[0002] In modern agricultural production, the use of chemical fertilizers is an important guarantee for increasing crop yields and food security. However, the irrational use of chemical fertilizers leads to problems such as soil compaction, acidification, reduced microbial diversity, and increased soil pests and diseases. The fundamental reason for the above problems is that ordinary fertilizers release nutrients quickly and have a short shelf life. After application, fertilizer nutrients are lost in large quantities and the utilization rate is low. Microbial fertilizers have the functions of regulating the structure of soil flora, improving soil fertility, and improving the microenvironment of crop roots, thereby promoting crop growth and development, improving crop quality, and enhancing plant disease resistance and stress resistance. Therefore, while improving the nutrient utilization rate of fertilizer products, improving the soil environment through microbial agents is an effective means to solve the technical problems caused by the irrational use of chemical fertilizers. Biological fertilizers with slow-release functions can effectively improve soil compaction and acidification, increase soil microbial diversity, and enhance the ability of soil to resist diseases and pests. They are the development direction of new fertilizers in the future.

[0003] The survival of microbial agents requires suitable environmental conditions. Due to the influence of inorganic fertilizer salt, the survival rate of biological agents in inorganic fertilizer products is low, and the retention rate of live bacteria is low, which seriously limits the development of inorganic fertilizers containing biological agents. Therefore, it is necessary to further develop inorganic fertilizers containing biological agents with high retention rates of live bacteria, solve technical problems such as soil compaction, acidification, reduced microbial diversity, and increased soil pests and diseases caused by unreasonable use of inorganic fertilizers, and expand the application scope of inorganic fertilizers. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art to a certain extent. To this end, the present invention provides a fertilizer containing a biological microbial agent and a preparation method thereof. The fertilizer containing a biological microbial agent of the present invention has a high retention rate of live bacteria, high overall efficiency, a long nutrient release period, a long shelf life, and a slow-release function, and is suitable for wide promotion in agricultural production.

[0005] In the first aspect of the present invention, the present invention proposes a fertilizer containing biological microbial agents. According to an embodiment of the present invention, it includes, from the inside to the outside, inorganic fertilizer particles, a resin coating layer, a microbial agent coating layer, and an anti-caking protective layer; wherein the resin coating layer is formed by the reaction of a resin coating layer raw material liquid under the catalysis of an acid solution; the fertilizer containing biological microbial agents is calculated based on 100 parts by weight, and the weight of the inner core of the inorganic fertilizer particles is 95.5 to 99, and the weight of the acid solution is 0.2 to 1; the weight of the resin coating layer is 0.5 to 2; the weight of the microbial agent coating layer is 0.1 to 0.5; and the weight of the anti-caking protective layer is 0.2 to 1. The fertilizer containing biological microbial agents according to the embodiment of the present invention has a high live bacteria retention rate, high overall efficiency, a long nutrient release period, a long shelf life, and a slow-release function. It is suitable for wide promotion in agricultural production and has broad application prospects.

[0006] In the second aspect of the present invention, the present invention proposes a method for preparing the aforementioned fertilizer containing biological microbial agents. According to an embodiment of the present invention, the method comprises: subjecting the resin coating layer raw material liquid to a first coating treatment on the surface of the inorganic fertilizer particles to form the resin coating layer; wherein the first coating treatment is performed under the catalysis of the acid solution. Compared with the conventional method of resin coating fertilizers by two-step reactions of addition and polycondensation in urea-formaldehyde / phenol-formaldehyde coated fertilizers, the method according to the embodiment of the present invention creatively utilizes the resin coating liquid after the addition reaction to resin-coat the fertilizer through a one-step polycondensation reaction, and controls the one-step polycondensation reaction to be performed on the surface of the fertilizer particles, and utilizes the viscosity of the resin coating liquid after the addition reaction to adhere to the microbial agent. The inventor unexpectedly discovered that under the catalysis of the acid solution, the resin coating layer raw material liquid will slowly undergo a polycondensation reaction and then solidify into a dense resin coating layer, thereby improving the isolation effect of the resin coating layer between the microbial agent and the inorganic fertilizer. At the same time, the resin coating liquid after the addition reaction has viscosity, can adhere to the microbial agent, and is conducive to the formation of the microbial agent coating layer.

[0007] In the third aspect of the present invention, the present invention provides a fertilizer containing biological agents obtained by the aforementioned method.

[0008] Those skilled in the art will appreciate that the features and advantages described above for the fertilizer containing biological bacteria agents and the preparation method thereof are also applicable to the fertilizer containing biological bacteria agents, and will not be described in detail here.

[0009] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0011] Figure 1 is a schematic diagram of a cross-sectional structure of a bacteria-containing inorganic fertilizer with a slow-release function according to an embodiment of the present invention;

[0012] Figure 2 The present invention is a schematic flow chart of a method for preparing a bacterial inorganic fertilizer with a slow-release function according to an embodiment of the present invention.

[0013] Reference numerals:

[0014] 100. Inorganic fertilizer granule kernel;

[0015] 200, resin coating layer;

[0016] 300, bacterial agent coating layer;

[0017] 400. Anti-knot protective layer. DETAILED DESCRIPTION

[0018] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be understood as limiting the present invention.

[0019] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. Further, in the description of the present invention, unless otherwise specified, the meaning of "plurality" is two or more.

[0020] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0021] In this document, the terms “include” or “comprising” are open expressions, that is, including the contents specified in the present invention but not excluding other contents.

[0022] As used herein, the terms "optionally", "optional" or "optionally" generally mean that the subsequently described event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0023] As used herein, the term "NPK compound fertilizer" refers to a compound fertilizer containing nitrogen (N), phosphorus (P), and potassium (K).

[0024] In the embodiment of the present invention, the term "compound fertilizer 18-18-18" refers to a fertilizer with a nitrogen content of 18%, a phosphorus content of 18%, and a potassium content of 18%, which can be obtained commercially.

[0025] In the embodiment of the present invention, the term "compound fertilizer 26-10-12" is a fertilizer with a nitrogen content of 26%, a phosphorus content of 10%, and a potassium content of 12%, which can be obtained commercially.

[0026] In the embodiment of the present invention, the term "compound fertilizer 19-4-25" is a fertilizer with a nitrogen content of 19%, a phosphorus content of 4%, and a potassium content of 25%, which can be obtained commercially.

[0027] In this article, the term "ammonium phosphate fertilizer" refers to an inorganic water-soluble compound fertilizer, which mainly includes two types: monoammonium phosphate (MAP): contains about 11% nitrogen and 52% phosphorus pentoxide, and the total effective ingredients are about 63%; diammonium phosphate (DAP): contains about 18% nitrogen and 46% phosphorus pentoxide, and the total effective ingredients are about 64%.

[0028] In the embodiment of the present invention, the term "64% diammonium phosphate" refers to a diammonium phosphate (DAP) fertilizer containing about 18% nitrogen and 46% phosphorus pentoxide, with a total effective ingredient of about 64%.

[0029] In the embodiment of the present invention, the term "55% monoammonium phosphate" refers to a monoammonium phosphate (MAP) fertilizer containing about 11% nitrogen and 44% phosphorus pentoxide, with a total effective ingredient of about 55%.

[0030] In this article, the term "potassium fertilizer" refers to fertilizers that mainly provide potassium (K) nutrients, including potassium chloride fertilizers, potassium sulfate fertilizers, and single potassium fertilizers and compound potassium fertilizers. Potassium chloride fertilizer (KCl for short): usually contains about 50% to 60% potassium oxide (K2O), is an efficient potassium source, and also contains chlorine (Cl), and is a common potassium fertilizer. Potassium sulfate fertilizer (K2SO4 for short): contains about 50% potassium oxide (K2O) and provides sulfur (S) nutrients, suitable for crops that are sensitive to chlorine.

[0031] In the embodiment of the present invention, the term "60% granular potassium chloride" refers to a potassium chloride fertilizer containing about 60% potassium oxide (K2O) and chlorine (Cl).

[0032] In the embodiments of the present invention, the term "54% granular potassium sulfate" refers to a potassium sulfate fertilizer containing about 54% potassium oxide (K2O) and providing sulfur (S) nutrients.

[0033] In this document, the term "industrial soybean oil" refers to refined soybean oil, which is mainly used for industrial purposes and is commercially available.

[0034] In this article, the term "Iranian loose wax" is equivalent to "Iranian wax" and "Persian wax". It is a natural wax extracted from the leaves, branches or fruits of certain specific plants (compared to) such as fraxinus, Pistacia, and Sappanwood. It is a complex mixture, mainly composed of high-carbon esters, alcohols and hydrocarbon compounds. Natural wax, mainly produced in Iran, can be obtained commercially.

[0035] The present invention provides a fertilizer containing a biological bacterial agent and a preparation method thereof, a resin-coated raw material liquid and a preparation method and application thereof, and an anti-caking composition and a preparation method and application thereof, which will be described in detail below.

[0036] Fertilizers containing biological agents

[0037] The present invention proposes a fertilizer containing biological microbial agents. According to an embodiment of the present invention, it includes, from the inside to the outside, inorganic fertilizer particles, a resin coating layer, a microbial agent coating layer, and an anti-caking protective layer; wherein the resin coating layer is formed by the reaction of a resin coating layer raw material liquid under the catalysis of an acid solution; the fertilizer containing biological microbial agents is calculated based on 100 parts by weight, and the weight of the inner core of the inorganic fertilizer particles is 95.5 to 99, and the weight of the acid solution is 0.2 to 1; the weight of the resin coating layer is 0.5 to 2; the weight of the microbial agent coating layer is 0.1 to 0.5; and the weight of the anti-caking protective layer is 0.2 to 1. The fertilizer containing biological microbial agents according to the embodiment of the present invention has a high live bacteria retention rate, high overall efficiency, a long nutrient release period, a long shelf life, and a slow-release function. It is suitable for wide promotion in agricultural production and has broad application prospects.

[0038] According to an embodiment of the present invention, the fertilizer containing biological microbial agents of the present invention has a core-shell structure. Among them, the inorganic fertilizer particles serve as the inner core, and the raw material liquid for preparing the resin coating layer, on the one hand, is catalyzed by acid solution to react and solidify on the surface of the fertilizer particles to form a resin coating layer, and on the other hand, can adhere to the powdered microbial agent to form a microbial agent coating layer. The resin coating layer can isolate the microbial agent from direct contact with the inorganic fertilizer, prevent the microorganisms from contacting the salt and moisture on the surface of the inorganic fertilizer particles, and play a role in protecting the microbial activity of the microbial agent and delaying the release of fertilizer nutrients. The anti-caking protective layer outside the microbial agent coating layer can isolate the microbial agent from the external environment, prevent the microbial agent coating layer from contacting the external moisture and salt in the soil, etc., and play a role in protecting the microbial agent and preventing caking and pulverization. The core-shell structure of the fertilizer containing biological microbial agents of the present invention can be specifically referred to. Figure 1 .

[0039] After a large number of experiments, the inventors determined the above-mentioned preferred fertilizer components and ratios. According to an embodiment of the present invention, the inventors found in the process of developing a slow-release bio-microbial fertilizer that the coating amount of the resin coating layer affects the slow-release function of the fertilizer. Specific test results show that when the coating amount of the resin coating layer is too small, such as less than 0.5 parts by weight, the slow-release period of the obtained fertilizer will be less than the minimum requirement (28 days) for the release period of the slow-release fertilizer in the national standard "GB / T23348-2009 Slow-Release Fertilizer", so that the fertilizer cannot achieve a slow-release effect; when the coating amount of the resin coating layer is too large, such as more than 2 parts by weight, the coating material will cause the fertilizer to adhere and lose fluidity due to excessive addition. Therefore, according to the fertilizer of the embodiment of the present invention, by adjusting the coating amount of the resin coating layer to 0.5 to 2 parts by weight, the slow-release period of the fertilizer can be adjusted to within 1 to 3 months.

[0040] According to an embodiment of the present invention, the amount of acid added can be adjusted according to the changes in parameters such as the coating amount of the resin coating layer and the microbial performance of the specific bacterial agent coating layer. After a large number of experiments, the inventors found that the amount of acid added has an impact on the slow-release function of the fertilizer. Specific test results show that when the spraying amount is less than 0.2 parts by weight, the acid will not be able to fully coat the surface of the fertilizer particles, thereby affecting the catalytic reaction of the resin coating raw material liquid and reducing the slow-release performance of the resin coating layer; when the spraying amount is greater than 1 part by weight, the amount of corresponding resin coating raw material liquid added increases accordingly, and the fertilizer particles will lose fluidity due to the excessive surface liquid phase. At the same time, excessive acid will also reduce the activity of the bacterial agent.

[0041] According to an embodiment of the present invention, the pH value of the acid solution is 1 to 3, and preferably the pH value is 2. Thus, the density of the resin coating layer is further improved, and the formation of the resin coating layer is promoted.

[0042] According to an embodiment of the present invention, the acid solution is a sulfuric acid solution, thereby further improving the adhesion of the raw material liquid of the resin coating layer, which is conducive to the adhesion of the bacterial agent.

[0043] According to an embodiment of the present invention, the resin coating layer raw material liquid includes: formaldehyde solution, butyraldehyde, polyvinyl alcohol; and also includes: phenol and / or urea.

[0044] According to an embodiment of the present invention, the resin coating layer raw material liquid includes: 10 to 70 parts by weight of formaldehyde solution, 2.5 to 30 parts by weight of butyraldehyde, 5 to 45 parts by weight of polyvinyl alcohol; and 2 to 60 parts by weight of phenol and / or 5 to 50 parts by weight of urea; wherein the total weight of the formaldehyde solution, butyraldehyde, polyvinyl alcohol and phenol and / or urea is 100 parts by weight, and the concentration of the formaldehyde solution is 37%.

[0045] According to an embodiment of the present invention, the resin coating layer raw material liquid includes: 20 to 48 parts by weight of formaldehyde solution, 5 to 20 parts by weight of butyraldehyde, 10 to 30 parts by weight of polyvinyl alcohol; and 4 to 40 parts by weight of phenol and / or 10 to 40 parts by weight of urea; wherein the total weight of the formaldehyde solution, butyraldehyde, polyvinyl alcohol and phenol and / or urea is 100, and the concentration of the formaldehyde solution is 37%.

[0046] According to an embodiment of the present invention, the pH value of the resin coating layer raw material liquid is 8-10, preferably 9-10.

[0047] In a specific embodiment of the present invention, the raw material liquid of the resin coating layer includes: 41 parts by weight of formaldehyde solution, 7 parts by weight of butyraldehyde, 10 parts by weight of polyvinyl alcohol; and 21 parts by weight of phenol and 21 parts by weight of urea. The concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 9.0.

[0048] In a specific embodiment of the present invention, the raw material liquid of the resin coating layer includes: 41 parts by weight of formaldehyde solution, 5 parts by weight of butyraldehyde, 10 parts by weight of polyvinyl alcohol; and 4 parts by weight of phenol and 40 parts by weight of urea. The concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 9.5.

[0049] In a specific embodiment of the present invention, the raw material liquid of the resin coating layer includes: 48 parts by weight of formaldehyde solution, 7 parts by weight of butyraldehyde, 10 parts by weight of polyvinyl alcohol; and 5 parts by weight of phenol and 30 parts by weight of urea. The concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 9.0.

[0050] In a specific embodiment of the present invention, the raw material liquid of the resin coating layer includes: 20 parts by weight of formaldehyde solution, 20 parts by weight of butyraldehyde, 10 parts by weight of polyvinyl alcohol; and 40 parts by weight of phenol and 10 parts by weight of urea. The concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 9.0.

[0051] In a specific embodiment of the present invention, the raw material liquid of the resin coating layer includes: 40 parts by weight of formaldehyde solution, 7 parts by weight of butyraldehyde, 13 parts by weight of polyvinyl alcohol; and 10 parts by weight of phenol and 30 parts by weight of urea. The concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 9.0.

[0052] In a specific embodiment of the present invention, the resin coating layer raw material liquid includes: 45 parts by weight of formaldehyde solution, 5 parts by weight of butyraldehyde, 10 parts by weight of polyvinyl alcohol; and 40 parts by weight of phenol, the concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 10.0.

[0053] In a specific embodiment of the present invention, the resin coating layer raw material liquid includes: 40 parts by weight of formaldehyde solution, 10 parts by weight of butyraldehyde, 30 parts by weight of polyvinyl alcohol; and 20 parts by weight of urea, the concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 8.0.

[0054] According to an embodiment of the present invention, the raw material liquid of the anti-caking protective layer for preparing the anti-caking protective layer includes: cyclohexane oil and / or industrial soybean oil, paraffin and / or Iranian slack wax, carbon tetrachloride, and polyisobutylene.

[0055] According to an embodiment of the present invention, the anti-caking protective layer raw material liquid includes: 10 to 80 parts by weight of cyclohexane oil and / or 10 to 70 parts by weight of industrial soybean oil, 1 to 7.5 parts by weight of paraffin and / or 5 to 45 parts by weight of Iranian slack wax, 1.25 to 7.5 parts by weight of carbon tetrachloride, and 0.25 to 3.75 parts by weight of polyisobutylene; wherein the total weight of the cyclohexane oil and / or industrial soybean oil, paraffin and / or Iranian slack wax, carbon tetrachloride, and polyisobutylene is 100 parts by weight.

[0056] According to an embodiment of the present invention, the anti-caking protective layer raw material liquid includes: 20 to 70 parts by weight of cyclohexane oil and / or 20 to 60 parts by weight of industrial soybean oil, 2 to 5 parts by weight of paraffin wax and / or 10 to 30 parts by weight of Iranian slack wax, 2.5 to 5 parts by weight of carbon tetrachloride, and 0.5 to 2.5 parts by weight of polyisobutylene; wherein the total weight of the cyclohexane oil and / or industrial soybean oil, paraffin wax and / or Iranian slack wax, carbon tetrachloride, and polyisobutylene is 100 parts by weight.

[0057] According to an embodiment of the present invention, the anti-stabbing protective layer raw material solution further includes: pentaerythritol rosin.

[0058] According to an embodiment of the present invention, the anti-caking protective layer raw material liquid also includes: 1.5 to 7.5 parts by weight of pentaerythritol rosin; wherein the total weight of the cyclohexane oil and / or industrial soybean oil, paraffin and / or Iranian slack wax, carbon tetrachloride, polyisobutylene and pentaerythritol rosin is 100 parts by weight; and the pentaerythritol rosin is preferably 3 to 5 parts by weight.

[0059] According to an embodiment of the present invention, based on 100 parts by weight of the fertilizer containing the biological microbial agent, the weight parts of the inner core of the inorganic fertilizer particles are 95.5 to 99, the weight parts of the acid solution are 0.2 to 1; the weight parts of the resin coating layer are 0.5 to 2; the weight parts of the microbial agent coating layer are 0.1 to 0.5; and the weight parts of the anti-caking protective layer are 0.2 to 1.

[0060] In some optional embodiments of the present invention, the bacterial agent coating layer contains, including but not limited to: at least one of Bacillus amyloliquefaciens, Bacillus subtilis, Bacillus megaterium, Bacillus laterus, Bacillus pumilus, Trichoderma harzianum, Streptomyces avermectin, nitrogen-fixing bacteria, yeast, lactic acid bacteria, Trichoderma, photosynthetic bacteria or actinomycetes.

[0061] In some optional embodiments of the present invention, the inorganic fertilizer particles are selected from, including but not limited to: at least one of NPK compound fertilizer particles, ammonium phosphate fertilizer particles, potash fertilizer particles, and nitrogen fertilizer particles.

[0062] In some optional embodiments of the present invention, the inorganic fertilizer granules are selected from, including but not limited to: compound fertilizer 18-18-18 granules, compound fertilizer 26-10-12 granules, compound fertilizer 19-4-25 granules, monoammonium phosphate fertilizer granules, diammonium phosphate fertilizer granules, potassium chloride fertilizer granules, potassium sulfate fertilizer granules, single potassium fertilizer granules, compound potassium fertilizer granules, and at least one of urea granules.

[0063] Preparation method of fertilizer containing biological bacteria agent

[0064] The present invention proposes a method for preparing the above-mentioned fertilizer containing biological microbial agent. According to an embodiment of the present invention, the method comprises: subjecting the raw material liquid of the resin coating layer to a first coating treatment on the surface of the inorganic fertilizer particles to form the resin coating layer; wherein the first coating treatment is performed under the catalysis of the acid solution. Compared with the conventional method of resin coating the fertilizer by two-step reaction of addition and polycondensation of urea-formaldehyde / phenol-formaldehyde coated fertilizer, the method according to the embodiment of the present invention creatively utilizes the resin coating liquid after the addition reaction to resin-coat the fertilizer through a one-step polycondensation reaction, and controls the one-step polycondensation reaction to be performed on the surface of the fertilizer particles, and utilizes the viscosity of the resin coating liquid after the addition reaction to adhere the microbial agent. The inventor unexpectedly discovered that under the catalysis of the acid solution, the raw material liquid of the resin coating layer will slowly undergo a polycondensation reaction and then solidify into a dense resin coating layer, thereby improving the isolation effect of the resin coating layer between the microbial agent and the inorganic fertilizer. At the same time, the resin coating liquid after the addition reaction has viscosity, can adhere to the microbial agent, and is conducive to the formation of the microbial agent coating layer.

[0065] According to an embodiment of the present invention, the first coating treatment comprises: first contacting the surface of the inorganic fertilizer particles with the acid solution, and then coating the resin coating layer raw material solution.

[0066] Exemplarily, the contact treatment includes but is not limited to: adding the acid solution to the surface of the inorganic fertilizer particles by spraying, atomizing, dripping, etc., so that the surface of the inorganic fertilizer particles is in an acidic environment.

[0067] According to an embodiment of the present invention, the method for preparing the resin-coated raw material liquid includes: performing a first mixing treatment on the formaldehyde solution and the butyraldehyde to obtain a first mixed liquid; performing a second mixing treatment on the first mixed liquid with the polyvinyl alcohol, phenol and / or urea to obtain a second mixed liquid; performing a pH adjustment treatment on the second mixed liquid to obtain the resin-coated raw material liquid; the pH adjustment treatment includes: adjusting the pH value of the second mixed liquid to 8 to 10.

[0068] According to an embodiment of the present invention, the pH adjustment process further comprises: adjusting the pH value of the second mixed solution to 8-10, and then stirring the second mixed solution; the stirring time is 30-120 minutes, preferably 60 minutes; the temperature is 30-70° C., preferably 50° C. Thus, the uniformity of the resin coating raw material solution is further improved.

[0069] According to an embodiment of the present invention, the method further includes: performing a second coating treatment of the bacterial agent on the surface of the resin coating layer to form the bacterial agent coating layer; and performing a third coating treatment of the anti-caking protective layer raw material liquid on the surface of the bacterial agent coating layer to form the anti-caking protective layer.

[0070] Exemplarily, the methods of achieving film coating include but are not limited to: spraying, atomizing, and dripping.

[0071] In some optional embodiments of the present invention, the resin coating layer raw material liquid, the bacterial agent, and the anti-caking protective layer raw material liquid are sequentially added to the inorganic fertilizer particles by spraying, atomizing, dripping, etc., and the coating of each functional layer is achieved by the rolling process of the inorganic fertilizer particles in a mixer such as a drum, a disc, a coating machine, and a mixer, so as to obtain a slow-release fertilizer containing a biological bacterial agent with a specific core-shell structure.

[0072] According to an embodiment of the present invention, the method for preparing the anti-caking protective layer raw material liquid includes: subjecting the polyisobutylene and the carbon tetrachloride to a third mixing treatment to obtain a third mixed liquid; subjecting the cycloalkane oil and / or industrial soybean oil to a fourth mixing treatment with paraffin and / or Iranian slack wax and the third mixed liquid to obtain the anti-caking protective layer raw material liquid.

[0073] According to an embodiment of the present invention, the fourth mixing treatment comprises: stirring and heating the cyclohexane oil and / or industrial soybean oil with the paraffin wax and / or Iranian slack wax and the third mixed liquid, and the heating temperature is 50-80°C.

[0074] The fertilizer containing biological microbial agent prepared by the method of the embodiment of the present invention has a high live bacteria retention rate, a slow-release function, high overall efficiency, a long nutrient release period, and a long shelf life. It is suitable for wide promotion in agricultural production and has broad application prospects.

[0075] In a specific embodiment of the present invention, the method comprises:

[0076] S001: spraying an acid solution with a pH of 1 to 3 on the surface of the inorganic fertilizer particles to obtain acidified inorganic fertilizer particles;

[0077] S002: spraying a resin coating raw material liquid on the surface of the acidified inorganic fertilizer particles to obtain inorganic fertilizer particles sprayed with the resin coating raw material liquid;

[0078] S003: coating the inorganic fertilizer particles sprayed with the resin-coated raw material liquid with a powdered bacterial agent to obtain inorganic fertilizer particles coated with the powdered bacterial agent;

[0079] S004: Spraying an anti-caking composition (i.e. Figure 2 The anti-caking protective agent shown in the figure); obtain the fertilizer containing the biological bacterial agent.

[0080] Fertilizers containing biological agents

[0081] The present invention provides a fertilizer containing biological microbial agent prepared by the above method.

[0082] Those skilled in the art will appreciate that the features and advantages described above for the fertilizer containing biological bacteria agents and the preparation method thereof are also applicable to the fertilizer containing biological bacteria agents, and will not be described in detail here.

[0083] The scheme of the present invention will be explained below in conjunction with the embodiments. It will be appreciated by those skilled in the art that the following embodiments are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. Where specific techniques or conditions are not indicated in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used are not indicated by the manufacturer and are all conventional products that can be obtained commercially.

[0084] Example 1

[0085] (1) Preparation of resin coating raw material liquid: Based on 100 parts by weight of the resin coating raw material liquid, 41 parts by weight of formaldehyde solution (industrial formaldehyde solution, concentration of 37%) and 7 parts by weight of butyraldehyde are mixed evenly, and then 10 parts by weight of polyvinyl alcohol, 21 parts by weight of phenol and 21 parts by weight of urea are added. After the above materials are fully stirred, the pH value of the liquid is adjusted to 9, and then heated at 50° C. with stirring for 60 minutes to obtain the resin coating raw material liquid.

[0086] (2) Preparation of anti-caking protective agent: Based on 100 parts by weight of the anti-caking protective agent, 70 parts by weight of cyclohexane oil are heated to 60° C., and then 5 parts by weight of paraffin wax, 16.5 parts by weight of Iranian slack wax, 5 parts by weight of pentaerythritol rosin and 1 part by weight of polyisobutylene elastomer dissolved in 2.5 parts by weight of carbon tetrachloride are added to the above cyclohexane oil, and the above mixture is stirred and heated at 60° C. until the materials are completely dissolved, thereby obtaining the anti-caking protective agent.

[0087] (3) Preparation of a bacterial inorganic fertilizer with a slow-release function: 95.5 parts by weight of compound fertilizer 18-18-18 is used as the inner core of the inorganic fertilizer particles, and 1 part by weight of sulfuric acid solution with a pH of 2, 2 parts by weight of resin coating raw material liquid, 0.5 parts by weight of Bacillus amyloliquefaciens, and 1 part by weight of an anti-caking protective agent are sprayed on the surface in sequence to obtain a bacterial inorganic fertilizer with a slow-release function.

[0088] Example 2

[0089] (1) Preparation of resin coating raw material liquid: Based on 100 parts by weight of the resin coating raw material liquid, 41 parts by weight of formaldehyde solution (industrial formaldehyde solution, concentration of 37%) and 5 parts by weight of butyraldehyde are mixed evenly, and then 10 parts by weight of polyvinyl alcohol, 4 parts by weight of phenol and 40 parts by weight of urea are added. After the above materials are fully stirred, the pH of the liquid is adjusted to 9.5, and then heated at 70°C with stirring for 90 minutes to obtain the resin coating raw material liquid.

[0090] (2) Preparation of anti-caking protective agent: Based on 100 parts by weight of the anti-caking protective agent, 60 parts by weight of industrial soybean oil are heated to 75° C., and then 28 parts by weight of Iranian slack wax, 5 parts by weight of pentaerythritol rosin and 2 parts by weight of polyisobutylene elastomer dissolved in 5 parts by weight of carbon tetrachloride are added to the above cycloparaffin oil. The above mixture is stirred and heated at 75° C. until the materials are completely dissolved, thereby obtaining the anti-caking protective agent.

[0091] (3) Preparation of a bacterial inorganic fertilizer with a slow-release function: 97.6 parts by weight of compound fertilizer 26-10-12 is used as the inner core of the inorganic fertilizer particles, and 0.5 parts by weight of sulfuric acid solution with a pH of 2, 1 part by weight of a resin coating raw material liquid, 0.3 parts by weight of Bacillus subtilis, and 0.6 parts by weight of an anti-caking protective agent are sprayed on the surface of the particles in sequence to obtain a bacterial inorganic fertilizer with a slow-release function.

[0092] Example 3

[0093] (1) Preparation of resin coating raw material liquid: Based on 100 parts by weight of the resin coating raw material liquid, 48 parts by weight of formaldehyde solution (industrial formaldehyde solution, concentration of 37%) and 7 parts by weight of butyraldehyde are mixed evenly, and then 10 parts by weight of polyvinyl alcohol, 5 parts by weight of phenol and 30 parts by weight of urea are added. After the above materials are fully stirred, the pH value of the liquid is adjusted to 9, and then heated at 70°C with stirring for 30 minutes to obtain the resin coating raw material liquid.

[0094] (2) Preparation of anti-caking protective agent: Based on 100 parts by weight of the anti-caking protective agent, 65 parts by weight of cyclohexane oil are heated to 70° C., and then 2 parts by weight of paraffin wax, 26 parts by weight of Iranian slack wax, 4 parts by weight of pentaerythritol rosin and 0.5 parts by weight of polyisobutylene elastomer dissolved in 2.5 parts by weight of carbon tetrachloride are added to the above cyclohexane oil. The above mixture is stirred and heated at 70° C. until the materials are completely dissolved, thereby obtaining the anti-caking protective agent.

[0095] (3) Preparation of a bacterial inorganic fertilizer with a slow-release function: 98.5 parts by weight of compound fertilizer 19-4-25 is used as the inner core of the inorganic fertilizer particles, and 0.2 parts by weight of sulfuric acid solution with a pH of 2, 0.6 parts by weight of resin coating raw material liquid, 0.2 parts by weight of nitrogen-fixing bacteria, and 0.5 parts by weight of an anti-caking protective agent are sprayed on the surface in sequence to obtain a bacterial inorganic fertilizer with a slow-release function.

[0096] Example 4

[0097] (1) Preparation of resin coating raw material liquid: Based on 100 parts by weight of the resin coating raw material liquid, 20 parts by weight of formaldehyde solution (industrial formaldehyde solution, concentration of 37%) and 20 parts by weight of butyraldehyde are mixed evenly, and then 10 parts by weight of polyvinyl alcohol, 40 parts by weight of phenol and 10 parts by weight of urea are added. The above materials are fully stirred, the pH of the liquid is adjusted to 9, and then heated at 50° C. with stirring for 60 minutes to obtain the resin coating raw material liquid.

[0098] (2) Preparation of anti-caking protective agent: Based on 100 parts by weight of the anti-caking protective agent, 20 parts by weight of cyclohexane oil and 60 parts by weight of industrial soybean oil are mixed and heated to 50° C. Then, 3 parts by weight of paraffin wax, 10 parts by weight of Iranian slack wax, 4 parts by weight of pentaerythritol rosin and 0.5 parts by weight of polyisobutylene elastomer dissolved in 2.5 parts by weight of carbon tetrachloride are added to the above cyclohexane oil, and the above mixture is stirred and heated at 50° C. until the materials are completely dissolved, thereby obtaining the anti-caking protective agent.

[0099] (3) Preparation of a bacterial inorganic fertilizer with a sustained-release function: 96.6 parts by weight of 64% diammonium phosphate is used as the inner core of the inorganic fertilizer particles, and 0.7 parts by weight of sulfuric acid solution with a pH of 2, 1.5 parts by weight of a resin coating raw material liquid, 0.4 parts by weight of Bacillus amyloliquefaciens, and 0.8 parts by weight of an anti-caking protective agent are sprayed on the surface in sequence to obtain a bacterial inorganic fertilizer with a sustained-release function.

[0100] Example 5

[0101] (1) Preparation of resin coating raw material liquid: Based on 100 parts by weight of the resin coating raw material liquid, 45 parts by weight of formaldehyde solution (industrial formaldehyde solution, concentration of 37%) and 5 parts by weight of butyraldehyde are mixed evenly, and then 10 parts by weight of polyvinyl alcohol and 40 parts by weight of phenol are added. The above materials are fully stirred, and the pH value of the liquid is adjusted to 10. Then, the liquid is heated at 70°C with stirring for 90 minutes to obtain the resin coating raw material liquid.

[0102] (2) Preparation of anti-caking protective agent: Based on 100 parts of anti-caking protective agent, 28 parts by weight of cyclohexane oil and 30 parts by weight of industrial soybean oil are heated to 80°C, and then 5 parts by weight of paraffin wax, 30 parts by weight of Iranian slack wax and 2 parts by weight of polyisobutylene elastomer dissolved in 5 parts by weight of carbon tetrachloride are added to the above cyclohexane oil. The above mixture is stirred and heated at 80°C until the materials are completely dissolved, thereby obtaining the anti-caking protective agent.

[0103] (3) Preparation of a bacterial inorganic fertilizer with a sustained-release function: 95.9 parts by weight of 55% monoammonium phosphate is used as the inner core of the inorganic fertilizer particles, and 0.8 parts by weight of sulfuric acid solution with a pH of 2, 1.8 parts by weight of the resin coating raw material liquid prepared in this embodiment, 0.5 parts by weight of Bacillus subtilis, and 1 part by weight of an anti-caking protective agent are sprayed on the surface of the particles in sequence to obtain a bacterial inorganic fertilizer with a sustained-release function.

[0104] Example 6

[0105] (1) Preparation of resin coating raw material liquid: Based on 100 parts of resin coating raw material liquid, 40 parts by weight of formaldehyde solution (industrial formaldehyde solution, concentration of 37%) and 7 parts by weight of butyraldehyde are mixed evenly, and then 13 parts by weight of polyvinyl alcohol, 10 parts by weight of phenol and 30 parts by weight of urea are added. The above materials are fully stirred, and the pH value of the liquid is adjusted to 9. Then, the liquid is heated at 60° C. with stirring for 60 minutes to obtain the resin coating raw material liquid.

[0106] (2) Preparation of anti-caking protective agent: Based on 100 parts of the anti-caking protective agent, 55 parts by weight of cyclohexane oil and 20 parts by weight of industrial soybean oil are heated to 50° C., and then 5 parts by weight of paraffin wax, 10 parts by weight of Iranian slack wax, 3 parts by weight of pentaerythritol rosin and 2 parts by weight of polyisobutylene elastomer dissolved in 5 parts by weight of carbon tetrachloride are added to the above cyclohexane oil. The above mixture is stirred and heated at 50° C. until the materials are completely dissolved, thereby obtaining the anti-caking protective agent.

[0107] (3) Preparation of a bacterial inorganic fertilizer with a slow-release function: 99 parts by weight of 60% granular potassium chloride is used as the inner core of the inorganic fertilizer particles, and 0.2 parts by weight of sulfuric acid solution with a pH of 2, 0.5 parts by weight of a resin coating raw material liquid, 0.1 parts by weight of nitrogen-fixing bacteria, and 0.2 parts by weight of an anti-caking protective agent are sprayed on the surface of the particles in sequence to obtain a bacterial inorganic fertilizer with a slow-release function.

[0108] Example 7

[0109] (1) Preparation of resin coating raw material liquid: Based on 100 parts of resin coating raw material liquid, 40 parts by weight of formaldehyde solution (industrial formaldehyde solution, concentration of 37%) and 10 parts by weight of butyraldehyde are mixed evenly, and then 30 parts by weight of polyvinyl alcohol and 20 parts by weight of urea are added. The above materials are fully stirred, and the pH value of the liquid is adjusted to 8. Then, the liquid is heated with stirring at 30°C for 60 minutes to obtain the resin coating raw material liquid.

[0110] (2) Preparation of anti-caking protective agent: Based on 100 parts of the anti-caking protective agent, 45 parts by weight of cyclohexane oil and 30 parts by weight of industrial soybean oil are mixed and heated to 50° C. Then, 5 parts by weight of paraffin wax, 10 parts by weight of Iranian slack wax, 3 parts by weight of pentaerythritol rosin and 2 parts by weight of polyisobutylene elastomer dissolved in 5 parts by weight of carbon tetrachloride are added to the above cyclohexane oil. The above mixture is stirred and heated at 50° C. until the materials are completely dissolved, thereby obtaining the anti-caking protective agent.

[0111] (3) Preparation of a bacterial inorganic fertilizer with a sustained-release function: 97.2 parts by weight of 54% granular potassium sulfate is used as the inner core of the inorganic fertilizer particles, and 0.6 parts by weight of sulfuric acid solution with a pH of 2, 1.3 parts by weight of the resin coating raw material liquid prepared in this example, 0.3 parts by weight of Bacillus subtilis, and 0.6 parts by weight of the anti-caking protective agent prepared in this example are sprayed on the surface of the particles in sequence to obtain a bacterial inorganic fertilizer with a sustained-release function.

[0112] Comparative Example 1

[0113] Compared with Example 3, this comparative example uses compound fertilizer anti-caking oil instead of acid solution and resin coating raw material liquid to prepare bacteria-containing inorganic fertilizer. The specific method is as follows: 98.5 parts by weight of compound fertilizer 19-4-25 is used as the inner core of the inorganic fertilizer particles, and 0.8 parts by weight of compound fertilizer anti-caking oil, 0.2 parts by weight of nitrogen-fixing bacteria, and 0.5 parts by weight of the anti-caking protective agent prepared in Example 4 are sprayed on the surface of the particles in sequence to obtain the bacteria-containing inorganic fertilizer of this comparative example.

[0114] Comparative Example 2

[0115] Compared with Example 2, this comparative example uses commercially available compound fertilizer anti-caking oil (Hubei Fubang Technology Co., Ltd., brand: Fu Ruixue) instead of anti-caking protective agent to prepare slow-release bacteria-containing inorganic fertilizer. The specific method is as follows: 97.6 parts by weight of compound fertilizer 26-10-12 is used as the inner core of the inorganic fertilizer particles, and 0.5 parts by weight of sulfuric acid solution with a pH of 2, 1 part by weight of the resin coating raw material liquid prepared in Example 2, 0.3 parts by weight of Bacillus subtilis, and 0.6 parts by weight of compound fertilizer anti-caking oil are sprayed on the surface in sequence according to the preparation method of the bacteria-containing inorganic fertilizer with slow-release function of the present invention, so as to obtain the preparation of bacteria-containing inorganic fertilizer with slow-release function in this comparative example.

[0116] Comparative Example 3

[0117] Compared with Example 6, this comparative example reduces the spraying amount of sulfuric acid solution with a pH of 2 in step (3) to 0.1 parts by weight.

[0118] Comparative Example 4

[0119] Compared with Example 1, the difference of this comparative example is that the spraying amount of the sulfuric acid solution with a pH value of 2 is 1.1 parts by weight.

[0120] Furthermore, the inventors investigated the initial live bacteria count, initial live bacteria retention rate and nutrient release period of the bacterial inorganic fertilizers prepared in Examples 1 to 7 and Comparative Examples 1 to 4, as well as the live bacteria retention rate and nutrient release period after storage at room temperature for 24 months.

[0121] The live bacteria retention rate (%) is the number of live bacteria in the sample to be tested (bacterial inorganic fertilizer) / theoretical number of live bacteria × 100%.

[0122] The nutrient release period is tested according to the method in GB / T 23348-2009 Slow-release Fertilizer.

[0123] The results are shown in Table 1.

[0124] Table 1: Performance test results of the bacterial inorganic fertilizers obtained in Examples 1 to 7 and Comparative Examples 1 to 4

[0125]

[0126]

[0127] The results show that:

[0128] 1. High live bacteria retention rate means that more microbial agents can have a positive effect on soil and crops immediately after application, thereby improving the overall efficiency of fertilizers. The initial live bacteria retention rate of the bacterial inorganic fertilizers of Examples 1 to 7 exceeds 98%, which shows that the method of the present invention can effectively add powdered bacterial agents to inorganic fertilizer particles, and the obtained bacterial inorganic fertilizers have high bacterial agent activity and high overall fertilizer efficiency.

[0129] 2. Compared with Comparative Example 1, in Examples 1 to 7, the surface of the inorganic fertilizer particle core is sprayed with the bacterial inorganic fertilizer of the resin coating raw material liquid of the present invention, and the nutrient release period is significantly improved, and the sustained release function is achieved. The spraying amount of the resin coating raw material liquid is positively correlated with the nutrient release period (i.e., sustained release period) of the bacterial inorganic fertilizer, and the sustained release period of the inorganic fertilizer can be adjusted by adjusting the coating amount of the resin coating layer.

[0130] 3. Compared with Comparative Example 2, in Example 2, the bacterial inorganic fertilizer with the anti-caking protective agent of the present invention sprayed on the surface of the inorganic fertilizer particle core has a live bacteria retention rate of 87.5% after storage for 24 months, far exceeding Comparative Example 2 (20.1%). The bacterial inorganic fertilizers obtained in Examples 1 to 7 have a high live bacteria retention rate after storage for 24 months. Therefore, the bacterial inorganic fertilizer product with slow-release function of the present invention has a long shelf life and high overall fertilizer efficiency.

[0131] Further, according to the results of Examples 1 to 7, when the spraying amount of the anti-caking protective agent is in the range of 0.2% to 1%, there is no obvious difference between the initial live bacteria retention rate of the obtained bacterial inorganic fertilizer and the live bacteria retention rate after storage for 24 months.

[0132] According to the results of Example 2 and Comparative Examples 3 to 4, the spraying amount of sulfuric acid solution with a pH of 2 has a great influence on the live bacteria retention rate and the nutrient release period, and the preferred spraying amount is 0.2% to 1%. When the spraying amount of sulfuric acid solution with a pH of 2 is too low, its effect on the catalytic curing of the resin coating liquid to form a resin coating layer is reduced, resulting in a decrease in the sustained release performance (slow release period) of the fertilizer; when the spraying amount of sulfuric acid solution with a pH of 2 is too high, its process of catalytic curing of the resin coating liquid to form a resin coating layer has a great influence on the activity of the bacterial agent, and the initial live bacteria retention rate in the fertilizer and the live bacteria retention rate after long-term storage are significantly reduced.

[0133] In summary, the present invention provides a fertilizer containing a biological agent with slow-release performance, high live bacteria retention rate and long shelf life, and a preparation method thereof, which is suitable for wide promotion in agricultural production, has broad application prospects, and provides a reference for the development of slow-release biological fertilizers.

[0134] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A fertilizer containing a biological agent, characterized in that: The invention comprises, from the inside to the outside, inorganic fertilizer particles, a resin coating layer, a bacterial agent coating layer, and an anti-caking protective layer; wherein the resin coating layer is formed by reacting a raw material liquid of the resin coating layer under the catalysis of an acid solution; Based on 100 parts by weight of the fertilizer containing biological microbial agents, the inner core of the inorganic fertilizer particles has an amount of 95.5 to 99 parts by weight, the acid solution has an amount of 0.2 to 1 part by weight, the resin coating layer has an amount of 0.5 to 2 parts by weight, the microbial agent coating layer has an amount of 0.1 to 0.5 parts by weight, and the anti-caking protective layer has an amount of 0.2 to 1 part by weight.

2. The fertilizer according to claim 1, characterized in that The pH value of the acid solution is 1 to 3, preferably 2; Optionally, the acid solution is a sulfuric acid solution.

3. The fertilizer according to claim 1, characterized in that The resin coating layer raw material liquid includes: formaldehyde solution, butyraldehyde, polyvinyl alcohol; and also includes: phenol and / or urea; Optionally, the resin coating layer raw material liquid comprises: 10 to 70 parts by weight of formaldehyde solution, 2.5 to 30 parts by weight of butyraldehyde, 5 to 45 parts by weight of polyvinyl alcohol; and 2 to 60 parts by weight of phenol and / or 5 to 50 parts by weight of urea; wherein the total weight of the formaldehyde solution, butyraldehyde, polyvinyl alcohol and phenol and / or urea is 100 parts by weight, and the concentration of the formaldehyde solution is 37%; Further, the resin coating layer raw material liquid comprises: 20 to 48 parts by weight of formaldehyde solution, 5 to 20 parts by weight of butyraldehyde, 10 to 30 parts by weight of polyvinyl alcohol; and 4 to 40 parts by weight of phenol and / or 10 to 40 parts by weight of urea; wherein the total weight of the formaldehyde solution, butyraldehyde, polyvinyl alcohol and phenol and / or urea is 100, and the concentration of the formaldehyde solution is 37%; Optionally, the pH value of the resin coating layer raw material solution is 8 to 10, preferably 9 to 10; Optionally, the resin coating layer raw material liquid comprises: 41 parts by weight of formaldehyde solution, 7 parts by weight of butyraldehyde, 10 parts by weight of polyvinyl alcohol; and 21 parts by weight of phenol, 21 parts by weight of urea, the concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 9.0; Optionally, the resin coating layer raw material solution comprises: 41 parts by weight of formaldehyde solution, 5 parts by weight of butyraldehyde, 10 parts by weight of polyvinyl alcohol; and 4 parts by weight of phenol, 40 parts by weight of urea, the concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 9.5; Optionally, the resin coating layer raw material solution comprises: 48 parts by weight of formaldehyde solution, 7 parts by weight of butyraldehyde, 10 parts by weight of polyvinyl alcohol; and 5 parts by weight of phenol, 30 parts by weight of urea, the concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 9.0; Optionally, the resin coating layer raw material solution comprises: 20 parts by weight of formaldehyde solution, 20 parts by weight of butyraldehyde, 10 parts by weight of polyvinyl alcohol; and 40 parts by weight of phenol, 10 parts by weight of urea, the concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 9.0; Optionally, the resin coating layer raw material solution comprises: 40 parts by weight of formaldehyde solution, 7 parts by weight of butyraldehyde, 13 parts by weight of polyvinyl alcohol; and 10 parts by weight of phenol, 30 parts by weight of urea, the concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 9.0; Optionally, the resin coating layer raw material solution comprises: 45 parts by weight of formaldehyde solution, 5 parts by weight of butyraldehyde, 10 parts by weight of polyvinyl alcohol; and 40 parts by weight of phenol, the concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 10.0; Optionally, the resin coating layer comprises: 40 parts by weight of formaldehyde solution, 10 parts by weight of butyraldehyde, 30 parts by weight of polyvinyl alcohol; and 20 parts by weight of urea, the concentration of the formaldehyde solution is 37%, and the pH of the resin coating layer is 8.

0.

4. The fertilizer according to claim 1, characterized in that The raw material liquid for preparing the anti-caking protective layer comprises: naphthenic oil and / or industrial soybean oil, paraffin and / or Iranian slack wax, carbon tetrachloride, and polyisobutylene; Optionally, the anti-caking protective layer raw material liquid comprises: 10 to 80 parts by weight of cyclohexane oil and / or 10 to 70 parts by weight of industrial soybean oil, 1 to 7.5 parts by weight of paraffin wax and / or 5 to 45 parts by weight of Iranian slack wax, 1.25 to 7.5 parts by weight of carbon tetrachloride, and 0.25 to 3.75 parts by weight of polyisobutylene; wherein the total weight of the cyclohexane oil and / or industrial soybean oil, paraffin wax and / or Iranian slack wax, carbon tetrachloride, and polyisobutylene is 100 parts by weight; Further, the anti-caking protective layer raw material liquid comprises: 20 to 70 parts by weight of cyclohexane oil and / or 20 to 60 parts by weight of industrial soybean oil, 2 to 5 parts by weight of paraffin wax and / or 10 to 30 parts by weight of Iranian slack wax, 2.5 to 5 parts by weight of carbon tetrachloride, and 0.5 to 2.0 parts by weight of polyisobutylene; wherein the total weight of the cyclohexane oil and / or industrial soybean oil, paraffin wax and / or Iranian slack wax, carbon tetrachloride, and polyisobutylene is 100 parts by weight; Furthermore, the anti-caking protective layer raw material solution also includes: pentaerythritol rosin; Furthermore, the anti-caking protective layer raw material liquid also includes: 1.5 to 7.5 parts by weight of pentaerythritol rosin; wherein the total weight of the cyclohexane oil and / or industrial soybean oil, paraffin and / or Iranian slack wax, carbon tetrachloride, polyisobutylene and pentaerythritol rosin is 100 parts by weight; and the pentaerythritol rosin is preferably 3 to 5 parts by weight.

5. The fertilizer according to claim 1, characterized in that The bacterial agent coating layer includes, but is not limited to: at least one of Bacillus amyloliquefaciens, Bacillus subtilis, Bacillus megaterium, Bacillus lateralis, Bacillus pumilus, Trichoderma harzianum, Streptomyces avermectin, nitrogen-fixing bacteria, yeast, lactic acid bacteria, Trichoderma, photosynthetic bacteria or actinomycetes; Optionally, the inorganic fertilizer particles are selected from, including but not limited to: at least one of NPK compound fertilizer particles, ammonium phosphate fertilizer particles, potash fertilizer particles, and nitrogen fertilizer particles; Optionally, the inorganic fertilizer granules are selected from, including but not limited to: at least one of compound fertilizer 18-18-18 granules, compound fertilizer 26-10-12 granules, compound fertilizer 19-4-25 granules, monoammonium phosphate fertilizer granules, diammonium phosphate fertilizer granules, potassium chloride fertilizer granules, potassium sulfate fertilizer granules, single potash fertilizer granules, compound potash fertilizer granules, and urea granules.

6. The method for preparing the fertilizer containing biological microbial agent according to any one of claims 1 to 5, characterized in that: The method comprises: Performing a first coating treatment on the surface of the inorganic fertilizer particles by applying the resin coating layer raw material liquid to form the resin coating layer; Wherein, the first coating treatment is carried out under the catalysis of the acid solution.

7. The method according to claim 6, characterized in that The first coating treatment comprises: first contacting the surface of the inorganic fertilizer particles with the acid solution, and then coating the surface with the resin coating layer raw material solution.

8. The method according to claim 6, characterized in that The method for preparing the resin coating raw material liquid comprises: Performing a first mixing process on the formaldehyde solution and the butyraldehyde to obtain a first mixed solution; Performing a second mixing treatment on the first mixed solution and the polyvinyl alcohol, phenol and / or urea to obtain a second mixed solution; The second mixed solution is subjected to a pH adjustment treatment to obtain the resin coating raw material solution; the pH adjustment treatment comprises: adjusting the pH value of the second mixed solution to 8-10; Optionally, the pH adjustment treatment further comprises: adjusting the pH value of the second mixed solution to 8-10, and then stirring; the stirring treatment time is 30-120 minutes, preferably 60 minutes; the temperature is 30-70°C, preferably 50°C.

9. The method according to claim 6, characterized in that The method further comprises: Performing a second coating treatment on the surface of the resin coating layer to form the bacterial agent coating layer; Performing a third coating treatment on the surface of the bacterial agent coating layer with the anti-caking protective layer raw material liquid to form the anti-caking protective layer; Optionally, the method for preparing the anti-stacking protective layer raw material solution comprises: performing a third mixing process on the polyisobutylene and the carbon tetrachloride to obtain a third mixed liquid; The naphthenic oil and / or industrial soybean oil, paraffin wax and / or Iranian slack wax and the third mixed liquid are subjected to a fourth mixing treatment to obtain the anti-caking protective layer raw material liquid; Optionally, the fourth mixing treatment comprises: stirring and heating the naphthenic oil and / or industrial soybean oil with the paraffin wax and / or Iranian slack wax and the third mixed liquid, and the heating temperature is 50-80°C.

10. A fertilizer containing biological agents obtained by the method according to any one of claims 6 to 9.

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