Composite bio-organic fertilizer and preparation method thereof

Abstract

The invention discloses a composite bio-organic fertilizer and a preparation method thereof, and relates to the technical field of organic fertilizer and microbial fertilizer manufacturing. The composite biological organic fertilizer is prepared from the following raw materials in parts by mass: 30-60 parts of an organic material, 10-30 parts of an inorganic fertilizer, 0.1-5 parts of a functional strain mixture, 5-15 parts of humic acid, 5-10 parts of diatomite, 1-5 parts of a trace element additive and 2.5 parts of an antioxidant stabilizer. The special antioxidant stabilizer is adopted, so that the oxidation phenomenon of the fertilizer in the storage and transportation processes is effectively inhibited, the nutrient loss is reduced, the contents of total nitrogen, total phosphorus, total potassium and organic matters can still be kept at a relatively high level after storage, the validity period of the fertilizer is prolonged, and the fertilizer efficiency is relatively lasting. Due to the reasonable proportion of the humic acid and the diatomite, the microenvironment of the soil is optimized, the water and fertilizer retention capacity of the soil is enhanced, the loss of the fertilizer is reduced, and the utilization rate of the fertilizer is increased.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic fertilizer and microbial fertilizer manufacturing, in particular to a compound biological organic fertilizer and a preparation method thereof. BACKGROUND

[0002] In modern agricultural production, fertilizers play an irreplaceable role in increasing yield and income of crops. Although traditional chemical fertilizers can quickly provide nutrients, long-term use will lead to soil compaction, decline in soil fertility, and pollution of the ecological environment. Biological organic fertilizers are concerned for their advantages of improving soil structure, enhancing soil fertility, promoting crop growth, and being environmentally friendly.

[0003] However, there are some deficiencies in the biological organic fertilizers on the market. On the one hand, the nutrient content is relatively low, which is difficult to meet the high yield demand of crops. On the other hand, the activity and stability of functional bacteria in the fertilizer are not ideal, and the activity is easily lost during storage and transportation, affecting the fertilizer efficiency. In addition, some organic materials are easily oxidized during the fermentation process, not only causing the loss of nutrient components, but also possibly producing harmful substances, which has a negative impact on crop growth, limiting the large-scale application and promotion of biological organic fertilizers.

[0004] With the increasing demand for the quality of agricultural products and environmental protection, there is an urgent need for a compound biological organic fertilizer with comprehensive nutrients, long-lasting fertilizer efficiency, high activity and good stability of functional bacteria, and effective avoidance of oxidation. This has prompted relevant scientific researchers and enterprises to invest a lot of effort in researching and developing new compound biological organic fertilizers and their preparation processes to make up for the shortcomings of existing products and promote the sustainable development of agriculture. SUMMARY

[0005] The purpose of the present application is to solve the problems of low nutrient content, poor activity of bacteria, and easy oxidation of biological organic fertilizers in the prior art, and to provide a compound biological organic fertilizer with comprehensive nutrients, long-lasting fertilizer efficiency, high activity and good stability of functional bacteria, and effective avoidance of oxidation, and a preparation method thereof, to meet the demand for high-quality fertilizers in modern agriculture.

[0006] To achieve the above purpose, the technical scheme adopted by the present application is as follows: a compound biological organic fertilizer is made from the following raw materials by mass fraction: organic material 30-60 parts, inorganic fertilizer 10-30 parts, functional bacteria mixture 0.1-5 parts, humic acid 5-15 parts, diatomite 5-10 parts, trace element additive 1-5 parts, and antioxidant stabilizer 2.5 parts. The antioxidant stabilizer is a compound represented by formula 1: Formula 1; R1 is methyl, amino, cyano, or ethyl.

[0007] Furthermore, the organic material is one or a combination of any of the following: livestock and poultry manure, crop straw, edible mushroom residue, kitchen waste organic fertilizer, biogas residue, and urban sludge organic fertilizer, and has been fully decomposed.

[0008] Furthermore, the inorganic fertilizer is composed of nitrogen, potassium, and phosphorus sources; The mass ratio of the nitrogen source, potassium source and phosphorus source is 10-30: 10-30: 5-25; The nitrogen source can be any one of urea, ammonium sulfate, ammonium chloride, monoammonium phosphate, diammonium phosphate, or potassium nitrate. The phosphorus source can be any one of superphosphate or calcium magnesium phosphate fertilizer; The potassium source can be any one of potassium sulfate, potassium chloride, or potassium nitrate.

[0009] Furthermore, the functional microbial mixture contains at least two of the following viable bacteria: Bacillus licheniformis, Bacillus subtilis, Paenibacillus mucilaginosus, Streptomyces microflavus, Trichoderma harzianum, and Saccharomyces spp.

[0010] Furthermore, the total concentration of viable bacteria in the functional bacterial strain mixture is 1×10⁻⁶. 8 CFU / g or higher.

[0011] Furthermore, the trace element additive is one or a combination of several of the following: ferrous sulfate, zinc sulfate, manganese sulfate, copper sulfate, borax, and ammonium molybdate.

[0012] Furthermore, the antioxidant stabilizer is any one of the compounds shown in the following structures:

[0013]

[0014] A method for preparing a compound bio-organic fertilizer includes the following steps: 1) The organic material is crushed and the moisture content is adjusted to 65-75%. Microbial fermentation agent is added for composting and fermentation. During the fermentation process, the temperature is controlled at 65-70℃. The pile is turned regularly to provide oxygen. The fermentation time is not less than 15 days to obtain fully decomposed organic fertilizer. 2) Add the decomposed organic fertilizer, inorganic fertilizer, humic acid, diatomaceous earth, and trace element additives into the mixing equipment in proportion, and mix them thoroughly to obtain a mixture. 3) Add an appropriate amount of water and the antioxidant stabilizer to the mixture, and granulate it using a granulation device to form particles with a particle size of 2-5 mm; 4) The functional microbial mixture is evenly sprayed or adsorbed onto the surface of the particles, dried at low temperature, and the material temperature is controlled not to exceed 45°C, so that the moisture content of the particles is reduced to below 10%. After cooling to room temperature, a compound biological organic fertilizer is obtained.

[0015] Furthermore, the fermentation agent is at least one of actinomycetes and yeasts.

[0016] Furthermore, the inoculation method for the functional bacterial mixture in step 4) is as follows: using a liquid containing functional bacterial solution or powder adsorbed by a solid carrier of bacterial strains, and uniformly spraying or mixing it when the particle temperature is below 40°C.

[0017] The antioxidant stabilizer described in this invention is mainly used to prevent oxidation reactions in organic materials during fermentation, storage, and transportation, thereby avoiding nutrient loss, the generation of harmful substances, and ensuring the activity stability of functional microorganisms. Its structure includes a polyaryl structure, hydroxyl groups, and cyano groups. The polyaryl structure, through its π-electron conjugation system, can stably capture free radicals. Specifically, the delocalized electrons of the aromatic ring can accept unpaired electrons from free radicals, forming a relatively stable resonance structure, thus interrupting the free radical chain reaction. In fertilizer preparation, this mechanism effectively prevents lipid peroxidation or carbohydrate degradation during the composting process of organic materials, reducing the generation of harmful substances such as volatile organic acids. The hydroxyl group acts as a "hydrogen donor," directly quenching free radicals. In an oxidizing environment, the hydroxyl group converts highly reactive free radicals into inert products by providing hydrogen atoms. The hydrogen-donating capacity of the hydroxyl group is affected by the electronic effect of the aromatic ring: the polyaryl structure enhances the acidity of the phenolic hydroxyl group, increasing its reactivity. In fertilizers, this helps protect components such as humic acid and diatomaceous earth, preventing humic acid degradation or trace element inactivation caused by oxidation. The cyano group, acting as an "electron-attracting group," enhances the antioxidant efficiency of compounds. The polyaryl structure, hydroxyl group, and cyano group together constitute a "multi-mechanism antioxidant system." The polyaryl group captures free radicals, the hydroxyl group provides hydrogen atoms to quench free radicals, and the cyano group enhances electron transfer and metal passivation; these three elements synergistically significantly improve antioxidant efficiency.

[0018] The compound bio-organic fertilizer of this invention is composed of organic materials, inorganic fertilizers, a mixture of functional microbial strains, humic acid, diatomaceous earth, trace element additives, and antioxidant stabilizers in a specific ratio. The components are dynamically integrated through the preparation process to form a four-dimensional system of "nutrient supply - structural improvement - microbial protection - oxidation inhibition." 1) In nutrient supply, organic materials provide organic matter and slow-release nutrients, improving soil aggregate structure; inorganic fertilizers provide readily available nitrogen, phosphorus, and potassium. The two work synergistically during the mixing stage: the microporous structure of decomposed organic materials adsorbs inorganic nutrients to reduce loss, while inorganic fertilizers promote the mineralization and release of organic materials, forming a "fast-acting + long-lasting" nutrient system, significantly improving the total amount and persistence of nutrients.

[0019] 2) The structural improvement layer relies on humic acid and diatomaceous earth: Humic acid acts as a natural chelating agent to optimize the soil microenvironment, while diatomaceous earth provides a porous carrier for adsorbing water and fertilizer. The two are mixed in step 2 to create a buffered microenvironment for subsequent colonization of microorganisms and enhance the soil's water and fertilizer retention capacity.

[0020] 3) The microbial protective layer is achieved through the synergistic effect of functional microbial mixture, humic acid and diatomaceous earth: In step 4, the functional microbial mixture is sprayed onto the surface of the particles at low temperature in liquid or powder form (particle temperature ≤40℃). The protective layer formed by the premixed humic acid and diatomaceous earth wraps the microbial strain to reduce environmental stress, and the slow-release nutrients of diatomaceous earth support the metabolism of the microbial strain, ensuring that the microbial strain maintains high activity during storage and transportation.

[0021] 4) The oxidation inhibition layer is synergistically constructed from antioxidant stabilizers and trace element additives: the antioxidant stabilizer is the compound shown in Formula 1, which is added to the mixture with water during granulation in step 3 to form a protective film. Its multi-mechanism antioxidant system—the multi-aryl structure captures free radicals through π-electron conjugation, the hydroxyl group quenches free radicals as a hydrogen donor, and the cyano group enhances metal passivation—preferentially blocks the oxidation chain reaction, protecting the easily oxidized trace element additives and humic acid, while diatomaceous earth forms a double barrier with them through physical adsorption.

[0022] Compared with the prior art, the beneficial effects of the present invention are: 1. Stable nutrients and long-lasting fertilizer effect: The use of specific antioxidant stabilizers effectively inhibits the oxidation of fertilizers during storage and transportation, reduces nutrient loss, and ensures that the content of total nitrogen, total phosphorus, total potassium and organic matter can still maintain a high level after storage, thus extending the fertilizer's shelf life and making the fertilizer effect last longer.

[0023] 2. High activity and good stability of the strains: The inoculation method and preparation process of the functional strain mixture ensure that the strains can maintain high activity during storage and transportation, so that they can quickly take effect after application and promote soil improvement and crop growth.

[0024] 3. Improved soil structure and enhanced fertilizer retention capacity: The reasonable ratio of humic acid and diatomaceous earth optimizes the soil microenvironment, enhances the soil's water and fertilizer retention capacity, reduces fertilizer loss, and improves fertilizer utilization. Attached Figure Description

[0025] Figure 1 The antioxidant stabilizer 1 described in this invention1 HNMR image. Detailed Implementation

[0026] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Preparation Example 1 Synthesis of Antioxidant Stabilizer 1:

[0028] A1: Under a nitrogen atmosphere, 20.00 g of raw material 1, 33.54 g of raw material 2, 65.26 g of potassium phosphate trihydrate, 0.15 g of pyridine-2-carboxylic acid, 1.17 g of CuI and 400 g of DMSO were added to the reaction system, and the mixture was heated to 85 °C and reacted for 16 h. After cooling, the reaction mixture was extracted with ammonia solution and methyl tert-butyl ether, the organic phase was retained, evaporated to dryness, purified by silica gel column chromatography, and the solution was evaporated to dryness using a mixed solution of petroleum ether and ethyl acetate as the eluent to obtain 29.34 g of intermediate 1.

[0029] M / Z[M+H] of intermediate 1 + =311.

[0030] A2: Under a nitrogen atmosphere, 29.34 g of intermediate 1, 29.40 g of raw material 3, 0.95 g of tri-tert-butylphosphine, 0.33 g of palladium on carbon, 26.12 g of anhydrous potassium carbonate, and 350 g of toluene were added to the reaction system. The mixture was heated to 120 °C and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered using diatomaceous earth. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness. The mixture was then subjected to silica gel column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent. After evaporation, 36.54 g of antioxidant stabilizer 1 was obtained.

[0031] M / Z [M+H] of antioxidant stabilizer 1 + =486; Antioxidant stabilizer 1 1 HNMR Chloroform-d, Figure 1: δ7.29(s,7H),6.83-6.67(m,4H),6.50(m,1H),4.95(t,2H),4.49(d,1H),4.34(t,1H),4.11(dd,1H),4.03(s,1H),3.93 -3.80(m,2H),3.63(dd,1H),3.38(q,2H),2.95(m,1H),2.87(s,3H),2.70(m,1H),2.17(m,1H),1.14(t,3H),1.00(d,3H).

[0032] Preparation Examples 2-4 In Preparation Examples 2-4, antioxidant stabilizer 2-antioxidant 4 were synthesized sequentially, following the same synthesis method as in Preparation Example 1, except that raw material 1 was replaced, while the rest remained the same. Specific details regarding the structure of raw material 1, the structures of antioxidant stabilizer 2-antioxidant 4, and the M / Z[M+H] ratio are provided. + The data is shown in Table 1.

[0033] Table 1. Structures of raw material 1, antioxidant stabilizer 2-antioxidant stabilizer 4, and M / Z [M+H] involved in preparation examples 2-4. + data.

[0034]

[0035] Example 1 Preparation of a compound bio-organic fertilizer: 1. Raw material mass ratio: Organic materials: 45 parts (a combination of fully decomposed livestock and poultry manure and crop straw in a mass ratio of 2:1, wherein the livestock and poultry manure is selected from chicken manure and the crop straw is corn straw). Inorganic fertilizer: 30 parts (a combination of urea, calcium phosphate and potassium sulfate in a mass ratio of 10:10:10). Functional microbial mixture: 3 portions (containing a live bacterial combination of Bacillus licheniformis and Bacillus subtilis, with a total live bacterial concentration of 2 × 10⁻⁶). 8 CFU / g); Humic acid: 10 parts; Diatomaceous earth: 8 parts; Trace element additive: 3 parts (a combination of ferrous sulfate, zinc sulfate and borax in a mass ratio of 1:1:1). Antioxidant stabilizer: 2.5 parts (using antioxidant stabilizer 1 prepared in Synthesis Example 1).

[0036] 2. Preparation method: S1. Crush 45 portions of organic material (a combination of livestock and poultry manure and crop straw) to a particle size ≤2mm, adjust the moisture content to 70%, and add a microbial fermentation agent (in this example, actinomycete inoculant is used, with a live bacteria concentration of 1×10⁻⁶). 7 The composting process involves fermenting the compost with CFU / g. During fermentation, the temperature is controlled at 70℃±2℃, and the compost is turned regularly to provide oxygen (once every 24 hours). The fermentation time lasts for 18 days to ensure full decomposition and obtain fully decomposed organic fertilizer. S2. Add the decomposed organic fertilizer, 20 parts inorganic fertilizer, 10 parts humic acid, 8 parts diatomaceous earth and 3 parts trace element additives into a twin-shaft mixer in proportion, mix at room temperature for 30 minutes at a speed of 40 rpm to obtain a mixture. S3. Add an appropriate amount of water to the mixture (adjust to a total moisture content of 15%), and add 2.5 parts of antioxidant stabilizer 1. Granulate the mixture using a twin-screw granulator, controlling the granulation pressure to 0.5 MPa, to form uniform particles with a particle size of 3 mm ± 0.5 mm.

[0037] S4. Prepare a bacterial solution from the mixture of 3 functional bacterial strains (bacterial solution concentration of 1×10⁻⁶). 9 (CFU / mL). When the temperature of the granules obtained in S3 drops to 35°C (below 40°C), the bacterial solution is evenly sprayed onto the surface of the granules using a spraying device. Subsequently, the granules are dried in a low-temperature drying oven, with the material temperature controlled not to exceed 45°C for 2 hours, reducing the moisture content of the granules to 8%. After cooling to room temperature, a compound bio-organic fertilizer of this embodiment is obtained.

[0038] Examples 2-4 The preparation of a compound bio-organic fertilizer is carried out by referring to the preparation method of Example 1, except that the antioxidant stabilizer is replaced in sequence with antioxidant stabilizer 2-antioxidant 4 synthesized in Preparation Examples 2-4, and the rest is the same as in Example 1.

[0039] Comparative Example 1 The preparation of a compound bio-organic fertilizer is carried out according to the preparation method of Example 1, except that the antioxidant stabilizer is replaced with comparative compound 1, and the rest is the same as in Example 1.

[0040] Comparative compound 1: .

[0041] Comparative Example 2 The preparation of a compound bio-organic fertilizer is carried out according to the preparation method of Example 1, except that the antioxidant stabilizer is replaced with antioxidant 1010, and the rest is the same as in Example 1.

[0042] Antioxidant 1010 is a common antioxidant in the fertilizer industry, and its structure is as follows:

[0043] Comparative Example 3 The preparation of a compound bio-organic fertilizer is the same as in Example 1, except that the antioxidant stabilizer is not added.

[0044] Comparative Example 4 The preparation of a compound bio-organic fertilizer is carried out by referring to the preparation method of Example 1, except that the mass fraction of humic acid is replaced with 1 part, and the rest is the same as in Example 1.

[0045] Comparative Example 5 The preparation of a compound bio-organic fertilizer is carried out by referring to the preparation method of Example 1, except that the mass fraction of diatomaceous earth is replaced with 15 parts, and the rest remains the same as in Example 1.

[0046] Performance testing: The compound bio-organic fertilizer prepared in the examples and comparative examples was stored in the dark for 30 days under natural summer conditions with an average temperature of 33-37℃, without any intervention. The changes in total nitrogen (as N), total phosphorus (as P2O5), total potassium (as K2O), and organic matter content in the compound bio-organic fertilizer prepared in the examples and comparative examples were tested according to GB / T 22923-2008 standard. The detection standard for organic matter content was NY / T 304-1995, and the test results are shown in Table 2.

[0047] Table 2. Performance test data of a compound bio-organic fertilizer prepared in the examples and comparative examples.

[0048]

[0049] After 30 days of storage, the nutrient indicators (including total nitrogen, total phosphorus, and total potassium) and organic matter content of all fertilizer samples showed a downward trend, indicating that oxidation and degradation were prevalent during storage. However, significant differences existed between different groups: the decrease in the examples was relatively small, showing better stability, thanks to the effective inhibition of nutrient loss by the added specific antioxidant stabilizer; while in the comparative proportions, especially those without antioxidant stabilizers, using alternative antioxidants, or adjusting the proportions of key components (such as humic acid or diatomaceous earth), the decrease was more pronounced, with the group completely lacking antioxidant stabilizers showing the most severe degradation. Overall, the antioxidant stabilizer of this invention significantly improves the storage durability of fertilizers and reduces nutrient loss, while optimized component ratios and antioxidant selection play a crucial role in maintaining fertilizer efficacy.

[0050] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A composite bio-organic fertilizer, characterized in that, It is made from the following raw materials by mass fraction: organic material: 30-60 parts, inorganic fertilizer: 10-30 parts, functional bacteria mixture: 0.1-5 parts, humic acid: 5-15 parts, diatomite: 5-10 parts, trace element additive: 1-5 parts, and anti-oxidation stabilizer 2.5 parts. The anti-oxidation stabilizer is a compound shown in formula 1: Formula 1; The R1 is methyl, amino, cyano, ethyl.

2. The compound bio-organic fertilizer according to claim 1, characterized in that, The organic material is one or a combination of any of the following: livestock and poultry manure, crop straw, edible fungus residue, kitchen waste organic fertilizer, biogas residue, and municipal sludge organic fertilizer, and is subjected to sufficient composting treatment.

3. The compound bio-organic fertilizer according to claim 1, characterized in that, The inorganic fertilizer is composed of a nitrogen source, a potassium source, and a phosphorus source. The mass fraction ratio of the nitrogen source, the potassium source, and the phosphorus source is: 10-30:10-30:5-25. The nitrogen source is any one of urea, ammonium sulfate, ammonium chloride, monoammonium phosphate, diammonium phosphate, and potassium nitrate. The phosphorus source is any one of superphosphate of lime and calcium-magnesium phosphate fertilizer. The potassium source is any one of potassium sulfate, potassium chloride, and potassium nitrate. One or a combination of any of urea, ammonium sulfate, ammonium chloride, monoammonium phosphate, diammonium phosphate, superphosphate of lime, calcium-magnesium phosphate fertilizer, potassium sulfate, potassium chloride, and potassium nitrate.

4. The compound bio-organic fertilizer according to claim 1, characterized in that, The functional bacteria mixture contains at least two of the following effective live bacteria: Bacillus licheniformis, Bacillus subtilis, Paenibacillus mucilaginosus, Streptomyces microflavus, Trichoderma harzianum, and Saccharomyces spp.

5. The compound bio-organic fertilizer as claimed in claim 1, characterized in that, The total concentration of viable bacteria in the functional bacterial mixture is 1 x 10 8 CFU / g or more.

6. The compound bio-organic fertilizer as claimed in claim 1, characterized in that, The trace element additive is one or a combination of any of ferrous sulfate, zinc sulfate, manganese sulfate, copper sulfate, borax, and ammonium molybdate.

7. The compound bio-organic fertilizer as claimed in claim 1, characterized in that, The anti-oxidation stabilizer is a compound shown in any of the following structures: ； 。 8. The preparation method of the composite bio-organic fertilizer according to any one of claims 1-7, characterized in that, It comprises the following steps: 1) The organic material is subjected to crushing treatment, the moisture content is adjusted to 65-75%, a bacteria fermentation agent is added for composting fermentation, the temperature is controlled at 65-70℃ during the fermentation process, the pile is turned regularly for oxygen supply, and the fermentation time is not less than 15 days, so that a fully composted organic fertilizer is obtained; 2) The composted organic fertilizer, the inorganic fertilizer, the humic acid, the diatomite, and the trace element additive are put into a mixing device in proportion, and are fully mixed uniformly, so that a mixture is obtained; 3) An appropriate amount of water and the anti-oxidation stabilizer are added to the mixture, granulation equipment is used for granulation, and particles with a particle size of 2-5 mm are formed; 4) The functional bacteria mixture is uniformly sprayed or adsorbed on the surface of the particles, low-temperature drying is performed, the material temperature is controlled to be not higher than 45℃, the moisture content of the particles is reduced to below 10%, and after cooling to room temperature, a composite biological organic fertilizer is obtained.

9. The preparation method of the compound bio-organic fertilizer according to claim 8, characterized in that, The bacteria fermentation agent is at least one of an actinomycete and a yeast.

10. The preparation method of the compound bio-organic fertilizer according to claim 8, characterized in that, The inoculation of the functional bacterial mixture in step 4) is carried out by spraying or mixing the liquid containing the functional bacteria or the powder after adsorption on a bacterial solid carrier, at a granule temperature of less than 40°C.

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