Preparation method of composite bio-organic fertilizer for rapidly improving soil fertility

Abstract

The application discloses a preparation method of a composite biological organic fertilizer for rapidly improving soil fertility, which adopts pig manure, soybean meal, biogas residue and phosphorus tailings as raw materials of the biological organic fertilizer, compounding macroporous strong adsorption type zeolite and green compound sterilizing agents to remove heavy metals, harmful bacteria and insect eggs in the raw material components, effectively reducing the negative effects of the heavy metals, harmful bacteria and insect eggs on soil structure and beneficial microorganisms, so that the biological organic fertilizer can effectively and rapidly enhance the soil fertility, meanwhile, the biological organic fertilizer is subjected to coating treatment, the phenomenon of surface burning caused by excessively high fertility in the early stage of the biological organic fertilizer is avoided, and the loss of fertility caused by the rainwater leaching and volatilization of the nutrients released too early is avoided, the utilization rate of the biological organic fertilizer is improved, the application frequency of the organic fertilizer is reduced, and the labor intensity of workers is reduced.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of organic fertilizer, in particular to a preparation method of a composite biological organic fertilizer for rapidly improving soil fertility. BACKGROUND

[0002] The biological organic fertilizer is a kind of fertilizer with the effects of microbial fertilizer and organic fertilizer, which is composed of specific functional microorganisms and organic materials mainly derived from animal and plant residues (such as livestock and poultry manure, crop straw, etc.) and subjected to harmless treatment and composting.

[0003] Phosphorus tailings contain essential plant nutrients such as phosphorus, calcium and magnesium, which can be used as a component of biological organic fertilizer. It can not only solve the environmental pollution problem caused by the storage of phosphorus tailings, but also promote the secondary utilization of the abandoned mineral resources. However, the heavy metals in the phosphorus tailings are not completely treated and will be enriched in plants after being added to the biological organic fertilizer. Livestock and poultry manure is also one of the main components of biological organic fertilizer. However, due to the large amount of trace elements such as copper, iron, zinc, manganese, cobalt, selenium and iodine added in livestock and poultry feed, many trace elements that are not absorbed by livestock and poultry accumulate in livestock and poultry manure, resulting in excessive content of trace elements in livestock and poultry manure, especially the toxic elements such as copper, arsenic and mercury. The excessive content of these elements not only causes soil pollution, but also leads to excessive content of heavy metals in vegetables and fruits. In addition, heavy metals can inhibit the activity of soil microorganisms and damage the soil structure, thereby affecting the fertility of the soil. Therefore, it is necessary to control the content of heavy metals in the biological organic fertilizer.

[0004] Livestock and poultry manure not only contains a large amount of trace elements, but also contains a large amount of harmful bacteria and insect eggs, which may cause plant diseases and insect pests, pollute the environment and threaten human health. Plant diseases and insect pests can also cause plant malnutrition and destroy the balance of beneficial microorganisms, thereby affecting the fertility of the soil. At present, when livestock and poultry manure is used to prepare organic fertilizer, the temperature generated by fermentation is generally used to kill harmful bacteria and insect eggs. However, the highest temperature generated by fermentation is only 70-80℃, which cannot completely kill harmful bacteria and insect eggs. SUMMARY

[0005] The purpose of the present application is to provide a preparation method of a composite biological organic fertilizer for rapidly improving soil fertility.

[0006] In order to solve the above technical problems, the technical scheme adopted by the present application comprises the following steps:

[0007] The preparation method of the composite biological organic fertilizer for rapidly improving soil fertility comprises the following specific steps:

[0008] (1) 30-40 parts by mass of pig manure, 10-15 parts by mass of soybean meal, 10-15 parts by mass of biogas residue, 8-10 parts by mass of phosphorus tailings, 6-8 parts by mass of macroporous strong adsorption type zeolite and 1-2 parts by mass of green compound sterilizing agent are mixed, water is added to control the moisture content at 55-60%, and then stirring is carried out at a speed of 200-300 r / min for 200-220 min to obtain a mixture A;

[0009] (2) 3-4 parts by mass of fermentation agent is added to the mixture A and stirred uniformly, the initial fermentation temperature is controlled at 20℃, and the fermentation is started, and the pile is turned over once a day, the fermentation temperature is controlled at 60-70℃, and the fermentation is completed after 10 days;

[0010] (3) After the fermentation is completed, the mixture A is transferred into a pulverizer and pulverized at a speed of 400-500 r / min for 60-70 min to obtain a mixture B;

[0011] (4) The mixture B is granulated using a granulator and then coated in a fluidized bed containing a slow-release coating agent, and then dried to obtain a composite bio-organic fertilizer.

[0012] Further, the pig manure in step (1) is dehydrated pig manure, and the water content is 40-50%.

[0013] Further, the preparation steps of the macroporous strong adsorption type zeolite in step (1) are as follows:

[0014] The zeolite is crushed and ground and then screened to obtain zeolite particles with a particle size of 60-80 meshes, then water is added and stirred and washed until no impurities are present, the zeolite particles are then immersed in a saturated carbonic acid solution, soaked for 3-4 h, then washed with water and dried, and then the zeolite particles are transferred into a tube furnace, heated to 500-520℃ at a speed of 8-10℃ / min, and sintered for 4-5 h, and then naturally cooled to room temperature to obtain a preliminary modified zeolite.

[0015] The preliminary modified zeolite is immersed in a 0.6-0.7% by mass of distearyl dimethyl ammonium chloride solution, stirred at a speed of 200-220 r / min at room temperature for 260-270 min, then washed with water until neutral, and then dried to obtain the product.

[0016] Further, the green compound sterilizing agent in step (2) is specifically as follows:

[0017] D-limonene, maltotriose stearic acid monoester, soybean phospholipid and water are mixed in a mass ratio of 3-5:0.2-0.3:0.3-0.4:20, then sheared using a shearing machine at a speed of 12000-13000 rmp for 1-2 min, and then homogenized at room temperature and 80 MPa to obtain the product.

[0018] Further, the fermentation agent in step (2) is specifically prepared as follows: the Aspergillus niger seed liquid, Bacillus subtilis seed liquid and Bacillus megaterium seed liquid are uniformly mixed at a volume ratio of 1:1:1.

[0019] Further, the slow-release coating agent in step (4) is specifically prepared as follows:

[0020] A first mixed solution is prepared by dissolving 3-4 parts by mass of polycaprolactone in 10-12 parts by volume of toluene, and a second mixed solution is prepared by dissolving 0.6-0.8 parts by mass of hydrophobic chelated lignin in 10-12 parts by volume of ethylene glycol; then the first mixed solution and the second mixed solution are mixed at a volume ratio of 1:1, and 1.4-1.6 parts by mass of biochar with a particle size of 60-80 mesh is added and stirred uniformly to obtain the slow-release coating agent.

[0021] The hydrophobic chelated lignin is specifically prepared as follows:

[0022] The lignin is crushed, and 40-80 mesh particles are washed with water for 3 times to obtain lignin particles; then 2-4 parts by mass of the lignin particles are immersed in a sodium hydroxide solution with a pH of 8-8.5 and stirred until dissolved; then 2-3% of the volume of the sodium hydroxide solution is added to 30% by mass of hydrogen peroxide solution, the system is heated to 50-55℃, and stirred for 2-3h; after the reaction is completed, solid A is obtained by filtration; solid A is immersed in a 5-10% by mass sodium hydroxide solution, and then 1-2 parts of N,N-dimethylbenzylamine and 25-30 parts by mass of (2,3-epoxypropyl) ethyl bis(2-hydroxyethyl) ammonium chloride are added; then the system is heated to 60-70℃ and stirred for 1.5-2.5h; after the reaction is completed, the solid is filtered and washed to obtain solid B; solid B is added to an alkaline solution with a pH of 9, 2-4 parts by mass of sodium sulfite is added, the system is heated to 85-90℃, and stirred for 2-3h; then the system is cooled to room temperature, the pH is adjusted to 2-2.5, the solid is filtered and washed to neutral, and dried to obtain the hydrophobic chelated lignin.

[0023] Further, the particle size of the granules after granulation in step (4) is 4-6mm.

[0024] The present application has the following advantages:

[0025] (1) The present application uses pig manure, soybean meal, biogas residue and phosphorus tailings as raw materials of bio-organic fertilizer, which can not only provide rich nutrient elements, improve soil structure, enhance soil fertility and increase crop yield, but also has significant environmental protection benefits, which is helpful to realize the sustainable development of agriculture, and the large-pore strong adsorption zeolite and green compound sterilizing agent are compounded to remove heavy metals, harmful bacteria and insect eggs in the raw material components, which effectively reduces the negative effects of heavy metals, harmful bacteria and insect eggs on soil structure and beneficial microorganisms, so that the bio-organic fertilizer can effectively and quickly enhance the fertility of the soil, and the bio-organic fertilizer is coated to avoid the occurrence of burning phenomenon caused by excessive release of early bio-organic fertilizer, and to avoid the loss of fertility caused by the leaching and volatilization of the nutrients released too early, which can enhance the soil fertility and improve the utilization rate of bio-organic fertilizer, reduce the application frequency of organic fertilizer and reduce the labor intensity of the workers;

[0026] (2) The present application uses zeolite to remove heavy metals in organic fertilizer, because the natural zeolite pore is easy to block, and the degree of mutual communication is poor, the adsorption capacity cannot meet the requirements, and the effect of removing heavy metal ions is not good, therefore the zeolite is modified by washing, soaking with weak acid solution and sintering process, which can effectively increase the pore size of zeolite, and also remove various impurities contained therein, facilitating the subsequent quaternary ammonium salt treatment process, the di-stearyl dimethyl ammonium chloride used in the present application has stronger emulsifying property and dispersibility compared with the conventional quaternary ammonium salt such as dodecyl trimethyl ammonium chloride, which can make the zeolite uniformly dispersed in the organic fertilizer, and it does not have foaming property, so that the zeolite modification is not uniform during modification, thereby affecting the modification effect;

[0027] (3) The present application uses sterilizing agent to kill harmful bacteria and insect eggs in bio-organic fertilizer, D-limonene is an excellent bactericide and insecticide, which can effectively kill harmful bacteria and insect eggs in poultry manure, but due to its hydrophobicity, it cannot be effectively mixed with bio-organic fertilizer, thereby affecting its killing effect, therefore, the emulsifying agent is compounded, compared with other emulsifying agents such as tween 20 and maltotriose stearic acid monoester, which has excellent emulsifying property and also has the effect of inhibiting harmful bacteria and promoting the growth of beneficial bacteria, which can play a synergistic effect with D-limonene, and the stability of maltotriose stearic acid monoester is stronger and not easy to deteriorate, and it is also easy to biodegrade, which will not harm the soil and environment;

[0028] (4) Because the oxidation stability of D-limonene is poor, and the preparation process of bio-organic fertilizer requires a long time, it is necessary to compound an antioxidant for D-limonene to enhance its oxidation resistance. Soybean phospholipid has strong emulsifying, wetting and dispersing effects, and can have a synergistic effect with maltotriose stearate, further enhancing the uniform distribution of D-limonene in bio-organic fertilizer. Soybean phospholipid itself also has the effects of promoting root growth and improving soil structure, and can enhance the efficacy of bio-organic fertilizer;

[0029] (5) The present application releases the fertility of bio-organic fertilizer by coating treatment. The slow-release coating agent prepared in the present application comprises lignin, polycaprolactone and biochar. Lignin has the functions of slow release, chelation, adhesion and dispersion, can adsorb and store nutrients, and can also make bio-organic fertilizer uniformly dispersed in the soil. After decomposition, humus can be formed, which has the effect of improving soil structure. Polycaprolactone has good biocompatibility and does not affect plant growth, and can be completely decomposed into water and carbon dioxide. Biochar has the effects of improving the physical, chemical and biological properties of soil, and can also be used as a carrier for nutrients and heavy metal fixation, and has a synergistic effect with zeolite and lignin.

[0030] (6) Although lignin has a synergistic effect on soil and bio-organic fertilizer, when it is used as a coating material, its hydrophilicity will make the coating material unstable, so that the coating material is more prone to decomposition and rupture, resulting in poor slow-release effect of bio-organic fertilizer. Therefore, the lignin is modified in the present application. Compared with other modifiers such as propylene oxide and (2,3-epoxypropyl) ethyl bis(2-hydroxyethyl) ammonium chloride, the modified lignin has lower hydrophilicity and higher dispersibility, making the components of the slow-release coating agent more uniform. In addition, the modified lignin also has enhanced chelation performance, which can not only adsorb heavy metals in the soil, but also adsorb trace elements in the soil, so that the trace elements are not easily washed away by rainwater, achieving the effect of fertilizer preservation.

[0031] The Aspergillus niger strain used in the present application is CMCC(F)98003, purchased from Beijing Sanji Technology Co., Ltd. The Bacillus subtilis strain used is BU1814, purchased from Guangzhou Zhen Microbial Technology Co., Ltd. The Bacillus megaterium strain used is QMB1551, purchased from Hangzhou Baosai Biological Technology Co., Ltd. DETAILED DESCRIPTION

[0032] The present application will be further described in detail below in conjunction with examples. Example 1

[0033] The zeolite is broken and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes. Then, the zeolite particles are washed with water until no impurities are present. The zeolite particles are then immersed in a saturated carbonic acid solution, soaked for 3.5 hours, and then washed with water and dried. After drying, the zeolite particles are transferred into a tube furnace, heated to 510℃ at a rate of 9℃ / min, and sintered for 4.5 hours. After natural cooling to room temperature, a preliminary modified zeolite is obtained.

[0034] The preliminary modified zeolite is immersed in a 0.65% mass fraction of distearyl dimethyl ammonium chloride solution, stirred at a speed of 210 r / min at room temperature for 265 min, and then washed with water until neutral. After drying, a macroporous strong adsorption type zeolite is obtained.

[0035] D-limonene, maltotriose stearic acid monoester, soybean phospholipid, and water are mixed in a mass ratio of 4:0.25:0.35:20, and then sheared using a shearing machine at a speed of 12500 rmp for 1.5 min. Then, homogenization is performed at room temperature and 80 MPa to obtain a green compound sterilizing agent.

[0036] The black mold seed liquid, the bacillus subtilis seed liquid, and the bacillus megaterium seed liquid are uniformly mixed in a volume ratio of 1:1:1 to obtain a fermentation agent.

[0037] (1) 35 parts of pig manure, 12 parts of soybean meal, 13 parts of biogas residue, 9 parts of phosphorus tailings, 7 parts of macroporous strong adsorption type zeolite, and 1.5 parts of green compound sterilizing agent are mixed, water is added to control the moisture content to 57%, and then stirred at a speed of 250 r / min for 210 min to obtain a mixture A;

[0038] (2) 3.5 parts of fermentation agent are added to the mixture A and stirred uniformly. The initial fermentation temperature is controlled at 20℃. After the fermentation starts, the pile is turned over once a day, and the fermentation temperature is controlled at 65℃. After 10 days of fermentation, the fermentation is completed.

[0039] (3) After the fermentation is completed, the mixture A is transferred into a pulverizer and pulverized at a speed of 450 r / min for 65 min to obtain a mixture B. Example 2

[0040] The zeolite is broken and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes. Then, the zeolite particles are washed with water until no impurities are present. The zeolite particles are then immersed in a saturated carbonic acid solution, soaked for 3 hours, and then washed with water and dried. After drying, the zeolite particles are transferred into a tube furnace, heated to 520℃ at a rate of 8℃ / min, and sintered for 4 hours. After natural cooling to room temperature, a preliminary modified zeolite is obtained.

[0041] The pre-modified zeolite was immersed in a 0.6% (w / w) solution of distearyldimethylammonium chloride and stirred at 200 r / min for 270 min at room temperature. It was then washed with water until neutral and dried to obtain a large-pore, strongly adsorbing zeolite.

[0042] D-limonene, maltotriose stearate monoester, soybean lecithin and water were mixed in a mass ratio of 3:0.3:0.3:20 and sheared at 12000 rpm for 2 minutes using a shearing machine. The mixture was then homogenized at room temperature and 80 MPa to obtain the green compound sterilizing agent.

[0043] The fermentation agent is obtained by uniformly mixing Aspergillus niger seed liquid, Bacillus subtilis seed liquid and Bacillus megaterium seed liquid in a volume ratio of 1:1:1.

[0044] (1) Mix 30 parts by weight of pig manure, 15 parts by weight of soybean meal, 10 parts by weight of biogas residue, 10 parts by weight of phosphate tailings, 8 parts by weight of large-pore strong adsorption zeolite and 1 part by weight of green compound sterilizing agent, add water to control the moisture content at 55%, and stir at 200 r / min for 220 min to obtain mixture A.

[0045] (2) Add 3 parts by weight of fermentation agent to mixture A and stir evenly. Control the initial fermentation temperature at 20℃. After the fermentation starts, turn the pile once a day and control the fermentation temperature at 60℃. Fermentation will be completed after 10 days.

[0046] (3) After fermentation, the mixture A is transferred to a pulverizer and pulverized at a speed of 400 r / min for 70 min to obtain mixture B. Example 3

[0047] Zeolite was crushed, ground, and screened to obtain zeolite particles with a particle size of 60-80 mesh. Then, water was added and stirred and washed until no impurities were found. The zeolite particles were then immersed in a saturated carbonic acid solution for 4 hours. After that, they were washed with water and dried. After drying, the zeolite particles were transferred to a tube furnace and heated to 500°C at a rate of 10°C / min. The temperature was then held for sintering for 5 hours. After naturally cooling to room temperature, the preliminarily modified zeolite was obtained.

[0048] The pre-modified zeolite was immersed in a 0.7% (w / w) solution of distearyldimethylammonium chloride and stirred at 220 r / min for 260 min at room temperature. It was then washed with water until neutral and dried to obtain a large-pore, strongly adsorbing zeolite.

[0049] D-limonene, maltotriose stearate monoester, soybean lecithin and water were mixed in a mass ratio of 5:0.2:0.4:20 and sheared at 13000 rpm for 1 min using a shearing machine. The mixture was then homogenized at room temperature and 80 MPa to obtain the green compound sterilizing agent.

[0050] The fermentation agent is obtained by uniformly mixing Aspergillus niger seed liquid, Bacillus subtilis seed liquid and Bacillus megaterium seed liquid in a volume ratio of 1:1:1.

[0051] (1) Mix 40 parts by weight of pig manure, 10 parts by weight of soybean meal, 15 parts by weight of biogas residue, 8 parts by weight of phosphorus tailings, 6 parts by weight of large-pore strong adsorption zeolite and 2 parts by weight of green compound sterilizing agent, add water to control the moisture content to 60%, and stir at 300 r / min for 200 min to obtain mixture A.

[0052] (2) Add 4 parts by weight of fermentation agent to mixture A and stir evenly. Control the initial fermentation temperature at 20℃. After the fermentation starts, turn the pile once a day and control the fermentation temperature at 70℃. Fermentation will be completed after 10 days.

[0053] (3) After fermentation, the mixture A is transferred to a pulverizer and pulverized at a speed of 500 r / min for 60 min to obtain mixture B. Example 4

[0054] Zeolite was crushed, ground, and screened to obtain zeolite particles with a particle size of 60-80 mesh. Then, water was added and the particles were stirred and washed until no impurities were found. The zeolite particles were then immersed in a saturated carbonic acid solution for 3.5 hours. After that, they were washed with water and dried. After drying, the zeolite particles were transferred to a tube furnace and heated to 510°C at a rate of 9°C / min. The temperature was then held for sintering for 4.5 hours. After naturally cooling to room temperature, the preliminarily modified zeolite was obtained.

[0055] The pre-modified zeolite was immersed in a 0.65% (w / w) solution of dodecyltrimethylammonium chloride and stirred at 210 r / min for 265 min at room temperature. It was then washed with water until neutral and dried to obtain a large-pore, strongly adsorbing zeolite.

[0056] The rest is the same as in Example 1. Example 5

[0057] Zeolite was crushed, ground, and screened to obtain zeolite particles with a particle size of 60-80 mesh. Then, water was added and stirred and washed until no impurities were found. The zeolite particles were then immersed in a saturated carbonic acid solution for 1 hour. After washing with water and drying, the zeolite particles were transferred to a tube furnace and heated to 510°C at a rate of 9°C / min. The temperature was held for 4.5 hours and then naturally cooled to room temperature to obtain the preliminarily modified zeolite.

[0058] The pre-modified zeolite was immersed in a 0.65% (w / w) distearyldimethylammonium chloride solution and stirred at 210 r / min for 265 min at room temperature. It was then washed with water until neutral and dried to obtain a large-pore, strongly adsorbing zeolite.

[0059] The rest is the same as in Example 1. Example 6

[0060] Zeolite was crushed, ground, and screened to obtain zeolite particles with a particle size of 60-80 mesh. Then, water was added and the particles were stirred and washed until no impurities were found. The zeolite particles were then immersed in a saturated carbonic acid solution for 3.5 hours. After that, they were washed with water and dried. After drying, the zeolite particles were transferred to a tube furnace and heated to 650°C at a rate of 9°C / min. The temperature was then held for sintering for 4.5 hours. After naturally cooling to room temperature, the preliminarily modified zeolite was obtained.

[0061] The pre-modified zeolite was immersed in a 0.65% (w / w) solution of distearyldimethylammonium chloride, heated to 38°C and stirred at 210 r / min for 265 min. It was then washed with water until neutral and dried to obtain a large-pore, strongly adsorbing zeolite.

[0062] The rest is the same as in Example 1. Example 7

[0063] Zeolite was crushed, ground, and screened to obtain zeolite particles with a particle size of 60-80 mesh. Then, water was added and the particles were stirred and washed until no impurities were found. The zeolite particles were then immersed in a saturated carbonic acid solution for 3.5 hours. After that, they were washed with water and dried. After drying, the zeolite particles were transferred to a tube furnace and heated to 510°C at a rate of 9°C / min. The temperature was then held for sintering for 4.5 hours. After naturally cooling to room temperature, the preliminarily modified zeolite was obtained.

[0064] The pre-modified zeolite was immersed in a 1.2% (w / w) solution of distearyldimethylammonium chloride and stirred at 210 r / min for 265 min at room temperature. It was then washed with water until neutral and dried to obtain a large-pore, strongly adsorbing zeolite.

[0065] The rest is the same as in Example 1. Example 8

[0066] Zeolite was crushed, ground, and screened to obtain zeolite particles with a particle size of 60-80 mesh. Then, water was added and the particles were stirred and washed until no impurities were found. The zeolite particles were then immersed in a saturated carbonic acid solution for 3.5 hours. After that, they were washed with water and dried. After drying, the zeolite particles were transferred to a tube furnace and heated to 510°C at a rate of 9°C / min. The temperature was then held for sintering for 4.5 hours. After naturally cooling to room temperature, the preliminarily modified zeolite was obtained.

[0067] The pre-modified zeolite was immersed in a 0.65% (w / w) solution of distearyldimethylammonium chloride, heated to 38°C and stirred at 210 r / min for 265 min. It was then washed with water until neutral and dried to obtain a large-pore, strongly adsorbing zeolite.

[0068] The rest is the same as in Example 1. Example 9

[0069] Zeolite was crushed, ground, and screened to obtain zeolite particles with a particle size of 60-80 mesh. Then, water was added and the particles were stirred and washed until no impurities were found. The zeolite particles were then immersed in a saturated carbonic acid solution for 3.5 hours. After that, they were washed with water and dried. After drying, the zeolite particles were transferred to a tube furnace and heated to 510°C at a rate of 9°C / min. The temperature was then held for sintering for 4.5 hours. After naturally cooling to room temperature, the preliminarily modified zeolite was obtained.

[0070] The pre-modified zeolite was immersed in a 0.65% (w / w) solution of distearyldimethylammonium chloride and stirred at 400 r / min for 265 min at room temperature. It was then washed with water until neutral and dried to obtain a large-pore, strongly adsorbing zeolite.

[0071] The rest is the same as in Example 1.

[0072] Experiment 1:

[0073] The total arsenic, total cadmium, and total lead content in mixtures B prepared in Examples 1 to 9 were determined according to the NY / T1978 standard. The specific data are shown in Table 1.

[0074]

[0075] As can be seen from the data in Table 1, Examples 1-3 showed the best heavy metal removal effect, while Example 7 showed no difference in heavy metal removal effect from Example 1, indicating that the concentration of the distearyldimethylammonium chloride solution in Example 1 was already the optimal concentration. Example 4 showed the worst heavy metal removal effect, possibly because dodecyltrimethylammonium chloride has weaker emulsifying and dispersing properties than distearyldimethylammonium chloride, resulting in poorer dispersibility of zeolite in organic fertilizer. Furthermore, its foaming properties caused uneven modification of the zeolite during modification due to bubbles, thus affecting the modification effect. The reason why Example 5 showed a worse heavy metal removal effect than Example 1 might be that the zeolite was soaked in saturated carbonate... The short time in the solution resulted in incomplete removal of alkalinity, affecting subsequent modification reactions. The reason why the heavy metal removal effect in Example 6 was not as good as in Example 1 may be that the calcination temperature of the zeolite was too high, which destroyed part of the zeolite's framework structure, thus affecting its adsorption effect. The reason why the heavy metal removal effect in Example 8 was not as good as in Example 1 may be that the increased temperature affected the ion exchange and adsorption between distearyldimethylammonium chloride and zeolite, thus affecting the heavy metal adsorption of zeolite. The reason why the heavy metal removal effect in Example 9 was not as good as in Example 1 may be that the stirring rate was too fast, which affected the ion exchange and adsorption between distearyldimethylammonium chloride and zeolite, thus affecting the heavy metal adsorption of zeolite. Example 10

[0076] D-limonene, Tween 20, soybean lecithin and water were mixed in a mass ratio of 3:0.3:0.3:20 and sheared at 12000 rpm for 2 minutes using a shearing machine. The mixture was then homogenized at room temperature and 80 MPa to obtain the green compound sterilizing agent.

[0077] The rest is the same as in Example 2. Example 11

[0078] D-limonene, maltotriose stearate monoester, butylated hydroxytoluene and water were mixed in a mass ratio of 3:0.3:0.3:20 and sheared at 12000 rpm for 2 minutes using a shearing machine. The mixture was then homogenized at room temperature and 80 MPa to obtain the green compound sterilizing agent.

[0079] The rest is the same as in Example 2. Example 12

[0080] D-limonene, maltotriose stearate monoester, soybean lecithin and water were mixed in a mass ratio of 3:0.8:0.3:20 and sheared at 12000 rpm for 2 minutes using a shearing machine. The mixture was then homogenized at room temperature and 80 MPa to obtain the green compound sterilizing agent.

[0081] The rest is the same as in Example 2. Example 13

[0082] The green compound sterilizing agent is obtained by mixing D-limonene, maltotriose stearate monoester, soybean lecithin and water in a mass ratio of 3:0.3:0.3:20.

[0083] The rest is the same as in Example 2.

[0084] Experiment 2:

[0085] The fecal coliform and ascarid egg mortality rates in mixtures B prepared in Examples 1-3 and Examples 10-13 were determined according to GB / T19524.1-2004 and GB / T19524.2-2004 standards. The specific data are shown in Table 2.

[0086]

[0087] Table 2 shows that Examples 1-3 exhibited the best killing effect against harmful bacteria and insect eggs. The reason Example 10 had the worst killing effect might be that replacing maltodextrin stearate with Tween 20 resulted in Tween 20 not inhibiting harmful bacteria and promoting beneficial bacteria growth, lacking synergistic effects with D-limonene, and having poorer stability, leading to auto-oxidation. Light and temperature also catalyze this auto-oxidation reaction, causing it to deteriorate and become ineffective. The reason Example 11's data was inferior to Example 2 might be that replacing soybean lecithin with butylated hydroxytoluene (BHT) resulted in BHT lacking emulsifying, wetting, and dispersing properties, and failing to effectively kill harmful bacteria and insect eggs. Maltotriose stearate monoester does not have a synergistic effect, affecting the overall stability and uniformity of the sterilizing agent, thus impacting the sterilization effect. The reason why the data in Example 12 is not as good as that in Example 2 may be that the dosage of maltotriose stearate monoester is too high, which disrupts the balance of the sterilizing agent, causing stratification and unevenness, thereby affecting the sterilization effect. The reason why the data in Example 13 is not as good as that in Example 2 may be that shearing and homogenization treatment was not performed, resulting in a larger particle size of D-limonene in the sterilizing agent and a smaller dispersion degree compared to Example 2. The uniformity after adding bio-organic fertilizer is also lower, reducing the sterilization and insect egg killing effect.

[0088] The mixture B obtained in Example 1 was used in Examples 14 to 22 to continue the preparation of compound bio-organic fertilizer. Example 14

[0089] After pulverizing lignin, 40-80 mesh particles were washed three times with water to obtain lignin granules. Then, 3 parts by weight of the lignin granules were immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved. Then, 2.5% by volume of 30% by weight hydrogen peroxide solution was added to the sodium hydroxide solution. The system was heated to 52°C and stirred for 2.5 hours. After the reaction was completed, the solid A was obtained by filtration. Solid A was immersed in an 8% by weight sodium hydroxide solution. Then, 1.5 parts by weight of N,N-dimethylbenzylamine and 27 parts by weight of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride were added. The system was then heated to 65°C and stirred for 2 hours. After the reaction was completed, the solid was filtered and washed to obtain solid B. Solid B was added to an alkaline solution with a pH of 9 and 3 parts by weight of sodium sulfite was added. The system was heated to 88°C and stirred for 2.5 hours. Then, the system was cooled to room temperature, the pH was adjusted to 2.3, the solid was filtered and washed until neutral, and dried to obtain hydrophobic chelated lignin.

[0090] Dissolve 3.5 parts by weight of polycaprolactone in 11 parts by volume of toluene to obtain a first mixed solution. Dissolve 0.7 parts by weight of hydrophobic chelated lignin in 11 parts by volume of ethylene diether to obtain a second mixed solution. Then mix the first and second mixed solutions in a 1:1 volume ratio and add 1.5 parts by weight of biochar with a particle size of 60-80 mesh. Stir until homogeneous to obtain a slow-release coating agent.

[0091] After granulating mixture B using a granulator, it is placed in a fluidized bed containing a slow-release coating agent for coating. After coating, it is dried to obtain a compound bio-organic fertilizer. Example 15

[0092] After pulverizing lignin, 40-80 mesh particles were washed three times with water to obtain lignin granules. Then, 2 parts by weight of the lignin granules were immersed in a sodium hydroxide solution with a pH of 8.5 and stirred until dissolved. Then, 2% by volume of 30% by weight hydrogen peroxide solution was added to the sodium hydroxide solution. The system was heated to 50°C and stirred for 3 hours. After the reaction was completed, the solid A was obtained by filtration. Solid A was immersed in a 5% by weight sodium hydroxide solution. Then, 1 part of N,N-dimethylbenzylamine and 25 parts by weight of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride were added. The system was then heated to 60°C and stirred for 2.5 hours. After the reaction was completed, the solid was filtered and washed to obtain solid B. Solid B was added to an alkaline solution with a pH of 9 and 2 parts by weight of sodium sulfite were added. The system was heated to 90°C and stirred for 2 hours. Then, the system was cooled to room temperature, the pH was adjusted to 2, and the solid was filtered and washed until neutral. After drying, hydrophobic chelated lignin was obtained.

[0093] Dissolve 3 parts by weight of polycaprolactone in 12 parts by volume of toluene to obtain a first mixed solution. Dissolve 0.8 parts by weight of hydrophobic chelated lignin in 10 parts by volume of ethylene diether to obtain a second mixed solution. Then mix the first and second mixed solutions in a 1:1 volume ratio and add 1.4 parts by weight of biochar with a particle size of 60-80 mesh. Stir until homogeneous to obtain a slow-release coating agent.

[0094] After granulating mixture B using a granulator, it is placed in a fluidized bed containing a slow-release coating agent for coating. After coating, it is dried to obtain a compound bio-organic fertilizer. Example 16

[0095] After pulverizing lignin, 40-80 mesh particles were washed three times with water to obtain lignin granules. Then, 4 parts by weight of the lignin granules were immersed in a sodium hydroxide solution with a pH of 8 and stirred until dissolved. Then, 3% by weight of a 30% by weight hydrogen peroxide solution (3% by volume of sodium hydroxide solution) was added. The system was heated to 55°C and stirred for 2 hours. After the reaction was completed, the solid A was obtained by filtration. Solid A was immersed in a 10% by weight sodium hydroxide solution. Then, 2 parts by weight of N,N-dimethylbenzylamine and 30 parts by weight of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride were added. The system was then heated to 70°C and stirred for 1.5 hours. After the reaction was completed, the solid was filtered and washed to obtain solid B. Solid B was added to an alkaline solution with a pH of 9 and 4 parts by weight of sodium sulfite was added. The system was heated to 85°C and stirred for 3 hours. Then, the system was cooled to room temperature, the pH was adjusted to 2.5, the solid was filtered and washed until neutral, and dried to obtain hydrophobic chelated lignin.

[0096] Four parts by weight of polycaprolactone were dissolved in 10 parts by volume of toluene to obtain a first mixed solution. 0.6 parts by weight of hydrophobic chelated lignin were dissolved in 12 parts by volume of ethylene diether to obtain a second mixed solution. The first and second mixed solutions were then mixed in a 1:1 volume ratio, and 1.6 parts by weight of 60-80 mesh biochar were added and stirred until homogeneous to obtain the sustained-release coating agent.

[0097] After granulating mixture B using a granulator, it is placed in a fluidized bed containing a slow-release coating agent for coating. After coating, it is dried to obtain a compound bio-organic fertilizer. Example 17

[0098] Dissolve 3.5 parts by weight of polycaprolactone in 11 parts by volume of toluene to obtain a first mixed solution. Dissolve 0.7 parts by weight of lignin in 11 parts by volume of ethylene diether to obtain a second mixed solution. Then mix the first and second mixed solutions in a 1:1 volume ratio and add 1.5 parts by weight of biochar with a particle size of 60-80 mesh. Stir until homogeneous to obtain a slow-release coating agent.

[0099] After granulating mixture B using a granulator, it is placed in a fluidized bed containing a slow-release coating agent for coating. After coating, it is dried to obtain a compound bio-organic fertilizer. Example 18

[0100] After pulverizing lignin, 40-80 mesh particles were washed three times with water to obtain lignin granules. Then, 3 parts by weight of the lignin granules were immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved. Then, 2.5% by volume of 30% by weight hydrogen peroxide solution was added to the sodium hydroxide solution. The system was heated to 52°C and stirred for 2.5 hours. After the reaction was completed, the solid A was obtained by filtration. Solid A was immersed in an 8% by weight sodium hydroxide solution. Then, 1.5 parts by weight of N,N-dimethylbenzylamine and 27 parts by weight of ethylene oxide were added. The system was then heated to 65°C and stirred for 2 hours. After the reaction was completed, the solid was filtered and washed to obtain solid B. Solid B was added to an alkaline solution with a pH of 9 and 3 parts by weight of sodium sulfite was added. The system was heated to 88°C and stirred for 2.5 hours. Then, the system was cooled to room temperature, the pH was adjusted to 2.3, and the solid was filtered and washed until neutral. After drying, hydrophobic chelated lignin was obtained.

[0101] The rest is the same as in Example 14. Example 19

[0102] After pulverizing lignin, take 3 parts by weight of 40-80 mesh lignin particles and immerse them in a sodium hydroxide solution with a pH of 8.3, stirring until dissolved. Then, add 2.5% by volume of 30% by weight hydrogen peroxide solution to the sodium hydroxide solution. Heat the system to 52°C and stir for 2.5 hours. After the reaction is complete, filter to obtain solid A. Immerse solid A in an 8% by weight sodium hydroxide solution, then add 1.5 parts by weight of N,N-dimethylbenzylamine and 27 parts by weight of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride. Then heat to 65°C and stir for 2 hours. After the reaction is complete, filter and wash the solid to obtain solid B. Add solid B to an alkaline solution with a pH of 9, add 3 parts by weight of sodium sulfite, heat the system to 88°C, and stir for 2.5 hours. Then cool to room temperature, adjust the pH to 2.3, filter and wash the solid until neutral, and dry to obtain hydrophobic chelated lignin.

[0103] The rest is the same as in Example 14. Example 20

[0104] After pulverizing lignin, 40-80 mesh particles were washed three times with water to obtain lignin granules. Then, 3 parts by weight of the lignin granules were immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved. Then, 1.5 parts by weight of N,N-dimethylbenzylamine and 27 parts by weight of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride were added. The mixture was then heated to 65°C and stirred for 2 hours. After the reaction was completed, the solid was filtered and washed to obtain solid B. Solid B was added to an alkaline solution with a pH of 9 and 3 parts by weight of sodium sulfite were added. The system was heated to 88°C and stirred for 2.5 hours. Then, the mixture was cooled to room temperature, the pH was adjusted to 2.3, and the solid was filtered and washed until neutral. After drying, hydrophobic chelated lignin was obtained.

[0105] The rest is the same as in Example 14. Example 21

[0106] After pulverizing lignin, 40-80 mesh particles were washed three times with water to obtain lignin granules. Then, 3 parts by weight of the lignin granules were immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved. Then, 2.5% by volume of 30% by weight hydrogen peroxide solution was added to the sodium hydroxide solution. The system was heated to 52°C and stirred for 2.5 hours. After the reaction was completed, the solid A was obtained by filtration. Solid A was immersed in an 8% by weight sodium hydroxide solution. Then, 0.2 parts by weight of N,N-dimethylbenzylamine and 27 parts by weight of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride were added. The system was then heated to 65°C and stirred for 2 hours. After the reaction was completed, the solid was filtered and washed to obtain solid B. Solid B was added to an alkaline solution with a pH of 9 and 3 parts by weight of sodium sulfite was added. The system was heated to 88°C and stirred for 2.5 hours. Then, the system was cooled to room temperature, the pH was adjusted to 2.3, and the solid was filtered and washed until neutral. After drying, hydrophobic chelated lignin was obtained.

[0107] The rest is the same as in Example 14. Example 22

[0108] After pulverizing lignin, 40-80 mesh particles were washed three times with water to obtain lignin granules. Then, 3 parts by weight of the lignin granules were immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved. Then, 2.5% by volume of 30% by weight hydrogen peroxide solution was added to the sodium hydroxide solution. The system was heated to 52°C and stirred for 2.5 hours. After the reaction was completed, the solid A was obtained by filtration. Solid A was immersed in an 8% by weight sodium hydroxide solution. Then, 1.5 parts by weight of N,N-dimethylbenzylamine and 27 parts by weight of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride were added. The system was then heated to 65°C and stirred for 2 hours. After the reaction was completed, the solid was filtered and washed to obtain solid B. Solid B was added to an alkaline solution with a pH of 9 and 3 parts by weight of sodium sulfite was added. The system was heated to 88°C and stirred for 1 hour. Then, the system was cooled to room temperature, the pH was adjusted to 2.3, and the solid was filtered and washed until neutral. After drying, hydrophobic chelated lignin was obtained.

[0109] The rest is the same as in Example 14.

[0110] Experiment 3:

[0111] The 1-day and 28-day nutrient release rates of the compound bio-organic fertilizers prepared in Examples 14 to 22 were determined according to the method in GB / T23348-2009. The specific data are shown in Table 3.

[0112] A 90-square-meter soil plot was selected, and after being turned over and evenly divided into 9 groups, the compound bio-organic fertilizer prepared in Examples 14 to 22 was applied to these 9 groups of soil. The organic matter and total nutrients in the soil were measured according to the method in the NY525-2021 standard at the beginning and 30 days later. The specific data are shown in Table 4.

[0113]

[0114] Table 3 shows that the compound bio-organic fertilizers prepared in Examples 14-16 have excellent slow-release effects, indicating that lignin modification can effectively reduce its hydrophilicity, thereby enhancing the stability of the coating film. The compound bio-organic fertilizer prepared in Example 17 has the worst slow-release effect, possibly because unmodified lignin was used. The hydrophilicity of lignin accelerates the destruction of the coating film, reducing its coating performance. The data for Example 18 is not as good as that for Example 14. This may be because after replacing (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride with ethylene oxide, on the one hand, ethylene oxide is not as effective as (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride in enhancing the hydrophobicity of lignin, and on the other hand... Ethylene oxide also failed to enhance the dispersibility of lignin, affecting its uniform dispersion in the slow-release coating agent and thus the coating effect. The reason why the data in Example 19 was not as good as that in Example 14 may be that the lignin particles were not cleaned, and impurities in the lignin would affect the subsequent modification treatment. The reason why the data in Example 20 was not as good as that in Example 14 may be that hydrogen peroxide was not used to activate the lignin, resulting in a worse effect of the subsequent modification reaction. The reason why the data in Example 21 was not as good as that in Example 14 may be that the amount of catalyst N,N-dimethylbenzylamine used was too small, resulting in a slower modification reaction rate and affecting the modification effect. The data in Example 22 were basically the same as those in Example 14, indicating that the subsequent sulfonation reaction had little effect on the hydrophobicity of lignin.

[0115]

[0116] Table 4 shows that the compound bio-organic fertilizers prepared in Examples 14-16 can effectively and rapidly improve soil fertility. Example 17 used unmodified lignin, resulting in a poorly stable coating film, thus leading to poor slow-release effect and even worse fertilizer retention. Example 18 used ethylene oxide to modify lignin, resulting in a poorly stable coating film and thus a poor slow-release effect, with some organic matter loss. However, the lignin underwent sulfonation treatment, thus retaining some chelating properties and retaining some trace elements and other nutrients. Examples 19-21 all changed the processing parameters of the first half of the lignin, resulting in a decrease in the modification effect of lignin, and therefore, their soil fertility data were lower than those of Example 14. Example 22 reduced the sulfonation treatment time of lignin, so its organic matter content was not much different from that of Example 14, but its total nutrient content was lower, indicating that sulfonation treatment can enhance the chelating properties of lignin and strengthen the fertilizer retention effect of bio-organic fertilizer.

Claims

1. A method for preparing a compound bio-organic fertilizer that rapidly enhances soil fertility, characterized in that: The specific steps are as follows: (1) Mix 30-40 parts by weight of pig manure, 10-15 parts by weight of soybean meal, 10-15 parts by weight of biogas residue, 8-10 parts by weight of phosphate tailings, 6-8 parts by weight of macroporous strong adsorption zeolite and 1-2 parts by weight of green compound sterilizing agent, add water to control the moisture content at 55-60%, and stir at a speed of 200-300 r / min for 200-220 min to obtain mixture A; (2) Add 3-4 parts by weight of fermentation agent to mixture A and stir evenly. Control the initial fermentation temperature at 20℃. After the fermentation starts, turn the pile once a day and control the fermentation temperature at 60-70℃. Fermentation is completed after 10 days. (3) After fermentation, transfer mixture A into a pulverizer and pulverize it at a speed of 400~500r / min for 60~70min to obtain mixture B; (4) After granulating mixture B using a granulator, it is placed in a fluidized bed containing a slow-release coating agent for coating. After coating, it is dried to obtain a compound bio-organic fertilizer. The preparation steps of the macroporous strong adsorption zeolite are as follows: Zeolite is crushed, ground, and screened to obtain zeolite particles with a particle size of 60-80 mesh. Then, water is added and stirred and washed until no impurities are found. The zeolite particles are then immersed in a saturated carbonic acid solution for 3-4 hours. After that, they are washed with water and dried. After drying, the zeolite particles are transferred to a tube furnace and heated to 500-520℃ at a rate of 8-10℃ / min. The temperature is then held for sintering for 4-5 hours. After naturally cooling to room temperature, preliminary modified zeolite is obtained. The preliminarily modified zeolite was immersed in a 0.6-0.7% (w / w) distearyldimethylammonium chloride solution and stirred at 200-220 r / min for 260-270 min at room temperature. It was then washed with water until neutral and dried to obtain the final product. Specifically, the green compound sterilizing agent is: D-limonene, maltotriose stearate monoester, soybean lecithin and water were mixed in a mass ratio of 3~5:0.2~0.3:0.3~0.4:20 and sheared for 1~2 minutes at 12000~13000 rpm, and then homogenized at room temperature and 80 MPa to obtain the final product. Specifically, the fermentation agent is: The seed culture of Aspergillus niger, Bacillus subtilis seed culture and Bacillus megaterium seed culture are mixed evenly in a volume ratio of 1:1:1 to obtain the final product. Specifically, the sustained-release coating agent is: Dissolve 3-4 parts by weight of polycaprolactone in 10-12 parts by volume of toluene to obtain a first mixed solution. Dissolve 0.6-0.8 parts by weight of hydrophobic chelated lignin in 10-12 parts by volume of diethylene ether to obtain a second mixed solution. Then mix the first and second mixed solutions at a volume ratio of 1:1, and add 1.4-1.6 parts by weight of biochar with a particle size of 60-80 mesh and stir until homogeneous to obtain the final product. Specifically, the hydrophobic chelated lignin is: After pulverizing lignin, take 40-80 mesh particles and wash them three times with water to obtain lignin granules. Then, immerse 2-4 parts by weight of the lignin granules in a sodium hydroxide solution with a pH of 8-8.5 and stir until dissolved. Then, add 2-3% by volume of a 30% by weight hydrogen peroxide solution, heat the system to 50-55°C, and stir the reaction for 2-3 hours. After the reaction is complete, filter to obtain solid A. Immerse solid A in a 5-10% by weight sodium hydroxide solution, and then add 1-2 parts by weight of N,N Dimethylbenzylamine and 25-30 parts by weight of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride were reacted, and the mixture was heated to 60-70°C and stirred for 1.5-2.5 hours. After the reaction was completed, the solid was filtered and washed to obtain solid B. Solid B was added to an alkaline solution with a pH of 9, and 2-4 parts by weight of sodium sulfite were added. The system was heated to 85-90°C and stirred for 2-3 hours. Then it was cooled to room temperature, the pH was adjusted to 2-2.5, the solid was filtered and washed until neutral, and dried to obtain the final product.

2. The method for preparing a compound bio-organic fertilizer for rapidly improving soil fertility as described in claim 1, characterized in that: After granulation in step (4), the particle size is 4~6mm.

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