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

Abstract

The invention discloses a preparation method of a composite bio-organic fertilizer capable of rapidly improving soil fertility, which comprises the following steps: by taking pig manure, soybean meal, biogas residue and phosphate tailings as raw materials of the bio-organic fertilizer, compounding large-aperture strong adsorption type zeolite and a green compound sterilizing agent to remove heavy metals, harmful germs and worm eggs in the raw material components; the negative effects of heavy metals, harmful germs and worm eggs on the soil structure and beneficial microorganisms are effectively reduced, so that the bio-organic fertilizer can effectively and quickly enhance the fertility of the soil, and meanwhile, the bio-organic fertilizer is subjected to coating treatment; the method has the advantages that the surface burning phenomenon caused by too high fertility when the bio-organic fertilizer is released too fast in the early stage is avoided, the fertility loss caused by the fact that nutrient substances released too early are washed and volatilized by rainwater is avoided, the soil fertility is enhanced, the utilization rate of the bio-organic fertilizer is increased, the application frequency of the organic fertilizer can be reduced, and the cost is reduced. And the labor intensity of employees is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of organic fertilizers, and in particular to a method for preparing a composite bio-organic fertilizer capable of rapidly improving soil fertility. Background Art

[0002] Bio-organic fertilizer refers to a type of fertilizer that combines the effects of microorganisms and organic fertilizers, which are made from microorganisms with specific functions and organic materials that are mainly derived from animal and plant residues (such as livestock and poultry manure, crop straw, etc.) and have been harmlessly treated and decomposed. It has the characteristics of being diverse in variety, widely sourced, and highly efficient.

[0003] Phosphate tailings contain essential nutrients for plants such as phosphorus, calcium and magnesium, and can be used as a component for preparing bio-organic fertilizers. This 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, phosphorus tailings contain untreated heavy metals, which will be enriched in plants after adding bio-organic fertilizers. Livestock and poultry manure is also one of the main components of bio-organic fertilizers. However, due to the large amount of trace elements such as copper, iron, zinc, manganese, cobalt, selenium and iodine added to livestock and poultry feeds, many trace elements that are not absorbed by livestock and poultry accumulate in livestock and poultry manure, resulting in excessive trace element content in livestock and poultry manure, especially toxic elements such as copper, arsenic and mercury, which also exceed the standard individually, causing heavy metal pollution to the soil, resulting in excessive heavy metal content in vegetables and fruits. At the same time, heavy metals will also inhibit soil microbial activity and destroy soil structure, thereby affecting soil fertility. Therefore, it is necessary to control the heavy metal content of bio-organic fertilizers.

[0004] Livestock and poultry manure not only contains a large number of trace elements, but also contains a large number of harmful bacteria and insect eggs, which may cause pests and diseases, not only polluting the environment, but also threatening human health. Pests and diseases can also lead to malnutrition of plants and the destruction of the balance of beneficial microorganisms, thus affecting soil fertility. 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, but the maximum temperature generated by fermentation is 70~80℃, which cannot completely kill harmful bacteria and insect eggs. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing a composite bio-organic fertilizer which can quickly improve soil fertility.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention comprises the following steps: A method for preparing a composite bio-organic fertilizer for rapidly improving soil fertility, comprising the following specific steps: (1) 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 large-pore strong adsorption zeolite and 1-2 parts by weight of green compound sterilizer were mixed, water was added to control the water content to 55-60%, and then stirred at a speed of 200-300 r / min for 200-220 min to obtain a 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°C. Turn the compost once a day after fermentation begins. Control the fermentation temperature at 60-70°C. Fermentation is completed after 10 days. (3) After fermentation is completed, mixture A is transferred into a pulverizer and pulverized at a speed of 400-500 r / min for 60-70 min to obtain mixture B; (4) The mixture B is granulated by a granulator and then placed in a fluidized bed containing a slow-release coating agent for coating. After coating, the mixture is dried to obtain a composite bio-organic fertilizer.

[0007] Furthermore, the pig manure in step (1) is dehydrated pig manure, and its water content is 40-50%.

[0008] Furthermore, the preparation steps of the large-pore strong adsorption zeolite in step (1) are: The zeolite is crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water is added, stirred and washed until there are no impurities, and the zeolite particles are immersed in a saturated carbonic acid solution for 3-4 hours, and then washed with water and dried. After drying, the zeolite particles are transferred to a tubular furnace, heated to 500-520°C at a rate of 8-10°C / min, and sintered for 4-5 hours, and naturally cooled to room temperature to obtain a preliminary modified zeolite; The preliminary modified zeolite is immersed in a 0.6-0.7% mass fraction distearyl dimethyl ammonium chloride solution, stirred at a speed of 200-220 r / min for 260-270 min at room temperature, then washed with water until neutral, and dried to obtain the result.

[0009] Furthermore, the green compound sterilizing agent in step (2) is specifically: D-limonene, maltotriose stearate, soybean lecithin and water were mixed in a mass ratio of 3-5:0.2-0.3:0.3-0.4:20, sheared at 12000-13000 rpm for 1-2 min using a shearing machine, and then homogenized at room temperature and 80 MPa to obtain the mixture.

[0010] Furthermore, the fermentation agent in step (2) is specifically 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.

[0011] Furthermore, the sustained-release coating agent in step (4) is specifically: 3-4 parts by mass of polycaprolactone are added to 10-12 parts by volume of toluene to dissolve to obtain a first mixed solution, 0.6-0.8 parts by mass of hydrophobic chelated lignin are added to 10-12 parts by volume of ethylene diether to dissolve to obtain a second mixed solution, 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 meshes are added and stirred evenly to obtain; Among them, the hydrophobic chelated lignin is specifically: After the lignin is crushed, 40-80 mesh particles are taken and washed with water three 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, a 30% mass fraction hydrogen peroxide solution of 2-3% by volume of the sodium hydroxide solution is added, and the system is heated to 50-55°C and stirred for reaction for 2-3 hours. After the reaction is completed, solid A is filtered to obtain solid A. Solid A is immersed in a 5-10% mass fraction sodium hydroxide solution, and then 1-2 parts of N,N -dimethylbenzylamine and 25-30 parts by mass of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride, then heat to 60-70°C and stir to react for 1.5-2.5 hours. After the reaction is completed, filter and wash the solid to obtain solid B. Add solid B to an alkaline solution with a pH value of 9, add 2-4 parts by mass of sodium sulfite, heat the system to 85-90°C, stir and react for 2-3 hours, then cool to room temperature, adjust the pH to 2-2.5, filter and wash the solid to neutral, and dry to obtain.

[0012] Furthermore, the particle size of the particles after granulation in step (4) is 4-6 mm.

[0013] The beneficial effects of the present invention are: (1) The present invention adopts pig manure, soybean meal, biogas residue and phosphate tailings as raw materials of biological organic fertilizer, which can not only provide rich nutrients, improve soil structure, enhance soil fertility and increase crop yield, but also has significant environmental benefits, which is conducive to the sustainable development of agriculture. At the same time, large-pore strong adsorption zeolite and green compound sterilizer are compounded to remove heavy metals, harmful bacteria and insect eggs in the raw material components, effectively reducing the negative effects of heavy metals, harmful bacteria and insect eggs on soil structure and beneficial microorganisms, thereby ensuring that the biological organic fertilizer can effectively and quickly enhance the fertility of the soil. At the same time, the biological organic fertilizer is coated to avoid the occurrence of burning surface phenomenon due to excessive fertility when the biological organic fertilizer is released too quickly in the early stage, and avoid the loss of fertility caused by the leaching and volatilization of nutrients released too early. While enhancing soil fertility, the utilization rate of the biological organic fertilizer is also improved, which can reduce the number of times of organic fertilizer application and reduce the labor intensity of practitioners. (2) The present invention uses zeolite to remove heavy metals in organic fertilizer. Since the pores of natural zeolite are easily blocked and the degree of interconnection is poor, its adsorption capacity does not meet the requirements and the effect of removing heavy metal ions is poor. Therefore, the zeolite is modified by washing, soaking in a weak acid solution and sintering, etc., which can effectively increase the pore size of the zeolite and remove various impurities contained in it, so as to facilitate the subsequent quaternary ammonium salt treatment process. Compared with conventional quaternary ammonium salts such as dodecyltrimethylammonium chloride, the distearyldimethylammonium chloride used in the present invention has stronger emulsification and dispersibility, which can make the zeolite evenly dispersed in the organic fertilizer. At the same time, it does not have foaming properties. When the zeolite is modified, bubbles will not make the modification uneven, thereby affecting the modification effect; (3) The present invention uses a bactericide to kill harmful bacteria and insect eggs in biological organic fertilizer. D-limonene is an excellent bactericide and insecticide that can effectively kill harmful bacteria and insect eggs in livestock manure. However, since it is a hydrophobic compound, it cannot be effectively mixed with biological organic fertilizer, thereby affecting its killing effect. Therefore, an emulsifier is compounded with it. Compared with other emulsifiers such as Tween 20, maltotriose stearate has excellent emulsifying properties and also has the function of inhibiting harmful bacteria and promoting the growth of beneficial bacteria. It can play a synergistic role with D-limonene. Maltotriose stearate is also more stable and not easy to deteriorate. It is also easy to biodegrade and will not cause harm to the soil and the environment. (4) Since D-limonene has poor oxidative stability and the preparation process of bio-organic fertilizer takes a long time, it is necessary to compound antioxidants with D-limonene to enhance its antioxidant properties. Soybean lecithin not only has antioxidant properties but also has strong emulsifying, wetting and dispersing effects. It can have a synergistic effect with maltotriose stearate, further enhancing the uniform distribution of D-limonene in bio-organic fertilizer. Soybean lecithin itself also has the effects of promoting root growth and improving soil structure, which can enhance the efficacy of bio-organic fertilizer. (5) The present invention slowly releases the fertility of the bio-organic fertilizer by coating the bio-organic fertilizer. The slow-release coating agent prepared by the present invention includes lignin, polycaprolactone and biochar. Lignin has the functions of slow release, chelation, adhesion and dispersion, and can adsorb and seal nutrients. At the same time, it can make the bio-organic fertilizer evenly dispersed in the soil. After decomposition, it can also form humus, which has the effect of improving the soil structure; polycaprolactone has good biocompatibility, will not affect plant growth, and can be completely decomposed into water and carbon dioxide; biochar has the effect of improving the physical, chemical and biological properties of the soil, and can also be used as a carrier of nutrients and heavy metal fixation, and has a synergistic effect with zeolite and lignin; (6) Although lignin has a synergistic effect on soil and biological organic fertilizer, when it is used as a coating material, its hydrophilicity makes the coating material unstable, making the coating material more easily decomposed and broken, resulting in poor slow-release effect of the biological organic fertilizer. Therefore, the present application modifies the lignin. Compared with other modifiers such as propylene oxide, (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride can reduce the hydrophilicity of lignin while enhancing its dispersibility, making the entire slow-release coating component more uniform. At the same time, it can also enhance the chelating properties of lignin, which can not only adsorb heavy metals in the soil, but also adsorb trace elements in the soil, making the trace elements less likely to be washed away by rainwater, thereby achieving the effect of fertilizer preservation.

[0014] The Aspergillus niger strain used in this application is CMCC(F)98003, purchased from Beijing Sanyao Technology Co., Ltd.; the Bacillus subtilis strain used is BU1814, purchased from Guangzhou Zhenwei Microbiology Technology Co., Ltd.; the Bacillus megaterium strain used is QMB1551, purchased from Hangzhou Baosai Biotechnology Co., Ltd. DETAILED DESCRIPTION

[0015] The present invention is further described in detail below with reference to the embodiments. Example 1

[0016] The zeolite was crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water was added to stir and wash until there were no impurities, and the zeolite particles were immersed in a saturated carbonic acid solution for 3.5 hours, and then washed with water and dried. After drying, the zeolite particles were transferred to a tubular furnace, heated to 510°C at a rate of 9°C / min, and sintered for 4.5 hours, and naturally cooled to room temperature to obtain a preliminary modified zeolite; The preliminary modified zeolite was immersed in a 0.65% mass fraction distearyl dimethyl ammonium chloride solution, stirred at a speed of 210 r / min at room temperature for 265 minutes, then washed with water to neutrality, and dried to obtain a large-pore strong adsorption zeolite.

[0017] D-limonene, maltotriose stearate, soybean lecithin and water were mixed in a mass ratio of 4:0.25:0.35:20, sheared at 12500 rpm for 1.5 min using a shearing machine, and then homogenized at room temperature and 80 MPa to obtain a green compound sterilizer.

[0018] The Aspergillus niger 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.

[0019] (1) 35 parts by weight of pig manure, 12 parts by weight of soybean meal, 13 parts by weight of biogas residue, 9 parts by weight of phosphate tailings, 7 parts by weight of large-pore strong adsorption zeolite and 1.5 parts by weight of green compound sterilizer were mixed, water was added to control the water content to 57%, and then stirred at a speed of 250 r / min for 210 min to obtain a mixture A; (2) Add 3.5 parts by weight of fermentation agent to mixture A and stir evenly. Control the initial fermentation temperature at 20°C. Turn the compost once a day after fermentation begins. Control the fermentation temperature at 65°C. Fermentation is completed after 10 days. (3) After fermentation is completed, mixture A is transferred to a grinder and crushed at a speed of 450 r / min for 65 min to obtain mixture B. Example 2

[0020] The zeolite was crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water was added, stirred and washed until there were no impurities, and the zeolite particles were immersed in a saturated carbonic acid solution for 3 hours, and then washed with water and dried. After drying, the zeolite particles were transferred to a tubular furnace, heated to 520°C at a rate of 8°C / min, and sintered for 4 hours, and naturally cooled to room temperature to obtain a preliminary modified zeolite; The preliminary modified zeolite was immersed in a 0.6% mass fraction distearyl dimethyl ammonium chloride solution, stirred at a speed of 200 r / min at room temperature for 270 minutes, then washed with water to neutrality, and dried to obtain a large-pore strong adsorption zeolite.

[0021] D-limonene, maltotriose stearate, soybean lecithin and water were mixed in a mass ratio of 3:0.3:0.3:20, sheared at 12000 rpm for 2 min using a shearing machine, and then homogenized at room temperature and 80 MPa to obtain a green compound sterilizer.

[0022] The Aspergillus niger 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.

[0023] (1) 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 sterilizer were mixed, water was added to control the water content to 55%, and then stirred at a speed of 200 r / min for 220 minutes to obtain a mixture A; (2) Add 3 parts by weight of fermentation agent to mixture A and stir evenly. Control the initial fermentation temperature at 20°C. Turn the compost once a day after fermentation begins. Control the fermentation temperature at 60°C. Fermentation is completed after 10 days. (3) After fermentation is completed, mixture A is transferred to a grinder and crushed at a speed of 400 r / min for 70 min to obtain mixture B. Example 3

[0024] The zeolite was crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water was added, stirred and washed until there were no impurities, and the zeolite particles were immersed in a saturated carbonic acid solution for 4 hours, and then washed with water and dried. After drying, the zeolite particles were transferred to a tubular furnace, heated to 500°C at a rate of 10°C / min, and sintered for 5 hours, and naturally cooled to room temperature to obtain a preliminary modified zeolite; The preliminary modified zeolite was immersed in a 0.7% mass fraction distearyl dimethyl ammonium chloride solution, stirred at a speed of 220 r / min at room temperature for 260 minutes, then washed with water to neutrality, and dried to obtain a large-pore strong adsorption zeolite.

[0025] D-limonene, maltotriose stearate, soybean lecithin and water were mixed in a mass ratio of 5:0.2:0.4:20, sheared at 13000 rpm for 1 min using a shearing machine, and then homogenized at room temperature and 80 MPa to obtain a green compound sterilizer.

[0026] The Aspergillus niger 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.

[0027] (1) 40 parts by mass of pig manure, 10 parts by mass of soybean meal, 15 parts by mass of biogas residue, 8 parts by mass of phosphate tailings, 6 parts by mass of large-pore strong adsorption zeolite and 2 parts by mass of green compound sterilizer were mixed, water was added to control the water content to 60%, and then stirred at a speed of 300 r / min for 200 minutes to obtain a mixture A; (2) Add 4 parts by weight of fermentation agent to mixture A and stir evenly. Control the initial fermentation temperature at 20°C. Turn the compost once a day after fermentation begins. Control the fermentation temperature at 70°C. Fermentation is completed after 10 days. (3) After fermentation is completed, mixture A is transferred to a grinder and crushed at a speed of 500 r / min for 60 min to obtain mixture B. Example 4

[0028] The zeolite was crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water was added to stir and wash until there were no impurities, and the zeolite particles were immersed in a saturated carbonic acid solution for 3.5 hours, and then washed with water and dried. After drying, the zeolite particles were transferred to a tubular furnace, heated to 510°C at a rate of 9°C / min, and sintered for 4.5 hours, and naturally cooled to room temperature to obtain a preliminary modified zeolite; The preliminary modified zeolite was immersed in a 0.65% mass fraction dodecyltrimethylammonium chloride solution, stirred at a speed of 210 r / min for 265 min at room temperature, then washed with water to neutrality, and dried to obtain a large-pore strong adsorption zeolite.

[0029] The rest is the same as in Example 1. Example 5

[0030] The zeolite was crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water was added to stir and wash until there were no impurities, and the zeolite particles were immersed in a saturated carbonic acid solution for 1 hour, and then washed with water and dried. After drying, the zeolite particles were transferred to a tubular furnace, heated to 510°C at a rate of 9°C / min, and sintered for 4.5 hours, and naturally cooled to room temperature to obtain a preliminary modified zeolite; The preliminary modified zeolite was immersed in a 0.65% mass fraction distearyl dimethyl ammonium chloride solution, stirred at a speed of 210 r / min at room temperature for 265 minutes, then washed with water to neutrality, and dried to obtain a large-pore strong adsorption zeolite.

[0031] The rest is the same as in Example 1. Example 6

[0032] The zeolite was crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water was added, stirred and washed until there were no impurities, and the zeolite particles were immersed in a saturated carbonic acid solution for 3.5 hours, and then washed with water and dried. After drying, the zeolite particles were transferred to a tubular furnace, heated to 650°C at a rate of 9°C / min, and sintered for 4.5 hours. After naturally cooling to room temperature, the preliminary modified zeolite was obtained; The preliminary modified zeolite was immersed in a 0.65% mass fraction distearyl dimethyl ammonium chloride solution, heated to 38°C and stirred at a speed of 210 r / min for 265 min, then washed with water to neutrality, and dried to obtain a large-pore strong adsorption zeolite.

[0033] The rest is the same as in Example 1. Example 7

[0034] The zeolite was crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water was added to stir and wash until there were no impurities, and the zeolite particles were immersed in a saturated carbonic acid solution for 3.5 hours, and then washed with water and dried. After drying, the zeolite particles were transferred to a tubular furnace, heated to 510°C at a rate of 9°C / min, and sintered for 4.5 hours, and naturally cooled to room temperature to obtain a preliminary modified zeolite; The preliminary modified zeolite was immersed in a 1.2% mass fraction distearyl dimethyl ammonium chloride solution, stirred at a speed of 210 r / min for 265 min at room temperature, then washed with water to neutrality, and dried to obtain a large-pore strong adsorption zeolite.

[0035] The rest is the same as in Example 1. Example 8

[0036] The zeolite was crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water was added to stir and wash until there were no impurities, and the zeolite particles were immersed in a saturated carbonic acid solution for 3.5 hours, and then washed with water and dried. After drying, the zeolite particles were transferred to a tubular furnace, heated to 510°C at a rate of 9°C / min, and sintered for 4.5 hours, and naturally cooled to room temperature to obtain a preliminary modified zeolite; The preliminary modified zeolite was immersed in a 0.65% mass fraction distearyl dimethyl ammonium chloride solution, heated to 38°C and stirred at a speed of 210 r / min for 265 min, then washed with water to neutrality, and dried to obtain a large-pore strong adsorption zeolite.

[0037] The rest is the same as in Example 1. Example 9

[0038] The zeolite was crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water was added to stir and wash until there were no impurities, and the zeolite particles were immersed in a saturated carbonic acid solution for 3.5 hours, and then washed with water and dried. After drying, the zeolite particles were transferred to a tubular furnace, heated to 510°C at a rate of 9°C / min, and sintered for 4.5 hours, and naturally cooled to room temperature to obtain a preliminary modified zeolite; The preliminary modified zeolite was immersed in a 0.65% mass fraction distearyl dimethyl ammonium chloride solution, stirred at a speed of 400 r / min at room temperature for 265 minutes, then washed with water to neutrality, and dried to obtain a large-pore strong adsorption zeolite.

[0039] The rest is the same as in Example 1.

[0040] Test 1: The contents of total arsenic, total cadmium and total lead in the mixture B prepared in Examples 1 to 9 were determined according to NY / T1978 standard. The specific data are shown in Table 1.

[0041]

[0042] It can be seen from the data in Table 1 that the heavy metal removal effects of Examples 1 to 3 are the best, and the heavy metal removal effect of Example 7 is no different from that of Example 1, indicating that the concentration of the distearyl dimethyl ammonium chloride solution in Example 1 is already the optimal concentration; the heavy metal removal effect of Example 4 is the worst, which may be due to the fact that the emulsification and dispersibility of dodecyl trimethyl ammonium chloride are weaker than those of distearyl dimethyl ammonium chloride, making the dispersibility of zeolite worse in organic fertilizer, and it has foaming properties, which will make the zeolite modification uneven due to bubbles during modification, thereby affecting the modification effect; the reason why the heavy metal removal effect of Example 5 is not as good as that of Example 1 may be that the zeolite is immersed in saturated carbonic acid The time in the solution was too short and the alkalinity was not completely removed, which affected the subsequent modification reaction; the reason why the heavy metal removal effect of Example 6 was not as good as that of Example 1 may be that the calcination temperature of the zeolite was too high, which destroyed part of the skeleton structure of the zeolite, thereby affecting its adsorption effect; the reason why the heavy metal removal effect of Example 8 was not as good as that of Example 1 may be that the heating would affect the ion exchange and adsorption between distearyl dimethyl ammonium chloride and zeolite, thereby affecting the heavy metal adsorption of the zeolite; the reason why the heavy metal removal effect of Example 9 was not as good as that of Example 1 may be that the stirring rate was too fast, which affected the ion exchange and adsorption between distearyl dimethyl ammonium chloride and zeolite, thereby affecting the heavy metal adsorption of the zeolite. Example 10

[0043] 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 min using a shearing machine. The mixture was then homogenized at room temperature and 80 MPa to obtain a green compound sterilizer.

[0044] The rest is the same as Example 2. Embodiment 11

[0045] D-limonene, maltotriose stearate, butylated hydroxytoluene and water were mixed in a mass ratio of 3:0.3:0.3:20, and sheared at 12000 rpm for 2 min using a shearing machine. The mixture was then homogenized at room temperature and 80 MPa to obtain a green compound sterilizer.

[0046] The rest is the same as Example 2. Example 12

[0047] D-limonene, maltotriose stearate, soybean lecithin and water were mixed in a mass ratio of 3:0.8:0.3:20, sheared at 12000 rpm for 2 min using a shearing machine, and then homogenized at room temperature and 80 MPa to obtain a green compound sterilizer.

[0048] The rest is the same as Example 2. Example 13

[0049] D-limonene, maltotriose stearate, soybean lecithin and water are mixed and stirred in a mass ratio of 3:0.3:0.3:20 to obtain a green compound sterilizer.

[0050] The rest is the same as Example 2.

[0051] Test 2: The fecal coliform group and ascaris egg mortality rates in the mixtures B prepared in Examples 1 to 3 and 10 to 13 were measured according to GB / T19524.1-2004 and GB / T19524.2-2004 standards. The specific data are shown in Table 2.

[0052]

[0053] From the data in Table 2, it can be seen that Examples 1 to 3 have the best killing effects on harmful bacteria and eggs; the reason why Example 10 has the worst killing effect may be that after maltotriose stearate is replaced with Tween 20, Tween 20 does not have the effect of inhibiting harmful bacteria and promoting the growth of beneficial bacteria, does not have a synergistic effect with D-limonene, and Tween 20 is also less stable, it will undergo auto-oxidation, and light and temperature will also catalyze the progress of the auto-oxidation reaction, causing it to deteriorate and become ineffective; the reason why the data in Example 11 is not as good as that in Example 2 may be that after soybean lecithin is replaced with butylated hydroxytoluene, butylated hydroxytoluene does not have emulsifying, wetting and dispersing effects, and has no synergistic effect with wheat Maltotriose stearic acid monoester does not have a synergistic effect, which affects the overall stability and uniformity of the sterilizer, thus affecting 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 stearic acid monoester is too high, which destroys the balance of the sterilizer, causing stratification and unevenness in the sterilizer, thereby affecting the sterilization effect of the sterilizer; the reason why the data in Example 13 is not as good as that in Example 2 may be that no shearing and homogenization treatment was performed, the particle size of D-limonene in the sterilizer is larger, and its degree of dispersion is smaller than that in Example 2, and the uniformity after adding biological organic fertilizer is also lower, which reduces the sterilization and insect egg killing effects.

[0054] The mixture B prepared in Example 1 was used in Examples 14 to 22 to continue preparing the composite bio-organic fertilizer. Embodiment 14

[0055] After the lignin is crushed, 40-80 mesh particles are taken and washed with water three times to obtain lignin particles, and then 3 parts by mass of the lignin particles are immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved, and then a 30% mass fraction hydrogen peroxide solution of 2.5% by volume of the sodium hydroxide solution is added, and the system is heated to 52°C, stirred and reacted for 2.5 hours, and after the reaction is completed, solid A is filtered to obtain solid A, and solid A is immersed in an 8% mass fraction sodium hydroxide solution, and then 1.5 parts of N, N-dimethylbenzylamine and 27 parts by mass of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride are added, and then the temperature is raised to 65°C and stirred and reacted for 2 hours. After the reaction is completed, the solid is filtered and washed to obtain solid B, and solid B is added to an alkaline solution with a pH of 9, and 3 parts by mass of sodium sulfite are added, and the system is heated to 88°C, stirred and reacted for 2.5 hours, and then cooled to room temperature, the pH is adjusted to 2.3, the solid is filtered and washed to neutral, and the hydrophobic chelated lignin is obtained after drying; 3.5 parts by mass of polycaprolactone are added to 11 parts by volume of toluene and dissolved to obtain a first mixed solution, 0.7 parts by mass of hydrophobic chelated lignin is added to 11 parts by volume of ethylene diether and dissolved to obtain a second mixed solution, then the first mixed solution and the second mixed solution are mixed in a volume ratio of 1:1, and 1.5 parts by mass of biochar with a particle size of 60-80 mesh is added and stirred evenly to obtain a sustained-release coating agent.

[0056] The mixture B is granulated by a granulator and then placed in a fluidized bed containing a slow-release coating agent for coating. After coating, the mixture is dried to obtain a composite bio-organic fertilizer. Embodiment 15

[0057] After the lignin is crushed, 40-80 mesh particles are taken and washed with water three times to obtain lignin particles, and then 2 parts by mass of the lignin particles are immersed in a sodium hydroxide solution with a pH of 8.5 and stirred until dissolved, and then a 30% mass fraction hydrogen peroxide solution with a volume of 2% of the sodium hydroxide solution is added, and the system is heated to 50°C, stirred and reacted for 3 hours, and after the reaction is completed, solid A is filtered to obtain solid A, and solid A is immersed in a 5% mass fraction sodium hydroxide solution, and then 1 part of N, N-dimethylbenzylamine and 25 parts by mass of (2, 3-epoxypropyl) ethylbis (2-hydroxyethyl) ammonium chloride are added, and then the temperature is raised to 60°C and stirred for 2.5 hours. After the reaction is completed, the solid is filtered and washed to obtain solid B, and solid B is added to an alkaline solution with a pH of 9, and 2 parts by mass of sodium sulfite are added, and the system is heated to 90°C, stirred and reacted for 2 hours, and then cooled to room temperature, the pH is adjusted to 2, and the solid is filtered and washed to neutral, and the hydrophobic chelated lignin is obtained after drying; 3 parts by mass of polycaprolactone were added to 12 parts by volume of toluene and dissolved to obtain a first mixed solution, 0.8 parts by mass of hydrophobic chelated lignin were added to 10 parts by volume of ethylene diether and dissolved to obtain a second mixed solution, and then the first mixed solution and the second mixed solution were mixed in a volume ratio of 1:1, and 1.4 parts by mass of biochar with a particle size of 60-80 mesh was added and stirred evenly to obtain a sustained-release coating agent.

[0058] The mixture B is granulated by a granulator and then placed in a fluidized bed containing a slow-release coating agent for coating. After coating, the mixture is dried to obtain a composite bio-organic fertilizer. Example 16

[0059] After the lignin is crushed, 40-80 mesh particles are taken and washed with water three times to obtain lignin particles, and then 4 parts by mass of the lignin particles are immersed in a sodium hydroxide solution with a pH of 8 and stirred until dissolved, and then a 30% mass fraction hydrogen peroxide solution of 3% by volume of the sodium hydroxide solution is added, and the system is heated to 55°C, stirred and reacted for 2 hours, and after the reaction is completed, solid A is filtered to obtain solid A, and solid A is immersed in a 10% mass fraction sodium hydroxide solution, and then 2 parts of N, N-dimethylbenzylamine and 30 parts by mass of (2, 3-epoxypropyl) ethylbis (2-hydroxyethyl) ammonium chloride are added, and then the temperature is raised to 70°C and stirred for 1.5 hours. After the reaction is completed, the solid is filtered and washed to obtain solid B, and solid B is added to an alkaline solution with a pH of 9, and 4 parts by mass of sodium sulfite are added, and the system is heated to 85°C, stirred and reacted for 3 hours, and then cooled to room temperature, the pH is adjusted to 2.5, the solid is filtered and washed to neutral, and the hydrophobic chelated lignin is obtained after drying; 4 parts by mass of polycaprolactone were added to 10 parts by volume of toluene and dissolved to obtain a first mixed solution, 0.6 parts by mass of hydrophobic chelated lignin were added to 12 parts by volume of ethylene diether and dissolved to obtain a second mixed solution, and then the first mixed solution and the second mixed solution were mixed in a volume ratio of 1:1, and 1.6 parts by mass of biochar with a particle size of 60-80 mesh was added and stirred evenly to obtain a sustained-release coating agent.

[0060] The mixture B is granulated by a granulator and then placed in a fluidized bed containing a slow-release coating agent for coating. After coating, the mixture is dried to obtain a composite bio-organic fertilizer. Embodiment 17

[0061] 3.5 parts by mass of polycaprolactone were added to 11 parts by volume of toluene and dissolved to obtain a first mixed solution, 0.7 parts by mass of lignin were added to 11 parts by volume of ethylene diether and dissolved to obtain a second mixed solution, then the first mixed solution and the second mixed solution were mixed in a volume ratio of 1:1, and 1.5 parts by mass of biochar with a particle size of 60-80 mesh was added and stirred evenly to obtain a sustained-release coating agent.

[0062] The mixture B is granulated by a granulator and then placed in a fluidized bed containing a slow-release coating agent for coating. After coating, the mixture is dried to obtain a composite bio-organic fertilizer. Embodiment 18

[0063] After the lignin was crushed, particles of 40-80 mesh were taken and washed with water three times to obtain lignin particles. Subsequently, 3 parts by mass of the lignin particles were immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved. Subsequently, a 30% mass fraction hydrogen peroxide solution of 2.5% by volume of the sodium hydroxide solution was added, the system was heated to 52°C, stirred for reaction for 2.5 hours, and after the reaction was completed, solid A was filtered to obtain solid A. Solid A was immersed in an 8% mass fraction sodium hydroxide solution, and then 1.5 parts of N,N-dimethylbenzylamine and 27 parts by mass of ethylene oxide were added. The temperature was then raised to 65°C and stirred for reaction 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, 3 parts by mass of sodium sulfite were added, the system was heated to 88°C, stirred for reaction for 2.5 hours, and then cooled to room temperature, the pH was adjusted to 2.3, the solid was filtered and washed to neutral, and the hydrophobic chelated lignin was obtained after drying.

[0064] The rest is the same as Example 14. Embodiment 19

[0065] After the lignin was crushed, 3 parts by mass of 40-80 mesh lignin particles were immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved, and then a 30% mass fraction hydrogen peroxide solution of 2.5% by volume of the sodium hydroxide solution was added, the system was heated to 52°C, stirred and reacted for 2.5 hours, and after the reaction was completed, solid A was filtered to obtain solid A, which was immersed in an 8% mass fraction sodium hydroxide solution, and then 1.5 parts of N,N-dimethylbenzylamine and 27 parts by mass of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride were added, and then the temperature was raised to 65°C and stirred and reacted for 2 hours. After the reaction was completed, the solid was filtered and washed to obtain solid B, and solid B was added to an alkaline solution with a pH of 9, and 3 parts by mass of sodium sulfite were added, the system was heated to 88°C, stirred and reacted for 2.5 hours, and then cooled to room temperature, the pH was adjusted to 2.3, the solid was filtered and washed to neutral, and the hydrophobic chelated lignin was obtained after drying.

[0066] The rest is the same as Example 14. Embodiment 20

[0067] After the lignin is crushed, particles of 40-80 mesh are taken and washed with water three times to obtain lignin particles. Subsequently, 3 parts by mass of the lignin particles are immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved. Subsequently, 1.5 parts by mass of N,N-dimethylbenzylamine and 27 parts by mass of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride are added, and the temperature is then raised to 65°C and stirred to react for 2 hours. 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, and 3 parts by mass of sodium sulfite are added. The system is heated to 88°C, stirred and reacted for 2.5 hours at this temperature, and then cooled to room temperature, the pH is adjusted to 2.3, the solid is filtered and washed to neutral, and the hydrophobic chelated lignin is obtained after drying.

[0068] The rest is the same as Example 14. Embodiment 21

[0069] After the lignin was crushed, 40-80 mesh particles were taken and washed with water three times to obtain lignin particles. Subsequently, 3 parts by mass of the lignin particles were immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved. Subsequently, a 30% mass fraction hydrogen peroxide solution of 2.5% by volume of the sodium hydroxide solution was added, the system was heated to 52°C, stirred and reacted for 2.5 hours, and after the reaction was completed, solid A was filtered to obtain solid A. Solid A was immersed in an 8% mass fraction sodium hydroxide solution, and then 0.2 parts of N,N-dimethylbenzylamine and 27 parts by mass of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride were added, and then the temperature was raised to 65°C and stirred and reacted 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 mass of sodium sulfite were added. The system was heated to 88°C, stirred and reacted for 2.5 hours, and then cooled to room temperature, the pH was adjusted to 2.3, the solid was filtered and washed to neutral, and the hydrophobic chelated lignin was obtained after drying.

[0070] The rest is the same as Example 14. Embodiment 22

[0071] After the lignin was crushed, particles of 40-80 mesh were taken and washed with water three times to obtain lignin particles. Subsequently, 3 parts by mass of the lignin particles were immersed in a sodium hydroxide solution with a pH of 8.3 and stirred until dissolved. Subsequently, a 30% mass fraction hydrogen peroxide solution of 2.5% by volume of the sodium hydroxide solution was added, the system was heated to 52°C, stirred for reaction for 2.5 hours, and after the reaction was completed, solid A was filtered to obtain solid A. Solid A was immersed in an 8% mass fraction sodium hydroxide solution, and then 1.5 parts of N,N-dimethylbenzylamine and 27 parts by mass of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride were added. The temperature was then raised to 65°C and stirred for reaction 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, 3 parts by mass of sodium sulfite were added, the system was heated to 88°C, stirred for reaction for 1 hour, and then cooled to room temperature, the pH was adjusted to 2.3, the solid was filtered and washed to neutral, and the hydrophobic chelated lignin was obtained after drying.

[0072] The rest is the same as Example 14.

[0073] Test 3: The 1d nutrient release rate and 28d nutrient release rate of the composite bio-organic fertilizer prepared in Examples 14 to 22 were measured according to the method in GB / T23348-2009 standard. The specific data are shown in Table 3.

[0074] A 90 square meter piece of soil was selected, and it was evenly turned and divided into 9 groups. The composite bio-organic fertilizer prepared in Example 14 to Example 22 was applied to the 9 groups of soil. The organic matter and total nutrients in the soil were determined according to the method in the NY525-2021 standard at the beginning and after 30 days. The specific data are shown in Table 4.

[0075]

[0076] From the data in Table 3, it can be seen that the composite bio-organic fertilizers prepared in Examples 14 to 16 have excellent slow-release effects, indicating that modification of lignin can effectively reduce its hydrophilicity, thereby enhancing the stability of the coating film; the composite bio-organic fertilizer prepared in Example 17 has the worst slow-release effect, which may be due to the use of unmodified lignin, and the hydrophilicity of lignin will accelerate the destruction of the coating film and reduce the coating performance of the coating film; the reason why the data in Example 18 is not as good as that in Example 14 may be that after (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride is replaced with ethylene oxide, on the one hand, the effect of ethylene oxide on enhancing the hydrophobicity of lignin is not as good as that of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride, and on the other hand, Ethylene oxide also cannot enhance the dispersibility of lignin, affecting the uniform dispersion of lignin in the slow-release coating agent, and further affecting the coating effect; the reason why the data of Example 19 is not as good as that of Example 14 may be that the lignin particles are not cleaned, and the impurities in the lignin will affect the subsequent modification treatment; the reason why the data of Example 20 is not as good as that of Example 14 may be that the lignin is not activated by hydrogen peroxide, resulting in worse effect of subsequent modification reaction; the reason why the data of Example 21 is not as good as that of Example 14 may be that the amount of catalyst N,N-dimethylbenzylamine used is relatively small, resulting in a slower modification reaction rate, affecting the modification effect; the data of Example 22 is basically the same as that of Example 14, indicating that the subsequent sulfonation reaction has little effect on the hydrophobicity of lignin.

[0077]

[0078] From the data in Table 4, it can be seen that the composite biological organic fertilizer prepared in Examples 14 to 16 can effectively and quickly improve the fertility of the soil; Example 17 uses unmodified lignin, and the obtained coating film has poor stability, so the slow release effect is not good, and the fertilizer retention performance is even worse; Example 18 uses ethylene oxide to modify the lignin, and the stability of the coating film is also poor, so the slow release effect is not good, and the organic matter will be partially lost, but the lignin has been sulfonated, so it still has partial chelating properties, and can retain some trace elements and other nutrients; Examples 19 to 21 all change the processing parameters of the first half of the lignin, so that the modification effect of the lignin is reduced, so the soil fertility data thereof are all reduced compared with Example 14; Example 22 reduces the sulfonation treatment time of the lignin, so its organic matter content is not much different from that of Example 14, but the total nutrient content will be lower, indicating that the lignin can enhance its chelating properties after sulfonation treatment, and enhance the fertilizer retention effect of the biological organic fertilizer.

Claims

1. A method for preparing a composite bio-organic fertilizer for rapidly improving soil fertility, characterized in that: The specific steps are: (1) 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 large-pore strong adsorption zeolite and 1-2 parts by weight of green compound sterilizer were mixed, water was added to control the water content to 55-60%, and then stirred at a speed of 200-300 r / min for 200-220 min to obtain a 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°C. Turn the compost once a day after fermentation begins. Control the fermentation temperature at 60-70°C. Fermentation is completed after 10 days. (3) After fermentation is completed, mixture A is transferred to a grinder and crushed at a speed of 400-500 r / min for 60-70 min to obtain mixture B; (4) The mixture B is granulated by a granulator and then placed in a fluidized bed containing a slow-release coating agent for coating. After coating, the mixture is dried to obtain a composite bio-organic fertilizer.

2. A method for preparing a composite bio-organic fertilizer for rapidly improving soil fertility as claimed in claim 1, characterized in that: The preparation steps of the large-pore strong adsorption zeolite are: The zeolite is crushed and ground, and then screened to obtain zeolite particles with a particle size of 60-80 meshes, and then water is added, stirred and washed until there are no impurities, and the zeolite particles are immersed in a saturated carbonic acid solution for 3-4 hours, and then washed with water and dried. After drying, the zeolite particles are transferred to a tubular furnace, heated to 500-520°C at a rate of 8-10°C / min, and sintered for 4-5 hours, and naturally cooled to room temperature to obtain a preliminary modified zeolite; The preliminary modified zeolite is immersed in a 0.6-0.7% mass fraction distearyl dimethyl ammonium chloride solution, stirred at a speed of 200-220 r / min for 260-270 min at room temperature, then washed with water until neutral, and dried to obtain the result.

3. A method for preparing a composite bio-organic fertilizer for rapidly improving soil fertility as claimed in claim 1, characterized in that: The green compound sterilizing agent is specifically: D-limonene, maltotriose stearate, soybean lecithin and water were mixed in a mass ratio of 3-5:0.2-0.3:0.3-0.4:20, sheared at 12000-13000 rpm for 1-2 min using a shearing machine, and then homogenized at room temperature and 80 MPa to obtain the mixture.

4. A method for preparing a composite bio-organic fertilizer for rapidly improving soil fertility as claimed in claim 1, characterized in that: The fermentation agent is specifically: The method 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.

5. A method for preparing a composite bio-organic fertilizer for rapidly improving soil fertility as claimed in claim 1, characterized in that: The sustained-release coating agent is specifically: 3 to 4 parts by mass of polycaprolactone are added to 10 to 12 parts by volume of toluene and dissolved to obtain a first mixed solution, 0.6 to 0.8 parts by mass of hydrophobic chelated lignin are added to 10 to 12 parts by volume of ethylene diether and dissolved to obtain a second mixed solution, then the first mixed solution and the second mixed solution are mixed in a volume ratio of 1:1, and 1.4 to 1.6 parts by mass of biochar with a particle size of 60 to 80 meshes are added and stirred evenly to obtain the obtained solution.

6. A method for preparing a composite bio-organic fertilizer for rapidly improving soil fertility as claimed in claim 5, characterized in that: The hydrophobic chelated lignin is specifically: After the lignin is crushed, 40-80 mesh particles are taken and washed with water three 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, a 30% mass fraction hydrogen peroxide solution of 2-3% by volume of the sodium hydroxide solution is added, and the system is heated to 50-55°C and stirred for reaction for 2-3 hours. After the reaction is completed, solid A is filtered to obtain solid A. Solid A is immersed in a 5-10% mass fraction sodium hydroxide solution, and then 1-2 parts of N,N -dimethylbenzylamine and 25-30 parts by mass of (2,3-epoxypropyl)ethylbis(2-hydroxyethyl)ammonium chloride, then heat to 60-70°C and stir to react for 1.5-2.5 hours. After the reaction is completed, filter and wash the solid to obtain solid B. Add solid B to an alkaline solution with a pH value of 9, add 2-4 parts by mass of sodium sulfite, heat the system to 85-90°C, stir and react for 2-3 hours, then cool to room temperature, adjust the pH to 2-2.5, filter and wash the solid to neutral, and dry to obtain.

7. A method for preparing a composite bio-organic fertilizer for rapidly improving soil fertility as claimed in claim 1, characterized in that: The particle size of the granules after granulation in step (4) is 4-6 mm.

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