Method for preparing organic fertilizer from abamectin fungus residues
By modifying iron tetraoxide and ultraviolet lamp treatment combined with magnet separation, antibiotic residues in avermectin bacteria residue were removed, and safe and efficient organic fertilizer was prepared through aerobic compost fermentation and aging, and antibiotics were solved. Residual problem achieved a 99.9% avermectin removal rate.
Patent Information
- Application Number
- CN202411892496.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-20
- Publication Date
- 2025-02-14
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
When preparing organic fertilizer using avermectin residue, there are antibiotic residue problems, which may pose a threat to plant growth and enter the human body through the food chain, bringing health risks.
Premodified iron tetraoxide was obtained by treating γ-glycidyl etheroxypropyl trimethoxysilane and reacting with amino-A-cyclodextrin and N,N-dimethylformamide. Then, the avermectin residue was mixed with modified ferrous tetraoxide and acetone, and treated under an ultraviolet lamp, separated with a magnet, and removed avermectin residue. Subsequently, the pretreated bacterial residue was mixed with Bacillus subtilis, Aspergillus niger and soluble starch, and aerobic compost fermentation and aging to prepare organic fertilizer.
The efficient removal of antibiotic residues in avermectin bacteria residue was achieved, ensuring the safety and effectiveness of organic fertilizers, and the avermectin removal rate reached 99.9%.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic fertilizers, in particular to a method for preparing organic fertilizer from avermectin residues. Background Art
[0002] In my country, the widespread use of antibiotics is like a double-edged sword. While effectively preventing and controlling crop diseases and pests and ensuring agricultural production, it also brings about the significant problem of a sharp increase in the use of antibiotics. This increase has directly led to the production of a large amount of antibiotic residues. These residues are inevitable by-products in the production process of antibiotics. They have complex components and contain unused antibiotics, culture medium residues, and a variety of other organic substances. Faced with this huge amount of waste resources, how to prevent them from becoming a burden on the environment and at the same time tap their potential reuse value has become an urgent problem to be solved.
[0003] Abamectin, as a shining pearl in the field of agricultural antibiotics, plays a pivotal role in the prevention and control of crop diseases and pests with its broad-spectrum insecticidal and acaricidal activity. However, in the process of producing avermectin, a large amount of fungal residue containing incompletely separated avermectin and other organic components will also be produced. If these fungal residues are not properly treated and directly used to prepare organic fertilizers, although it seems to achieve the recycling of resources, it actually hides dangers.
[0004] When directly using avermectin residue to prepare organic fertilizer, the first problem faced is antibiotic residue. These residual antibiotic components may exist in the soil for a long time, posing a potential threat to plant growth, interfering with their normal physiological functions, and may even cause abnormal plant growth and development. What is more serious is that these antibiotic residues may also accumulate step by step through the food chain and eventually enter the human body, posing a long-term risk to human health. In addition, antibiotic residues may also contain other unknown chemical components or microorganisms. Their potential impact on the soil ecosystem should not be ignored. They may destroy the biodiversity in the soil, interfere with the ecological balance, and thus affect the yield and quality of crops.
[0005] Therefore, before incorporating avermectin residue into the organic fertilizer preparation system, a series of strict harmless treatment measures must be taken to ensure that the antibiotic residues and other harmful substances therein are effectively removed or degraded. Summary of the invention
[0006] The object of the present invention is to provide a method for preparing organic fertilizer from avermectin residues to solve the problems existing in the prior art.
[0007] In order to solve the above technical problems, the present invention provides the following technical solutions: A method for preparing organic fertilizer from avermectin residues comprises the following preparation steps: (1) Mix γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water for 10 minutes, add ferric oxide in an amount of 0.5 times the mass of γ-glycidyloxypropyltrimethoxysilane, heat to 110°C, reflux for 3-4 hours, filter and wash with anhydrous ethanol for 4 times, and vacuum dry to obtain pretreated ferric oxide. Mix the pretreated ferric oxide, amino-A-cyclodextrin and N,N-dimethylformamide in a mass ratio of 1:(5-6) and disperse by ultrasonication. Heat to 80-90°C under nitrogen protection for 24 hours. After the reaction, filter and wash with methanol for 3-4 times to obtain pre-modified ferric oxide. (2) Spinach leaves and an extractant were mixed at a mass ratio of 1:(1.5-2.0) and ultrasonically treated for 30-40 min, the filtrate was filtered and retained, and chlorophyll was obtained by vacuum rotary evaporation; chlorophyll and ethanol were mixed at a mass ratio of 1:(20-30), the pH was adjusted to 10-11 with 10 mol / L sodium hydroxide, the temperature was raised to 65°C and the reaction was continued for 1 h, and after the reaction, the ethanol was removed by vacuum rotary evaporation, and pure water was used for separation. After the lower layer was retained by petroleum ether extraction, the pH was adjusted to 6 with a 30 wt% hydrochloric acid solution, and the reaction was stirred at 65°C for 1 h to obtain chlorophyll acid; chlorophyll acid, ferrous sulfate, and ethanol were mixed at a mass ratio of 1:(0.7-0.9):(20-30), the temperature was raised to 60°C and the reaction was continued for 3 h under nitrogen protection, the mixture was filtered and washed with pure water 4 times, and the modified chlorophyll was obtained by vacuum drying; (3) Modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide were mixed and reacted at room temperature for 12 hours. After the reaction, the mixture was filtered and washed with pure water for 4 times, and then vacuum dried to obtain modified ferrosoferric oxide; (4) Mixing avermectin residue, potassium hydroxide, modified ferroferric oxide and acetone, irradiating with ultraviolet light at an intensity of 13 mW / cm2 for 40-50 min at 80-90°C, separating with a magnet, retaining the filtrate after solid-liquid separation, and adjusting the pH to 6-8 with 10 wt% sulfuric acid to obtain pretreated residue; (5) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch are mixed in a mass ratio of 1:(0.1-0.2):(0.2-0.3):(20-30), and pure water is added to make the moisture content of the pretreated fungus residue 60%-70%. After stirring evenly, the mixture is subjected to aerobic composting, fermentation, aging, drying, crushing and granulation to obtain organic fertilizer.
[0008] As an optimization, the mass ratio of γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water in step (1) is 1:1:5.
[0009] As an optimization, the extractant in step (2) is a mixture of 95 wt % ethanol solution and acetone in a volume ratio of 2:1.
[0010] As an optimization, the moisture content of the avermectin residue in step (3) is 10%-20%, and the avermectin residual concentration is 1400-1700 mg / kg.
[0011] As an optimization, the mass ratio of the modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide in step (3) is 1:2:0.5:2:40.
[0012] As an optimization, the mass ratio of the avermectin residue, potassium hydroxide, modified ferrosoferric oxide and acetone in step (4) is 1:(0.1-0.2):(0.01-0.03):(80-100).
[0013] As an optimization, the aerobic composting fermentation method in step (5) is as follows: after the fermentation temperature reaches 60-75°C, the compost is kept warm for 3-4 days, and then the compost is turned over. The frequency of turning the compost is once every 1-2 days, and the fermentation time is 7-9 days.
[0014] As an optimization, the aging conditions in step (5) are: temperature of 30-50°C and fermentation period of 4-7 days.
[0015] As an optimization, the particle size of the ferrosoferric oxide in step (1) is 20-40 mesh.
[0016] As an optimization, the soluble starch model in step (5) is S104452.
[0017] Compared with the prior art, the beneficial effects achieved by the present invention are: When the avermectin residue is used to prepare the organic fertilizer, the method comprises the following steps: firstly, treating ferroferric oxide with gamma-glycidyloxypropyltrimethoxysilane, and then grafting aminocyclodextrin to obtain pre-modified ferroferric oxide; reacting chlorophyll extracted from spinach leaves with hydrochloric acid, and then reacting with ferric sulfate to obtain modified chlorophyll; reacting the modified chlorophyll with the pre-modified ferroferric oxide to obtain modified ferroferric oxide; secondly, mixing the avermectin residue, the modified ferroferric oxide and acetone, treating them under an ultraviolet lamp, and separating them by using a magnet to obtain the pre-treated residue; and finally, mixing the pre-treated residue, bacillus subtilis, aspergillus niger and soluble starch, and performing aerobic composting fermentation, aging, drying, crushing and granulation to obtain the organic fertilizer.
[0018] Firstly, γ-glycidyloxypropyltrimethoxysilane is used to treat ferrous oxide so that the surface of ferrous oxide has epoxy groups, and cyclodextrin is grafted onto it through the reaction between epoxy groups and amino groups. The cyclodextrin-grafted ferrous oxide has a similar effect as a surfactant, which can improve the dispersion of fungus residue in the solution and is conducive to the subsequent degradation reaction. Chlorophyll is a natural photocatalyst, but its own photocatalytic efficiency is limited and its structure is unstable. The unstable magnesium ions in the molecular structure of chlorophyll can be removed through modification, and the iron ions can be complexed to improve the photocatalytic efficiency. The modified ferrous oxide can load the modified chlorophyll, which can not only further improve the photocatalytic performance of chlorophyll, but also improve its stability and has the potential possibility of recycling and reuse. The cyclodextrin and chlorophyll grafted onto the surface of ferrous oxide are both environmentally friendly substances and will not cause pollution to organic fertilizers. Secondly, the avermectin residue, modified ferroferric oxide and acetone are mixed, treated under ultraviolet light, separated by a magnet, and the pretreated residue is obtained. Abamectin is easily soluble in acetone. Acetone can be used as a solvent to dissolve a part of the residual avermectin. Abamectin is sensitive to light and is easily decomposed under the action of light. The residual avermectin in the avermectin residue can be decomposed at a lower temperature and in a shorter time under the action of photocatalyst modified ferroferric oxide and ultraviolet light. DETAILED DESCRIPTION
[0019] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.
[0020] The extractant used in the following examples and comparative examples is a mixture of 95wt% ethanol solution and acetone in a volume ratio of 2:1; the water content of the avermectin slag used is 14%, and the avermectin residual concentration is 1657.9mg / kg; the particle size of the ferrosoferric oxide used is 20-40 mesh; and the soluble starch model used is S104452.
[0021] Embodiment 1: (1) γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, 0.5 times the mass of γ-glycidyloxypropyltrimethoxysilane was added to ferroferric oxide, the temperature was raised to 110°C, refluxed for 4 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated ferroferric oxide. The pretreated ferroferric oxide, amino-A-cyclodextrin and N,N-dimethylformamide were mixed at a mass ratio of 1:5 and ultrasonically dispersed. Under nitrogen protection, the temperature was raised to 90°C for reaction for 24 hours. After the reaction, it was filtered and washed with methanol for 4 times to obtain pre-modified ferroferric oxide; (2) Spinach leaves and an extractant were mixed at a mass ratio of 1:1.5 and subjected to ultrasonic treatment for 40 minutes. The filtrate was filtered and retained, and chlorophyll was obtained by vacuum rotary evaporation. Chlorophyll and ethanol were mixed at a mass ratio of 1:20, and the pH was adjusted to 11 with 10 mol / L sodium hydroxide. The mixture was heated to 65°C and reacted for 1 hour. After the reaction, the ethanol was removed by vacuum rotary evaporation. Pure water was used for separation. The lower layer was retained after extraction with petroleum ether. The pH was adjusted to 6 with 30 wt% hydrochloric acid solution. The mixture was heated to 65°C and stirred for reaction for 1 hour to obtain chlorophyll acid. Chlorophyll acid, ferrous sulfate and ethanol were mixed at a mass ratio of 1:0.7:20, and the mixture was heated to 60°C and reacted for 3 hours under nitrogen protection. The mixture was filtered and washed with pure water 4 times, and modified chlorophyll was obtained by vacuum drying. (3) Modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide were mixed in a mass ratio of 1:2:0.5:2:40, reacted at room temperature for 12 hours, filtered after the reaction, washed with pure water for 4 times, and vacuum dried to obtain modified ferrosoferric oxide; (4) Avermectin residue, potassium hydroxide, modified ferroferric oxide and acetone were mixed in a mass ratio of 1:0.1:0.01:50 and heated at 90°C with an intensity of 13 mW / cm 2 The mixture was irradiated with ultraviolet light for 50 minutes, separated by magnet, and the filtrate was retained for solid-liquid separation. The pH value was adjusted to 8 with 10 wt % sulfuric acid to obtain pretreated fungus residue. (5) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch were mixed in a mass ratio of 1:0.1:0.2:20, and pure water was added to make the moisture content of the pretreated fungus residue 70%. After stirring evenly, the mixture was aerobically composted and fermented at a fermentation temperature of 75°C. The compost was kept warm for 4 days and then turned over at a frequency of once every 2 days. The fermentation time was 9 days, the aging temperature was 50°C, and the fermentation cycle was 7 days. Finally, the organic fertilizer was dried, crushed and granulated.
[0022] The content of avermectin in the organic fertilizer was tested by high performance liquid chromatography, and the removal rate of avermectin in the organic fertilizer prepared in this embodiment was 99.9%.
[0023] Embodiment 2: A method for preparing organic fertilizer from avermectin residues, the method comprising the following preparation steps: (1) γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, 0.5 times the mass of γ-glycidyloxypropyltrimethoxysilane was added with ferroferric oxide, the temperature was raised to 110°C, refluxed for 3.5 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated ferroferric oxide. The pretreated ferroferric oxide, amino-A-cyclodextrin and N,N-dimethylformamide were mixed at a mass ratio of 1:5.5 and ultrasonically dispersed. Under nitrogen protection, the temperature was raised to 85°C for reaction for 24 hours. After the reaction, the mixture was filtered and washed with methanol for 3 times to obtain pre-modified ferroferric oxide. (2) Spinach leaves and an extractant were mixed at a mass ratio of 1:1.7 and ultrasonically treated for 35 minutes. The filtrate was filtered and retained, and chlorophyll was obtained by vacuum rotary evaporation and vacuum drying. Chlorophyll and ethanol were mixed at a mass ratio of 1:25, and the pH was adjusted to 10 with 10 mol / L sodium hydroxide. The mixture was heated to 65°C and reacted for 1 hour. After the reaction, the ethanol was removed by vacuum rotary evaporation, and pure water was used for separation. After the lower layer was retained by petroleum ether extraction, the pH was adjusted to 6 with 30 wt% hydrochloric acid solution, and the mixture was heated to 65°C and stirred for reaction for 1 hour to obtain chlorophyll acid. Chlorophyll acid, ferrous sulfate, and ethanol were mixed at a mass ratio of 1:0.8:25, and the mixture was heated to 60°C and reacted for 3 hours under nitrogen protection. The mixture was filtered and washed with pure water 4 times, and modified chlorophyll was obtained by vacuum drying. (3) Modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide were mixed in a mass ratio of 1:2:0.5:2:40, reacted at room temperature for 12 hours, filtered after the reaction, washed with pure water for 4 times, and vacuum dried to obtain modified ferrosoferric oxide; (4) Avermectin residue, potassium hydroxide, modified ferroferric oxide and acetone were mixed in a mass ratio of 1:0.15:0.002:55 and heated at 85°C with an intensity of 13 mW / cm 2 The mixture was irradiated with ultraviolet light for 45 minutes, separated by magnet, and the filtrate was retained for solid-liquid separation. The pH value was adjusted to 7 with 10 wt % sulfuric acid to obtain pretreated fungus residue. (5) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch were mixed in a mass ratio of 1:0.15:0.25:25, and pure water was added to make the moisture content of the pretreated fungus residue 65%. After stirring evenly, the mixture was aerobically composted and fermented at a fermentation temperature of 70°C. The mixture was kept warm for 3 days and then turned over once a day. The fermentation time was 7 days. The aging temperature was 40°C and the fermentation cycle was 5 days. Finally, the mixture was dried, crushed and granulated to obtain organic fertilizer.
[0024] The content of avermectin in the organic fertilizer was tested by high performance liquid chromatography, and the removal rate of avermectin in the organic fertilizer prepared in this embodiment was 99.9%.
[0025] Embodiment 3: A method for preparing organic fertilizer from avermectin residues, the method comprising the following preparation steps: (1) γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, 0.5 times the mass of γ-glycidyloxypropyltrimethoxysilane was added to ferroferric oxide, the temperature was raised to 110°C, refluxed for 3.4 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated ferroferric oxide. The pretreated ferroferric oxide, amino-A-cyclodextrin and N,N-dimethylformamide were mixed at a mass ratio of 1:5.2 and ultrasonically dispersed. Under nitrogen protection, the temperature was raised to 87°C for reaction for 24 hours. After the reaction, the mixture was filtered and washed with methanol for 3 times to obtain pre-modified ferroferric oxide. (2) Spinach leaves and an extractant were mixed at a mass ratio of 1:1.6 and subjected to ultrasonic treatment for 32 minutes. The filtrate was filtered and retained, and chlorophyll was obtained by vacuum rotary evaporation and vacuum drying. Chlorophyll and ethanol were mixed at a mass ratio of 1:27, and the pH was adjusted to 10.6 using 10 mol / L sodium hydroxide. The mixture was heated to 65°C and reacted for 1 hour. After the reaction, the ethanol was removed by vacuum rotary evaporation, and pure water was used for separation. After the lower layer was retained by petroleum ether extraction, the pH was adjusted to 6 using 30 wt% hydrochloric acid solution. The mixture was heated to 65°C and stirred for reaction for 1 hour to obtain chlorophyll acid. Chlorophyll acid, ferrous sulfate, and ethanol were mixed at a mass ratio of 1:0.74:23, and the mixture was heated to 60°C and reacted for 3 hours under nitrogen protection. The mixture was filtered and washed with pure water 4 times, and modified chlorophyll was obtained by vacuum drying. (3) Modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide were mixed in a mass ratio of 1:2:0.5:2:40, reacted at room temperature for 12 hours, filtered after the reaction, washed with pure water for 4 times, and vacuum dried to obtain modified ferrosoferric oxide; (4) Avermectin residue, potassium hydroxide, modified ferroferric oxide and acetone were mixed in a mass ratio of 1:0.13:0.002:53 and heated at 82°C with a strength of 13 mW / cm 2 The mixture was irradiated with ultraviolet light for 43 minutes, separated by magnet, and the filtrate was retained for solid-liquid separation. The pH value was adjusted to 6.3 with 10 wt % sulfuric acid to obtain pretreated fungus residue. (5) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch were mixed in a mass ratio of 1:0.12:0.27:26, and pure water was added to make the moisture content of the pretreated fungus residue 63%. After stirring evenly, the mixture was aerobically composted and fermented at a fermentation temperature of 72°C. The compost was kept warm for 3 days and then turned over at a frequency of once every 2 days. The fermentation time was 7 days, the aging temperature was 50°C, and the fermentation cycle was 7 days. Finally, the organic fertilizer was dried, crushed and granulated.
[0026] The avermectin content in the organic fertilizer prepared in this embodiment was detected by high performance liquid chromatography and the avermectin removal rate was calculated to be 99.9%.
[0027] Embodiment 4: A method for preparing organic fertilizer from avermectin residues, the method comprising the following preparation steps: (1) γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, 0.5 times the mass of γ-glycidyloxypropyltrimethoxysilane was added to ferroferric oxide, the temperature was raised to 110°C, refluxed for 3.2 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated ferroferric oxide. The pretreated ferroferric oxide, amino-A-cyclodextrin and N,N-dimethylformamide were mixed at a mass ratio of 1:6 and ultrasonically dispersed. Under nitrogen protection, the temperature was raised to 80°C for reaction for 24 hours. After the reaction, the mixture was filtered and washed with methanol for 3 times to obtain pre-modified ferroferric oxide. (2) Spinach leaves and an extractant were mixed at a mass ratio of 1:2.0 and ultrasonically treated for 30 minutes. The filtrate was filtered and retained, and chlorophyll was obtained by vacuum rotary evaporation. Chlorophyll and ethanol were mixed at a mass ratio of 1:30, and the pH was adjusted to 11 with 10 mol / L sodium hydroxide. The mixture was heated to 65°C and reacted for 1 hour. After the reaction, the ethanol was removed by vacuum rotary evaporation. Pure water was used for separation. The lower layer was retained after extraction with petroleum ether. The pH was adjusted to 6 with 30 wt% hydrochloric acid solution. The mixture was heated to 65°C and stirred for reaction for 1 hour to obtain chlorophyll acid. Chlorophyll acid, ferrous sulfate, and ethanol were mixed at a mass ratio of 1:0.9:30. The mixture was heated to 60°C and reacted for 3 hours under nitrogen protection. The mixture was filtered and washed with pure water 4 times, and modified chlorophyll was obtained by vacuum drying. (3) Modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide were mixed in a mass ratio of 1:2:0.5:2:40, reacted at room temperature for 12 hours, filtered after the reaction, washed with pure water for 4 times, and vacuum dried to obtain modified ferrosoferric oxide; (4) Avermectin residue, potassium hydroxide, modified ferroferric oxide and acetone were mixed in a mass ratio of 1:0.2:0.03:60 and heated at 80°C with an intensity of 13 mW / cm 2 The mixture was irradiated with ultraviolet light for 40 minutes, separated by magnet, and the filtrate was retained for solid-liquid separation. The pH value was adjusted to 6 with 10 wt % sulfuric acid to obtain pretreated fungus residue; (5) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch were mixed in a mass ratio of 1:0.2:0.3:30, and pure water was added to make the moisture content of the pretreated fungus residue 60%. After stirring evenly, the mixture was aerobically composted and fermented at a fermentation temperature of 60°C. The compost was kept warm for 3 days and then turned over once a day. The fermentation time was 7 days. The aging temperature was 30°C and the fermentation cycle was 4 days. Finally, the organic fertilizer was dried, crushed and granulated.
[0028] The content of avermectin in the organic fertilizer was tested by high performance liquid chromatography, and the removal rate of avermectin in the organic fertilizer prepared in this embodiment was 99.9%.
[0029] Embodiment 5: (1) γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, 0.5 times the mass of γ-glycidyloxypropyltrimethoxysilane was added to ferrous oxide, the temperature was raised to 110°C, refluxed for 3.6 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated ferrous oxide. The pretreated ferrous oxide, amino-A-cyclodextrin and N,N-dimethylformamide were mixed at a mass ratio of 1:5.7 and ultrasonically dispersed. Under nitrogen protection, the temperature was raised to 86°C for reaction for 24 hours. After the reaction, it was filtered and washed with methanol for 3 times to obtain pre-modified ferrous oxide; (2) Spinach leaves and an extractant were mixed at a mass ratio of 1:1.7 and ultrasonically treated for 36 minutes. The filtrate was filtered and retained, and chlorophyll was obtained by vacuum rotary evaporation. Chlorophyll and ethanol were mixed at a mass ratio of 1:27, and the pH was adjusted to 10.4 with 10 mol / L sodium hydroxide. The mixture was heated to 65°C and reacted for 1 hour. After the reaction, the ethanol was removed by vacuum rotary evaporation. Pure water was used for separation. The lower layer was retained after petroleum ether extraction. The pH was adjusted to 6 with a 30 wt% hydrochloric acid solution. The mixture was heated to 65°C and stirred for reaction for 1 hour to obtain chlorophyll acid. Chlorophyll acid, ferrous sulfate, and ethanol were mixed at a mass ratio of 1:0.8:26. The mixture was heated to 60°C and reacted for 3 hours under nitrogen protection. The mixture was filtered and washed with pure water 4 times, and modified chlorophyll was obtained by vacuum drying. (3) Modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide were mixed in a mass ratio of 1:2:0.5:2:40, reacted at room temperature for 12 hours, filtered after the reaction, washed with pure water for 4 times, and vacuum dried to obtain modified ferrosoferric oxide; (4) Avermectin residue, potassium hydroxide, modified ferroferric oxide and acetone were mixed in a mass ratio of 1:0.14:0.015:87 and heated at 86°C with an intensity of 13 mW / cm 2 The mixture was irradiated with ultraviolet light for 46 minutes, separated by magnet, and the filtrate was retained for solid-liquid separation. The pH value was adjusted to 6.7 with 10 wt % sulfuric acid to obtain pretreated fungus residue. (5) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch were mixed in a mass ratio of 1:0.14:0.25:25, and pure water was added to make the moisture content of the pretreated fungus residue 66%. After stirring evenly, the mixture was aerobically composted and fermented at a fermentation temperature of 68°C. The mixture was kept warm for 3 days and then turned over once a day. The fermentation time was 9 days. The mixture was aged under the following conditions: a temperature of 36°C and a fermentation period of 5 days. The organic fertilizer was then dried, crushed and granulated to obtain the organic fertilizer.
[0030] The content of avermectin in the organic fertilizer was tested by high performance liquid chromatography, and the removal rate of avermectin in the organic fertilizer prepared in this embodiment was 99.9%.
[0031] Embodiment 6: (1) γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, 0.5 times the mass of γ-glycidyloxypropyltrimethoxysilane was added with ferrous oxide, the temperature was raised to 110°C, refluxed for 3.6 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated ferrous oxide. The pretreated ferrous oxide, amino-A-cyclodextrin and N,N-dimethylformamide were mixed at a mass ratio of 1:5.6 and ultrasonically dispersed. Under nitrogen protection, the temperature was raised to 89°C for reaction for 24 hours. After the reaction, the mixture was filtered and washed with methanol for 3 times to obtain pre-modified ferrous oxide; (2) Spinach leaves and an extractant were mixed at a mass ratio of 1:1.9 and subjected to ultrasonic treatment for 36 minutes. The filtrate was filtered and retained, and chlorophyll was obtained by vacuum rotary evaporation and vacuum drying. Chlorophyll and ethanol were mixed at a mass ratio of 1:24, and the pH was adjusted to 10.4 using 10 mol / L sodium hydroxide. The mixture was heated to 65°C and reacted for 1 hour. After the reaction, the ethanol was removed by vacuum rotary evaporation, and pure water was used for separation. After the lower layer was retained by petroleum ether extraction, the pH was adjusted to 6 using 30 wt% hydrochloric acid solution. The mixture was heated to 65°C and stirred for reaction for 1 hour to obtain chlorophyll acid. Chlorophyll acid, ferrous sulfate, and ethanol were mixed at a mass ratio of 1:0.8:26, and the mixture was heated to 60°C and reacted for 3 hours under nitrogen protection. The mixture was filtered and washed with pure water 4 times, and modified chlorophyll was obtained by vacuum drying. (3) Modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide were mixed in a mass ratio of 1:2:0.5:2:40, reacted at room temperature for 12 hours, filtered after the reaction, washed with pure water for 4 times, and vacuum dried to obtain modified ferrosoferric oxide; (4) Avermectin residue, potassium hydroxide, modified ferroferric oxide and acetone were mixed in a mass ratio of 1:0.14:0.02:90 and heated at 85°C with an intensity of 13 mW / cm 2 The mixture was irradiated with ultraviolet light for 45 minutes, separated by magnet, and the filtrate was retained for solid-liquid separation. The pH value was adjusted to 6 with 10 wt % sulfuric acid to obtain pretreated fungus residue. (5) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch were mixed in a mass ratio of 1:0.15:0.26:27, and pure water was added to make the moisture content of the pretreated fungus residue 63%. After stirring evenly, the mixture was aerobically composted and fermented at a fermentation temperature of 68°C. The mixture was kept warm for 3 days and then turned over at a frequency of once every 2 days. The fermentation time was 7 days, and the mixture was aged at a temperature of 50°C and a fermentation period of 7 days. The organic fertilizer was then dried, crushed and granulated to obtain the organic fertilizer.
[0032] The content of avermectin in the organic fertilizer was tested by high performance liquid chromatography, and the removal rate of avermectin in the organic fertilizer prepared in this embodiment was 99.9%.
[0033] Embodiment 7: (1) γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, 0.5 times the mass of γ-glycidyloxypropyltrimethoxysilane was added with ferrous oxide, the temperature was raised to 110°C, refluxed for 3.4 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated ferrous oxide. The pretreated ferrous oxide, amino-A-cyclodextrin and N,N-dimethylformamide were mixed at a mass ratio of 1:5.3 and ultrasonically dispersed. Under nitrogen protection, the temperature was raised to 84°C for reaction for 24 hours. After the reaction, it was filtered and washed with methanol for 3 times to obtain pre-modified ferrous oxide; (2) Spinach leaves and an extractant were mixed at a mass ratio of 1:1.76 and ultrasonically treated for 36 minutes. The filtrate was filtered and retained, and chlorophyll was obtained by vacuum rotary evaporation. Chlorophyll and ethanol were mixed at a mass ratio of 1:27, and the pH was adjusted to 10.4 with 10 mol / L sodium hydroxide. The mixture was heated to 65°C and reacted for 1 hour. After the reaction, the ethanol was removed by vacuum rotary evaporation. Pure water was used for separation. The lower layer was retained after petroleum ether extraction. The pH was adjusted to 6 with a 30 wt% hydrochloric acid solution. The mixture was heated to 65°C and stirred for reaction for 1 hour to obtain chlorophyll acid. Chlorophyll acid, ferrous sulfate, and ethanol were mixed at a mass ratio of 1:0.88:25. The mixture was heated to 60°C and reacted for 3 hours under nitrogen protection. The mixture was filtered and washed with pure water 4 times, and modified chlorophyll was obtained by vacuum drying. (3) Modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide were mixed in a mass ratio of 1:2:0.5:2:40, reacted at room temperature for 12 hours, filtered after the reaction, washed with pure water for 4 times, and vacuum dried to obtain modified ferrosoferric oxide; (4) Avermectin residue, potassium hydroxide, modified ferroferric oxide and acetone were mixed in a mass ratio of 1:0.13:0.01:80 and heated at 83°C with an intensity of 13 mW / cm 2 The mixture was irradiated with ultraviolet light for 43 minutes, separated by magnet, and the filtrate was retained for solid-liquid separation. The pH value was adjusted to 6.4 with 10 wt % sulfuric acid to obtain pretreated fungus residue. (5) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch were mixed in a mass ratio of 1:0.13:0.25:25, and pure water was added to make the moisture content of the pretreated fungus residue 63%. After stirring evenly, the mixture was aerobically composted and fermented at a fermentation temperature of 73°C. The mixture was kept warm for 3 days and then turned over at a frequency of once every 2 days. The fermentation time was 7 days, and the mixture was aged at a temperature of 30°C and a fermentation period of 7 days. The organic fertilizer was then dried, crushed and granulated to obtain the organic fertilizer.
[0034] The content of avermectin in the organic fertilizer was tested by high performance liquid chromatography, and the removal rate of avermectin in the organic fertilizer prepared in this embodiment was 99.9%.
[0035] Comparative Example 1: (1) Avermectin residue, potassium hydroxide and pure water were mixed in a mass ratio of 1:0.15:55 and heated at 85°C with a strength of 13 mW / cm 2 The mixture was irradiated with ultraviolet light for 45 minutes, separated by magnet, and the filtrate was retained after solid-liquid separation. The pH was adjusted to 7 with 10 wt % sulfuric acid to obtain the pretreated fungus residue. (2) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch were mixed in a mass ratio of 1:0.15:0.25:25, and pure water was added to make the moisture content of the pretreated fungus residue 65%. After stirring evenly, the mixture was aerobically composted and fermented at a fermentation temperature of 70°C. The compost was kept warm for 3 days and then turned over once a day. The fermentation time was 7 days. The aging temperature was 40°C and the fermentation cycle was 5 days. Finally, the organic fertilizer was dried, crushed and granulated.
[0036] The content of avermectin in the organic fertilizer was tested by high performance liquid chromatography, and the removal rate of avermectin in the organic fertilizer prepared in this embodiment was 75.7%.
[0037] Comparative Example 2: (1) Avermectin residue, potassium hydroxide, modified ferroferric oxide and acetone were mixed in a mass ratio of 1:0.15:0.002:55, treated at 85°C for 45 minutes, separated by a magnet, and the filtrate was retained for solid-liquid separation. The pH was adjusted to 7 with 10 wt% sulfuric acid to obtain pretreated residue; (2) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch were mixed in a mass ratio of 1:0.15:0.25:25, and pure water was added to make the moisture content of the pretreated fungus residue 65%. After stirring evenly, the mixture was aerobically composted and fermented at a fermentation temperature of 70°C. The compost was kept warm for 3 days and then turned over once a day. The fermentation time was 7 days. The aging temperature was 40°C and the fermentation cycle was 5 days. Finally, the organic fertilizer was dried, crushed and granulated.
[0038] The content of avermectin in the organic fertilizer was tested by high performance liquid chromatography. The removal rate of avermectin in the organic fertilizer prepared in this embodiment was 59.7%.
[0039] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.
Claims
1. A method for preparing organic fertilizer from avermectin residues, characterized in that: The method comprises the following preparation steps: (1) Mix γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water for 10 minutes, add ferric oxide in an amount of 0.5 times the mass of γ-glycidyloxypropyltrimethoxysilane, heat to 110°C, reflux for 3-4 hours, filter and wash with anhydrous ethanol for 4 times, and vacuum dry to obtain pretreated ferric oxide. Mix the pretreated ferric oxide, amino-A-cyclodextrin and N,N-dimethylformamide in a mass ratio of 1:(5-6) and disperse by ultrasonication. Heat to 80-90°C under nitrogen protection for 24 hours. After the reaction, filter and wash with methanol for 3-4 times to obtain pre-modified ferric oxide. (2) Spinach leaves and an extractant were mixed at a mass ratio of 1:(1.5-2.0) and ultrasonically treated for 30-40 min, the filtrate was filtered and retained, and chlorophyll was obtained by vacuum rotary evaporation; chlorophyll and ethanol were mixed at a mass ratio of 1:(20-30), the pH was adjusted to 10-11 with 10 mol / L sodium hydroxide, the temperature was raised to 65°C and the reaction was continued for 1 h, and after the reaction, the ethanol was removed by vacuum rotary evaporation, and pure water was used for separation. After the lower layer was retained by petroleum ether extraction, the pH was adjusted to 6 with a 30 wt% hydrochloric acid solution, and the reaction was stirred at 65°C for 1 h to obtain chlorophyll acid; chlorophyll acid, ferrous sulfate, and ethanol were mixed at a mass ratio of 1:(0.7-0.9):(20-30), the temperature was raised to 60°C and the reaction was continued for 3 h under nitrogen protection, the mixture was filtered and washed with pure water 4 times, and the modified chlorophyll was obtained by vacuum drying; (3) Modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide were mixed and reacted at room temperature for 12 hours. After the reaction, the mixture was filtered and washed with pure water for 4 times, and then vacuum dried to obtain modified ferrosoferric oxide; (4) Mix avermectin residue, potassium hydroxide, modified ferroferric oxide and acetone, and heat them at 80-90°C with an intensity of 13mW / cm 2 The mixture was irradiated with ultraviolet light for 40-50 minutes, separated by magnet, and the filtrate was retained for solid-liquid separation. The pH value was adjusted to 6-8 with 10wt% sulfuric acid to obtain pretreated bacterial residue; (5) Pretreated fungus residue, Bacillus subtilis, Aspergillus niger and soluble starch are mixed in a mass ratio of 1:(0.1-0.2):(0.2-0.3):(20-30), and pure water is added to make the moisture content of the pretreated fungus residue 60%-70%. After stirring evenly, the mixture is subjected to aerobic composting, fermentation, aging, drying, crushing and granulation to obtain organic fertilizer.
2. The method for preparing organic fertilizer from avermectin bacteria residue according to claim 1, wherein The mass ratio of the γ-glycidyloxypropyltrimethoxysilane, anhydrous ethanol and pure water in step (1) is 1:1:
5.
3. a method for preparing organic fertilizer from avermectin bacteria residue according to claim 1, characterized in that, The extractant in step (2) is a mixture of 95 wt % ethanol solution and acetone in a volume ratio of 2:
1.
4. a method for preparing organic fertilizer from avermectin bacteria residue according to claim 1, characterized in that, The water content of the avermectin residue in step (3) is 10%-20%, and the residual concentration of avermectin is 1400-1700 mg / kg.
5. The method for preparing organic fertilizer from avermectin bacteria residue according to claim 1, wherein In step (3), the mass ratio of the modified ferrosoferric oxide, modified chlorophyll, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, diisopropylethylamine, and N,N-dimethylformamide is 1:2:0.5:2:
40.
6. The method for preparing organic fertilizer from avermectin bacteria residue according to claim 1, wherein In step (4), the mass ratio of the avermectin residue, potassium hydroxide, modified ferrosoferric oxide and acetone is 1:(0.1-0.2):(0.01-0.03):(80-100).
7. The method for preparing organic fertilizer from avermectin bacteria residue according to claim 1, wherein The aerobic composting fermentation method in step (5) is as follows: after the fermentation temperature reaches 60-75° C., the compost is kept warm for 3-4 days, and then the compost is turned over. The frequency of turning the compost is once every 1-2 days, and the fermentation time is 7-9 days.
8. a method for preparing organic fertilizer from a kind of avermectin bacteria residue according to claim 1, is characterized in that, The aging conditions in step (5) are: temperature of 30-50° C. and fermentation period of 4-7 days.
9. a method for preparing organic fertilizer from avermectin bacteria residue according to claim 1, characterized in that, The ferrosoferric oxide particle size in step (1) is 20-40 mesh.
10. The method for preparing organic fertilizer from avermectin slag according to claim 1, wherein: The soluble starch model in step (5) is S104452.