Preparation method and application of purified and refined components of chicken manure biogas slurry

Abstract

The application provides a preparation method and application of a purified and refined component of chicken manure biogas slurry. The purified and refined component obtained by the method is a crop phytotoxicity product with a wide application range and friendly to an ecological environment, can realize a phytotoxicity relieving and pesticide efficiency increasing application method in multiple ways and at different times on crops, and realizes bidirectional functional effects of phytotoxicity relieving and pesticide efficiency increasing.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of resource utilization of breeding waste and agricultural production, and particularly relates to a preparation method and application of a chicken manure biogas slurry purification and refining component. BACKGROUND

[0002] Pesticides are important inputs in agricultural production, and play an important role in the prevention and control of pests and weeds, and chemical weeding. In the actual agricultural production practice, excessive application of pesticides often occurs due to improper human operation, causing crop phytotoxicity stress and phytotoxicity, mainly including crop wilting, leaf abscission, leaf scorching and curling, growth stagnation and even death, and crop physiological and biochemical indexes mainly manifesting in a sharp increase in the content of antioxidant enzymes and malondialdehyde in plant cells. At present, there are various phytotoxicity relief products on the market, among which the main components of plant growth regulator products are brassinolide, indole acetic acid, sodium complex nitrophenol and other single or composite plant growth regulator phytotoxicity relief substances. However, plant hormone products have strong specificity for phytotoxicity, and the application range of a single product is narrow. In the process of application, the dosage and concentration need to be highly concerned. The conventional phytotoxicity relief agents are applied after pesticide application, and the time node is difficult to grasp. Once the growth point of the crop is damaged by the pesticide, the phytotoxicity relief agent cannot play an effective role. If the concentration and timing are not appropriate, not only the efficacy of the phytotoxicity relief agent is affected, but also further hormone excess hazards are caused. The phytotoxicity relief products of chloroacetamides, chloroacetamides and chloroacetamides mainly reduce the influence of phytotoxicity by specifically inducing crop detoxification metabolism mechanism, and are mainly used to solve the phytotoxicity problem of herbicides. However, they have no obvious effect on the phytotoxicity of other pesticides. At the same time, the chemical safeners inevitably bring new potential environmental pollution risks or crop safety hazards in the process of synthesis and use.

[0003] In addition, in the prior art, there are few phytotoxicity relief products that can simultaneously increase pesticide efficacy and reduce pesticide use. The method for enhancing the herbicidal effect of flupicolide and relieving phytotoxicity function proposes to use a plant hormone combination to increase the herbicidal effect of flupicolide and reduce phytotoxicity. The selection of pesticides has specificity, and is limited to a single form of stem and leaf spraying. Therefore, there is an important need to develop a phytotoxicity relief product with a wide application range for crops, which is friendly to the ecological environment, reduces the influence of crop phytotoxicity, and ensures the normal growth of phytotoxicity crops. SUMMARY

[0004] In view of the above problems, the application provides a preparation method of a purified and refined component of chicken manure biogas slurry, based on the specificity of component material composition, and through a large number of tests and tests, the technical personnel find that different application methods can play a dual role of drug damage and drug effect, the application further innovates the application method of drug damage and drug effect in multiple ways and at different times on crops on the basis of innovating the purification and refining method of chicken manure biogas slurry, realizes the dual functional role of drug damage and drug effect, and has outstanding application value and obvious creativity.

[0005] To achieve the above object, the specific technical scheme provided by the application is as follows:

[0006] The first aspect of the application provides a preparation method of a purified and refined component of chicken manure biogas slurry, the preparation method comprising: fully anaerobic fermentation of chicken manure to obtain original biogas slurry material; the original biogas slurry material is transported into an acidification adjustment tank, air is introduced for acidification hydrolysis, an ultrasonic wave generating device is arranged at the output pipeline of the acidification adjustment tank, and ultrasonic wave treatment is continuously performed; the biogas slurry after acidification hydrolysis and ultrasonic wave treatment is transported to an ultrafiltration raw material tank for ultrafiltration treatment to obtain an ultrafiltration clear liquid; the ultrafiltration clear liquid is subjected to nanofiltration treatment to obtain a nanofiltration concentrated liquid; the nanofiltration concentrated liquid is subjected to dewatering treatment to obtain a primary biogas slurry concentrated component; anhydrous methanol is added to the primary biogas slurry concentrated component, and ultrasonic wave is combined for leaching separation, anhydrous methanol is leached for 3-5 times, and methanol extraction liquid is separated and collected; the methanol extraction liquid is combined and subjected to reduced pressure distillation to obtain a methanol extract, water is added for redissolution, ethyl acetate is extracted to obtain ethyl acetate extraction liquid, and the extraction is performed for 3-5 times; after the second ethyl acetate extraction is completed, hydrochloric acid is added to the water phase solution separated and collected for pH adjustment, and ethyl acetate solvent extraction is further performed; the ethyl acetate extraction liquid extracted for multiple times is combined and subjected to reduced pressure distillation to obtain an ethyl acetate extract, a 50% methanol solution is added for redissolution to obtain the purified and refined component.

[0007] In some embodiments, the acidification hydrolysis is performed at 25-30 DEG C for 24 h.

[0008] Further, the acidification hydrolysis is performed at 25 DEG C for 24 h.

[0009] In some embodiments, the ultrasonic wave treatment is 20-25 kHz ultrasonic wave treatment.

[0010] Further, the ultrasonic wave treatment is 25 kHz ultrasonic wave treatment.

[0011] In some embodiments, the ultrafiltration pore size of the ultrafiltration is 100-200 nm.

[0012] Further, the ultrafiltration pore size of the ultrafiltration is 100 nm.

[0013] Further, the nanofiltration pore size is 1 nm.

[0014] In some embodiments, the dehydration process is as follows: the nanofiltration concentrated solution is pumped into a reaction kettle for primary dehydration treatment, low-pressure distillation, vacuum degree is lower than -0.09 Mpa, 30-35℃, to obtain concentrated solution; the concentration multiple is 5-10 times; the concentrated solution obtained by low-pressure distillation is subjected to secondary freeze-drying dehydration treatment by a freeze dryer, freeze-drying treatment parameters: pre-freezing temperature -25--20℃; drying temperature 30-35℃, pressure <100 pa.

[0015] Further, the dehydration process is as follows: the nanofiltration concentrated solution is pumped into a reaction kettle for primary dehydration treatment, low-pressure distillation, vacuum degree is lower than -0.09 Mpa, 35℃, to obtain concentrated solution; the concentration multiple is 10 times; the concentrated solution obtained by low-pressure distillation is subjected to secondary freeze-drying dehydration treatment by a freeze dryer, freeze-drying treatment parameters: pre-freezing temperature -25℃; drying temperature 30℃, pressure <100 pa.

[0016] In some embodiments, the leaching separation process is as follows: the primary biogas liquid concentrated component is placed in a reaction kettle with an ultrasonic device, anhydrous methanol is added according to a mass ratio of 1:4-1:8, the ultrasonic wave parameters are 25-30 kHz, and each leaching time is 1-2 h; the centrifugal parameters of the centrifugal separation of the leaching liquid are 1000 g, and the centrifugal time is 20-30 min.

[0017] Further, the leaching separation process is as follows: the primary biogas liquid concentrated component is placed in a reaction kettle with an ultrasonic device, anhydrous methanol is added according to a mass ratio of 1:8, the ultrasonic wave parameters are 25-30 kHz, and each leaching time is 1-2 h; the centrifugal parameters of the centrifugal separation of the leaching liquid are 1000 g, and the centrifugal time is 20-30 min.

[0018] In some embodiments, the vacuum distillation conditions of the methanol extraction liquid are as follows: vacuum degree is lower than -0.09 Mpa, 30-35℃.

[0019] Further, the vacuum distillation conditions of the methanol extraction liquid are as follows: vacuum degree is lower than -0.09 Mpa, 35℃.

[0020] In some embodiments, the water addition and resolubilization ratio is water to methanol extract mass ratio 1:1-1:1.5.

[0021] Further, the water addition and resolubilization ratio is water to methanol extract mass ratio 1:1.5.

[0022] In some embodiments, the ethyl acetate extraction ratio is ethyl acetate to methanol extract resolubilization solution weight ratio 1:1-1:4.

[0023] Further, the ratio of the ethyl acetate extraction is ethyl acetate to methanol extract re-dissolution solution weight ratio 1:4.

[0024] Further, the process of the ethyl acetate extraction is as follows: oscillation 0.5-1 h, standing 1 h, separating the ethyl acetate phase by a liquid separator.

[0025] In some embodiments, after the end of the second ethyl acetate extraction, 1 mol / L hydrochloric acid is added to the water phase solution separated by extraction to adjust the pH to 2.5-3.0, and then ethyl acetate solvent extraction is continued, ethyl acetate is added at a water phase solution mass ratio of 1:1-1:4, oscillation is performed for 0.5-1 h, standing is performed for 1 h, the ethyl acetate phase is separated by a liquid separator, and extraction is continued for 1-3 times.

[0026] Further, after the end of the second ethyl acetate extraction, 1 mol / L hydrochloric acid is added to the water phase solution separated by extraction to adjust the pH to 3.0, and then ethyl acetate solvent extraction is continued, ethyl acetate is added at a water phase solution mass ratio of 1:4, oscillation is performed for 0.5 h, standing is performed for 1 h, the ethyl acetate phase is separated by a liquid separator, and extraction is continued for 2 times.

[0027] In some embodiments, the reduced pressure distillation condition of the ethyl acetate extraction solution is that the vacuum degree is lower than -0.09 Mpa, and the temperature is 30-40℃.

[0028] Further, the reduced pressure distillation condition of the ethyl acetate extraction solution is that the vacuum degree is lower than -0.09 Mpa, and the temperature is 35℃.

[0029] In some embodiments, the re-dissolution ratio of the 50% methanol solution is 50% methanol solution to ethyl acetate extract mass ratio 1:1-1:5.

[0030] Further, the re-dissolution ratio of the 50% methanol solution is 50% methanol solution to ethyl acetate extract mass ratio 1:2.5.

[0031] The second aspect of the present application provides a purified and refined component prepared by the preparation method according to the first aspect of the present application.

[0032] The third aspect of the present application provides a method for relieving pesticide phytotoxicity, which comprises applying the purified and refined component according to the second aspect of the present application.

[0033] Further, the pesticide comprises herbicides, insecticides, and fungicides.

[0034] Further, the pesticide is nicosulfuron.

[0035] In specific embodiments of the present application, nicosulfuron, also known as Yunnongle and nicosulfuron, is a selective herbicide of the sulfonylurea class, with the molecular formula C 15 H 18 N6O6S.

[0036] Further, the pesticide is 2,4-D isooctyl ester.

[0037] In specific embodiments of the present application, 2,4-D isooctyl ester refers to a selective post-emergence contact herbicide with the molecular formula C 16 H 22 Cl2O3, suitable for soybean, corn, and wheat.

[0038] In some embodiments, the method comprises applying the purified refined component of the second aspect of the present application before sowing.

[0039] Further, the method of applying the purified refined component is seed soaking after dilution.

[0040] Further, the dilution factor is 10,000 to 50,000 times.

[0041] Further, the dilution factor is 10,000 times.

[0042] Further, the temperature of seed soaking is 25 to 30°C.

[0043] Further, the time of seed soaking is 8 to 12 hours.

[0044] In some embodiments, the method comprises applying the purified refined component of the second aspect of the present application before applying the pesticide.

[0045] Further, the method of applying the purified refined component is foliar spraying after dilution.

[0046] Further, the dilution factor is 20,000 to 100,000 times.

[0047] Further, the dilution factor is 20,000 times.

[0048] Further, the number of times of applying the purified refined component is 2 to 3 times, with an interval of 3 to 5 days.

[0049] Further, the method of applying the purified refined component is as follows: foliar spraying after dilution of the purified refined component before applying the pesticide, with an interval of 3 to 5 days, and continuous application of 2 times or more, followed by application of the pesticide.

[0050] Further, the interval between the last application of the purified refined component and the application of the pesticide is within 48 hours.

[0051] In some embodiments, the method comprises applying the purified refined component of the second aspect of the present application after the crop has been affected by phytotoxicity.

[0052] Further, the purified refined component is applied by foliar spraying after dilution.

[0053] Further, the dilution is 20,000 to 100,000 times.

[0054] Further, the dilution is 50,000 times.

[0055] Further, the purified refined component is applied 2 to 3 times with an interval of 1 to 3 days.

[0056] Further, the purified refined component is applied by foliar spraying after dilution, and the application is performed 2 or more times with an interval of 1 to 3 days.

[0057] Further, the purified refined component is applied at the early stage of the appearance of phytotoxicity symptoms.

[0058] Further, the purified refined component is applied within 24 hours of the appearance of phytotoxicity symptoms.

[0059] Further, the purified refined component is applied after the removal of the severely phytotoxic tissues of the crop.

[0060] The fourth aspect of the present application provides a method for enhancing the efficacy of a pesticide, which comprises mixing and applying the purified refined component of the second aspect of the present application with the pesticide.

[0061] Further, the pesticide comprises herbicides, insecticides, and fungicides.

[0062] Further, the pesticide is tebuconazole.

[0063] In a specific embodiment of the present application, tebuconazole is an organic compound with a molecular formula of C 16 H 22 ClN3O, which is a highly effective, broad-spectrum, and systemic triazole fungicide, and is mainly used for preventing and treating various fungal diseases on crops such as wheat, rice, peanuts, vegetables, bananas, apples, pears, and corn.

[0064] Further, the mixing and application is performed by diluting the purified refined component, mixing it with the pesticide, and applying it to the surface of the soil and / or foliar spraying; and the amount of the pesticide is reduced by 10% to 20% compared to the amount without the purified refined component.

[0065] Further, the dilution is 20,000 to 100,000 times.

[0066] Further, the dilution factor is 20,000 times, and the amount of pesticide is reduced by 20% compared to the non-purified component.

[0067] The fifth aspect of the application provides the use of the purified component according to the second aspect of the application, which includes any one of the following:

[0068] 1) application in relieving soil pesticide residue phytotoxicity before sowing; 2) application in relieving soil pesticide phytotoxicity after sowing; 3) application in preventing pesticide phytotoxicity before applying pesticide to crops; 4) application in promoting recovery after the occurrence of phytotoxicity symptoms in crops; 5) application in enhancing pesticide efficacy and reducing pesticide use.

[0069] Further, the pesticide includes herbicides, insecticides, and fungicides.

[0070] Further, the pesticide is nicosulfuron.

[0071] Further, the pesticide is 2,4-D isooctyl ester.

[0072] Further, the pesticide is tebuconazole.

[0073] Further, the crop is selected from field crops and economic crops.

[0074] Further, the crop is corn.

[0075] Further, the crop is apple.

[0076] Advantages and beneficial effects of the application:

[0077] 1) The purified component provided by the application is derived from anaerobic fermentation of biogas slurry and prepared by multi-stage purification and refinement, which has biological safety. The extraction conditions of the purification and refinement process are the best condition parameters obtained through long-term comparison and test, and the selected extractants can be recycled and reused, and the preparation process is environmentally friendly.

[0078] 2) The purified component provided by the application realizes the integration of phytotoxicity relief and pesticide efficacy enhancement through the innovation and optimization of the application method.

[0079] 3) The purified component provided by the application can realize multi-scene and multi-path phytotoxicity relief application, and the application method of seed soaking, pre-pesticide application, and post-phytotoxicity relief is more practical, which can meet the multi-scene phytotoxicity relief application requirements of crops. DETAILED DESCRIPTION

[0080] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0081] Example 1 Preparation of specific chicken manure biogas slurry concentrated purification refined components

[0082] a. The chicken manure is subjected to sufficient mesophilic anaerobic fermentation to obtain a raw biogas slurry material.

[0083] b. The raw biogas slurry material is transported to an acidification adjustment tank, air is continuously introduced into the adjustment tank, and 25℃ acidification hydrolysis is performed for 24h to realize raw biogas slurry hydrolysis and precipitation. An ultrasonic wave generating device is installed at the output pipeline of the acidification adjustment tank, and 25kHz ultrasonic wave treatment is continuously performed to promote the degradation of insoluble or hardly soluble substances in the biogas slurry and further promote the conversion of macromolecular substances into small molecular substances, thereby facilitating the separation and collection of small molecular substances by a subsequent membrane.

[0084] c. The biogas slurry after acidification hydrolysis and ultrasonic wave treatment is transported to an ultrafiltration raw material tank, and ultrafiltration clear liquid is collected by an ultrafiltration membrane. The ultrafiltration clear liquid is further concentrated and separated by a nanofiltration membrane to collect nanofiltration membrane concentrated liquid. Specifically, the ultrafiltration pore size is 100nm, and the nanofiltration pore size is 1nm.

[0085] d. The nanofiltration concentrated liquid is subjected to dehydration treatment to obtain a primary biogas slurry concentrated component. Specifically, the nanofiltration concentrated liquid is pumped into a reaction kettle for primary dehydration treatment, low-pressure distillation, and vacuum degree lower than -0.09Mpa at 35℃ to obtain concentrated liquid. The concentration multiple is 10 times. The concentrated liquid obtained by low-pressure distillation is further subjected to secondary freeze-drying dehydration treatment by a freeze-drying machine, and the freeze-drying treatment parameters are: pre-freezing temperature -25℃, drying temperature 30℃, and pressure <100pa to obtain the primary biogas slurry concentrated component.

[0086] e. Anhydrous methanol is added to the primary biogas slurry concentrated component, and ultrasonic wave is used for extraction separation to collect the filtrate after methanol extraction. Specifically, the primary biogas slurry concentrated component is taken into a reaction kettle (with an ultrasonic device), anhydrous methanol is added at a mass ratio of 1:8, and the ultrasonic wave parameters are 25-30kHz, and each extraction is performed for 1~2h. The extraction liquid is separated by centrifugation, and the centrifugation parameters are 1000g and 20~30min. The anhydrous methanol is extracted for 3 times.

[0087] f. The methanol extraction liquid is combined and subjected to reduced-pressure distillation to remove methanol and obtain methanol extract. The reduced-pressure distillation parameters are: vacuum degree lower than -0.09Mpa and 35℃. The recovered methanol can be reused for extraction.

[0088] g. Redissolve the methanol extract in water. Specifically, redissolve in water at a weight ratio of 1:1.5 with the methanol extract.

[0089] h. Add pure ethyl acetate to the reconstituted methanol extract and shake to promote extraction. Allow to stand and separate the ethyl acetate phase. Specifically, take the reconstituted methanol extract and add ethyl acetate at a weight ratio of 1:4. Shake for 0.5 hours each time, let stand for 1 hour, and separate the ethyl acetate phase using a separatory device. Repeat the extraction 3-5 times.

[0090] i. After the second ethyl acetate extraction, adjust the pH to 3.0 by adding 1 mol / L hydrochloric acid to the aqueous phase solution from the extraction separation, and then continue the ethyl acetate solvent extraction. Add ethyl acetate at a weight ratio of 1:4 with the aqueous phase solution, shaking for 0.5 h each time, letting stand for 1 h, and separating the ethyl acetate phase using a separatory device. Repeat the extraction twice. Combine the obtained ethyl acetate extract with the ethyl acetate extracts obtained from the first two extractions.

[0091] According to the experimental results, after two extractions of ethyl acetate, the pH was adjusted to 3.0 with hydrochloric acid, and then the ethyl acetate was extracted twice more. The final combined ethyl acetate extract weight was 18% higher than that of four extractions without hydrochloric acid adjustment (p < 0.05).

[0092] j. Combine the multiple ethyl acetate extracts and perform vacuum distillation to remove ethyl acetate. The vacuum distillation parameters are below -0.09 MPa and 35°C. The recovered ethyl acetate can be reused for extraction.

[0093] k. Collect the ethyl acetate extract, and redissolve the extract in 50% methanol solution at a weight ratio of 1:2.5 with the ethyl acetate extract. Collect the solution, which is the concentrated, purified and refined component of chicken manure biogas slurry.

[0094] Example 2: Application method and efficacy test of purified and refined components in crop pesticide damage relief.

[0095] Application Method 1: Apply by soaking seeds. This avoids situations where excessive pesticide residues in the previous crop soil negatively impact seed germination or seedling growth, ensuring normal crop growth. The specific application method is as follows: Before sowing in soil with excessive pesticide residues from the previous crop, dilute the purified and refined components 10,000-50,000 times, soak the seeds at 25℃ for 12 hours, and then sow. This method is also suitable for situations where pesticides need to be sprayed on the soil surface after sowing, preventing excessive pesticides from affecting seed germination or seedling growth and ensuring normal crop growth. Pesticides include herbicides, insecticides, and fungicides.

[0096] Efficacy verification: Indoor test on the effect of purified and refined components in seed soaking to reduce nicosulfuron-induced herbicide damage to maize.

[0097] 1. Test material: corn variety "Denghai 605"; nicosulfuron 4%; purified refined component; raw biogas liquid.

[0098] 2. Test method

[0099] 1) Seed soaking: The purified refined component was prepared into solutions with dilution of 100,000 times, 50,000 times, 20,000 times, 10,000 times, and 5,000 times, respectively, using deionized water; the raw biogas liquid was prepared into a solution with dilution of 100 times (based on the characteristics of high-concentration chicken manure biogas liquid, a 100-fold dilution solution is suitable for seed soaking treatment) using deionized water; deionized water was used as a control. According to the dosage of 2 L of solution per kilogram of corn seeds, the seeds were soaked for 12 h at 25°C.

[0100] 2) Drug soil preparation: The soil of a vegetable greenhouse was used, and the nicosulfuron addition concentration in the soil was set to 0.25 mg / kg. Nicosulfuron 4% was first diluted 16,000 times to prepare a 2.5 mg / L solution, then 100 mL of the solution was added to each kilogram of soil, and the soil was mixed and placed in a cool place for 24 h.

[0101] 3) Sowing: Three trays were set up for each test group, and the seeds soaked were sown in 32-hole nursery plug trays using the drug soil as the seedling substrate, with 1 seed per hole, and the seeds were gently pressed into the substrate to a depth of 1 cm using tweezers.

[0102] 4) Cultivation: The nursery plug trays were placed in a light incubator under 14 h light / 10 h darkness at 30°C / 25°C.

[0103] 5) Determination index: The germination rate was counted after 6 days of sowing, and the plant height and aboveground fresh weight were measured after 15 days.

[0104] 3. Test treatment

[0105] Table 1. Grouping of indoor test for reducing nicosulfuron phytotoxicity to corn by seed soaking

[0106]

[0107] 4. Test results

[0108] Table 2. Results of indoor test for reducing nicosulfuron phytotoxicity to corn by seed soaking

[0109]

[0110] The letters in the table represent the results of difference analysis between different test groups, and the same letter represents no significant difference, and different letters represent significant difference.

[0111] The results are shown in Table 2. In terms of seedling emergence rate and plant height, the T3-T5 groups, i.e. the corn seed test groups treated by soaking with the purified and refined component diluted 50,000 times to 10,000 times, were significantly improved compared with the water control CK1 treated by soaking with water and then spraying with nicosulfuron, and had no significant difference with the blank control CK0. In terms of plant fresh weight, the T3-T5 groups were significantly improved compared with the water control CK1, and the T5 group had no significant difference with the blank control CK0, showing a drug damage alleviating effect. The T1 raw biogas liquid treatment had no significant difference with the CK1 in seedling emergence rate, plant fresh weight and plant height, and did not show a drug damage alleviating effect. In summary, the purified and refined component prepared according to the method of the present patent, when diluted 50,000 times to 10,000 times and used for soaking corn seeds, can effectively alleviate the drug damage of nicosulfuron sprayed on the soil surface before seedling emergence.

[0112] Application mode two is to spray the application before pesticide application, to achieve the pretreatment of crops before pesticide application, and to reduce the drug damage of subsequent pesticide application on crops. The specific application method is: dilute the purified and refined component to 20,000-100,000 times, spray on the leaves, apply 3-5 days each time, continuously apply more than 2 times, and then apply pesticides. The optimal time interval between the last application of the purified and refined component and the application of pesticides is within 48 hours. This can reduce the drug damage of subsequent pesticide application on crops, and the pesticides include herbicides, insecticides and fungicides.

[0113] Effect test: application test of the purified and refined component for preventing 2,4-D isooctyl ester from causing drug damage to corn

[0114] 1. Test conditions: corn (Denghai 605) was used as the test crop. All test groups had consistent cultivation conditions, and water, fertilizer and pesticide management was consistent.

[0115] 2. Test treatment: after the 3rd true leaf unfolded, the raw biogas liquid and the purified and refined component pesticide with different dilution multiples were sprayed, 3 days apart, a total of 2 times. One day after the 2nd spraying, 77% 2,4-D isooctyl ester herbicide 500 times dilution liquid was sprayed. Each test group had 3 replicates, with 60 plants in each replicate. The drug damage was investigated 5 days after spraying 2,4-D isooctyl ester herbicide, and the detoxification effect was calculated.

[0116] Table 3. Application test of the purified and refined component for preventing 2,4-D isooctyl ester from causing drug damage to corn

[0117]

[0118] 3. Measurement method

[0119] Phytotoxicity classification: 0 level - normal growth, consistent with the growth of the water control; 1 level - slightly abnormal heart leaf, no wilting of the plant; 2 level - obviously abnormal heart leaf, slightly wilting of the plant; 3 level - obviously abnormal heart leaf, mild wilting of the plant; 4 level - severely abnormal heart leaf, obvious wilting of the plant; 5 level - severe wilting of the plant, severe yellowing of the whole leaf.

[0120]

[0121]

[0122] 4、Test results

[0123] Table 4. Application test results of preventing 2,4-D isooctyl ester phytotoxicity on corn

[0124]

[0125] The letters in the table represent the results of difference analysis between different test groups, and the same letter represents no significant difference, and different letters represent significant difference.

[0126] The results are shown in Table 4. Before spraying herbicide, spraying purified refined component diluent twice in succession can prevent herbicide 2,4-D isooctyl ester phytotoxicity on corn plants, and the detoxification effect is more affected by the concentration of purified refined component. The detoxification effect of T3-T5 group is better, and the plants basically have no obvious phytotoxicity, which is significantly different from the detoxification effect index of CK group, and the detoxification effect is significantly higher than that of T1 group, T2 group and T6 group. The T1 group, T2 group and T6 group treated with biogas slurry still show obvious phytotoxicity, such as leaf edge distortion and new leaf shrinkage. In summary, according to the method of the present patent, spraying 100,000 to 20,000 times diluted solution of purified refined component before spraying 2,4-D isooctyl ester can effectively reduce the phytotoxicity of excessive 2,4-D isooctyl ester on crops.

[0127] Application mode three, after the occurrence of phytotoxicity, to achieve the effect of reducing crop phytotoxicity and promoting the plant to recover growth performance as soon as possible. The specific application method is: dilute the purified refined component to 20,000 to 100,000 times, and apply it by stem and leaf spraying, with an interval of 1-3 days each time, and continuously apply for more than 2 times, which can reduce the phytotoxicity to crops and promote the plant to recover as soon as possible. Note: it needs to be applied in the early stage of phytotoxicity symptoms, preferably within 24 hours of the occurrence of phytotoxicity symptoms. Trim off the plant tissues with more serious phytotoxicity before application.

[0128] Effect test: application of purified refined component to alleviate 2,4-D isooctyl ester phytotoxicity on corn

[0129] 1. Test conditions: corn (Denghai 605) as test crop. All test groups have consistent cultivation conditions, consistent water, fertilizer and pesticide management.

[0130] 2. Test treatment: After the 4th true leaf unfolds, the leaf surface is sprayed with 77% 2,4-D isooctyl ester herbicide 500 times dilution liquid. On the first day of the occurrence of phytotoxicity symptoms, the original biogas liquid, the purified refined component pesticide of different dilution multiples are sprayed, and the spraying is interval 2 days for 1 time, a total of 2 times. Each test group is set up 3 repeats, and each repeat is 60 plants. 5 days after the second spraying of each test group of pesticides, the phytotoxicity is investigated, and the detoxification effect is calculated.

[0131] Table 5. Application test grouping for relieving 2,4-D isooctyl ester phytotoxicity to corn

[0132]

[0133] 3. Determination method

[0134] Phytotoxicity classification: 0 level--normal growth, consistent with the growth of the water control; 1 level--heart leaf slightly deformed, plant without wilting; 2 level--heart leaf obviously deformed, plant slightly wilting; 3 level--heart leaf obviously deformed, plant mild wilting; 4 level--heart leaf severely deformed, plant obviously wilting; 5 level--plant severely wilting, leaf yellowing.

[0135]

[0136]

[0137] 4. Test results

[0138] Table 6. Application test results for relieving 2,4-D isooctyl ester phytotoxicity to corn

[0139]

[0140] The results are shown in Table 6. After the corn occurs phytotoxicity, the purified refined component dilution liquid is sprayed continuously for 2 times, which can relieve the phytotoxicity of herbicide 2,4-D isooctyl ester to corn plants, and the detoxification effect is more affected by the concentration of the purified refined component. The phytotoxicity index of T3~T5 groups is low, and the detoxification effect is good, which is significantly different from the phytotoxicity index of the CK group. The T1 group treated with the original biogas liquid has no significant difference with the CK group, and still shows obvious phytotoxicity symptoms. The detoxification effect of T3~T5 groups is significantly higher than that of T2, T6 groups and T1 group treated with the original biogas liquid. In summary, the purified refined component prepared according to the method of the patent can effectively reduce the phytotoxicity of excessive 2,4-D isooctyl ester to crops and promote the recovery of crops after spraying 2,4-D isooctyl ester phytotoxicity by spraying the purified refined component 10 times to 2 times dilution liquid.

[0141] Application method and effect test of the application of the purified refined component to crop increasing effect

[0142] Application method: the purified refined component can enhance the effect of crops when mixed with pesticides, wherein the pesticides include agents applied in the form of soil surface spraying and crop leaf spraying. The specific application method is: before mixed application with the agent, the purified refined component is diluted by 20,000-100,000 times, and then mixed with the diluted agent. It is necessary to note that the amount of pesticide is reduced by 10%-20%, so as to achieve the effect of increasing pesticide and reducing pesticide.

[0143] Effect test: field test of the synergistic effect of the purified refined component mixed with tebuconazole

[0144] 1. Test conditions: the test site is located in Hongfushi apple orchard in Nanwang Street, Penglai District, Yantai City, Shandong Province, with a tree age of 10 years. All test plots have consistent cultivation conditions, except for the difference in tebuconazole agent application, other water, fertilizer and pesticide management are consistent.

[0145] 2. Test treatment: according to the pesticide application scheme of the apple orchard, spraying is started before the occurrence of apple ring rot, once a month. That is, a total of 4 times in June, July, August and September. Each test group has 3 repetitions, and each repetition has 3 trees. The control agent is 43% tebuconazole suspension concentrate, which is diluted by 4000 times and 5000 times respectively as the control group. The 43% tebuconazole suspension concentrate diluent is mixed with the original biogas liquid and the purified refined component diluent for application as each test group, and the test group is set to use the purified refined component 10,000, 5,000 and 20,000 times diluent alone to determine the effect of the purified refined component.

[0146] Table 7. Field test of the synergistic effect of the purified refined component mixed with tebuconazole

[0147]

[0148] 3. Measurement method: at the harvest period (October), 2 trees are selected in each plot, all fruits are investigated, total fruit number and diseased fruit number are recorded, and control effect is calculated according to the rate of diseased fruit.

[0149]

[0150]

[0151] 4. Test results

[0152] Table 8. Field test results of the synergistic effect of the purified refined component mixed with tebuconazole

[0153]

[0154] The letters in the table represent the results of difference analysis between different test groups, and the same letter represents no significant difference, and different letters represent significant difference.

[0155] The results are shown in Table 8. When the purified and refined component is mixed with the fungicide tebuconazole, the control effect of T6 group has no significant difference with the conventional dosage of tebuconazole CK1 group, and is significantly better than the CK2 group with 20% less dosage of tebuconazole. The control effect of T7 and T8 groups is significantly better than the conventional dosage of tebuconazole CK1 group and the CK2 group with 20% less dosage of tebuconazole. When the dosage of tebuconazole is reduced by 20%, the application of 10 million to 2 million times diluted solution of the mixed purified and refined component can achieve the control effect of the conventional dosage, and even the control effect is better than that of the conventional dosage.

[0156] The control effect of T5 group has no significant difference with T9 group, although it shows a certain synergistic effect on tebuconazole, but it has significant difference with the conventional dosage of tebuconazole CK1 group, and does not effectively play the synergistic effect of tebuconazole on the prevention and control of apple ring rot. The control effect of T4 raw marsh liquid group has no significant difference with the CK2 group with 20% less dosage of tebuconazole, and does not show the synergistic effect. In order to further verify whether the purified and refined component itself has the effect of preventing and controlling apple ring rot, the test groups of 10 million times, 5 million times and 2 million times diluted solution of the purified and refined component are set. The test results show that the single application of the purified and refined component cannot prevent and control apple ring rot. In summary, the purified and refined component prepared according to the method of the patent can enhance the effect of tebuconazole on the prevention and control of apple ring rot when it is diluted 10 million to 2 million times and mixed with tebuconazole, and can achieve the effect of synergistic reduction of pesticide dosage.

[0157] The above description of the embodiments is only for understanding the method of the present application and its core idea. It should be noted that for those skilled in the art, without departing from the principles of the present application, some improvements and modifications can be made to the present application, and these improvements and modifications will also fall within the protection scope of the claims of the present application.

Claims

1. A method for preparing purified and refined components of chicken manure biogas slurry, characterized in that, The preparation method includes: Chicken manure undergoes thorough mesophilic anaerobic fermentation to obtain raw biogas slurry. The raw biogas slurry material is transported to an acidification and conditioning tank, where air is introduced for acidification and hydrolysis. An ultrasonic generator is installed at the output pipe of the acidification and conditioning tank to continuously perform ultrasonic treatment. The biogas slurry after acidification, hydrolysis, and ultrasonic treatment is transported to the ultrafiltration feed tank for ultrafiltration treatment to obtain ultrafiltration clear liquid. The ultrafiltrate is subjected to nanofiltration to obtain nanofiltration concentrate; The nanofiltration concentrate is dehydrated to obtain a primary biogas slurry concentrate. Anhydrous methanol was added to the primary biogas slurry concentrate, and the extraction and separation were carried out by ultrasonic extraction. The anhydrous methanol was extracted 3 to 5 times, and the methanol extract was collected. The methanol extracts were combined and subjected to vacuum distillation to obtain a methanol extract. After redissolving in water, the extracts were extracted with ethyl acetate to obtain an ethyl acetate extract. The extraction was repeated 3 to 5 times. After the second ethyl acetate extraction, hydrochloric acid was added to the aqueous phase solution to adjust the pH, and ethyl acetate solvent extraction was continued. The ethyl acetate extracts obtained from multiple extractions were combined and subjected to vacuum distillation to obtain an ethyl acetate extract. The extract was then redissolved in 50% methanol solution to obtain the purified component.

2. The preparation method according to claim 1, characterized in that, The acidification and hydrolysis conditions are 25~30℃ for 24 hours.

3. The preparation method according to claim 1, characterized in that, The acidification and hydrolysis conditions are 25°C for 24 hours.

4. The preparation method according to claim 1, characterized in that, The ultrasonic treatment is a 20-25 kHz ultrasonic treatment.

5. The preparation method according to claim 1, characterized in that, The ultrasonic treatment is a 25 kHz ultrasonic treatment.

6. The preparation method according to claim 1, characterized in that, The ultrafiltration pore size is 100~200 nm.

7. The preparation method according to claim 1, characterized in that, The ultrafiltration pore size is 100 nm.

8. The preparation method according to claim 1, characterized in that, The nanofiltration pore size is 1 nm.

9. The preparation method according to claim 1, characterized in that, The dehydration process is as follows: the nanofiltration concentrate is pumped into the reactor for primary dehydration treatment, followed by low-pressure distillation at a vacuum level below -0.09 MPa and a temperature of 30~35℃ to obtain a concentrated solution with a concentration ratio of 5~10 times; the concentrated solution obtained from low-pressure distillation is then subjected to secondary freeze-drying dehydration treatment using a freeze dryer with the following freeze-drying parameters: pre-freezing temperature -25~-20℃; drying temperature 30~35℃; and pressure <100 Pa.

10. The preparation method according to claim 1, characterized in that, The dehydration process is as follows: the nanofiltration concentrate is pumped into the reactor for primary dehydration treatment, followed by low-pressure distillation at a vacuum level below -0.09 MPa and a temperature of 35°C to obtain a concentrated solution with a concentration factor of 10 times. The concentrated solution obtained from low-pressure distillation is then subjected to secondary freeze-drying dehydration treatment using a freeze dryer. The freeze-drying parameters are: pre-freezing temperature -25°C; drying temperature 30°C; and pressure <100 Pa.

11. The preparation method according to claim 1, characterized in that, The extraction and separation process is as follows: the primary biogas slurry concentrate is placed in a reactor equipped with an ultrasonic device, and anhydrous methanol is added at a mass ratio of 1:4 to 1:

8. The ultrasonic parameters are 25 to 30 kHz, and the extraction is carried out for 1 to 2 hours each time. The extract is centrifuged at 1000g for 20 to 30 minutes.

12. The preparation method according to claim 1, characterized in that, The extraction and separation process is as follows: the primary biogas slurry concentrate is placed in a reactor equipped with an ultrasonic device, and anhydrous methanol is added at a mass ratio of 1:

8. The ultrasonic parameters are 25~30 kHz, and the extraction is carried out for 1~2 hours each time. The extract is centrifuged at 1000g for 20~30 minutes.

13. The preparation method according to claim 1, characterized in that, The reduced pressure distillation conditions for the methanol extract are: vacuum degree below -0.09 MPa, 30~35℃.

14. The preparation method according to claim 1, characterized in that, The methanol extract was distilled under reduced pressure under the following conditions: vacuum level below -0.09 MPa, 35°C.

15. The preparation method according to claim 1, characterized in that, The ratio of water to methanol extract is 1:1 to 1:1.5 by mass.

16. The preparation method according to claim 1, characterized in that, The ratio of water to methanol extract is 1:1.5 by mass.

17. The preparation method according to claim 1, characterized in that, The ratio of ethyl acetate extraction to methanol extract reconstituted solution is 1:1 to 1:4 by weight.

18. The preparation method according to claim 1, characterized in that, The ratio of ethyl acetate extraction to the weight of the methanol extract reconstituted solution is 1:

4.

19. The preparation method according to claim 1, characterized in that, The ethyl acetate extraction process is as follows: shake for 0.5-1 h, let stand for 1 h, and separate the ethyl acetate phase using a separator.

20. The preparation method according to claim 1, characterized in that, After the second ethyl acetate extraction, 1 mol / L hydrochloric acid was added to the aqueous phase solution to adjust the pH to 2.5-3.0, and then ethyl acetate solvent extraction was continued. Ethyl acetate was added at a mass ratio of 1:1 to 1:4 with the aqueous phase solution, the mixture was shaken for 0.5-1 h, allowed to stand for 1 h, and the ethyl acetate phase was separated by a separator. The extraction was repeated 1-3 times.

21. The preparation method according to claim 1, characterized in that, After the second ethyl acetate extraction, 1 mol / L hydrochloric acid was added to the aqueous phase solution to adjust the pH to 3.0, and then ethyl acetate solvent extraction was continued. Ethyl acetate was added at a mass ratio of 1:4 with the aqueous phase solution, shaken for 0.5 h, allowed to stand for 1 h, and the ethyl acetate phase was separated by a separator. The extraction was repeated twice.

22. The preparation method according to claim 1, characterized in that, The vacuum distillation conditions for the ethyl acetate extract are: vacuum degree below -0.09 MPa, 30℃~40℃.

23. The preparation method according to claim 1, characterized in that, The vacuum distillation conditions for the ethyl acetate extract were: vacuum degree below -0.09 MPa, 35°C.

24. The preparation method according to claim 1, characterized in that, The reconstitution ratio of the 50% methanol solution is 1:1 to 1:5 by mass of 50% methanol solution to ethyl acetate extract.

25. The preparation method according to claim 1, characterized in that, The reconstitution ratio of the 50% methanol solution is 1:2.5 (mass ratio of 50% methanol solution to ethyl acetate extract).

26. The purified component obtained by the preparation method according to any one of claims 1-25.

27. A method for relieving pesticide damage, characterized in that, The method includes applying the purified component as described in claim 26.

28. The method according to claim 27, characterized in that, The pesticides mentioned include herbicides, insecticides, and fungicides.

29. The method according to claim 27, characterized in that, The pesticide in question is nicosulfuron.

30. The method according to claim 27, characterized in that, The pesticide is 2,4-D isooctyl ester.

31. The method according to claim 27, characterized in that, The method includes applying the purified and refined component of claim 26 before sowing.

32. The method according to claim 31, characterized in that, The method of applying the purified and refined components is to soak the seeds after dilution.

33. The method according to claim 32, characterized in that, The dilution factor is 10,000 to 50,000 times.

34. The method according to claim 32, characterized in that, The dilution factor is 10,000 times.

35. The method according to claim 32, characterized in that, The soaking temperature is 25~30℃.

36. The method according to claim 32, characterized in that, The soaking time is 8-12 hours.

37. The method according to claim 27, characterized in that, The method includes applying the purified and refined component of claim 26 before applying pesticides.

38. The method according to claim 37, characterized in that, The purified and refined components are applied by foliar spraying after dilution.

39. The method according to claim 38, characterized in that, The dilution factor is 20,000 to 100,000 times.

40. The method according to claim 38, characterized in that, The dilution factor is 20,000 times.

41. The method according to claim 38, characterized in that, The purified and refined components are applied 2 to 3 times, with an interval of 3 to 5 days.

42. The method according to claim 38, characterized in that, The method for applying the purified and refined components is as follows: Before applying the pesticide, dilute the purified and refined components and spray them on the leaves. Apply the components at intervals of 3 to 5 days, and repeat the application at least twice before applying the pesticide.

43. The method according to claim 42, characterized in that, The interval between the last application of the purified and refined component and the application of the pesticide should be within 48 hours.

44. The method according to claim 27, characterized in that, The method includes applying the purified and refined component of claim 26 after crop damage has occurred.

45. The method according to claim 44, characterized in that, The purified and refined components are applied by dilution and then sprayed onto the stems and leaves.

46. ​​The method according to claim 45, characterized in that, The dilution factor is 20,000 to 100,000 times.

47. The method according to claim 45, characterized in that, The dilution factor is 50,000 times.

48. The method according to claim 45, characterized in that, The purified and refined components are applied 2 to 3 times, with an interval of 1 to 3 days.

49. The method according to claim 45, characterized in that, The method for applying the purified and refined components is as follows: after the crop suffers phytotoxicity, the purified and refined components are diluted and sprayed on the stems and leaves, with an application interval of 1 to 3 days, and applied continuously for more than 2 times.

50. The method according to claim 45, characterized in that, The purified and refined components are applied at the initial stage of drug-induced damage symptoms.

51. The method according to claim 45, characterized in that, The purified and refined components are applied within 24 hours of the onset of phytotoxicity symptoms.

52. The method according to claim 45, characterized in that, The purified and refined components are used to remove severely phytotoxic tissues from crops before application.

53. A method for enhancing the efficacy of pesticides, characterized in that, The method includes mixing and applying the purified and refined component of claim 26 with a pesticide.

54. The method according to claim 53, characterized in that, The pesticides mentioned include herbicides, insecticides, and fungicides.

55. The method according to claim 53, characterized in that, The pesticide in question is tebuconazole.

56. The method according to claim 53, characterized in that, The method of mixed application is as follows: dilute the purified and refined components, mix them with pesticides, and apply them to the soil surface and / or foliar spray; the amount of pesticide used is reduced by 10% to 20% compared with that without purified and refined components.

57. The method according to claim 56, characterized in that, The dilution factor is 20,000 to 100,000 times.

58. The method according to claim 56, characterized in that, The dilution factor is 20,000 times, and the amount of pesticide used is reduced by 20% compared to the unrefined component.

59. The application of the purified component according to claim 26, characterized in that, The application includes any of the following: 1) Application in eliminating pesticide residue damage in soil before sowing; 2) Application in relieving soil pesticide damage after sowing; 3) Application in preventing pesticide damage before applying pesticides to crops; 4) Application in promoting crop recovery after pesticide damage symptoms appear; 5) Application in enhancing pesticide efficacy and reducing pesticide usage.

60. The application according to claim 59, characterized in that, The pesticides mentioned include herbicides, insecticides, and fungicides.

61. The application according to claim 59, characterized in that, The pesticide in question is nicosulfuron.

62. The application according to claim 59, characterized in that, The pesticide is 2,4-D isooctyl ester.

63. The application according to claim 59, characterized in that, The pesticide in question is tebuconazole.

64. The application according to claim 59, characterized in that, The crops are selected from field crops and cash crops.

65. The application according to claim 59, characterized in that, The crop in question is corn.

66. The application according to claim 59, characterized in that, The crop in question is apple.

Images