Agricultural emulsified asphalt and preparation method thereof

Abstract

The invention discloses agricultural emulsified asphalt and a preparation method thereof. The agricultural emulsified asphalt provided by the invention comprises the following components in parts by mass: 20-80 parts of asphalt; 20 to 100 parts of water; 1-20 parts of a composite emulsifier; 0.2 to 5 parts of a defoaming agent; 50 to 120 parts of biological powder; 1-5 parts of a compound fertilizer agent; and 5-40 parts of insect-expelling and weight-gaining microcapsules. After the emulsified asphalt is sprayed on the surface layer of soil, the water retention capacity of the soil can be remarkably improved, loss of the soil and fertilizer is effectively restrained, and the emulsified asphalt has efficient and lasting insect repelling capacity and nutrient slow release capacity.

Description

Technical Field

[0001] This invention belongs to the field of special asphalt, specifically relating to an agricultural emulsified asphalt and its preparation method. Background Technology

[0002] In some parts of China, soil erosion, desertification, and pest infestations have long been pressing issues that require solutions. These problems not only affect the sustainable development of agricultural production but also cause serious damage to the ecological environment. Soil erosion leads to the loss of fertile soil, reducing land productivity; desertification exacerbates the desertification process, making previously arable land unsuitable for cultivation; and pest infestations directly threaten crop growth, reducing both yield and quality.

[0003] CN115433587B discloses a soil erosion control agent, its preparation method, and its application, attempting to alleviate the aforementioned problems. However, this solution still has some shortcomings. For example, it is difficult to provide the necessary insulation effect for the soil in cold seasons, and its soil-fixing efficiency is easily weakened under strong sunlight. In the long run, its effect on fixing loose soil may not be ideal. In addition, this solution lacks a direct solution to the widespread problem of insect pests.

[0004] CN102911375A discloses an agricultural emulsified asphalt method. This method emulsifies asphalt directly with a single emulsifier and spreads it on the ground. Although it has a certain effect in preventing soil erosion, it does not have a significant effect in increasing fertilizer and repelling insects. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides an agricultural emulsified asphalt and its preparation method. When sprayed onto the soil surface, this emulsified asphalt not only significantly improves the soil's water retention capacity and effectively prevents soil and fertilizer loss, but also possesses highly efficient and long-lasting insect-repelling capabilities and nutrient slow-release capabilities.

[0006] The first aspect of this invention provides an agricultural emulsified asphalt, which, by weight, comprises the following components:

[0007] Asphalt: 20-80 parts;

[0008] Water: 20-100 parts;

[0009] Compound emulsifier: 1-20 parts;

[0010] Defoamer: 0.2-5 parts;

[0011] Biological powder: 50-120 parts;

[0012] Compound fertilizer: 1-5 parts

[0013] Deworming and weight-gain microcapsules: 5-40 servings.

[0014] Furthermore, the insect-repellent and fattening microcapsule comprises a shell material and a core material, wherein the shell material comprises urea-formaldehyde resin (UF) / nano-tourmaline, and the core material comprises one or more of insecticides and plant extracts; the surface of the shell material is loaded with metal chelates.

[0015] Furthermore, the asphalt is commercially available No. 70 base asphalt and / or No. 90 base asphalt.

[0016] Furthermore, the composite emulsifier comprises a quaternary ammonium salt surfactant and an imidazoline surfactant. The mass ratio of the quaternary ammonium salt surfactant to the imidazoline surfactant is 1:(0.1-10), preferably 1:(0.5-2).

[0017] Furthermore, the quaternary ammonium salt surfactant contains >14 carbon atoms, and is preferably one or more of dodecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, lauryltrimethylammonium bromide, and octadecyldimethylbenzylammonium chloride.

[0018] Furthermore, the azoline surfactant contains >13 carbon atoms, and is preferably one or more of 2-undecylimidazoline, dodecylimidazoline, tetradecylimidazoline, hexadecylimidazoline, oleyl hydroxyethylimidazoline, and lauryl hydroxyethylimidazoline.

[0019] Furthermore, the defoamer is one or more of sunflower seed oil, cottonseed oil, olive oil, peanut oil, corn oil, soybean oil, rice sugar oil, and tea seed oil.

[0020] Furthermore, the biological powder is one or more of the following: shrimp shell powder, oyster shell powder, fish bone powder, coral powder, clam shell powder, cow bone powder, and eggshell powder.

[0021] Further, the particle size of the biopowder is 300-1000 mesh; preferably, based on the total mass of the biopowder, the mass percentage of biopowder with a particle size greater than or equal to 300 mesh and less than 500 mesh is 30-40%, the mass percentage of biopowder with a particle size of 500-800 mesh is 40-50%, and the mass percentage of biopowder with a particle size greater than 800 mesh and less than or equal to 1000 mesh is 10-30%.

[0022] Furthermore, the compound fertilizer is selected from one or more of potassium phosphate, ammonium phosphate, sodium borate, potassium nitrate, and zinc nitrate.

[0023] Furthermore, the diameter of the insect-repelling and fattening microcapsules is 3-20 μm.

[0024] Furthermore, the mass ratio of the shell material to the core material of the insect-repelling and fattening microcapsule is 1:(0.5-2.5).

[0025] Furthermore, the core material preferably comprises both an insecticide and a plant extract. The mass ratio of the insecticide to the plant extract is 1:(0.5-4).

[0026] Furthermore, the insecticide is one or more of the following: neonicotinoid insecticides, pyrethroid insecticides, and insect growth regulator insecticides.

[0027] Furthermore, the number of carbon atoms in the neonicotinoid insecticide is >6; preferably, it is one or more of imidacloprid, acetamiprid, flonicamid, dinotefuran, chlorthiazoline, and thiamethoxam.

[0028] Furthermore, the pyrethroid insecticide has >21 carbon atoms; preferably, it is one or more of cypermethrin, bifenthrin, deltamethrin, cypermethrin, ethionyl cyanide, and deltamethrin.

[0029] Furthermore, the insect growth regulator insecticide has >20 carbon atoms; preferably, it is one or more of chlorfenapyr, tebufenozide, methoxyfenozide, and cyclotebufenozide.

[0030] Furthermore, the boiling point of the plant extract is >160℃; preferably, it is one or more of lemon essential oil, camphor essential oil, and peppermint essential oil.

[0031] Furthermore, in the shell material, the mass ratio of urea-formaldehyde resin to nano-tourmaline is (2-10):1.

[0032] Furthermore, the shell material surface is loaded with a metal chelate, wherein the metal is preferably one or more of iron, manganese, zinc, copper, calcium, and nickel.

[0033] Furthermore, the shell material surface is loaded with metal chelates, and the metal loading accounts for 0.1wt%-2wt% of the total mass of the insect-repellent and fattening microcapsules.

[0034] Furthermore, the preparation method of the insect-repellent and weight-enhancing microcapsules includes:

[0035] S1: Mix nano-tourmaline powder, surfactant and solvent, modify under stirring, wash after modification, freeze dry to obtain modified nano-tourmaline powder;

[0036] S2: Mix one or more of the insecticide and plant extract to obtain the core material mixture;

[0037] S3: Add the modified nano-tourmaline powder obtained in step S1 and the core material mixture obtained in step S2 to the urea aqueous solution and stir.

[0038] S4: Add formaldehyde solution to the reaction system of step S3, and carry out the reaction with stirring. After the reaction is completed, the mixture is aged, washed, filtered, and freeze-dried to obtain the insect-repellent and fattening microcapsule matrix.

[0039] S5: Disperse the insect-repellent and fattening microcapsule matrix obtained in step S4 in methanol, then add a coupling agent methanol solution, adjust the pH value, process under stirring, then filter, wash, and freeze dry.

[0040] S6: Disperse the solid powder obtained after freeze-drying in step S5 in a buffer solution, add a chelating agent, process under stirring, filter, wash, and freeze-dry.

[0041] S7: Disperse the solid powder obtained after freeze-drying in step S6 in a metal ion salt - N,N-dimethylformamide (DMF) solution, and process it with stirring. After the reaction is completed, filter, wash, and freeze-dry to obtain insect-repellent and fattening microcapsules.

[0042] Furthermore, in step S1, the particle size of the nano-tourmaline powder is 10-100 nm.

[0043] Further, in step S1, the surfactant is an anionic surfactant, preferably at least one of sodium dodecylbenzenesulfonate (SDBS), sodium dodecyl sulfate (SDS), and 2-morpholine ethanesulfonic acid, and more preferably sodium dodecylbenzenesulfonate.

[0044] Further, in step S1, the solvent is an aprotic solvent with a boiling point >100℃, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide, and more preferably formamide.

[0045] Further, in step S1, the mass ratio of the nano-tourmaline powder to the surfactant is (1-10):1, and the mass ratio of the solvent to the surfactant is (20-40):1.

[0046] Further, in step S1, the stirring speed is 400-600 rpm; the modification temperature is 100-200℃; and the modification time is 4-8 hours.

[0047] Furthermore, in step S1, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0048] Further, in step S2, the mixing is carried out under stirring, the stirring speed is 300-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 3-10 minutes.

[0049] Further, in step S3, the mass ratio of urea to water in the aqueous solution of urea is 1:(5-50).

[0050] Furthermore, in step S3, the pH of the urea aqueous solution is adjusted to 2.5-5.5 before use. The pH can be adjusted using organic acids, such as one or more of citric acid, formic acid, and acetic acid.

[0051] Further, in step S3, the mass ratio of the core material mixture to the modified nano-tourmaline powder is 1:(0.1-0.5); the mass ratio of the core material mixture to urea is 1:(0.2-1).

[0052] Furthermore, in step S3, the stirring speed is 400-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 1-2 hours.

[0053] Further, in step S4, the formaldehyde solution is an aqueous solution of formaldehyde with a mass concentration of 35%-40%. The amount of formaldehyde solution added satisfies the molar ratio of formaldehyde to urea in the reaction system of step S3 as (1.5-2.5):1.

[0054] Furthermore, in step S4, the stirring speed is 400-600 rpm, the stirring temperature is 50-80℃, and the reaction time under stirring is 4-6 hours.

[0055] Further, in step S4, the aging conditions are: standing at 50-80℃ for 1-12 hours. The freeze-drying conditions are: vacuum drying at -40--20℃ for 4-8 hours.

[0056] Furthermore, in step S5, the insect-repellent and fattening microcapsule matrix is ​​dispersed in methanol, which can be achieved by ultrasonic dispersion.

[0057] Further, in step S5, the coupling agent methanol solution is prepared by mixing the coupling agent and methanol, and the mass ratio of methanol to coupling agent is (1-15):1.

[0058] Further, in step S5, the coupling agent is a silane coupling agent, preferably at least one of 3-chloropropyltrimethylsilane, (dichloromethyl)trimethylsilane, (trichloromethyl)trimethylsilane, and (chlorodifluoromethyl)trimethylsilane, and more preferably 3-chloropropyltrimethylsilane.

[0059] Further, in step S5, the mass ratio of methanol to the insect-repellent and fattening microcapsule matrix is ​​(1-20):1. The mass ratio of the coupling agent methanol solution to the insect-repellent and fattening microcapsule matrix is ​​(0.1-10):1.

[0060] Furthermore, in step S5, the pH can be adjusted using an alkaline solution, such as ammonia.

[0061] Furthermore, in step S5, the stirring speed is 200-450 rpm; the processing temperature is 40-60℃; and the processing time is 4-6 hours.

[0062] Furthermore, in step S5, the treatment is carried out under the protection of nitrogen or an inert gas.

[0063] Furthermore, in step S5, the freeze-drying conditions are: vacuum drying at -40°C to -20°C for 4-8 hours.

[0064] Furthermore, in step S6, the dispersion can be carried out by ultrasonic dispersion.

[0065] Furthermore, the buffer solution mentioned in step S6 is preferably one or more of phosphate buffer and carbonate buffer, and more preferably carbonate buffer.

[0066] Further, in step S6, the pH value of the buffer solution is 9-12.

[0067] Further, in step S6, the mass ratio of the buffer solution to the solid powder obtained after lyophilization in step S5 is (5-50):1.

[0068] Further, in step S6, the chelating agent has a ligand tooth number >2, preferably iminodiacetic acid, triethylenediamine, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, and more preferably ethylenediaminetetraacetic acid.

[0069] Furthermore, in step S6, the stirring speed is 200-450 rpm, the processing temperature is 40-60℃, and the processing time is 2-5 hours.

[0070] Furthermore, in step S6, the freeze-drying conditions are: vacuum drying at -40°C to -20°C for 4-8 hours.

[0071] Furthermore, in step S7, the solid powder obtained after drying in step S6 is dispersed in a metal ion salt-DMF (N,N-dimethylformamide) solution, which can be done by ultrasonic dispersion.

[0072] Further, in step S7, the metal ion salt is preferably one or more of iron ion salt, manganese ion salt, zinc ion salt, copper ion salt, calcium ion salt, and nickel ion salt, and more preferably one or more of ferric chloride, manganese chloride, zinc chloride, copper chloride, calcium chloride, and nickel chloride.

[0073] Further, in step S7, the molar ratio of the metal ion salt to DMF in the metal ion salt-DMF solution is (0.1-2):1.

[0074] Further, in step S7, the mass ratio of the metal ion salt-DMF solution to the solid powder obtained after drying in step S6 is (10-30):1.

[0075] Furthermore, in step S7, the stirring speed is 200-450 rpm, the processing temperature is 100-150℃, and the processing time is 2-5 hours.

[0076] Furthermore, in step S7, the freeze-drying conditions are: vacuum drying at -40°C to -20°C for 4-8 hours.

[0077] A second aspect of the present invention provides a method for preparing the above-mentioned agricultural emulsified asphalt, comprising:

[0078] P1: Mix a portion of the compound emulsifier and water, adjust the pH value, and obtain soap solution;

[0079] P2: The asphalt and the soap solution obtained in step P1 are heated separately and then mixed and sheared to obtain emulsified asphalt;

[0080] P3: Add the remaining composite emulsifier, defoamer, and insect repellent and fertilizer-enhancing microcapsules to the emulsified asphalt obtained in step P2, and stir to mix;

[0081] P4: Pretreatment of biopowder with phosphoric acid solution;

[0082] P5: Add compound fertilizer and pretreated biological powder from step P4 to the reaction system of step P3, stir and mix to obtain agricultural emulsified asphalt.

[0083] Furthermore, in steps P1 and P3, the composite emulsifier can be a mixture of quaternary ammonium salt surfactant and imidazoline surfactant.

[0084] Further, in step P1, the water is preferably deionized water. The mass ratio of the water to the composite emulsifier is (5-20):1.

[0085] Furthermore, in step P1, the stirring speed is 100-600 rpm, the stirring temperature is 50-90℃, and the stirring time is 5-20 minutes.

[0086] Furthermore, in step P1, the pH value is adjusted to 2-4. The pH can be adjusted using an aqueous acetic acid solution.

[0087] Furthermore, in step P2, the heating temperature of the asphalt is 113-183℃. The heating temperature of the soap solution is 30-90℃.

[0088] Furthermore, in step P2, the shearing is preferably performed in multiple cycles, more preferably 3-5 cycles. The rate of each shearing is 3000-5000 rpm, and the duration of each shearing is 2-20 minutes.

[0089] Furthermore, the mass ratio of the composite emulsifier added in step P3 to the composite emulsifier added in step P1 is 1:(1-10).

[0090] Furthermore, in step P3, the stirring speed is 100-600 rpm, the stirring temperature is 30-90℃, and the stirring time is 30-120 minutes.

[0091] Furthermore, in step P3, the preferred method for adding the remaining composite emulsifier, defoamer, and insect repellent and fattening microcapsules is as follows: first add the remaining composite emulsifier and stir for 10-40 minutes, then add the defoamer and stir for 10-40 minutes, and finally add the insect repellent and fattening microcapsules and stir for 10-40 minutes.

[0092] Further, in step P4, the pretreatment specifically involves: mixing the biological powder with a phosphoric acid solution, stirring and reacting, then filtering, washing, and lyophilizing.

[0093] Further, in step P4, the stirring speed is 300-500 rpm, the stirring temperature is 30-90℃, and the stirring time is 10-50 minutes. The washing process can be performed using deionized water.

[0094] Further, in step P4, the concentration of the phosphoric acid solution is 1wt%-10wt%, and the mass ratio of the phosphoric acid solution to the biological powder is (10-100):1.

[0095] Furthermore, in step P4, the freeze-drying conditions are: vacuum drying at -40°C to -20°C for 4-8 hours.

[0096] Furthermore, in step P5, the stirring speed is 100-600 rpm, the stirring temperature is 40-90℃, and the stirring time is 30-120 minutes.

[0097] Compared with the prior art, the present invention has the following advantages:

[0098] (1) The agricultural emulsified asphalt of the present invention can effectively improve the soil structure after being spread on the soil surface. It can not only improve the stability of the soil and avoid the loss of water, soil, fertilizer and pesticides, but also play an obvious role in heat preservation and improve the soil structure.

[0099] (2) After the agricultural emulsified asphalt of the present invention is spread on the soil surface, the insect repellent and fertilizer-enhancing microcapsules in its system will slowly release insect repellent, avoiding the impact of insects on crops or plant landscapes and surrounding residents, and has a long-lasting insect repellent effect, which can avoid repeated construction.

[0100] (3) After the agricultural emulsified asphalt of the present invention is spread on the soil surface, the urea-formaldehyde resin shell of the insect-repelling and fertilizer-enhancing microcapsules in the system will be subjected to the combined action of water and microorganisms, slowly releasing nitrogen and various trace metal elements immobilized on the surface, so as to achieve the purpose of long-term fertilizer enhancement.

[0101] (4) The agricultural emulsified asphalt of the present invention contains insect-repelling and fertilizer-enhancing microcapsules, the shell of which is a composite shell material including urea-formaldehyde resin / nano-tourmaline. In the preparation process of the insect-repelling and fertilizer-enhancing microcapsules, tourmaline powder can replace the template agent in the synthesis of microcapsules to maintain the stability of the microcapsule core droplets. In addition, in the process of modifying the shell material with metal ions, the negative ion field released by tourmaline can adsorb metal ions onto the surface of the microcapsules, effectively increasing the loading of transition metal ions in the microcapsule shell material. Furthermore, after the agricultural emulsified asphalt is spread on the soil surface, the negative ion field released by the nano-tourmaline in the insect-repelling and fertilizer-enhancing microcapsules in the system can purify the air, promote crop metabolism, enhance crop enzyme activity, promote crop photosynthesis, and thus promote plant growth. Attached Figure Description

[0102] Figure 1 The image shown is a scanning electron microscope (SEM) image of the insect-repelling and fattening microcapsules obtained in Example 1. Detailed Implementation

[0103] To further illustrate the relevant features and technical means of the present invention, the present invention will be clearly and thoroughly described below in conjunction with embodiments.

[0104] The morphology of the insect-repellent and fattening microcapsules of this invention was tested using a ZEISS Supra 55 scanning electron microscope with an accelerating voltage of 20kV. Since the microcapsule wall material is non-conductive, the samples need to be sputtered with gold before testing.

[0105] The insect-repellent and fattening microcapsules of the present invention were subjected to surface elemental testing using an X-ray energy dispersive spectroscopy (EDS) instrument to confirm that metal ions were successfully modified onto the surface of the microcapsules.

[0106] In this invention, the weight gain effect is evaluated using the following method:

[0107] Place the air-dried soil in a square box (600mm x 450mm x 300mm) and add water until the soil moisture content is approximately 20%. Sow the lettuce. Then, sprinkle insect-repellent and fertilizing emulsified asphalt on the soil surface at a rate of 200g / m².3 The boxes were then moved to a planting area for a planting experiment.

[0108] In this invention, the soil stabilization effect is evaluated by the following method: the content of soil aggregates >0.25mm in the soil is examined using the wet sieving method.

[0109] In this invention, the insect-repelling effect is evaluated using the following method:

[0110] A low-powered light source of the same specification was placed on top of the box, and the number of insects in the test area was monitored and recorded by a camera at night (6 p.m. to 7 a.m. the next day) to examine the insect repellent effect.

[0111] The base asphalt used in the following examples and comparative examples is Sinopec Donghai brand No. 70 Grade A asphalt.

[0112] Example 1

[0113] Preparation of anthelmintic and weight-gain microcapsules:

[0114] S1: Add tourmaline powder with a particle size of 80nm, sodium dodecylbenzenesulfonate and formamide to the first container. The mass ratio of tourmaline powder, sodium dodecylbenzenesulfonate and formamide is 3:1:30. Stir at 400 rpm for 5 hours at 140℃ to modify the surface of the nano tourmaline powder. After modification, wash the modified nano tourmaline with ethanol several times and vacuum dry at -30℃ for 5 hours for later use.

[0115] S2: Add fipronil, cypermethrin, tebufenozide and lemon essential oil in a mass ratio of 1:1:1:6 to the second container, and stir at 400 rpm for 5 minutes at 50°C to obtain the core material mixture.

[0116] S3: Add urea and deionized water in a mass ratio of 1:10 to the third container, stir at 400 rpm for 1 hour at 50°C, and then adjust the pH of the system to 4 using acetic acid.

[0117] Then add the modified nano tourmaline powder and core material mixture, with a mass ratio of core material mixture, urea and modified nano tourmaline powder of 4:2:1, and continue stirring at 400 rpm for 1 hour at 50°C.

[0118] S4: Add 37wt% formaldehyde solution, with a molar ratio of urea to formaldehyde of 1:2, raise the reaction temperature to 65℃, stir the reaction for 6 hours, keep the reaction temperature constant after stirring, age for 2 hours, filter and wash the solid in the reaction system after aging, and vacuum dry at -30℃ for 5 hours to obtain the insect-repellent and fattening microcapsule matrix.

[0119] S5: The insect-repellent and fattening microcapsule matrix was dispersed in methanol by ultrasonic dispersion, and then 20 wt% 3-chloropropyltrimethylsilane methanol solution was added dropwise. The pH value was adjusted to 11 with ammonia water. The mixture was stirred for 5 hours at 400 rpm and 60°C. The mass ratio of methanol, insect-repellent and fattening microcapsule matrix and 3-chloropropyltrimethylsilane methanol solution was 5:1:1. The reaction was carried out under nitrogen protection throughout. After stirring, the solid powder was filtered, washed, and vacuum dried at -30°C for 5 hours.

[0120] S6: The solid powder obtained in step S5 is ultrasonically dispersed in a carbonate buffer solution with pH=11, and then ethylenediaminetetraacetic acid is added. The mass ratio of carbonate buffer solution, solid powder and ethylenediaminetetraacetic acid is 200:15:1. The mixture is stirred for 5 hours at 400 rpm and 50°C. After stirring, the solid powder is filtered, washed and vacuum dried at -30°C for 5 hours.

[0121] S7: The solid powder obtained in step S6 is ultrasonically dispersed in a metal ion salt-DMF solution. The molar ratio of metal ions to DMF is 0.5:1. The metal ion salts are copper chloride, zinc chloride, manganese chloride, and calcium chloride in the same molar ratio. The mass ratio of solid powder to metal ion salt-DMF solution is 1:20. The mixture is stirred at 400 rpm and 140°C for 5 hours. After stirring, the solid powder is filtered, washed, and vacuum dried at -30°C for 5 hours to obtain the insect-repellent and fattening microcapsules. The electron micrograph is shown below. Figure 1 .

[0122] The preparation method of agricultural emulsified asphalt is as follows. It should be noted that the product must be protected from light during preparation and transportation:

[0123] P1: Add 4 parts by mass of octadecyltrimethylammonium chloride and 4 parts by mass of tetradecylimidazoline to the fourth container, and stir evenly to obtain a composite emulsifier;

[0124] Add 63 parts by mass of deionized water and 7 parts by mass of compound emulsifier to the fifth container. Stir and mix for 20 minutes at 60°C and 400 rpm. Adjust the pH to 3 with an aqueous acetic acid solution to obtain soap solution.

[0125] P2: Add 70 parts by weight of No. 70 Grade A asphalt heated to 163°C and soap solution obtained in step P1 heated to 60°C to a colloid mill, shear at 4000 rpm for 5 minutes, and circulate shearing 3 times to obtain emulsified asphalt.

[0126] P3: Add 1 part by mass of the composite emulsifier prepared in step P1 to the emulsified asphalt obtained in step P2, and stir and mix for 20 minutes at 400 rpm and 60°C.

[0127] Add 3 parts by weight of cottonseed oil and stir and mix at 400 rpm and 60°C for 20 minutes.

[0128] Slowly add 30 parts by weight of the insect-repelling and fattening microcapsules, and stir and mix at 400 rpm and 60°C for 30 minutes.

[0129] P4: Add 40 parts by weight of oyster shell powder and 40 parts by weight of mussel shell powder (of which the bio-powder with a mesh size greater than or equal to 300 mesh and less than 500 mesh accounts for 35% by weight, the bio-powder with a mesh size of 500-800 mesh accounts for 45% by weight, and the bio-powder with a mesh size greater than 800 mesh and less than or equal to 1000 mesh accounts for 20% by weight) to 1000 parts by weight of a 5 wt% phosphoric acid solution. Stir at 400 rpm and 50°C for 20 minutes. After the reaction is complete, filter the solid powder, wash it, and vacuum dry it at -30°C for 5 hours.

[0130] P5: Add the biological powder prepared in P4 and 3 parts by mass of sodium borate, potassium phosphate and zinc nitrate (the mass ratio of the three is 1:1:1) to the system in step P3, and stir and mix for 50 minutes at 500 rpm and 60°C to obtain agricultural emulsified asphalt.

[0131] Example 2

[0132] Except for step P1, in which 4 parts by mass of octadecyltrimethylammonium bromide and 4 parts by mass of dodecyl imidazoline are added to the fourth container, the rest is the same as in Example 1.

[0133] Example 3

[0134] Except for step P3, in which 3 parts by weight of cottonseed oil are replaced with 3 parts by weight of sunflower seed oil, the rest is the same as in Example 1.

[0135] Example 4

[0136] Except for step P4, in which the biological powder consists of 40 parts by weight of fish bone powder and 40 parts by weight of bovine bone powder, the rest is the same as in Example 1.

[0137] Example 5

[0138] Except for step P5, where the compound fertilizer is sodium borate, potassium nitrate, and ammonium phosphate (in a mass ratio of 1:1:1), the rest is the same as in Example 1.

[0139] Example 6

[0140] Except for the insecticide and plant extract in step S2, which are thiamethoxam, permethrin, methoxyfenozide and camphor oil in a mass ratio of 1:1:1:6, the rest are the same as in Example 1.

[0141] Example 7

[0142] Except for step P3, where the amount of insect-repellent and fattening microcapsules added is 20 parts by weight, the rest is the same as in Example 1.

[0143] Comparative Example 1

[0144] Planting boxes for romaine lettuce that were not sprayed with agricultural emulsified asphalt were moved to a planting area for a comparative planting experiment.

[0145] Comparative Example 2

[0146] P1: Add 4 parts by mass of octadecyltrimethylammonium chloride and 4 parts by mass of tetradecylimidazoline to the first container, and stir evenly to obtain a composite emulsifier;

[0147] Add 63 parts by mass of deionized water and 7 parts by mass of the prepared composite emulsifier to the second container. Stir and mix for 20 minutes at 60°C and 400 rpm. Adjust the pH to 3 with an aqueous acetic acid solution to obtain soap solution.

[0148] P2: Add 70 parts by weight of No. 70 Grade A asphalt heated to 163°C and soap solution obtained in step P1 heated to 60°C to a colloid mill, shear at 4000 rpm for 5 minutes, and circulate shearing 3 times to obtain emulsified asphalt.

[0149] P3: Add 1 part by mass of the composite emulsifier prepared in step P1 to the emulsified asphalt obtained in step P2, and stir and mix for 20 minutes at 400 rpm and 60°C.

[0150] Add 3 parts by weight of cottonseed oil and stir and mix at 400 rpm and 60°C for 20 minutes.

[0151] P4: Add 40 parts by weight of oyster shell powder and 40 parts by weight of mussel shell powder (of which the bio-powder with a mesh size greater than or equal to 300 mesh and less than 500 mesh accounts for 35% by weight, the bio-powder with a mesh size of 500-800 mesh accounts for 45% by weight, and the bio-powder with a mesh size greater than 800 mesh and less than or equal to 1000 mesh accounts for 20% by weight) to 1000 parts by weight of a 5 wt% phosphoric acid solution. Stir at 400 rpm and 50°C for 20 minutes. After the reaction is complete, filter the solid powder, wash it, and vacuum dry it at -30°C for 5 hours.

[0152] P5: Add the biological powder prepared in P4 and 3 parts by mass of sodium borate, potassium phosphate and zinc nitrate (the mass ratio of the three is 1:1:1) to the system in step P3, and stir and mix for 50 minutes at 500 rpm and 60°C to obtain agricultural emulsified asphalt.

[0153] Comparative Example 3

[0154] The preparation of the insect-repellent and weight-gain microcapsules is the same as in Example 1;

[0155] The preparation method of agricultural emulsified asphalt is as follows. It should be noted that the product must be protected from light during preparation and transportation:

[0156] P1: Add 4 parts by mass of octadecyltrimethylammonium chloride and 4 parts by mass of tetradecylimidazoline to the fourth container, and stir evenly to obtain a composite emulsifier;

[0157] Add 63 parts by mass of deionized water and 7 parts by mass of compound emulsifier to the fifth container. Stir and mix for 20 minutes at 60°C and 400 rpm. Adjust the pH to 3 with an aqueous acetic acid solution to obtain soap solution.

[0158] P2: Add 70 parts by weight of No. 70 Grade A asphalt heated to 163°C and soap solution obtained in step P1 heated to 60°C to a colloid mill, shear at 4000 rpm for 5 minutes, and circulate shearing 3 times to obtain emulsified asphalt.

[0159] P3: Add 1 part by mass of the composite emulsifier prepared in step P1 to the emulsified asphalt obtained in step P2, and stir and mix for 20 minutes at 400 rpm and 60°C.

[0160] Add 3 parts by weight of cottonseed oil and stir and mix at 400 rpm and 60°C for 20 minutes.

[0161] Slowly add 30 parts by weight of the insect-repelling and fattening microcapsules, and stir and mix at 400 rpm and 60°C for 30 minutes.

[0162] P4: Add 3 parts by mass of sodium borate, potassium phosphate and zinc nitrate (in a mass ratio of 1:1:1) to the system in step P3, and stir and mix for 50 minutes at 500 rpm and 60°C to obtain agricultural emulsified asphalt.

[0163] Comparative Example 4

[0164] The preparation of the insect-repellent and weight-gain microcapsules is the same as in Example 1;

[0165] The preparation method of agricultural emulsified asphalt is as follows. It should be noted that the product must be protected from light during preparation and transportation:

[0166] P1: Add 4 parts by mass of octadecyltrimethylammonium chloride and 4 parts by mass of tetradecylimidazoline to the fourth container, and stir evenly to obtain a composite emulsifier;

[0167] Add 63 parts by mass of deionized water and 7 parts by mass of compound emulsifier to the fifth container. Stir and mix for 20 minutes at 60°C and 400 rpm. Adjust the pH to 3 with an aqueous acetic acid solution to obtain soap solution.

[0168] P2: Add 70 parts by weight of No. 70 Grade A asphalt heated to 163°C and soap solution obtained in step P1 heated to 60°C to a colloid mill, shear at 4000 rpm for 5 minutes, and circulate shearing 3 times to obtain emulsified asphalt.

[0169] P3: Add 1 part by mass of the composite emulsifier prepared in step P1 to the emulsified asphalt obtained in step P2, and stir and mix for 20 minutes at 400 rpm and 60°C.

[0170] Add 3 parts by weight of cottonseed oil and stir and mix at 400 rpm and 60°C for 20 minutes.

[0171] Slowly add 30 parts by weight of the insect-repelling and fattening microcapsules, and stir and mix at 400 rpm and 60°C for 30 minutes.

[0172] P4: Add 40 parts by weight of oyster shell powder and 40 parts by weight of mussel shell powder (of which the bio-powder with a mesh size greater than or equal to 300 mesh and less than 500 mesh accounts for 35% by weight, the bio-powder with a mesh size of 500-800 mesh accounts for 45% by weight, and the bio-powder with a mesh size greater than 800 mesh and less than or equal to 1000 mesh accounts for 20% by weight) to 1000 parts by weight of a 5 wt% phosphoric acid solution. Stir at 400 rpm and 50°C for 20 minutes. After the reaction is complete, filter the solid powder, wash it, and vacuum dry it at -30°C for 5 hours.

[0173] P5: Add the biological powder prepared in P4 to the system in step P3, and stir and mix for 50 minutes at 500 rpm and 60°C to obtain agricultural emulsified asphalt.

[0174] Comparative Example 5

[0175] Preparation of anthelmintic and weight-gain microcapsules:

[0176] S1: Add fipronil, cypermethrin, tebufenozide and lemon essential oil in a mass ratio of 1:1:1:6 to the first container, and stir at 400 rpm for 5 minutes at 50°C to obtain the core material mixture.

[0177] S2: Add urea and deionized water in a mass ratio of 1:10 to the second container, stir at 400 rpm for 1 hour at 50°C, and then adjust the pH of the system to 4 using acetic acid.

[0178] Then add sodium dodecylbenzenesulfonate and core material mixture, with a mass ratio of core material mixture, urea and sodium dodecylbenzenesulfonate of 4:2:0.5, and continue stirring at 400 rpm for 1 hour at 50°C.

[0179] S3: Add 37wt% formaldehyde solution, with a molar ratio of urea to formaldehyde of 1:2, raise the reaction temperature to 65℃, stir the reaction for 6 hours, keep the reaction temperature constant after stirring, age for 2 hours, filter and wash the solid in the reaction system after aging, and vacuum dry at -30℃ for 5 hours to obtain the insect-repellent and fattening microcapsule matrix.

[0180] S4: The insect-repellent and fattening microcapsule matrix was dispersed in methanol by ultrasonic dispersion, and then 20 wt% 3-chloropropyltrimethylsilane methanol solution was added dropwise. The pH value was adjusted to 11 with ammonia water. The mixture was stirred for 5 hours at 400 rpm and 60°C. The mass ratio of methanol, insect-repellent and fattening microcapsule matrix and 3-chloropropyltrimethylsilane methanol solution was 5:1:1. The reaction was carried out under nitrogen protection throughout. After stirring, the solid powder was filtered, washed, and vacuum dried at -30°C for 5 hours.

[0181] S5: The solid powder obtained in step S4 is ultrasonically dispersed in a carbonate buffer solution with pH=11, and then ethylenediaminetetraacetic acid is added. The mass ratio of carbonate buffer solution, solid powder and ethylenediaminetetraacetic acid is 200:15:1. The mixture is stirred for 5 hours at 400 rpm and 50°C. After stirring, the solid powder is filtered, washed and vacuum dried at -30°C for 5 hours.

[0182] S6: The solid powder obtained in step S5 is ultrasonically dispersed in a metal ion salt-DMF solution. The molar ratio of metal ion salt to DMF is 0.5:1. The metal ion salts are copper chloride, zinc chloride, manganese chloride, and calcium chloride with the same molar ratio. The mass ratio of solid powder to metal ion salt-DMF solution is 1:20. The mixture is stirred at 400 rpm and 140°C for 5 hours. After stirring, the solid powder is filtered, washed, and vacuum dried at -30°C for 5 hours to obtain insect-repellent and fattening microcapsules.

[0183] The preparation method of agricultural emulsified asphalt is the same as in Example 1.

[0184] Comparative Example 6

[0185] P1: Add 30 parts by mass of fipronil, cypermethrin, tebufenozide and lemon essential oil in a mass ratio of 1:1:1:6 to the first container, and stir at 400 rpm for 5 minutes at 50°C to obtain the insect repellent mixture.

[0186] P2: Add 4 parts by mass of octadecyltrimethylammonium chloride and 4 parts by mass of tetradecylimidazoline to the second container, and stir evenly to obtain a composite emulsifier;

[0187] Add 63 parts by mass of deionized water and 7 parts by mass of the prepared composite emulsifier to the third container. Stir and mix for 20 minutes at 60°C and 400 rpm. Adjust the pH to 3 with an aqueous acetic acid solution to obtain soap solution.

[0188] P3: Add 70 parts by weight of No. 70 Grade A asphalt heated to 163°C, the insect repellent mixture prepared in P1, and the soap solution prepared in step P3 heated to 60°C to a colloid mill. Shear at 4000 rpm for 5 minutes and repeat the shearing process 3 times to obtain emulsified asphalt.

[0189] P4: Add 1 part by mass of the composite emulsifier prepared in step P2 to the emulsified asphalt obtained in step P3, and stir and mix for 20 minutes at 400 rpm and 60°C.

[0190] Add 3 parts by weight of cottonseed oil and stir and mix at 400 rpm and 60°C for 20 minutes.

[0191] Slowly add another 30 parts by weight of the insect repellent mixture;

[0192] P5: Add 40 parts by weight of oyster shell powder and 40 parts by weight of mussel shell powder (of which the bio-powder with a mesh size greater than or equal to 300 mesh and less than 500 mesh accounts for 35% by weight, the bio-powder with a mesh size of 500-800 mesh accounts for 45% by weight, and the bio-powder with a mesh size greater than 800 mesh and less than or equal to 1000 mesh accounts for 20% by weight) to 1000 parts by weight of a 5 wt% phosphoric acid solution. Stir at 400 rpm and 50°C for 20 minutes. After the reaction is complete, filter the solid powder, wash it, and vacuum dry it at -30°C for 5 hours.

[0193] P6: Add the biological powder prepared in P5 and 3 parts by mass of sodium borate, potassium phosphate and zinc nitrate (in a mass ratio of 1:1:1) to the system in step P4. Stir and mix for 50 minutes at 500 rpm and 60°C to obtain agricultural emulsified asphalt.

[0194] Table 1 Results of weight gain and deworming tests for each case.

[0195]

[0196] It should be emphasized that the above-mentioned content is only a specific embodiment of the present invention and should not be construed as limiting the present invention to the above description in specific implementation. For researchers and those skilled in the art to which this invention pertains, any simple deductions and improvements made without departing from the spirit and principles of the present invention should be considered within the scope of protection of the present invention.

Claims

1. An agricultural emulsified asphalt, characterized in that, The agricultural emulsified asphalt, by weight, comprises the following components: Asphalt: 20-80 parts; Water: 20-100 parts; Compound emulsifier: 1-20 parts; Defoamer: 0.2-5 parts; Biological powder: 50-120 parts; Compound fertilizer: 1-5 parts Deworming and weight-gain microcapsules: 5-40 servings.

2. The agricultural emulsified asphalt according to claim 1, characterized in that, The insect-repellent and fattening microcapsule comprises a shell material and a core material. The shell material comprises urea-formaldehyde resin / nano-tourmaline, and the core material comprises one or more of insecticides and plant extracts. The surface of the shell material is loaded with metal chelates.

3. The agricultural emulsified asphalt according to claim 1, characterized in that, The composite emulsifier comprises quaternary ammonium salt surfactants and imidazoline surfactants; the mass ratio of the quaternary ammonium salt surfactants to the imidazoline surfactants is 1:(0.1-10), preferably 1:(0.5-2); And / or, the defoamer is one or more of sunflower seed oil, cottonseed oil, olive oil, peanut oil, corn oil, soybean oil, rice sugar oil, and tea seed oil; And / or, the biological powder is one or more of shrimp shell powder, oyster shell powder, fish bone powder, coral powder, clam shell powder, cow bone powder, and eggshell powder; And / or, the compound fertilizer is selected from one or more of potassium phosphate, ammonium phosphate, sodium borate, potassium nitrate, and zinc nitrate.

4. The agricultural emulsified asphalt according to claim 1, characterized in that, The diameter of the insect-repelling and fattening microcapsules is 3-20 μm; And / or, the mass ratio of the shell material to the core material of the insect-repellent and fattening microcapsule is 1:(0.5-2.5).

5. The agricultural emulsified asphalt according to claim 1, characterized in that, The core material includes both insecticide and plant extract; the mass ratio of the insecticide to the plant extract is 1:(0.5-4).

6. The agricultural emulsified asphalt according to claim 1, characterized in that, In the shell material, the mass ratio of urea-formaldehyde resin to nano-tourmaline is (2-10):1; And / or, the shell material surface is loaded with a metal chelate, wherein the metal is preferably one or more of iron, manganese, zinc, copper, calcium, and nickel; And / or, the shell material surface is loaded with metal chelates, the metal loading amount accounting for 0.1wt%-2wt% of the total mass of the insect repellent and fattening microcapsules.

7. The agricultural emulsified asphalt according to claim 1, characterized in that, The method for preparing the insect-repellent and weight-gain microcapsules includes: S1: Mix nano-tourmaline powder, surfactant and solvent, modify under stirring, wash after modification, freeze dry to obtain modified nano-tourmaline powder; S2: Mix one or more of the insecticide and plant extract to obtain the core material mixture; S3: Add the modified nano-tourmaline powder obtained in step S1 and the core material mixture obtained in step S2 to the urea aqueous solution and stir. S4: Add formaldehyde solution to the reaction system of step S3, and carry out the reaction with stirring. After the reaction is completed, the mixture is aged, washed, filtered, and freeze-dried to obtain the insect-repellent and fattening microcapsule matrix. S5: Disperse the insect-repellent and fattening microcapsule matrix obtained in step S4 in methanol, then add a coupling agent methanol solution, adjust the pH value, process under stirring, then filter, wash, and freeze dry. S6: Disperse the solid powder obtained after freeze-drying in step S5 in a buffer solution, add a chelating agent, process under stirring, filter, wash, and freeze-dry. S7: Disperse the solid powder obtained after freeze-drying in step S6 in a metal ion salt - N,N-dimethylformamide solution, and process it under stirring. After the reaction is complete, filter, wash, and freeze-dry to obtain insect-repellent and fattening microcapsules.

8. The agricultural emulsified asphalt according to claim 7, characterized in that, In step S1, the mass ratio of the nano-tourmaline powder to the surfactant is (1-10):1, and the mass ratio of the solvent to the surfactant is (20-40):

1. And / or, in step S1, the stirring speed is 400-600 rpm; The modification temperature is 100-200℃, and the modification time is 4-8 hours.

9. The agricultural emulsified asphalt according to claim 7, characterized in that, In step S2, the mixing is carried out under stirring, the stirring speed is 300-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 3-10 minutes.

10. The agricultural emulsified asphalt according to claim 7, characterized in that, In step S3, the mass ratio of the core material mixture to the modified nano-tourmaline powder is 1:(0.1-0.5); the mass ratio of the core material mixture to urea is 1:(0.2-1). And / or, in step S3, the stirring speed is 400-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 1-2 hours.

11. The agricultural emulsified asphalt according to claim 7, characterized in that, In step S4, the stirring speed is 400-600 rpm, the stirring temperature is 50-80℃, and the reaction time under stirring is 4-6 hours.

12. The agricultural emulsified asphalt according to claim 7, characterized in that, In step S5, the mass ratio of methanol to the insect-repellent and fattening microcapsule matrix is ​​(1-20):1; the mass ratio of the coupling agent methanol solution to the insect-repellent and fattening microcapsule matrix is ​​(0.1-10):

1. And / or, in step S5, the stirring speed is 200-450 rpm; the processing temperature is 40-60°C; and the processing time is 4-6 hours.

13. The agricultural emulsified asphalt according to claim 7, characterized in that, In step S7, the mass ratio of the metal ion salt-DMF solution to the solid powder obtained after drying in step S6 is (10-30):1; And / or, in step S7, the stirring speed is 200-450 rpm, the processing temperature is 100-150℃, and the processing time is 2-5 hours.

14. A method for preparing agricultural emulsified asphalt according to any one of claims 1-13, comprising: P1: Mix a portion of the compound emulsifier and water, adjust the pH value, and obtain soap solution; P2: The asphalt and the soap solution obtained in step P1 are heated separately and then mixed and sheared to obtain emulsified asphalt; P3: Add the remaining composite emulsifier, defoamer, and insect repellent and fertilizer-enhancing microcapsules to the emulsified asphalt obtained in step P2, and stir to mix; P4: Pretreatment of biopowder with phosphoric acid solution; P5: Add compound fertilizer and pretreated biological powder from step P4 to the reaction system of step P3, stir and mix to obtain agricultural emulsified asphalt.

15. The method according to claim 14, characterized in that, In step P1, the mass ratio of water to composite emulsifier is (5-20):1; And / or, in step P1, the stirring speed is 100-600 rpm, the stirring temperature is 50-90℃, and the stirring time is 5-20 minutes; And / or, in step P1, adjust the pH value to 2-4.

16. The method according to claim 14, characterized in that, In step P2, the heating temperature of the asphalt is 113-183℃; the heating temperature of the soap solution is 30-90℃.

17. The method according to claim 14, characterized in that, The mass ratio of the composite emulsifier added in step P3 to the composite emulsifier added in step P1 is 1:(1-10); And / or, in step P3, the stirring speed is 100-600 rpm, the stirring temperature is 30-90℃, and the stirring time is 30-120 minutes.

18. The method according to claim 14, characterized in that, In step P4, the pretreatment specifically involves mixing the biological powder with a phosphoric acid solution, stirring and reacting, then filtering, washing, and lyophilizing; the stirring speed is 300-500 rpm, the stirring temperature is 30-90℃, and the stirring time is 10-50 minutes.

19. The method according to claim 14, characterized in that, In step P5, the stirring speed is 100-600 rpm, the stirring temperature is 40-90℃, and the stirring time is 30-120 minutes.

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