An oil film remover applicable to aquaculture water bodies and a preparation method thereof

Abstract

The present invention relates to the technical field of oil film removers, and particularly relates to an oil film remover applicable to aquaculture water bodies and a preparation method thereof. The oil film remover comprises the following components in parts by weight: 25-30 parts of organic acid; 1-3 parts of surfactant; 1-2 parts of Artemisia argyi extract; 0.5-1 part of stabilizer; 0.2-0.5 part of auxiliary agent; 20-30 parts of deionized water; The preparation method is as follows: Weigh the organic acid, surfactant, Artemisia argyi extract, stabilizer, auxiliary agent, and deionized water respectively according to the weight ratio, and set aside; Add the organic acid, surfactant, Artemisia argyi extract, and stabilizer to the deionized water in sequence, stir at a speed of 100-200 r / min for 20-30 min, then add the auxiliary agent, and continue to stir for 5-10 min to obtain the oil film remover. The oil film remover prepared by the present invention can quickly remove the oil film, increase the content of dissolved oxygen in the water body, has a high oil film removal rate, can also reduce the content of heavy metals in the water body, and better meets the market demand.

Description

Technical Field

[0001] The present invention relates to the technical field of oil film removers, and particularly relates to an oil film remover applicable to aquaculture water bodies and a preparation method thereof. Background Art

[0002] Factors such as bait residues, fecal discharges, decomposition of animal and plant and algal corpses, and bottom heat return of ponds with thick silt in aquaculture water bodies lead to an increasing amount of dissolved organic matter in the water. If the pond cannot be thoroughly and timely sun-dried and cleared, the organic matter with a density smaller than that of water is likely to aggregate on the water surface to form an oil film. When there is an oil film on the water surface, it is not conducive to the dissolution of oxygen in the water body, hinders sunlight from irradiating the water body, affects the photosynthesis of algae, leads to a decrease in the dissolved oxygen content of the water body, and most oil films are aggregates of dirt, which are easy to breed pathogenic bacteria and pests when sealed on the surface of the pond water body. Therefore, timely removing the oil film and improving the water environment are crucial for realizing healthy aquaculture.

[0003] Currently, the oil film in aquaculture water bodies can be manually removed through an oil film removal device. The patent with the application number 201621182129.X discloses an oil film removal device for fish breeding ponds. The device includes a film skimming pipe and a sewage collection frame. The left and right sides of the sewage collection frame are made of wood boards, the upper, lower, and rear sides are made of wire meshes, and the front side is an opening. A rotating shaft is arranged in the center of the film skimming pipe and is sleeved with connecting rods on both sides of the sewage collection frame; the film skimming pipe rotates in the water body of the breeding pond, and the oil film is transferred into the sewage collection frame or between the sewage collection frame and the film skimming pipe during the rotation process, and then enters the sewage collection frame when the sewage collection frame moves, realizing the collection of the oil film while moving in the water body. The patent with the application number 202220480749.0 discloses a device for removing suspended oil film impurities on the water surface. The device includes a floating head, a pipe A, a pipe B, a pipe C, and a network pipe. Its structural components are simplified, the volume is smaller, the integration degree is higher, and the adjustment is convenient, efficient, and intuitive; there is no need to hang pipe fittings on the cylinder wall, and it operates through an external filter, reducing the visual interference to the aquarium; the material cost and processing cost are greatly reduced; using the above oil film removal device for manual oil film removal has a poor oil film removal effect, is time-consuming and laborious, and is difficult to use on a large scale. In addition, the oil film can also be removed by spraying an organic acid oil film remover, but most of the organic acid oil film removers produced by enterprises are pure organic acids, which have problems such as slow oil film removal speed and poor effect. Summary of the Invention

[0004] The purpose of the present invention is to provide an oil film remover applicable to aquaculture water bodies and a preparation method thereof in view of the deficiencies of the prior art. The prepared oil film remover can quickly remove the oil film, increase the dissolved oxygen content in the water body, has a high oil film removal rate, can also reduce the heavy metal content in the water body, and better meets the market demand.

[0005] The technical solutions adopted by the present invention to achieve the above purpose are as follows:

[0006] An oil film remover applicable to aquaculture water bodies, wherein the oil film remover comprises the following components in parts by weight: 25-30 parts of organic acid; 1-3 parts of surfactant; 1-2 parts of Artemisia argyi extract; 0.5-1 part of stabilizer; 0.2-0.5 part of auxiliary agent; 20-30 parts of deionized water;

[0007] The surfactant is Compound 1, and the chemical structural formula is:

[0008]

[0009] Furthermore, the preparation method of Compound 1 is as follows:

[0010] S1. Add p-nitrophenylethanol and pyridine into an anhydrous dichloromethane solution. Under ice bath conditions, slowly drop thionyl chloride. After dropping, naturally rise to room temperature and react for 6-8 h to obtain Compound 2. The molar ratio of p-nitrophenylethanol, thionyl chloride, and pyridine is 1:1.5-2.0:2.0-2.5; the reaction process is:

[0011]

[0012] S2. Add Compound 2 and palladium-carbon into a methanol solution, introduce hydrogen at 0.1 MPa, and react at room temperature for 4-6 h to obtain Compound 3. The mass ratio of Compound 2 to palladium-carbon is 1:0.1-0.15; the reaction process is:

[0013]

[0014] S3. Dissolve N,N'-carbonyldiimidazole in an acetonitrile solution, stir at room temperature for 10-30 min, add methoxyamine hydrochloride and triethylamine, continue to stir for 6-10 h, then add Compound 3, raise the temperature to 60-70 °C and react for 1-3 h to obtain Compound 4. The molar ratio of Compound 3, methoxyamine hydrochloride, N,N'-carbonyldiimidazole, and triethylamine is 1:1.2-1.5:1.5-1.8:2.0-2.5; the reaction process is:

[0015]

[0016] S4. Add Compound 4 and dodecyldimethylamine in sequence into an ethanol solution, reflux and react at 80-85 °C for 8-10 h to obtain Compound 1. The molar ratio of Compound 4 to dodecyldimethylamine is 1:1.5-2.0; the reaction process is:

[0017]

[0018] Further, the organic acid is one or more of acetic acid, citric acid, tartaric acid, and malic acid; the stabilizer is one or more of magnesium stearate, calcium stearate, and zinc stearate; the auxiliary is one or more of sodium chloride, sodium tripolyphosphate, sodium carbonate, sodium sulfate, or carboxymethyl cellulose.

[0019] Further, the extraction method of the Artemisia argyi extract is as follows: dry the Artemisia argyi, crush it and sieve it through a 50-60 mesh sieve to obtain Artemisia argyi powder, then add the Artemisia argyi powder, cellulase, and compound 1 into the solvent in sequence, soak for 1-2 h, then perform ultrasonic extraction for 20-30 min, filter, and concentrate the filtrate under reduced pressure to obtain the Artemisia argyi extract.

[0020] Further, the mass ratio of the Artemisia argyi powder to the solvent is 1:25-30; the dosage of the cellulase is 0.8-1.0 g / L of the solvent; the dosage of the compound 1 is 1.0-1.5 g / L of the solvent; the solvent is a 60-80% ethanol solution; the ultrasonic extraction power is 150-250 W, and the extraction temperature is 50-70 °C.

[0021] The present invention provides a preparation method of an oil film remover applicable to aquaculture water bodies, comprising the following steps:

[0022] (1) Weigh organic acid, surfactant, Artemisia argyi extract, stabilizer, auxiliary, and deionized water according to the weight ratio, and set aside;

[0023] (2) Add the organic acid, surfactant, Artemisia argyi extract, and stabilizer into the deionized water in sequence, stir at a speed of 100-200 r / min for 20-30 min, then add the auxiliary, and continue to stir for 5-10 min to obtain the oil film remover.

[0024] The present invention has the following beneficial effects:

[0025] The present invention uses p-nitrophenylethanol as a raw material, and obtains the surfactant compound 1 through substitution, reduction, condensation, and quaternization reactions. Its molecular structure contains a hydrophilic quaternary ammonium cation and a hydrophobic long-chain alkane, and has good ability to reduce the oil-water interface tension, and good wetting and emulsifying properties; it also contains a urea group (-NHCONH-), in which the carbonyl group and amino group can form coordination bonds with metal ions, and has strong adsorption to metal ions.

[0026] The Artemisia argyi extract added in the present invention has a significant bactericidal effect and has obvious bactericidal effects on Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Candida albicans and Aspergillus niger; using surfactant compound 1 for the extraction of Artemisia argyi extract can improve the extraction rate of Artemisia argyi extract; compound 1 acts on the enzymatic hydrolysis process, can increase the activity of cellulase, helps cellulase to destroy the cell wall, and enables more active ingredients to escape; compound 1 acts on the ultrasonic extraction process at the same time, has a wetting and solubilizing effect on Artemisia argyi powder, can reduce the interfacial tension between Artemisia argyi powder and liquid solvent, makes the solvent easier to enter Artemisia argyi powder, increases the dissolution degree of active ingredients, and further improves the extraction rate of Artemisia argyi extract; adding the obtained Artemisia argyi extract to the oil film remover makes it have a certain bactericidal and disinfection effect, which helps to improve the overall water environment.

[0027] The present invention adds surfactant compound 1 to the oil film remover and uses it in combination with organic acid to remove the oil film in water. On the one hand, it helps the organic acid to be fully dispersed on the surface of the oil film and contact with the oil film quickly and fully, so as to achieve the effect of quickly removing the oil film; on the other hand, it can act together with the carboxylic acid (-COOH) in the organic acid, can adsorb and complex heavy metal ions in the water body, reduces the content of heavy metals in the water body, and helps to create a healthy water environment and green ecological aquaculture. The oil film remover prepared by the present invention can quickly remove the oil film, increase the content of dissolved oxygen in the water body, has a high oil film removal rate, can also reduce the content of heavy metals in the water body, and can better meet the market demand. Description of the Drawings

[0028] Figure 1 Graph of the relationship between the mass fraction of surfactant compound 1 and the interfacial tension;

[0029] Figure 2 Graph of the change trend of dissolved oxygen before and after removing the oil film in water. Detailed Embodiments

[0030] Next, the technical solutions in the embodiments of the present application will be described clearly and completely in combination with the embodiments of the present application. Obviously, the described embodiments are only a 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 of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.

[0031] p-Nitrophenethyl alcohol, CAS No. 100-27-6; thionyl chloride, CAS No. 7719-09-7; pyridine, CAS No. 110-86-1; palladium on carbon, CAS No. 7440-05-3; methoxyamine hydrochloride, CAS No. 593-56-6; N,N'-carbonyldiimidazole, CAS No. 530-62-1; triethylamine, CAS No. 121-44-8; dodecyldimethylamine, CAS No. 112-18-5; dichloromethane, CAS No. 75-09-2; methanol, CAS No. 67-56-1; acetonitrile, CAS No. 75-05-8; ethanol, CAS No. 64-17-5; all chemical reagents are commercially available.

[0032] Example 1

[0033] This example provides an oil film remover applicable to aquaculture water bodies and a preparation method thereof.

[0034] An oil film remover applicable to aquaculture water bodies comprises the following components in parts by weight: 30 parts of organic acid; 3 parts of surfactant; 2 parts of Artemisia argyi extract; 1 part of stabilizer; 0.5 part of auxiliary; 30 parts of deionized water; wherein the organic acid is acetic acid; the stabilizer is magnesium stearate; the auxiliary is sodium chloride; the surfactant is Compound 1, and the chemical structural formula is:

[0035]

[0036] A preparation method of an oil film remover applicable to aquaculture water bodies comprises the following steps:

[0037] (1) Weigh the organic acid, surfactant, Artemisia argyi extract, stabilizer, auxiliary, and deionized water respectively according to the weight ratio and set aside;

[0038] (2) Add the organic acid, surfactant, Artemisia argyi extract, and stabilizer to the deionized water in sequence, stir at a speed of 200 r / min for 20 min, then add the auxiliary, and continue to stir for 5 min to obtain the oil film remover.

[0039] The preparation method of Compound 1 is as follows:

[0040] S1. Add 26.0 g of p-nitrophenethyl alcohol and 24.6 g of pyridine to 800 mL of anhydrous dichloromethane solution. Under ice bath conditions, slowly dropwise add 27.8 g of thionyl chloride. After dropping, naturally rise to room temperature and react for 8 h. After the reaction is completed, add 800 mL of water for extraction. The organic phase is dried and concentrated under reduced pressure to obtain 24.5 g of Compound 2, wherein the molar ratio of p-nitrophenethyl alcohol, thionyl chloride, and pyridine is 1:1.5:2.0; the reaction process is:

[0041]

[0042] Compound 2: ESI(m / z): 186.6 [M+H] + , 1 H-NMR(600 MHz, DMSO-d 6 , δ ppm): 8.14 (d, J = 8.7 Hz, 2H), 7.52 (d, J = 8.7 Hz, 2H), 3.71 (t, J = 7.1 Hz, 2H), 2.83 (t, J = 7.1 Hz, 2H).

[0043] S2. Add 24.5 g of Compound 2 and 2.45 g of palladium carbon to 400 mL of methanol solution, introduce 0.1 MPa of hydrogen, react at room temperature for 6 h. After the reaction is completed, filter off the palladium carbon, wash with 40 mL of methanol, and concentrate the filtrate under reduced pressure to obtain 18.2 g of Compound 3, where the mass ratio of Compound 2 to palladium carbon is 1:0.1; the reaction process is as follows:

[0044]

[0045] Compound 3: ESI(m / z): 156.6 [M+H] + , 1 H-NMR(600 MHz, DMSO-d 6 , δ ppm): 6.92 (d, J = 8.7 Hz, 2H), 6.45 (d, J = 8.7 Hz, 2H), 4.91 (s, 2H), 3.72 (t, J = 7.1 Hz, 2H), 2.71 (t, J = 7.1 Hz, 2H).

[0046] S3. Dissolve 34.1 g of N,N'-carbonyldiimidazole in 600 mL of acetonitrile solution, stir at room temperature for 10 - 30 min, add 14.7 g of methoxyamine hydrochloride and 29.6 g of triethylamine, continue to stir for 10 h, then add 18.2 g of Compound 3, heat up to 60 °C and react for 3 h. After the reaction is completed, naturally cool to room temperature, distill off acetonitrile under reduced pressure, and add 600 mL of dichloromethane and 600 mL of water for extraction. Dry the organic phase and concentrate under reduced pressure to obtain 24.6 g of Compound 4, where the molar ratio of Compound 3, methoxyamine hydrochloride, N,N'-carbonyldiimidazole, and triethylamine is 1:1.5:1.8:2.5; the reaction process is as follows:

[0047]

[0048] Compound 4: ESI(m / z): 229.6 [M+H] + , 1 H-NMR(600 MHz, DMSO-d 6, δ ppm): 8.90 (s, 1H), 7.53 (d, J = 8.7 Hz, 2H), 7.17 (d, J = 8.7 Hz, 2H), 6.0 (s, 1H), 3.89 (s, 3H), 3.71 (t, J = 7.0 Hz, 2H), 2.70 (t, J = 6.9 Hz, 2H).

[0049] S4. Add 24.6 g of compound 4 and 34.4 g of dodecyl dimethyl tertiary amine to 550 mL of ethanol solution in sequence. React under reflux at 85 °C for 10 h. After the reaction is completed, cool to room temperature naturally, concentrate the reaction solution to remove most of the ethanol, add 550 mL of water and 550 mL of dichloromethane for extraction. Back-extract the organic phase once, combine the aqueous phases, and concentrate under reduced pressure to obtain 41.5 g of compound 1, where the molar ratio of compound 4 to dodecyl dimethyl tertiary amine is 1:1.5; the reaction process is as follows:

[0050]

[0051] Compound 1: ESI (m / z): 406.6 [M-Cl] + , 1 1H-NMR (600 MHz, DMSO-d 6 , δ ppm): 8.92 (s, 1H), 7.51 (d, J = 8.7 Hz, 2H), 7.20 (d, J = 8.7 Hz, 2H), 6.3 (s, 1H), 3.92 (s, 3H), 3.57 (t, J = 7.0 Hz, 2H), 3.25 - 3.30 (m, 8H), 2.87 (t, J = 7.1 Hz, 2H), 1.71 - 1.72 (m, 2H), 1.26 - 1.29 (m, 18H), 0.88 - 0.89 (m, 3H).

[0052] Testing of the oil-water interfacial tension of surfactant compound 1: Prepare aqueous solutions of compound 1 with mass fractions of 1×10 -6 , 2×10 -6 , 3×10 -6 , 4×10 -6 , 5×10 -6 , 6×10 -6 respectively, and measure their oil-water interfacial tensions. The aqueous phase solvent is physiological saline, and the oil phase is aviation kerosene; the results are as Figure 1 shown. The synthesized surfactant compound 1 can reduce the oil-water interfacial tension to 0.3×10 -6 - 2.8×10 -6 when the mass fraction is 1×10 -2 - 6×10 -2mN / m indicates that the surfactant compound 1 can achieve a relatively low oil-water interfacial tension within a wide concentration range, has good ability to reduce the oil-water interfacial tension, and has good wetting performance.

[0053] Emulsifying ability test of surfactant compound 1: Prepare aqueous solutions of surfactant compound 1, dodecyltrimethylammonium bromide, and sodium dodecylbenzenesulfonate with a mass fraction of 0.1% respectively for standby. Add 20 mL of the prepared aqueous solutions of surfactant compound 1, dodecyltrimethylammonium bromide, and sodium dodecylbenzenesulfonate and 20 mL of paraffin oil (n-hexane) into 100 mL stoppered graduated cylinders respectively. Tighten the glass stopper, shake vigorously up and down about 20 times, let it stand horizontally for 1 min, then shake 20 times again, and let it stand for 1 min. Repeat the shaking and standing process 5 - 6 times. It can be found that the aqueous phase and the oil phase in the mixed system are gradually layered. Record the time taken to separate 10 mL of water as the standard to measure the emulsifying performance, and compare the water separation times of different surfactants, namely surfactant compound 1, dodecyltrimethylammonium bromide, and sodium dodecylbenzenesulfonate. The longer the time, the stronger the emulsifying ability of the surfactant; the results are shown in Table 1.

[0054] Table 1 Emulsifying performance of surfactant compound 1

[0055]

[0056]

[0057] It can be seen from the results in Table 1 that the water separation time of surfactant compound 1 is much longer than that of dodecyltrimethylammonium bromide and sodium dodecylbenzenesulfonate, indicating that the emulsifying performance of the surfactant compound 1 is significantly better than that of common surfactants (dodecyltrimethylammonium bromide, sodium dodecylbenzenesulfonate), and the surfactant compound 1 prepared in the present invention has good emulsifying performance.

[0058] The extraction method of the Artemisia argyi extract is as follows: Dry the Artemisia argyi, crush it through a 60-mesh sieve to obtain Artemisia argyi powder, then add the Artemisia argyi powder, cellulase, and compound 1 into the solvent in sequence. After soaking for 2 h, perform ultrasonic extraction for 30 min, filter, and concentrate the filtrate under reduced pressure to obtain the Artemisia argyi extract, with an extraction rate of 3.4%; the mass ratio of the Artemisia argyi powder to the solvent is 1:30; the dosage of cellulase is 0.8 g / L of the solvent; the dosage of compound 1 is 1.0 g / L of the solvent; the solvent is 80% ethanol solution; the ultrasonic extraction power is 250 W, and the extraction temperature is 70 °C; the calculation method of the extraction rate is: extraction rate = weight of Artemisia argyi extract / weight of Artemisia argyi powder × 100%.

[0059] Meanwhile, ultrasonic extraction was carried out on the same weight of wormwood powder according to the above extraction method of wormwood extract, without adding compound 1 to the solvent. The extraction rate of the obtained wormwood extract was 1.5%. In the present invention, the surfactant compound 1 is used in the extraction of wormwood extract. On the one hand, compound 1 can act on the enzymatic hydrolysis process, increase the activity of cellulase, help cellulase act on the cells of wormwood powder, break the cell wall, and enable more active ingredients to escape, thereby increasing the extraction rate. On the other hand, compound 1 acts on the ultrasonic extraction process, has a wetting and solubilizing effect on wormwood powder, can reduce the interfacial tension between wormwood powder and the liquid solvent, make the solvent more easily enter the wormwood powder, increase the dissolution degree of active ingredients, and help further increase the extraction rate.

[0060] Example 2

[0061] This example provides an oil film remover applicable to aquaculture water bodies and its preparation method.

[0062] An oil film remover applicable to aquaculture water bodies comprises the following components in parts by weight: 25 parts of organic acid; 1 part of surfactant; 1 part of wormwood extract; 0.5 part of stabilizer; 0.2 part of auxiliary; 20 parts of deionized water; wherein the organic acid is malic acid; the stabilizer is calcium stearate; the auxiliary is sodium tripolyphosphate; the surfactant is compound 1, and the chemical structural formula is:

[0063]

[0064] A preparation method of an oil film remover applicable to aquaculture water bodies comprises the following steps:

[0065] (1) Weigh the organic acid, surfactant, wormwood extract, stabilizer, auxiliary, and deionized water respectively according to the weight ratio for standby;

[0066] (2) Add the organic acid, surfactant, wormwood extract, and stabilizer to the deionized water in sequence, stir at a speed of 100 r / min for 30 min, then add the auxiliary, and continue to stir for 10 min to obtain the oil film remover.

[0067] The preparation method of compound 1 and the extraction method of wormwood extract are the same as those in Example 1.

[0068] Example 3

[0069] This example provides an oil film remover applicable to aquaculture water bodies and its preparation method.

[0070] An oil film remover applicable to aquaculture water bodies, comprising the following components in parts by weight: 27 parts of organic acid; 2 parts of surfactant; 1 part of Artemisia argyi extract; 0.8 part of stabilizer; 0.3 part of auxiliary; 25 parts of deionized water; wherein the organic acid is acetic acid and citric acid with a mass ratio of 1:1; the stabilizer is zinc stearate; the auxiliary is sodium carbonate; the surfactant is Compound 1, and the chemical structural formula is:

[0071]

[0072] A preparation method of an oil film remover applicable to aquaculture water bodies, comprising the following steps:

[0073] (1) Weigh the organic acid, surfactant, Artemisia argyi extract, stabilizer, auxiliary, and deionized water respectively according to the weight ratio for standby;

[0074] (2) Add the organic acid, surfactant, Artemisia argyi extract, and stabilizer into the deionized water in sequence, stir at a speed of 150 r / min for 25 min, then add the auxiliary, and continue to stir for 7 min to obtain the oil film remover.

[0075] Among them, the preparation method of Compound 1 and the extraction method of Artemisia argyi extract are the same as those in Example 1.

[0076] Comparative Example 1

[0077] This comparative example provides an oil film remover applicable to aquaculture water bodies and its preparation method. Compared with Example 1, the surfactant component of the oil film remover is dodecyl trimethyl ammonium bromide, and the rest is the same as that in Example 1.

[0078] Comparative Example 2

[0079] This comparative example provides an oil film remover applicable to aquaculture water bodies and its preparation method. Compared with Example 1, the oil film remover component does not contain surfactant, and the rest is the same as that in Example 1.

[0080] Related tests

[0081] Refer to the method in the literature [Influence of micro-surface oil film floating matter on water quality indicators of eutrophic water bodies. Green Science and Technology, 2016(08): 43 - 45. DOI: 10.16663 / j.cnki.lskj.2016.08.021.] to manufacture water body oil film. Use vegetable oil to simulate the water surface oil film. The water body is selected from the water area opposite the Jialu River section in the new area of Henan University. Samples of the water body at the same height are taken on the 1st - 5th day after covering the oil film. After sampling on the 5th day, the oil film removers prepared in Examples 1 - 3 and Comparative Examples 1 - 2 are used to remove the oil film respectively, and then samples of the water body at the same height are taken on the 6th - 10th day.

[0082] The usage method of the oil film remover is as follows: The oil film remover and water are fully mixed according to a mass ratio of 1:2, and then sprayed onto the surface of the oil film. Record the time when the oil film is no longer removed, and calculate the oil film removal rate. The oil film removal rate = the exposed area of the water surface after removing the oil film / the area of the oil film before removing the oil film × 100%; The results are shown in Table 2.

[0083] Table 2 Oil film removal rate of the oil film remover

[0084] Group Oil film removal time / min Oil film removal rate / % Example 1 5 80.5 Example 2 7 78.6 Example 3 6 79.2 Comparative Example 1 12 61.1 Comparative Example 2 18 55.4

[0085] As can be seen from Table 2, the oil film removal time of the oil film removers prepared in Examples 1-3 is much shorter than that of Comparative Examples 1-2, and the oil film removal rates are all higher than those of Comparative Examples 1-2, indicating that the oil film remover prepared by the present invention has a fast oil film removal speed and a high oil film removal rate; compared with Comparative Example 1 (the surfactant contained is dodecyltrimethylammonium bromide) and Comparative Example 2 (without surfactant), the surfactant contained in the oil film remover in Example 1 is Compound 1, whose molecular structure contains quaternary ammonium cations and long-chain alkanes, has good ability to reduce the interfacial tension between oil and water, and has good wetting and emulsifying properties. The compounding use of Compound 1 and organic acids helps the organic acids to be fully dispersed on the surface of the oil film and contact with the oil film quickly and fully, so as to achieve the effect of quickly removing the oil film.

[0086] The water samples on the 1st - 10th days were respectively used to test the dissolved oxygen content in the water body with a Multi 3420 portable water quality analyzer. The results are as Figure 2 shown. On the 1st - 5th days after covering the oil film, the dissolved oxygen content in the water bodies of Examples 1-3 and Comparative Examples 1-2 gradually decreased to 0.3 mg / L. The long-term coverage of the oil film on the water surface hindered the entry of oxygen into the water body, resulting in the gradual decrease of the dissolved oxygen content in the water body. After using the oil film remover to remove the oil film respectively, oxygen can enter the water body, making the dissolved oxygen content increase slowly. The effect of Examples 1-3 is better than that of Comparative Examples 1-2, which also shows that the oil film removers prepared in Examples 1-3 have a good oil film removal effect, and then oxygen can enter the water body better, increasing the dissolved oxygen content in the water body.

[0087] The contents of heavy metals Cd, Cr, Cu, Pd, and Zn in the water samples on the 5th day and the 10th day were respectively tested by the acid digestion inductively coupled plasma emission spectrometry method (the instrument used is Thermo IRIS Advantage 1000 of the United States). The heavy metal content standards for fishery water quality are: Cd ≤ 0.005 mg / L, Cr ≤ 0.1 mg / L, Cu ≤ 0.01 mg / L, Pd ≤ 0.05 mg / L, Zn ≤ 0.01 mg / L; The results are shown in Table 3.

[0088] Table 3 Influence of the oil film remover on the heavy metal content in the water body

[0089]

[0090]

[0091] As can be seen from Table 3, the oil film removers prepared in Examples 1-3 can significantly reduce the contents of heavy metals Cd, Cr, Cu, Pd, and Zn in water, making them all meet the standards. The adsorption and complexation effects on heavy metals are much better than those in Comparative Examples 1-2. Compared with Comparative Example 1 (the surfactant contained is dodecyltrimethylammonium bromide) and Comparative Example 2 (without surfactant), the surfactant contained in the oil film remover in Example 1 is Compound 1, whose molecular structure contains a urea group (-NHCONH-), in which the carbonyl group and amino group can form coordination bonds with metal ions and have strong adsorption on metal ions. Furthermore, acting together with the carboxylic acid (-COOH) in the organic acid, it can adsorb and complex heavy metal ions in water, reduce the contents of heavy metals Cd, Cr, Cu, Pd, and Zn in water, and is more conducive to creating a healthy water environment and green ecological aquaculture.

[0092] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

[0093] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An oil film remover applicable to aquaculture water bodies, characterized in that, the oil film remover comprises the following components in parts by weight: 25 - 30 parts of organic acid; 1 - 3 parts of surfactant; 1 - 2 parts of Artemisia argyi extract; 0.5 - 1 part of stabilizer; 0.2 - 0.5 part of auxiliary agent; 20 - 30 parts of deionized water; the surfactant is Compound 1, and the chemical structural formula is: 。 2. An oil film remover applicable to aquaculture water bodies according to claim 1, characterized in that, the preparation method of Compound 1 is: S1. Add p-nitrophenylethanol and pyridine into an anhydrous dichloromethane solution. Under ice bath conditions, slowly dropwise add thionyl chloride. After dropping, naturally rise to room temperature and react for 6 - 8 h to obtain Compound 2, and the chemical structural formula is: S2. Add Compound 2 and palladium carbon into a methanol solution, introduce 0.1 MPa of hydrogen, and react at room temperature for 4 - 6 h to obtain Compound 3, and the chemical structural formula is: S3. Dissolve N,N'-carbonyldiimidazole in an acetonitrile solution, stir at room temperature for 10 - 30 min, add methoxyamine hydrochloride and triethylamine, continue to stir for 6 - 10 h, then add Compound 3, raise the temperature to 60 - 70 °C and react for 1 - 3 h to obtain Compound 4, and the chemical structural formula is: S4. Add Compound 4 and dodecyldimethyl tertiary amine into an ethanol solution in sequence, reflux and react at 80 - 85 °C for 8 - 10 h to obtain Compound 1.

3. An oil film remover applicable to aquaculture water bodies according to claim 2, characterized in that, in step S1, the molar ratio of p-nitrophenylethanol, thionyl chloride, and pyridine is 1:1.5 - 2.0:2.0 - 2.5; in step S2, the mass ratio of Compound 2 and palladium carbon is 1:0.1 - 0.15; in step S3, the molar ratio of Compound 3, methoxyamine hydrochloride, N,N'-carbonyldiimidazole, and triethylamine is 1:1.2 - 1.5:1.5 - 1.8:2.0 - 2.5; in step S4, the molar ratio of Compound 4 and dodecyldimethyl tertiary amine is 1:1.5 - 2.

0.

4. An oil film remover applicable to aquaculture water bodies according to claim 1, characterized in that, the organic acid is one or more of acetic acid, citric acid, tartaric acid, and malic acid.

5. An oil film remover applicable to aquaculture water bodies according to claim 1, characterized in that, the stabilizer is one or more of magnesium stearate, calcium stearate, and zinc stearate.

6. An oil film remover applicable to aquaculture water bodies according to claim 1, characterized in that, the auxiliary agent is one or more of sodium chloride, sodium tripolyphosphate, sodium carbonate, sodium sulfate, or carboxymethyl cellulose.

7. An oil film remover applicable to aquaculture water bodies according to claim 1, characterized in that, The extraction method of the Artemisia argyi extract is as follows: The Artemisia argyi is dried and crushed through a 50-60 mesh sieve to obtain Artemisia argyi powder. Then, the Artemisia argyi powder, cellulase, and Compound 1 are successively added to a solvent. After soaking for 1-2 h, ultrasonic extraction is carried out for 20-30 min, followed by filtration. The filtrate is concentrated under reduced pressure to obtain the Artemisia argyi extract.

8. An oil film remover applicable to aquaculture water bodies according to claim 7, characterized in that the mass ratio of the Artemisia argyi powder to the solvent is 1:25-30; the dosage of the cellulase is 0.8-1.0 g / L of the solvent; the dosage of Compound 1 is 1.0-1.5 g / L of the solvent; and the solvent is a 60-80% ethanol solution.

9. An oil film remover applicable to aquaculture water bodies according to claim 7, characterized in that the ultrasonic extraction power is 150-250 W, and the extraction temperature is 50-70 °C.

10. A preparation method of an oil film remover applicable to aquaculture water bodies according to any one of claims 1-9, comprising the following steps: (1) Weigh organic acid, surfactant, Artemisia argyi extract, stabilizer, auxiliary agent, and deionized water according to the weight ratio and set aside; (2) Add the organic acid, surfactant, Artemisia argyi extract, and stabilizer to the deionized water in sequence and stir at a speed of 100-200 r / min for 20-30 min. Then add the auxiliary agent and continue to stir for 5-10 min to obtain the oil film remover.

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