An environmentally friendly restoration method for marine oil spill pollution

Abstract

The present invention proposes an environmentally friendly remediation method for marine oil spill pollution, which belongs to the technical field of sea surface oil floating treatment. The method comprises: (1) uniformly mixing a bio-based choline ionic liquid, a photocatalytic enzyme magnetic oil absorbent, immobilized bacteria and algae, and straw powder to prepare an oil dispersant; (2) adding the prepared oil dispersant to the oil spill area. After the remediation is completed, the photocatalytic enzyme magnetic oil absorbent is separated by a magnet, washed, dried, and reused. The present invention first disperses the oil pollution to form a microemulsion by using a bio-based choline ionic liquid. During the adsorption of the oil droplets by the photocatalytic enzyme magnetic oil absorbent and the degradation by photoenzyme, the immobilized bacteria and algae can also effectively degrade and absorb the oil droplets. At the same time, the photocatalytic enzyme magnetic oil absorbent can be separated and reused by a magnet, the bio-based choline ionic liquid can degrade itself, and the immobilized bacteria and algae can also decompose themselves, thereby avoiding pollution to the environment and having the characteristics of environmental protection.

Description

Technical Field

[0001] The present invention relates to the technical field of sea surface oil spill treatment, and in particular to an environmentally friendly restoration method for marine oil spill pollution. Background Art

[0002] Currently, the main methods for treating marine oil spills include physical, chemical, biological, and incineration. Physical methods primarily involve deploying booms in the spilled area to prevent the spread of the oil, and organizing cleanup vessels to remove the oil using mechanical recovery methods like skimmers, adsorption materials like oil absorbent mats, and other physical methods. Booms can also be combined with incineration. Chemical treatment methods primarily involve spraying dispersants, oil collectors, and solidifying agents into the water to disperse or solidify the oil before treatment. Bioremediation methods primarily utilize microbial degradation to remove oil spills, including the addition of nutrients and bacterial strains.

[0003] However, these oil spill cleanup methods all have limitations. Traditional physical methods are inefficient, labor-intensive, and difficult to completely remove. Most dispersants and oil collection agents are prone to secondary pollution to the ocean. The advantages of using biological methods to repair crude oil-contaminated seawater are safety, non-toxicity, biodegradability, and generally no secondary pollution to the environment. However, the use of microorganisms to repair crude oil-contaminated seawater has the following problems: low degradation efficiency and low utilization rate, making it unsuitable for large-scale marine oil spill remediation. Summary of the Invention

[0004] The purpose of the present invention is to provide an environmentally friendly remediation method for marine oil spill pollution. First, the oil is dispersed by a bio-based choline ionic liquid to form a microemulsion. During the adsorption of the oil droplets by a photocatalytic enzyme magnetic oil absorbent and the photoenzymatic degradation, immobilized bacteria and algae can also effectively degrade and absorb the oil droplets. At the same time, the photocatalytic enzyme magnetic oil absorbent can be separated and reused by a magnet, the bio-based choline ionic liquid can degrade itself, and the immobilized bacteria and algae can also decompose themselves, thereby avoiding pollution to the environment and having environmentally friendly characteristics.

[0005] The technical solution of the present invention is achieved as follows:

[0006] The present invention provides an environmentally friendly restoration method for marine oil spill pollution, comprising the following steps:

[0007] (1) The bio-based choline ionic liquid, the photocatalytic enzyme magnetic oil absorbent, the immobilized bacteria and algae, and the straw powder are mixed uniformly in a mass ratio of 2-3:15-20:7-10:10-15 to prepare an oil dispersant;

[0008] (2) Adding the prepared oil dispersant to the oil spill area, with the mass of the oil dispersant added being 8-10wt% of the oil spilled. After the repair is completed, the photocatalytic enzyme magnetic oil absorbent is separated by a magnet, washed, dried, and reused;

[0009] The photocatalytic enzyme magnetic oil absorbent is prepared by carbon quantum dots doped with TiO2 loaded on magnetic bentonite, modified by polydopamine coating, fixed with lipase, and ultrasonically treated.

[0010] The structural formula of the bio-based choline ionic liquid is shown in Formula I:

[0011] Formula I.

[0012] As a further improvement of the present invention, the preparation method of the bio-based choline ionic liquid is as follows:

[0013] S1. Dissolve oleic acid in ethanol, add 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, and stir to activate. Add glutamic acid, stir to react, add water, precipitate, filter, wash, and dry to obtain an intermediate with the following structure: ;

[0014] S2. The intermediate is added to ethanol, and a choline hydroxide alcohol solution is added dropwise. The reaction is stirred, the solvent is removed under reduced pressure, and the product is recrystallized from acetone. The product is filtered, washed, and dried to obtain a bio-based choline ionic liquid.

[0015] As a further improvement of the present invention, the molar ratio of oleic acid, glutamic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide in step S1 is 1:1.1-1.2:1.2-1.5:1.2-1.5; and the molar ratio of the intermediate and choline hydroxide in step S2 is 1:2.2-2.3.

[0016] As a further improvement of the present invention, the preparation method of the photocatalytic enzyme magnetic oil absorbent is as follows:

[0017] T1. Preparation of magnetic bentonite: Bentonite was added to water and uniformly dispersed by ultrasonication. Ferric chloride and ferrous chloride were then added dropwise. Under an inert gas atmosphere, aqueous ammonia was added dropwise. The mixture was heated with stirring, filtered, washed, dried, and calcined to obtain magnetic bentonite.

[0018] T2. Preparation of carbon quantum dot-doped TiO2@magnetic bentonite: Citric acid and tetrabutyl titanate were dissolved in ethanol, magnetic bentonite was added, and the mixture was stirred until uniform. Ammonia was added dropwise to adjust the pH of the solution. The mixture was hydrothermally reacted, separated by a magnet, washed, dried, and calcined to produce carbon quantum dot-doped TiO2@magnetic bentonite.

[0019] T3. Lipase Loading: Carbon quantum dot-doped TiO2@magnetic bentonite was added to a Tris-HCl solution, followed by dopamine hydrochloride. The mixture was heated and stirred. Lipase, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and N-hydroxysuccinimide were then added and stirred. The mixture was separated by a magnetic separator, washed, and dried to produce lipase / carbon quantum dot-doped TiO2@magnetic bentonite.

[0020] T4. Ultrasonic treatment: The prepared lipase / carbon quantum dot-doped TiO2@magnetic bentonite was added to water, ultrasonically treated, magnetically separated, washed, and dried to obtain a photocatalytic enzyme magnetic oil absorbent.

[0021] As a further improvement of the present invention, the mass ratio of bentonite, ferric chloride and ferrous chloride in step T1 is 20-30:3.24:1.26, the temperature of the heating and stirring reaction is 75-85°C, and the time is 3-5 hours; the mass ratio of citric acid, tetrabutyl titanate and magnetic bentonite in step T2 is 2-3:12-15:30-50, the pH value of the solution is adjusted to 9-10, the temperature of the hydrothermal reaction is 180-200°C, the time is 10-12 hours, and the calcination temperature is 400-450°C, and the time is an additional 3-5 hours.

[0022] As a further improvement of the present invention, the pH value of the Tris-HCl solution in step T3 is 8.5-9.5, the mass ratio of the carbon quantum dots doped TiO2@magnetic bentonite, dopamine hydrochloride, lipase, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 20-30:2-3:1-2:0.2-0.5:0.2-0.5, the lipase, the temperature of the heating and stirring reaction is 45-55 ° C, and the time is 2-4h; the power of the ultrasonic treatment in step T4 is 400-500W, on 1-3s, off 1-3s, and the treatment is 20-30min.

[0023] As a further improvement of the present invention, the preparation method of the immobilized bacteria and algae is as follows:

[0024] U1. Formaldehyde solution and melamine were added to water, the pH of the solution was adjusted, the reaction was stirred, centrifuged, washed, and dried to obtain formaldehyde-melamine microspheres;

[0025] U2. Zero-valent iron powder was placed on a stainless steel mesh, sulfur powder and formaldehyde-melamine microspheres were placed at the bottom of the crucible, and the crucible was placed in a tube furnace. Under an inert gas atmosphere, the crucible was heated and calcined to produce a carbon nanotube-sulfurized micronized zero-valent iron composite.

[0026] U3. A carbon nanotube-sulfurized micronized zero-valent iron complex, tetraethyl orthosilicate, and a porogen were added to ethanol. Ammonia was added dropwise. The reaction was stirred, centrifuged, washed, and dried to produce loaded SiO2 nanospheres.

[0027] U4. Add the loaded SiO2 nanospheres to water, add glucose and Pacific Alkanes, stir and mix evenly, evaporate the solvent to obtain bacterial microspheres;

[0028] U5. Add Chlorella vulgaris and Spirulina maxima to water, add bacterial microspheres, lecithin, and sodium alginate, stir and mix thoroughly, then add dropwise to fish oil. Emulsify, add calcium chloride solution dropwise, solidify at room temperature, filter, wash, and dry to produce immobilized bacteria and algae.

[0029] As a further improvement of the present invention, the mass ratio of the formaldehyde solution and melamine in step U1 is 8-10:2-3, and the pH value of the adjusted solution is 5-5.5; the mass ratio of the zero-valent iron powder, sulfur powder, and formaldehyde-melamine microspheres in step U2 is 2:0.3-0.5:0.5-1, and the heating and calcining conditions are 200-250° C., holding for 20-30 minutes, heating to 400-450° C., holding for 10-20 minutes, heating to 900-950° C., and holding for 30-50 minutes.

[0030] As a further improvement of the present invention, the mass ratio of the carbon nanotube@sulfurized micron zero-valent iron complex, ethyl orthosilicate, and porogen in step U3 is 1-2:12-15:2-3, and the porogen is hexadecyltrimethylammonium chloride or hexadecyltrimethylammonium bromide.

[0031] As a further improvement of the present invention, the mass ratio of the loaded SiO2 nanospheres, glucose and Pacific Alkanes in step U4 is 10-15:1-2:2-4; the mass ratio of Chlorella, Spirulina maxima, bacterial-loaded microspheres, lecithin and sodium alginate in step U5 is 2-3:1-3:7-10:0.5-1:13-20.

[0032] The present invention has the following beneficial effects:

[0033] The present invention prepares an oleic acid-glutamic acid choline ionic liquid, which can effectively disperse oil pollution, reduce the critical micelle concentration, have good dispersibility, and reduce interfacial tension, thereby dispersing the oil pollution into small droplets, thereby facilitating the adsorption of the oil pollution droplets by a photocatalytic enzyme magnetic oil absorbent and the photoenzyme-catalyzed degradation, and can also promote the degradation and absorption of the oil pollution droplets by immobilized bacteria and algae.

[0034] The present invention prepares a photocatalytic enzyme magnetic oil absorbent using bentonite as a carrier. On the one hand, the photocatalytic enzyme magnetic oil absorbent has a large specific surface area and is easy to separate with a magnet after being loaded with magnetic ferroferric oxide, thereby achieving reuse. On the other hand, the bentonite also has good oil absorption and can be reused after being separated from the magnet and subjected to deoiling treatment.

[0035] After carbon quantum dots doped with TiO2 are deposited on its surface, carbon quantum dots can act as electron acceptors or transfer media. After TiO2 is excited by light to generate electron-hole pairs, electron transmission channels are formed between it and TiO2, so that photogenerated electrons can quickly migrate to the surface of carbon quantum dots, thereby effectively inhibiting the recombination of electrons and holes. The efficiency of photocatalytic degradation of dyes is significantly improved, and the visible light part of sunlight can be more effectively utilized, thereby improving the utilization rate of light energy. The surface of carbon quantum dots is rich in various functional groups, such as carboxyl and hydroxyl groups. These functional groups can serve as active sites to adsorb and activate reaction substrates and promote the progress of photocatalytic reactions. Carbon quantum dots can play a certain protective role on TiO2, preventing TiO2 from agglomeration, sintering or photocorrosion during the photocatalytic reaction, thereby improving the stability and service life of the photocatalyst.

[0036] Lipase is coupled to the prepared carbon quantum dot-doped TiO2@magnetic bentonite via aminocarboxyl condensation, enabling enzymatic degradation of oil stains. The photocatalyst carbon quantum dot-doped TiO2 utilizes light energy to generate active substances with strong redox capabilities, such as electron-hole pairs and hydroxyl radicals, which can initially oxidize or reduce the substrate, changing its chemical structure and electronic state, making it more susceptible to lipase action. Simultaneously, the catalytic action of lipase further accelerates the conversion and degradation of intermediates produced in the photocatalytic reaction, improving the efficiency and thoroughness of the entire reaction and significantly increasing the oil removal rate.

[0037] After ultrasonic treatment of lipase / carbon quantum dots doped TiO2@magnetic bentonite,

[0038] The present invention heats and calcines zero-valent iron powder, sulfur powder and formaldehyde-melamine microspheres, and then chemically vapor deposits carbon nanotubes @ sulfide micron zero-valent iron composites, which are converted into Fe by replacing the Fe2O3 / Fe on the surface through sulfide. 1-x S / Fe, Fe 1-x The S phase has a smaller band gap than Fe2O3 and can promote electron transfer. Carbon nanotubes have good conductivity and increase the speed of electron transfer. Therefore, the iron-carbon nanotube microelectrolysis effect is used to enhance the electron transfer of the microbial respiratory chain and improve the removal rate of oil pollution.

[0039] The present invention coats the carbon nanotube@sulfurized micron zero-valent iron complex in the prepared silica microspheres, and the porogen makes them contain rich pores, thereby loading Pacific Alkanophaga, shortening the electron transfer channel of the microbial respiratory chain, and improving the efficiency of oil pollution removal.

[0040] The present invention also encapsulates Chlorella and Spirulina maxima in the immobilized bacteria and algae. Chlorella can degrade petroleum substances, and the biological enzymes in the cells of Spirulina maxima can oxidize, ring-open, degrade and transform petroleum hydrocarbons, thereby further improving the removal effect of oil pollution.

[0041] The present invention first disperses the oil stains by bio-based choline ionic liquid to form a microemulsion. During the adsorption of the oil stain droplets by the photocatalytic enzyme magnetic oil absorbent and the photoenzyme catalytic degradation, the immobilized bacteria and algae can also effectively degrade and absorb the oil stain droplets. At the same time, the photocatalytic enzyme magnetic oil absorbent can be separated and reused by a magnet, the bio-based choline ionic liquid can degrade itself, and the immobilized bacteria and algae can also decompose themselves, thereby avoiding pollution to the environment and having the characteristics of environmental protection. DETAILED DESCRIPTION

[0042] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0043] Lipase, 4000 U / mg, was purchased from Merck Life Science.

[0044] Preparation Example 1 Preparation of bio-based choline ionic liquid

[0045] Synthesis route:

[0046] ;

[0047] Here’s how:

[0048] S1. Dissolve 0.1 mol of oleic acid in 200 mL of ethanol, add 0.13 mol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 0.13 mol of N-hydroxysuccinimide, and stir to activate for 30 minutes. Add 0.115 mol of glutamic acid, stir and react for 12 hours, add 500 mL of water, precipitate for 1 hour, filter, wash, and dry to obtain the intermediate; ESI-MS calculated value: C 23 H 42 NO5(M+H) + 412.58, found: 412.6, yield: 67%.

[0049] NMR results: 1 H NMR (300MHz, CDCl3) δ11.0 (br, 2H), 8.0 (br, 1H), 5.44 (d, J =6.2Hz, 2H), 4.49 (t, 1H), 2.1-2.3 (m, 4H), 1.9-2.0 (m, 6H), 1.57 (m, 2H), 1.27-1.30 (m, 20H), 0.92 (t, 3H).

[0050] S2. Add 0.1 mol of the intermediate to 60 mL of ethanol, add dropwise 100 mL of an ethanol solution containing 0.225 mol of choline hydroxide, and stir for 6 h. Remove the solvent under reduced pressure, recrystallize from acetone, filter, wash, and dry to obtain a bio-based choline ionic liquid. ESI-MS calculated value: C 35 H 72 N3O5(M+H) + 614.96, found: 615.0, yield 90%.

[0051] NMR results: 1 H NMR (300MHz, CDCl3) δ8.0 (br, 1H), 5.4 (d, J =5.8Hz, 2H), 4.42 (t, 1H), 3.24-3.30 (m, 22H), 2.45 (t, 2H), 2.21 (m, 4H), 1.88 (m, 4H), 1.72 (m, 4H), 1.52 (m, 2H), 1.27-1.30 (m, 20H), 0.92 (m, 9H).

[0052] Preparation Example 2 Preparation of photocatalytic enzyme magnetic oil absorbent

[0053] Here’s how:

[0054] T1. Preparation of magnetic bentonite: 20 g of bentonite was added to 200 mL of water and ultrasonically dispersed at 1000 W for 20 min. 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added. Under nitrogen, 10 mL of aqueous ammonia was added dropwise. The mixture was heated to 75°C and stirred for 3 h. The mixture was filtered, washed, dried, and calcined to obtain magnetic bentonite.

[0055] T2. Preparation of carbon quantum dot-doped TiO2@magnetic bentonite: 0.2 g of citric acid and 1.2 g of tetrabutyl titanate were dissolved in 100 mL of ethanol, and 3 g of magnetic bentonite was added. The mixture was stirred for 20 minutes, and ammonia was added dropwise to adjust the pH of the solution to 9. The reaction was hydrothermally reacted at 180°C for 10 hours. The mixture was separated by a magnet, washed, dried, and calcined at 400°C for 3 hours to produce carbon quantum dot-doped TiO2@magnetic bentonite.

[0056] T3. Lipase loading: 2 g of carbon quantum dot-doped TiO2@magnetic bentonite was added to 100 mL of Tris-HCl solution (pH 8.5). 0.2 g of dopamine hydrochloride was added, and the mixture was heated to 45°C and stirred for 2 h. Then, 0.1 g of lipase, 0.02 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and 0.02 g of N-hydroxysuccinimide were added and stirred for 12 h. The mixture was separated by a magnetic separator, washed, and dried to prepare lipase / carbon quantum dot-doped TiO2@magnetic bentonite.

[0057] T4. Ultrasonic treatment: Add 1 g of lipase / carbon quantum dot-doped TiO2@magnetic bentonite to 50 mL of water and ultrasonicate at 400 W for 1 s on, 1 s off, for 30 min. Separate with a magnet, wash, and dry to obtain a photocatalytic enzyme magnetic oil absorbent.

[0058] Preparation Example 3 Preparation of photocatalytic enzyme magnetic oil absorbent

[0059] Here’s how:

[0060] T1. Preparation of magnetic bentonite: 30 g of bentonite was added to 200 mL of water and ultrasonically dispersed at 1000 W for 20 min. 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added. Under nitrogen, 10 mL of aqueous ammonia was added dropwise. The mixture was heated to 85°C and stirred for 5 h. The mixture was filtered, washed, dried, and calcined to obtain magnetic bentonite.

[0061] T2. Preparation of carbon quantum dot-doped TiO2@magnetic bentonite: 0.3 g of citric acid and 1.5 g of tetrabutyl titanate were dissolved in 100 mL of ethanol, and 5 g of magnetic bentonite was added. The mixture was stirred for 20 minutes, and ammonia was added dropwise to adjust the pH of the solution to 10. The reaction was hydrothermally reacted at 200°C for 12 hours, followed by magnetic separation, washing, drying, and calcination at 450°C for 5 hours to produce carbon quantum dot-doped TiO2@magnetic bentonite.

[0062] T3. Lipase Loading: 3 g of carbon quantum dot-doped TiO2@magnetic bentonite was added to 100 mL of Tris-HCl solution (pH 9.5). 0.3 g of dopamine hydrochloride was added, and the mixture was heated to 55°C and stirred for 4 h. Then, 0.2 g of lipase, 0.05 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and 0.05 g of N-hydroxysuccinimide were added and stirred for 12 h. The mixture was separated by a magnetic separator, washed, and dried to prepare lipase / carbon quantum dot-doped TiO2@magnetic bentonite.

[0063] T4. Ultrasonic treatment: Add 1 g of lipase / carbon quantum dot-doped TiO2@magnetic bentonite to 50 mL of water and ultrasonicate at 500 W for 3 seconds on and 3 seconds off for 20 minutes. Separate with a magnet, wash, and dry to obtain a photocatalytic enzyme magnetic oil absorbent.

[0064] Preparation Example 4 Preparation of photocatalytic enzyme magnetic oil absorbent

[0065] Here’s how:

[0066] T1. Preparation of magnetic bentonite: 25 g of bentonite was added to 200 mL of water and ultrasonically dispersed at 1000 W for 20 min. 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added. Under nitrogen, 10 mL of aqueous ammonia was added dropwise. The mixture was heated to 80°C and stirred for 4 h. The mixture was filtered, washed, dried, and calcined to obtain magnetic bentonite.

[0067] T2. Preparation of carbon quantum dot-doped TiO2@magnetic bentonite: 0.25 g of citric acid and 1.35 g of tetrabutyl titanate were dissolved in 100 mL of ethanol, and 4 g of magnetic bentonite was added. The mixture was stirred for 20 minutes. Ammonia was added dropwise to adjust the pH of the solution to 9.5. The reaction was hydrothermally reacted at 190°C for 11 hours. The mixture was separated by a magnet, washed, dried, and calcined at 420°C for 4 hours to produce carbon quantum dot-doped TiO2@magnetic bentonite.

[0068] T3. Lipase Loading: 2.5 g of carbon quantum dot-doped TiO2@magnetic bentonite was added to 100 mL of Tris-HCl solution (pH 9). 0.25 g of dopamine hydrochloride was added, and the mixture was heated to 50°C and stirred for 3 h. Then, 0.15 g of lipase, 0.035 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and 0.03 g of N-hydroxysuccinimide were added and stirred for 12 h. The mixture was then separated by a magnetic separator, washed, and dried to obtain lipase / carbon quantum dot-doped TiO2@magnetic bentonite.

[0069] T4. Ultrasonic treatment: Add 1 g of lipase / carbon quantum dot-doped TiO2@magnetic bentonite to 50 mL of water and ultrasonicate at 450 W for 2 s on, 2 s off, for 25 min. Separate with a magnet, wash, and dry to obtain a photocatalytic enzyme magnetic oil absorbent.

[0070] Comparative Preparation Example 1

[0071] Compared with Preparation Example 4, the difference is that citric acid is not added in step T2.

[0072] The details are as follows:

[0073] T2. Preparation of TiO2@magnetic bentonite: 1.6 g of tetrabutyl titanate was dissolved in 100 mL of ethanol, and 4 g of magnetic bentonite was added. The mixture was stirred for 20 min, and ammonia was added dropwise to adjust the pH of the solution to 9.5. The solution was hydrothermally reacted at 190°C for 11 h, separated by a magnet, washed, dried, and calcined at 420°C for 4 h to obtain TiO2@magnetic bentonite.

[0074] Comparative Preparation Example 2

[0075] Compared with Preparation Example 4, the difference is that step T2 is not performed.

[0076] The details are as follows:

[0077] T1. Preparation of magnetic bentonite: 25 g of bentonite was added to 200 mL of water and ultrasonically dispersed at 1000 W for 20 min. 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added. Under nitrogen, 10 mL of aqueous ammonia was added dropwise. The mixture was heated to 80°C and stirred for 4 h. The mixture was filtered, washed, dried, and calcined to obtain magnetic bentonite.

[0078] T2. Lipase loading: 2.5 g of magnetic bentonite was added to 100 mL of Tris-HCl solution (pH 9), followed by 0.25 g of dopamine hydrochloride. The mixture was heated to 50°C and stirred for 3 h. Then, 0.15 g of lipase, 0.035 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and 0.03 g of N-hydroxysuccinimide were added and stirred for 12 h. The mixture was separated with a magnet, washed, and dried to obtain lipase@magnetic bentonite.

[0079] T3. Ultrasonic treatment: Add 1 g of lipase@magnetic bentonite to 50 mL of water and ultrasonically treat at 450 W for 2 seconds on and 2 seconds off for 25 minutes. Separate with a magnet, wash, and dry to obtain a photocatalytic enzyme magnetic oil absorbent.

[0080] Comparative Preparation Example 3

[0081] Compared with Preparation Example 4, the difference is that step T3 is not performed.

[0082] The details are as follows:

[0083] T1. Preparation of magnetic bentonite: 25 g of bentonite was added to 200 mL of water and ultrasonically dispersed at 1000 W for 20 min. 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added. Under nitrogen, 10 mL of aqueous ammonia was added dropwise. The mixture was heated to 80°C and stirred for 4 h. The mixture was filtered, washed, dried, and calcined to obtain magnetic bentonite.

[0084] T2. Preparation of carbon quantum dot-doped TiO2@magnetic bentonite: 0.25 g of citric acid and 1.35 g of tetrabutyl titanate were dissolved in 100 mL of ethanol, and 4 g of magnetic bentonite was added. The mixture was stirred for 20 minutes. Ammonia was added dropwise to adjust the pH of the solution to 9.5. The reaction was hydrothermally reacted at 190°C for 11 hours. The mixture was separated by a magnet, washed, dried, and calcined at 420°C for 4 hours to produce carbon quantum dot-doped TiO2@magnetic bentonite.

[0085] T3. Ultrasonic treatment: Add 1 g of carbon quantum dot-doped TiO2@magnetic bentonite to 50 mL of water and ultrasonically treat at a power of 450 W for 2 seconds on and 2 seconds off for 25 minutes. Then separate with a magnet, wash, and dry to obtain a photocatalytic magnetic oil absorbent.

[0086] Comparative Preparation Example 4

[0087] Compared with Preparation Example 4, the difference is that step T4 is not performed.

[0088] The details are as follows:

[0089] T1. Preparation of magnetic bentonite: 25 g of bentonite was added to 200 mL of water and ultrasonically dispersed at 1000 W for 20 min. 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added. Under nitrogen, 10 mL of aqueous ammonia was added dropwise. The mixture was heated to 80°C and stirred for 4 h. The mixture was filtered, washed, dried, and calcined to obtain magnetic bentonite.

[0090] T2. Preparation of carbon quantum dot-doped TiO2@magnetic bentonite: 0.25 g of citric acid and 1.35 g of tetrabutyl titanate were dissolved in 100 mL of ethanol, and 4 g of magnetic bentonite was added. The mixture was stirred for 20 minutes. Ammonia was added dropwise to adjust the pH of the solution to 9.5. The reaction was hydrothermally reacted at 190°C for 11 hours. The mixture was separated by a magnet, washed, dried, and calcined at 420°C for 4 hours to produce carbon quantum dot-doped TiO2@magnetic bentonite.

[0091] T3. Lipase loading: 2.5 g of carbon quantum dot-doped TiO2@magnetic bentonite was added to 100 mL of Tris-HCl solution at pH 9, followed by 0.25 g of dopamine hydrochloride. The mixture was heated to 50°C and stirred for 3 h. 0.15 g of lipase, 0.035 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and 0.03 g of N-hydroxysuccinimide were then added and stirred for 12 h. The mixture was separated by a magnet, washed, and dried to obtain lipase / carbon quantum dot-doped TiO2@magnetic bentonite, which is a photocatalytic enzyme magnetic oil absorbent.

[0092] Preparation Example 5 Preparation of immobilized bacteria and algae

[0093] Here’s how:

[0094] U1. 8 g of formaldehyde solution and 2 g of melamine were added to 200 mL of water, the pH of the solution was adjusted to 5, the reaction was stirred for 20 min, centrifuged, washed, and dried to obtain formaldehyde-melamine microspheres;

[0095] U2. Place 2g of zero-valent iron powder on a stainless steel mesh, add 0.3g of sulfur powder and 0.5g of formaldehyde-melamine microspheres to the bottom of a crucible, and place the crucible in a tube furnace. Under nitrogen, heat and calcine at 200°C for 20 minutes, then raise the temperature to 400°C for 10 minutes, and finally raise the temperature to 900°C for 30 minutes to produce a carbon nanotube-sulfurized micronized zero-valent iron composite.

[0096] U3. 1g of carbon nanotubes and sulfide micronized zero-valent iron complex, 12g of ethyl orthosilicate, and 2g of hexadecyltrimethylammonium bromide were added to 200mL of ethanol. 5mL of aqueous ammonia was added dropwise. The mixture was stirred for 7h, centrifuged, washed, and dried to produce loaded SiO2 nanospheres.

[0097] U4. 10 g of loaded SiO2 nanospheres were added to 200 mL of water, 1 g of glucose and 2 g of Pacific Alkanes were added, stirred and mixed, and the solvent was evaporated to obtain bacterial microspheres.

[0098] U5. 2g of Chlorella vulgaris and 1g of Spirulina maxima were added to 250mL of water, along with 7g of bacterial-loaded microspheres, 0.5g of lecithin, and 13g of sodium alginate. The mixture was stirred for 20 minutes and then added dropwise to 500mL of fish oil. Emulsification was performed at 8000 rpm for 20 minutes, followed by the dropwise addition of 50mL of a 2wt% calcium chloride solution. The mixture was cured at room temperature for 30 minutes, filtered, washed, and dried to obtain immobilized bacteria and algae.

[0099] Preparation Example 6 Preparation of immobilized bacteria and algae

[0100] Here’s how:

[0101] U1. Add 10 g of formaldehyde solution and 3 g of melamine to 200 mL of water, adjust the solution pH to 5.5, stir and react for 20 min, centrifuge, wash, and dry to obtain formaldehyde-melamine microspheres.

[0102] U2. Place 2g of zero-valent iron powder on a stainless steel mesh, 0.5g of sulfur powder, and 1g of formaldehyde-melamine microspheres at the bottom of a crucible. The crucible was then placed in a tube furnace and calcined under nitrogen at 250°C for 30 minutes, then raised to 450°C for 20 minutes, and finally raised to 950°C for 50 minutes to produce a carbon nanotube-sulfurized micronized zero-valent iron composite.

[0103] U3. 2g of carbon nanotubes and sulfide micronized zero-valent iron complex, 15g of ethyl orthosilicate, and 3g of hexadecyltrimethylammonium chloride were added to 200mL of ethanol. 10mL of ammonia was added dropwise. The mixture was stirred for 10h, centrifuged, washed, and dried to produce loaded SiO2 nanospheres.

[0104] U4. 15g of loaded SiO2 nanospheres were added to 200mL of water, 2g of glucose and 4g of Pacific Alkanes were added, stirred and mixed, and the solvent was evaporated to obtain bacterial microspheres;

[0105] U5. 3g of Chlorella vulgaris and 3g of Spirulina maxima were added to 250mL of water, along with 10g of bacterial-loaded microspheres, 1g of lecithin, and 20g of sodium alginate. The mixture was stirred for 20 minutes and then added dropwise to 500mL of fish oil. Emulsification was performed at 8000 rpm for 20 minutes, followed by the dropwise addition of 50mL of a 2wt% calcium chloride solution. The mixture was cured at room temperature for 30 minutes, filtered, washed, and dried to obtain immobilized bacteria and algae.

[0106] Preparation Example 7 Preparation of immobilized bacteria and algae

[0107] Here’s how:

[0108] U1. 9 g of formaldehyde solution and 2.5 g of melamine were added to 200 mL of water, the pH of the solution was adjusted to 5.2, and the reaction was stirred for 20 min. The mixture was centrifuged, washed, and dried to obtain formaldehyde-melamine microspheres.

[0109] U2. Place 2g of zero-valent iron powder on a stainless steel screen, add 0.4g of sulfur powder and 0.7g of formaldehyde-melamine microspheres to the bottom of a crucible, and place it in a tube furnace. Under nitrogen, heat and calcine at 220°C for 25 minutes, then raise the temperature to 420°C for 15 minutes, and finally raise the temperature to 920°C for 40 minutes to produce a carbon nanotube-sulfurized micronized zero-valent iron composite.

[0110] U3. 1.5 g of carbon nanotubes and sulfide micronized zero-valent iron complex, 13.5 g of ethyl orthosilicate, and 2.5 g of hexadecyltrimethylammonium bromide were added to 200 mL of ethanol. 7 mL of aqueous ammonia was added dropwise. The mixture was stirred for 8.5 hours, centrifuged, washed, and dried to produce loaded SiO2 nanospheres.

[0111] U4. 12 g of loaded SiO2 nanospheres were added to 200 mL of water, 1.5 g of glucose, and 3 g of Pacific Alkanes were added, stirred, and the solvent was evaporated to obtain bacterial microspheres.

[0112] U5. Add 2.5g of Chlorella vulgaris and 2g of Spirulina maxima to 250mL of water, along with 8.5g of bacterial-loaded microspheres, 0.7g of lecithin, and 16g of sodium alginate. Stir and mix for 20 minutes. Add dropwise to 500mL of fish oil and emulsify at 8000r / min for 20 minutes. Add dropwise 50mL of 2wt% calcium chloride solution, solidify at room temperature for 30 minutes, filter, wash, and dry to obtain immobilized bacteria and algae.

[0113] Comparative Preparation Example 5

[0114] Compared with Preparation Example 7, the difference is that sulfur is not added in Step U2.

[0115] The details are as follows:

[0116] U2. Place 2 g of zero-valent iron powder on a stainless steel sieve and 1.1 g of formaldehyde-melamine microspheres at the bottom of a crucible. The crucible was then placed in a tube furnace and calcined under nitrogen at 220°C for 25 min, then raised to 420°C for 15 min, and finally raised to 920°C for 40 min to produce a carbon nanotube-zero-valent iron composite.

[0117] Comparative Preparation Example 6

[0118] Compared with Preparation Example 7, the difference is that no formaldehyde-melamine microspheres are added in Step U2.

[0119] The details are as follows:

[0120] U2. Place 2 g of zero-valent iron powder on a stainless steel mesh and 1.1 g of sulfur powder at the bottom of a crucible. Place the crucible in a tubular furnace and heat under nitrogen at 220°C for 25 min, then raise the temperature to 420°C for 15 min, and finally raise the temperature to 920°C for 40 min to obtain a sulfided micron zero-valent iron composite.

[0121] Comparative Preparation Example 7

[0122] Compared with Preparation Example 7, the difference is that glucose is not added in Step U4.

[0123] The details are as follows:

[0124] U4. Add 12 g of loaded SiO2 nanospheres to 200 mL of water, add 4.5 g of Alcanophaga pacificus, stir to mix evenly, and evaporate the solvent to prepare bacteria-loaded microspheres.

[0125] Comparative Preparation Example 8

[0126] Compared with Preparation Example 7, the difference is that Chlorella and Spirulina maxima are not added in Step U5.

[0127] The details are as follows:

[0128] U5. Add 13 g of bacterial-loaded microspheres to 250 mL of water, along with 0.7 g of lecithin and 16 g of sodium alginate. Stir and mix for 20 minutes. Add dropwise to 500 mL of fish oil and emulsify at 8000 rpm for 20 minutes. Add dropwise 50 mL of 2 wt% calcium chloride solution. Cure at room temperature for 30 minutes. Filter, wash, and dry to obtain immobilized algae.

[0129] Comparative Preparation Example 9

[0130] Compared with Preparation Example 7, the difference is that no bacteria-loaded microspheres are added in Step U5.

[0131] The details are as follows:

[0132] U5. 7 g of Chlorella vulgaris and 6 g of Spirulina maxima were added to 250 mL of water, along with 0.7 g of lecithin and 16 g of sodium alginate. The mixture was stirred for 20 minutes and then added dropwise to 500 mL of fish oil. Emulsification was performed at 8000 rpm for 20 minutes. 50 mL of 2 wt% calcium chloride solution was then added dropwise. The mixture was cured at room temperature for 30 minutes. The mixture was filtered, washed, and dried to obtain immobilized bacteria. Example 1

[0133] This embodiment provides an environmentally friendly method for remediating marine oil spill pollution, comprising the following steps:

[0134] (1) The bio-based choline ionic liquid prepared in Preparation Example 1, the photocatalytic enzyme magnetic oil absorbent prepared in Preparation Example 2, the immobilized bacteria and algae prepared in Preparation Example 4, and straw powder were mixed in a mass ratio of 2:15:7:10 to prepare an oil dispersant;

[0135] (2) Add the prepared oil dispersant to the oil spill area, with the mass of the oil dispersant added being 8wt% of the oil spill amount. After the repair is completed, separate the photocatalytic enzyme magnetic oil absorbent with a magnet, wash, dry, and reuse. Example 2

[0136] This embodiment provides an environmentally friendly method for remediating marine oil spill pollution, comprising the following steps:

[0137] (1) The bio-based choline ionic liquid prepared in Preparation Example 1, the photocatalytic enzyme magnetic oil absorbent prepared in Preparation Example 3, the immobilized bacteria and algae prepared in Preparation Example 5, and straw powder were mixed in a mass ratio of 3:20:10:15 to prepare an oil dispersant;

[0138] (2) Add the prepared oil dispersant to the oil spill area, with the mass of the oil dispersant added being 10 wt% of the oil spilled. After the repair is completed, separate the photocatalytic enzyme magnetic oil absorbent with a magnet, wash, dry, and reuse. Example 3

[0139] This embodiment provides an environmentally friendly method for remediating marine oil spill pollution, comprising the following steps:

[0140] (1) The bio-based choline ionic liquid prepared in Preparation Example 1, the photocatalytic enzyme magnetic oil absorbent prepared in Preparation Example 4, the immobilized bacteria and algae prepared in Preparation Example 7, and straw powder were mixed in a mass ratio of 2.5:17:8.5:12 to prepare an oil dispersant;

[0141] (2) The prepared oil dispersant is added to the oil spill area, with the mass of the oil dispersant added being 9wt% of the oil spill amount. After the repair is completed, the photocatalytic enzyme magnetic oil absorbent is separated by a magnet, washed, dried, and reused.

[0142] Comparative Example 1

[0143] Compared with Example 3, the difference is that the bio-based choline ionic liquid is replaced by an equal mass of Tween-20.

[0144] Comparative Example 2

[0145] Compared with Example 3, the difference is that the photocatalytic enzyme magnetic oil absorbent is prepared by Comparative Preparation Example 1.

[0146] Comparative Example 3

[0147] Compared with Example 3, the difference is that the photocatalytic enzyme magnetic oil absorbent is prepared by Comparative Preparation Example 2.

[0148] Comparative Example 4

[0149] Compared with Example 3, the difference is that the photocatalytic enzyme magnetic oil absorbent is prepared by Comparative Preparation Example 3.

[0150] Comparative Example 5

[0151] Compared with Example 3, the difference is that the photocatalytic enzyme magnetic oil absorbent is prepared by Comparative Preparation Example 4.

[0152] Comparative Example 6

[0153] Compared with Example 3, the difference is that the immobilized bacteria and algae are prepared by Comparative Preparation Example 5.

[0154] Comparative Example 7

[0155] Compared with Example 3, the difference is that the immobilized bacteria and algae are prepared by Comparative Preparation Example 6.

[0156] Comparative Example 8

[0157] Compared with Example 3, the difference is that the immobilized bacteria and algae are prepared by Comparative Preparation Example 7.

[0158] Comparative Example 9

[0159] Compared with Example 3, the difference is that the immobilized bacteria and algae are prepared by Comparative Preparation Example 8.

[0160] Comparative Example 10

[0161] Compared with Example 3, the difference is that the immobilized bacteria and algae are prepared by Comparative Preparation Example 9.

[0162] Test Example 1

[0163] Take 13 water pools of the same size (5m×3m×2m), inject 25L of seawater into each pool, and add 500g of crude oil. The crude oil is Daqing crude oil. The basic physical properties of the crude oil are as follows: density 0.8602g / cm 3 (Test standard GB / T 1884-2000). Pools 1-3 were treated using the methods of Examples 1-3 of the present invention, and pools 4-14 were treated using the methods of Comparative Examples 1-10 of the present invention. Ten hours after the oil dispersant obtained in step (4) was added to each treatment group, the weight of the residual oil was measured. The oil spill removal rate was calculated based on the initial amount of oil added. The measurement results are shown in Table 1.

[0164] Table 1

[0165] ;

[0166] As can be seen from the above table, after treatment by the methods in Examples 1-3 of the present invention, the oil spill removal rate is high and the oil spill repair effect is good.

[0167] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An environmentally friendly restoration method for marine oil spill pollution, characterized in that: The following steps are involved: (1) The bio-based choline ionic liquid, the photocatalytic enzyme magnetic oil absorbent, the immobilized bacteria and algae, and the straw powder are mixed uniformly in a mass ratio of 2-3:15-20:7-10:10-15 to prepare an oil dispersant; (2) Adding the prepared oil dispersant to the oil spill area, with the mass of the oil dispersant added being 8-10wt% of the oil spilled. After the repair is completed, the photocatalytic enzyme magnetic oil absorbent is separated by a magnet, washed, dried, and reused; The photocatalytic enzyme magnetic oil absorbent is prepared by carbon quantum dots doped with TiO2 loaded on magnetic bentonite, modified by polydopamine coating, fixed with lipase, and ultrasonically treated. The structural formula of the bio-based choline ionic liquid is shown in Formula I: Formula I.

2. The environmentally friendly restoration method for marine oil spill pollution according to claim 1, characterized in that: The preparation method of the bio-based choline ionic liquid is as follows: S1. Dissolve oleic acid in ethanol, add 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, and stir to activate. Add glutamic acid, stir to react, add water, precipitate, filter, wash, and dry to obtain an intermediate with the following structure: ; S2. The intermediate is added to ethanol, and a choline hydroxide alcohol solution is added dropwise. The reaction is stirred, the solvent is removed under reduced pressure, and the product is recrystallized from acetone. The product is filtered, washed, and dried to obtain a bio-based choline ionic liquid.

3. The environmentally friendly restoration method for marine oil spill pollution according to claim 2, characterized in that: The molar ratio of oleic acid, glutamic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide in step S1 is 1:1.1-1.2:1.2-1.5:1.2-1.5; the molar ratio of the intermediate and choline hydroxide in step S2 is 1:2.2-2.

3.

4. The environmentally friendly restoration method for marine oil spill pollution according to claim 1, characterized in that: The preparation method of the photocatalytic enzyme magnetic oil absorbent is as follows: T1. Preparation of magnetic bentonite: Bentonite was added to water and uniformly dispersed by ultrasonication. Ferric chloride and ferrous chloride were then added dropwise. Under an inert gas atmosphere, aqueous ammonia was added dropwise. The mixture was heated with stirring, filtered, washed, dried, and calcined to obtain magnetic bentonite. T2. Preparation of carbon quantum dot-doped TiO2@magnetic bentonite: Citric acid and tetrabutyl titanate were dissolved in ethanol, magnetic bentonite was added, and the mixture was stirred until uniform. Ammonia was added dropwise to adjust the pH of the solution. The mixture was hydrothermally reacted, separated by a magnet, washed, dried, and calcined to produce carbon quantum dot-doped TiO2@magnetic bentonite. T3. Lipase Loading: Carbon quantum dot-doped TiO2@magnetic bentonite was added to a Tris-HCl solution, followed by dopamine hydrochloride. The mixture was heated and stirred. Lipase, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and N-hydroxysuccinimide were then added and stirred. The mixture was separated by a magnetic separator, washed, and dried to produce lipase / carbon quantum dot-doped TiO2@magnetic bentonite. T4. Ultrasonic treatment: The prepared lipase / carbon quantum dot-doped TiO2@magnetic bentonite was added to water, ultrasonically treated, magnetically separated, washed, and dried to obtain a photocatalytic enzyme magnetic oil absorbent.

5. The environmentally friendly restoration method for marine oil spill pollution according to claim 4, characterized in that: The mass ratio of bentonite, ferric chloride and ferrous chloride described in step T1 is 20-30: 3.24:1.26, the temperature of the heating and stirring reaction is 75-85°C, and the time is 3-5h; the mass ratio of citric acid, tetrabutyl titanate, and magnetic bentonite in step T2 is 2-3:12-15:30-50, the pH value of the adjusted solution is 9-10, the temperature of the hydrothermal reaction is 180-200°C, the time is 10-12h, and the calcination temperature is 400-450°C, and the time is an additional 3-5h.

6. The environmentally friendly restoration method for marine oil spill pollution according to claim 4, characterized in that: The pH value of the Tris-HCl solution in step T3 is 8.5-9.5, the mass ratio of the carbon quantum dots doped TiO2@magnetic bentonite, dopamine hydrochloride, lipase, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 20-30:2-3:1-2:0.2-0.5:0.2-0.5, the lipase, the temperature of the heating and stirring reaction is 45-55 ° C, and the time is 2-4h; the power of the ultrasonic treatment in step T4 is 400-500W, on 1-3s, off 1-3s, and the treatment is 20-30min.

7. The environmentally friendly restoration method for marine oil spill pollution according to claim 1, characterized in that: The preparation method of the immobilized bacteria and algae is as follows: U1. Formaldehyde solution and melamine were added to water, the pH of the solution was adjusted, the reaction was stirred, centrifuged, washed, and dried to obtain formaldehyde-melamine microspheres; U2. Zero-valent iron powder was placed on a stainless steel mesh, sulfur powder and formaldehyde-melamine microspheres were placed at the bottom of the crucible, and the crucible was placed in a tube furnace. Under an inert gas atmosphere, the crucible was heated and calcined to produce a carbon nanotube-sulfurized micronized zero-valent iron composite. U3. A carbon nanotube-sulfurized micronized zero-valent iron complex, tetraethyl orthosilicate, and a porogen were added to ethanol. Ammonia was added dropwise. The reaction was stirred, centrifuged, washed, and dried to produce loaded SiO2 nanospheres. U4. Add the loaded SiO2 nanospheres to water, add glucose and Pacific Alkanes, stir and mix evenly, evaporate the solvent to obtain bacterial microspheres; U5. Add Chlorella vulgaris and Spirulina maxima to water, add bacterial microspheres, lecithin, and sodium alginate, stir and mix thoroughly, then add dropwise to fish oil. Emulsify, add calcium chloride solution dropwise, solidify at room temperature, filter, wash, and dry to produce immobilized bacteria and algae.

8. The environmentally friendly restoration method for marine oil spill pollution according to claim 7, characterized in that: In step U1, the mass ratio of the formaldehyde solution to melamine is 8-10:2-3, and the pH value of the adjusted solution is 5-5.

5. In step U2, the mass ratio of the zero-valent iron powder, sulfur powder, and formaldehyde-melamine microspheres is 2:0.3-0.5:0.5-1. The heating and calcining conditions are 200-250° C., holding for 20-30 minutes, heating to 400-450° C., holding for 10-20 minutes, heating to 900-950° C., and holding for 30-50 minutes.

9. The environmentally friendly restoration method for marine oil spill pollution according to claim 7, characterized in that: In step U3, the mass ratio of the carbon nanotube@sulfurized micron zero-valent iron complex, ethyl orthosilicate, and porogen is 1-2:12-15:2-3, and the porogen is hexadecyltrimethylammonium chloride or hexadecyltrimethylammonium bromide.

10. The environmentally friendly restoration method for marine oil spill pollution according to claim 7, characterized in that: The mass ratio of the loaded SiO2 nanospheres, glucose and Pacific Alkanes in step U4 is 10-15:1-2:2-4; the mass ratio of Chlorella, Spirulina maxima, bacteria-loaded microspheres, lecithin and sodium alginate in step U5 is 2-3:1-3:7-10:0.5-1:13-20.

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