Marine oil spill adsorption material based on mussel bionic structure, preparation method and device

Abstract

The application belongs to the technical field of marine environmental protection and functional materials, and particularly relates to a marine oil stain adsorbing material based on a mussel bionic structure, a preparation method and a device, which comprises a porous base material, a polydopamine interface layer and a metal-polyphenol network; the porous base material has three-dimensionally connected pores; the polydopamine interface layer is formed on the surface and internal pores of the porous base material through self-oxidation polymerization of dopamine; and the metal-polyphenol network is formed by coordination of transition metal ions and plant polyphenols on the polydopamine interface layer. By constructing a PDA-metal-polyphenol ternary synergistic interface, efficient capture and firm combination of high-viscosity crude oil are realized, a hierarchical porous structure is induced to form through an ozone rapid polymerization method, and the adsorption kinetics and thermodynamic performance are comprehensively improved, and after saturation of the material, the material can be quickly recovered through an external magnetic field, and regeneration can be realized through pH adjustment or heating.

Description

Technical Field

[0001] This invention belongs to the field of marine environmental protection and functional materials technology, specifically a marine oil pollution adsorption material based on mussel biomimetic structure, its preparation method and device. Background Technology

[0002] Oil spills during offshore oil extraction and transportation are serious sources of marine environmental pollution. High-viscosity crude oil (such as heavy crude oil and asphalt crude oil) is difficult to treat quickly and effectively with traditional adsorption materials due to its poor fluidity and severe emulsification.

[0003] Currently used polypropylene (PP) oil-absorbing felts, polyurethane foam, and other materials have the following significant drawbacks: 1. Limited adsorption capacity: Traditional polypropylene oil-absorbing felts can only adsorb 10-15 g / g of crude oil, and the adsorption rate for high-viscosity crude oil is slow, which cannot meet the emergency needs of large-scale oil spills; 2. Poor selectivity: Most oil-absorbing materials absorb a large amount of water while adsorbing oil, reducing the effective adsorption capacity and increasing the burden of subsequent treatment; 3. Difficult recycling: After adsorption saturation, it is difficult to achieve efficient oil-solid separation. Most materials can only be used once, causing secondary pollution and resource waste; 4. Weak environmental adaptability: Traditional materials are prone to structural degradation in high-salt and high-humidity seawater environments, resulting in a sharp decline in adsorption performance.

[0004] Mussels can firmly attach to surfaces such as rocks and ships in the intertidal zone where waves are strong. The key mechanism lies in the mucin secreted by their foot glands, which is rich in dopa (DOPA) groups and can form strong coordination bonds with metal ions (Fe³⁺, Cu²⁺, etc.). Inspired by this, polydopamine (PDA) biomimetic materials have shown great potential in the field of functional materials due to their excellent adhesion, metal chelating ability, and environmental stability.

[0005] Existing technologies include patents related to polydopamine coating modification (such as the oil-dispersible polydopamine nano-lubricant additive and its preparation method and application disclosed in CN202310219910.8), but these mainly focus on lubrication and antifouling. Currently, there is no systematic solution for the adsorption of high-viscosity crude oil at sea that combines mussel biomimetic mechanisms with hierarchical porous structures and magnetic recovery functions.

[0006] To address these issues, this invention provides a marine oil spill adsorption material, its preparation method, and an apparatus based on a mussel-inspired biomimetic structure, aiming to solve the problems of low adsorption capacity, poor selectivity, and difficulty in recovery of high-viscosity crude oil by traditional adsorption materials. By simulating the metal-polyphenol coordination mechanism of mussel foot glands, a highly efficient adsorption material with a three-dimensional network structure is constructed, significantly improving the adsorption performance and recycling capacity of marine oil spills. Summary of the Invention

[0007] In order to overcome the shortcomings of the prior art, at least one technical problem raised in the background art is solved.

[0008] The technical solution adopted by the present invention to solve its technical problem is: a marine oil pollution adsorption material based on mussel biomimetic structure, comprising a porous substrate, a polydopamine interface layer and a metal-polyphenol network;

[0009] The porous substrate serves as a carrier, with its surface and internal pores sequentially covered by a polydopamine interface layer and a metal-polyphenol network.

[0010] The porous substrate has three-dimensional interconnected channels with a pore size distribution of 50-500 μm and a porosity of not less than 90%.

[0011] The polydopamine interface layer is formed on the surface and internal channels of the porous substrate by dopamine self-oxidation polymerization, and has a thickness of 10-200 nm.

[0012] The metal-polyphenol network is formed by the coordination of transition metal ions and plant polyphenols on the polydopamine interface layer.

[0013] The present invention discloses a method for preparing marine oil spill absorbent material based on mussel biomimetic structure. This method, used to prepare the aforementioned marine oil spill absorbent material, includes the following steps:

[0014] S1. Pre-treat the porous substrate to obtain a surface-activated porous substrate;

[0015] S2. The pretreated porous substrate is immersed in a buffer solution containing dopamine hydrochloride. Ozone is introduced into the solution to induce the oxidative polymerization of dopamine, forming a polydopamine interface layer on the surface and internal pores of the substrate.

[0016] S3. Immerse the material obtained in S2 in a mixed solution containing transition metal ions and plant polyphenols, so that the metal ions coordinate with the polydopamine interface layer and plant polyphenols to form a metal-polyphenol network. After washing and drying, the marine oil pollution adsorbent material is obtained.

[0017] The detailed steps of S2 are as follows:

[0018] S201. Place the porous substrate into the mounting groove, and turn the adjusting rod to drive the adjusting rod to move the ejector pin towards the porous substrate. Insert the ejector pin into the surface of the substrate to position and fix the porous substrate.

[0019] S202. The lifting cover is lowered by the lifting drive mechanism to form a closed chamber with the reaction vessel. The ozone generator produces ozone and supplies it to the aeration plate through the delivery pipe. The ozone is evenly dispersed into microbubbles through the diversion holes.

[0020] S203. The bubbles generated by the peripheral diversion holes rise along the outer side of the porous substrate, while the bubbles generated by the central diversion holes directly impact the lower side of the substrate and enter the interior of the substrate through the pores of the substrate, causing the outer surface and internal channels of the porous substrate to form a polydopamine coating.

[0021] S204. The motor drives the mounting plate and porous substrate to rotate slowly, disturbing the reaction liquid and breaking the static state.

[0022] S205. The drive gear is driven by motor 2 to rotate, and the aeration disc is controlled by the transmission column to reciprocate in the reaction vessel, intermittently squeezing and releasing the porous substrate, thereby changing the internal pore structure of the substrate.

[0023] The present invention discloses a device for preparing marine oil pollution adsorbent material based on mussel biomimetic structure. The device is applied to the above-mentioned preparation method and includes a reaction container, an aeration disc, and a lifting cover.

[0024] The reaction vessel is equipped with a temperature sensor, a pH sensor, and an ozone concentration sensor; a support platform is fixedly connected to the bottom of the reaction vessel.

[0025] The aeration disc is disposed on the surface of the support platform; the aeration disc is connected to a conveying pipe; a set of flow holes are evenly distributed on the upper side of the aeration disc;

[0026] The lifting cover is connected to a lifting drive mechanism; an annular treatment chamber is fixedly connected to the upper side of the lifting cover; the interior of the treatment chamber is filled with ozone treatment agent; a set of air inlets are evenly distributed at the bottom of the treatment chamber and on the surface of the lifting cover; a set of air outlets are evenly distributed at the top of the treatment chamber.

[0027] Preferably, a mounting plate is provided on the lower side of the lifting cover; a mounting groove is provided at the bottom of the mounting plate; a set of ventilation holes are evenly distributed between the top of the mounting groove and the outer side of the mounting plate; a set of connecting holes are evenly distributed on the side of the mounting plate; an adjusting rod is detachably connected inside the connecting hole; a pin is fixedly connected to one end of the adjusting rod near the mounting groove.

[0028] Preferably, the mounting plate is rotatably connected to the lower side of the lifting cover; a motor is fixedly connected to the upper side of the lifting cover; the motor and the mounting plate are connected by a shaft.

[0029] Preferably, a transmission column is fixedly connected to the lower side of the aeration disc; the transmission column passes through the support platform and the reaction vessel and slides with them; a set of tooth blocks are provided on the surface of the transmission column and mesh with a drive gear; a second motor is fixedly connected to the lower side of the reaction vessel; the second motor and the drive gear are connected by a shaft.

[0030] Preferably, an upper limit cage and a lower limit cage are fixedly connected to the lower side of the mounting plate and the upper side of the aeration plate, respectively, and the diameter of the lower limit cage is larger than that of the upper limit cage.

[0031] Preferably, a set of isolation plates are evenly distributed inside the processing chamber; a set of air guide grooves are evenly distributed on the side of the isolation plates, and the air guide grooves of adjacent isolation plates are staggered.

[0032] Preferably, a set of permanent magnets are evenly distributed at the top edge of the mounting plate; magnetic blocks are fixedly connected to the surface of the isolation plate at the corresponding positions of the permanent magnets.

[0033] The beneficial effects of this invention are as follows:

[0034] 1. Significantly improved adsorption performance: The adsorption capacity for high-viscosity crude oil reaches 35-50g / g, which is about 60%-230% higher than that of traditional PP oil-absorbing felt (10-15g / g); the adsorption rate is fast, and more than 90% of the saturated adsorption capacity can be reached within 5 minutes, making it suitable for emergency response to sudden oil spills.

[0035] 2. Excellent selectivity and environmental adaptability: The material has a water contact angle greater than 140°, an oil-water selectivity coefficient (oil adsorption / water adsorption) greater than 40, and hardly absorbs water; it has stable performance in seawater environments with pH 5-9 and salinity 0-5%, and is adaptable to complex marine conditions.

[0036] 3. Recyclable and reusable: The magnetic functionalized material can achieve rapid magnetic recovery with a recovery rate of over 95%; more than 85% of the adsorbed oil can be desorbed by pH adjustment or heating; the performance of the material decreases by less than 15% after 10 cycles of recycling, reducing the cost of use.

[0037] 4. Green and efficient preparation process: The ozone rapid polymerization method shortens the traditional 24-hour polymerization to 30 minutes and reduces energy consumption by 70%; the preparation process is water-based and does not use organic solvents, making it environmentally friendly.

[0038] 5. High application flexibility: It can be made into various forms such as flakes, granules, and blocks, and is suitable for different oil spill treatment processes such as spreading, fencing, and absorption belts; a single piece of material (20×20cm) can treat about 0.8-1.2L of crude oil, and the treatment cost is reduced by about 40% compared with traditional materials. Attached Figure Description

[0039] The invention will now be further described with reference to the accompanying drawings.

[0040] Figure 1 This is a schematic diagram of the structure of the mussel-inspired biomimetic adsorption material in this invention;

[0041] Figure 2 This is a flowchart of the preparation method in this invention;

[0042] Figure 3 This is a schematic diagram of the preparation apparatus in this invention;

[0043] Figure 4 This is a schematic diagram illustrating the separation of the reaction vessel and the lifting cover in this invention;

[0044] Figure 5 This is a schematic diagram of the structure of the support platform and mounting plate in this invention;

[0045] Figure 6 This is a schematic diagram of the lower limit cage in this invention;

[0046] Figure 7 This is a cross-sectional view of the reaction vessel in this invention;

[0047] Figure 8 yes Figure 7 Enlarged view of a portion of point A in the middle.

[0048] In the figure: 1. Porous substrate; 2. Polydopamine interface layer; 3. Metal-polyphenol network; 10. Reaction vessel; 11. Aeration disc; 12. Lifting cover; 13. Support platform; 14. Delivery pipe; 15. Diversion hole; 16. Treatment chamber; 17. Air inlet; 18. Air outlet; 19. Mounting plate; 20. Mounting groove; 21. Vent hole; 22. Connecting hole; 23. Adjusting rod; 24. Ejector pin; 25. Motor 1; 26. Transmission column; 27. Drive gear; 28. Motor 2; 29. ​​Upper limit cage; 30. Lower limit cage; 31. Isolation plate; 32. Air guide groove; 33. Permanent magnet; 34. Magnetic block. Detailed Implementation

[0049] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0050] like Figure 1 As shown, the present invention discloses a marine oil spill adsorption material based on a mussel biomimetic structure. Using a porous substrate (such as polyurethane sponge, cellulose foam, or aerogel) as a carrier, a biomimetic adsorption layer of "polydopamine (PDA)-metal-polyphenol" ternary synergistic structure is constructed on its surface and internal pores, forming a hierarchical porous three-dimensional network structure. Specifically, it includes:

[0051] Porous substrate (1): a flexible or rigid material with three-dimensional interconnected channels, a pore size distribution of 50-500μm, and a porosity of ≥90%, preferably an oleophilic and hydrophobic modified polyurethane sponge or cellulose-based aerogel.

[0052] Polydopamine interface layer (2): A uniform coating formed on the surface of a porous substrate (1) by dopamine self-oxidation polymerization, with a thickness of 10-200 nm. This layer provides abundant catechol / quinone groups as an active platform for subsequent functionalization.

[0053] Metal-polyphenol network (3): a three-dimensional cross-linked network formed by the coordination of transition metal ions such as Fe³⁺, Cu²⁺, and Zn²⁺ with plant polyphenols such as tannic acid and gallic acid on the polydopamine interface layer (2);

[0054] This three-dimensional cross-linked network has the following characteristics: it enhances the mechanical strength and structural stability of the material; it provides additional hydrophobic and oil-affinity sites; and it imparts pH responsiveness to the material, facilitating adsorption-desorption regulation.

[0055] This invention applies the mussel's "dopamine-metal coordination" mechanism to the design of marine oil sludge adsorption materials. By constructing a "PDA-metal-polyphenol" ternary synergistic interface, it achieves efficient capture and robust binding of high-viscosity crude oil. A hierarchical porous structure is induced using ozone rapid polymerization, including macropores (100-500 μm, for rapid oil absorption), mesopores (10-100 nm, for enhanced capillary forces), and micropores (<2 nm, for increased specific surface area), comprehensively improving adsorption kinetics and thermodynamic performance. Adsorption enhancement, magnetic recovery, and stimulus-responsive desorption are modularly integrated. After the material becomes saturated, it can be rapidly recovered using an external magnetic field, and oil sludge desorption and material regeneration can be achieved through pH adjustment or heating.

[0056] like Figure 2 As shown, the present invention discloses a method for preparing a marine oil spill absorbent material based on a mussel biomimetic structure. This method, used to prepare the aforementioned marine oil spill absorbent material, includes the following steps:

[0057] S1. Pretreatment of porous substrate: The polyurethane sponge is ultrasonically cleaned with ethanol and deionized water in sequence, dried, and then immersed in 0.1mol / L NaOH solution for hydrolysis and activation for 30min to increase the surface hydroxyl density.

[0058] S2. Construction of the polydopamine interface layer: Prepare a Tris-HCl buffer solution containing dopamine hydrochloride (2 mg / mL) with a pH of 8.5. Immerse the pretreated substrate in the solution and use ozone rapid polymerization method. Introduce ozone (concentration 50 mg / L, flow rate 0.5 L / min) into the solution for 10-30 min to induce rapid oxidative polymerization of dopamine, forming a uniform PDA coating on the substrate surface and its pores. Compared with the traditional air oxidation method (requiring 12-24 h), this method shortens the polymerization time to less than 30 min and produces a more uniform and dense coating.

[0059] S3. Metal-polyphenol network assembly: The PDA-modified substrate was immersed in a water / ethanol mixed solution (volume ratio 1:1) containing 0.1 mol / L FeCl3 and 0.05 mol / L tannic acid, and the reaction was carried out at room temperature with shaking for 2-4 hours; Fe³⁺ coordinated with the catechol groups of PDA and the phenolic hydroxyl groups of tannic acid to form a blue-black metal-polyphenol network; after the reaction was completed, it was washed with deionized water and dried under vacuum at 60℃.

[0060] The detailed steps of S2 are as follows:

[0061] S201. Place the porous substrate 1 into the mounting groove 20. By turning the adjusting rod 23, the adjusting rod 23 drives the ejector pin 24 to move toward the porous substrate 1. Insert the ejector pin 24 into the surface of the substrate to position and fix the porous substrate 1.

[0062] S202. The lifting cover 12 is lowered by the lifting drive mechanism to form a closed chamber with the reaction container 10. The ozone generator produces ozone and supplies it to the aeration plate 11 through the delivery pipe 14. The ozone is evenly dispersed into microbubbles through the diversion hole 15.

[0063] S203. The bubbles generated by the peripheral diversion holes 15 rise along the outer side of the porous substrate 1, and the bubbles generated by the middle diversion holes 15 directly impact the lower side of the substrate and enter the interior of the substrate through the pores of the substrate, causing the outer surface and internal pores of the porous substrate 1 to form a polydopamine coating.

[0064] S204. The mounting plate 19 and the porous substrate 1 are slowly rotated by the motor 25 to disturb the reaction liquid and break the static state.

[0065] S205. The drive gear 27 is driven to rotate by the motor 28, and the aeration disc 11 is controlled to reciprocate in the reaction vessel 10 by the transmission column 26, intermittently squeezing and releasing the porous substrate 1, thereby changing the internal pore structure of the substrate.

[0066] When the material comes into contact with marine oil spills: Rapid wetting: The hierarchical porous structure generates strong capillary forces, driving high-viscosity crude oil rapidly into the macroporous channels. Efficient capture: The catechol groups in the PDA interface layer form π-π stacking and hydrogen bonding with polar components in the crude oil (such as asphaltenes and resins); the hydrophobic microdomains in the metal-polyphenol network generate strong van der Waals forces with non-polar components in the crude oil (saturated hydrocarbons and aromatic hydrocarbons). Firm locking: Metal ions such as Fe³⁺ form coordination bonds with sulfur- and nitrogen-containing heteroatoms in the crude oil, preventing the adsorbed crude oil from desorbing under wave impact. Intelligent recovery: Magnetic functionalized materials can be rapidly collected and recovered from seawater under an external magnetic field (≥0.3T); by adjusting the pH to alkaline (>10) or heating (>60℃), the metal-ligand bonds partially break, achieving crude oil desorption and material regeneration.

[0067] like Figures 3 to 8 As shown, the present invention provides a preparation device for marine oil pollution adsorbent material based on mussel biomimetic structure. The device is applied to the above preparation method and includes a reaction container 10, an aeration disc 11, and a lifting cover 12.

[0068] The reaction vessel 10 is equipped with a temperature sensor, a pH sensor and an ozone concentration sensor; a support platform 13 is fixedly connected to the bottom of the reaction vessel 10.

[0069] The aeration disc 11 is disposed on the surface of the support platform 13; the aeration disc 11 is connected to the conveying pipe 14; a set of flow holes 15 are evenly distributed on the upper side of the aeration disc 11;

[0070] The lifting cover 12 is connected to a lifting drive mechanism; an annular treatment chamber 16 is fixedly connected to the upper side of the lifting cover 12; the treatment chamber 16 is filled with ozone treatment agent; a set of air inlets 17 are evenly distributed at the bottom of the treatment chamber 16 and on the surface of the lifting cover 12; a set of air outlets 18 are evenly distributed at the top of the treatment chamber 16.

[0071] The ozone treatment agent can be one or more of the following composite forms: transition metal oxides, activated carbon, and special catalysts. Transition metal oxides include manganese dioxide, copper oxide, nickel oxide, cobalt oxide, etc., and special catalysts can be hogallat agents.

[0072] First, the pretreated porous substrate 1 is placed above the support platform 13 inside the reaction container 10. The reaction container 10 is pre-filled with a Tris-HCl buffer solution containing dopamine hydrochloride. The lifting cover 12 is lowered by an external lifting drive mechanism to form a sealed chamber with the reaction container 10. An external ozone generator produces ozone and supplies it to the aeration disc 11 through the delivery pipe 14. The ozone is evenly dispersed into microbubbles through the diversion holes 15, rises in the reaction solution, and comes into full contact with the dopamine solution. Under the real-time monitoring of temperature sensors, pH sensors, and ozone concentration sensors, it is beneficial to dynamically adjust the ozone injection rate. The reaction temperature and pH value are kept at the optimal polymerization conditions, inducing dopamine to rapidly oxidize and polymerize on the surface and internal pores of the porous substrate 1 to form a polydopamine coating PDA. During the reaction, residual ozone gas escaping from the surface of the reaction liquid enters the treatment chamber 16 through the air inlet 17 at the bottom of the treatment chamber 16 under the guidance of the lifting cover 12. It comes into full contact with the ozone treatment agent filled inside and is catalytically decomposed into oxygen. The purified gas is discharged through the air outlet 18 at the top of the treatment chamber 16, thereby avoiding ozone leakage. After the reaction is completed, the lifting cover 12 is raised, and the porous substrate 1 with the polydopamine interface layer 2 formed is taken out.

[0073] A mounting plate 19 is provided on the lower side of the lifting cover 12; a mounting groove 20 is provided at the bottom of the mounting plate 19; a set of ventilation holes 21 are evenly distributed between the top of the mounting groove 20 and the outer side of the mounting plate 19; a set of connecting holes 22 are evenly distributed on the side of the mounting plate 19; an adjusting rod 23 is threadedly connected inside the connecting hole 22; a pin 24 is fixedly connected to one end of the adjusting rod 23 near the mounting groove 20.

[0074] When placing the porous substrate 1, the substrate can be placed in the mounting groove 20 on the lower side of the mounting plate 19. Then, by turning multiple adjusting rods 23, the adjusting rods 23 drive the ejector pins 24 to move towards the porous substrate 1, and insert the ejector pins 24 into the surface of the substrate, thereby positioning and fixing the porous substrate 1 on the lower side of the lifting cover 12. This effectively prevents the substrate from drifting or shaking under the buoyancy of the reaction liquid and the impact of bubbles, ensuring that the substrate is always in the preset position. After the lifting cover 12 is lowered, the bottom of the porous substrate 1 is exactly located on the upper side of the aeration plate 11. Then, when the aeration plate 11 sprays air, the bubbles generated by the diversion holes 15 on the periphery can flow along the aeration plate 11. As the porous substrate 1 rises to the outside, it promotes the formation of a PDA coating on the substrate surface. Meanwhile, the bubbles generated by the diversion hole 15 in the middle can directly impact the lower side of the porous substrate 1 and enter the interior of the substrate through its pores, promoting the formation of a PDA coating in the internal channels of the porous substrate 1. After rising into the mounting groove 20, the bubbles can be discharged to the outside of the mounting plate 19 through the vent hole 21. This structural design achieves partitioned coating of the surface and internal channels of the porous substrate 1 through the spatial differential distribution of the outer and middle bubbles, effectively solving the problems of uneven coating on the inner and outer surfaces of the substrate and difficulty in covering the internal channels in traditional coating processes.

[0075] The mounting plate 19 is rotatably connected to the lower side of the lifting cover 12; a motor 25 is fixedly connected to the upper side of the lifting cover 12; the motor 25 and the mounting plate 19 are connected by a shaft.

[0076] During the reaction, the motor 25 drives the mounting plate 19 and the porous substrate 1 to rotate slowly, promoting liquid flow and creating disturbance to the reaction liquid. This ensures that all parts of the substrate can be in uniform contact with the reaction liquid. When the porous substrate 1 is impacted by the bubbles generated by the air jet from the aeration plate 11, it can be in uniform contact with the bubbles from all angles. Specifically, the bubbles generated by the peripheral diversion holes 15 no longer rise only along the fixed outer side of the substrate, but as the substrate rotates, each outer surface of the substrate can pass through the path of the rising bubbles in sequence. This ensures that every area of ​​the outer surface of the substrate is fully and uniformly covered by the PDA coating. Similarly, for the bubbles generated by the central diversion holes 15 that directly impact the lower side of the substrate and enter the internal channels, the rotation of the substrate will make the channels at different positions inside the substrate more uniformly impacted by the bubbles and the reaction liquid they carry, further promoting the uniformity and integrity of the coating in the internal channels.

[0077] A transmission column 26 is fixedly connected to the lower side of the aeration disc 11; the transmission column 26 passes through the support platform 13 and the reaction vessel 10 and slides with them; a set of tooth blocks are provided on the surface of the transmission column 26 and mesh with the drive gear 27; a second motor 28 is fixedly connected to the lower side of the reaction vessel 10; the second motor 28 and the drive gear 27 are connected by a shaft; the delivery pipe 14 is a flexible hose or a corrugated pipe.

[0078] During the reaction process, the motor 28 drives the drive gear 27 to rotate, controlling the transmission column 26 to slide up and down along the support platform 13, thereby realizing the reciprocating motion of the aeration disc 11 within the reaction container 10. When the aeration disc 11 moves upward, it can cooperate with the mounting disc 19 to squeeze the porous substrate 1 along its length, reducing the volume of the internal pores of the substrate and expelling the old reaction liquid and bubbles. When the aeration disc 11 moves downward, the porous substrate 1 is released and restored under its own elasticity, the internal pores are restored, and the external reaction liquid and bubbles are drawn into the substrate under the pressure difference. By intermittently squeezing and expanding the porous substrate 1, the spatial structure of the internal pores of the substrate can be effectively changed, causing the reaction liquid that might have been stagnant due to tight accumulation to flow, while allowing fresh reaction liquid and bubbles to penetrate more fully into the depths of the pores, achieving dynamic breathing and forced perfusion, improving the contact efficiency and renewal speed between the reaction liquid and the surface of the internal pores of the substrate, and further ensuring the uniform deposition and good adhesion of the PDA coating on the inner and outer surfaces and deep pores of the substrate.

[0079] It is worth noting that, in order to prevent the porous substrate 1 from being torsional damaged under the combined action of rotation and compression, motor 25 and motor 28 should not be started simultaneously. Instead, they can be operated alternately using a time-sharing control method. Specifically, the working sequence can be preset through the PLC control system. After motor 25 drives the mounting plate 19 to rotate the porous substrate 1 to a set angle, the system automatically triggers motor 28 to start, controlling the aeration plate 11 to compress and stretch the substrate. After the aeration plate 11 completes one reciprocating cycle and resets, the PLC sends a command to start motor 25 to enter the next rotation process. This time-sharing control mechanism can ensure that the porous substrate 1 only bears one mechanical force at a time, effectively avoiding fiber breakage or structural deformation of the substrate caused by the superposition of rotational torque and axial compression force. This not only ensures the integrity of the substrate but also fully utilizes the synergistic effect of rotational stirring and dynamic flow.

[0080] The upper limit cage 29 and the lower limit cage 30 are fixedly connected to the lower side of the mounting plate 19 and the upper side of the aeration plate 11, respectively. Liquid can pass through the upper limit cage 29 and the lower limit cage 30. The diameter of the lower limit cage 30 is larger than that of the upper limit cage 29, so the two can rotate or slide up and down.

[0081] After the porous substrate 1 is installed on the lower side of the mounting plate 19, the upper limit cage 29 is located on the outside of the substrate. After the lifting cover 12 is lowered, the upper limit cage 29 can be inserted into the lower limit cage 30. The two limit cages can form a three-dimensional limiting structure that surrounds the porous substrate 1 from the top and bottom. This prevents the substrate from deforming out of control when it is subjected to rotation or compression. In particular, when the porous substrate 1 is axially compressed, the lower limit cage 30 moves upward with the aeration plate 11. When the substrate contracts, it is blocked by the two limit cages, so the substrate can only contract vertically along its length and cannot expand and deform laterally. This improves the extrusion efficiency of the reaction liquid and bubbles inside the substrate and prevents the substrate from bending laterally, which can lead to irreversible damage. This structure ensures the stable positioning of the substrate in the axial direction and provides sufficient stroke space for the compression and expansion action of the aeration plate 11, so that the substrate is always within the controlled limiting range during dynamic processing.

[0082] The processing chamber 16 has a set of isolation plates 31 evenly distributed inside; the isolation plates 31 have a set of air guide grooves 32 evenly distributed on their sides, and the air guide grooves 32 of adjacent isolation plates 31 are staggered with each other.

[0083] The evenly distributed isolation plates 31 and the staggered air guide grooves 32 together form a labyrinthine flow channel structure. When residual bubbles enter the treatment chamber 16 through the air inlet 17, they are blocked by the isolation plates 31. Since the air guide grooves 32 of adjacent isolation plates 31 are staggered, the bubbles cannot pass through in a straight line directly. They can only flow horizontally or upward in an S-shape along the tortuous path of adjacent isolation plates 31 and air guide grooves 32. During this process, the movement path of the bubbles is significantly extended, and the contact time and contact area with the ozone treatment agent in the treatment chamber 16 are also increased, ensuring that the bubbles have enough time to fully react with the ozone treatment agent and improve the treatment effect of residual ozone.

[0084] A set of permanent magnets 33 are evenly distributed at the top edge of the mounting plate 19; magnetic blocks 34 are fixedly connected to the surface of the isolation plate 31 at the corresponding positions of the permanent magnets 33.

[0085] During the rotation of the mounting plate 19, the permanent magnet 33 will intermittently rotate to the underside of the magnetic block 34 and attract it. The magnetic attraction will drive the isolation plate 31 to vibrate continuously, effectively breaking the adhesion state formed by the bubbles on the surface of the isolation plate 31. This will prevent the bubbles from accumulating and forming large bubbles due to prolonged retention, thereby further increasing the contact opportunity between the bubbles and the ozone treatment agent. At the same time, the vibration of the isolation plate 31 can also disturb the ozone treatment agent in the treatment chamber 16, promoting its flow and mixing, making the concentration distribution of the treatment agent more uniform, and avoiding the reaction effect being affected by the low concentration of the treatment agent in some areas.

[0086] Example 1: Emergency Treatment of Oil Spill on Offshore Platform Deck A heavy crude oil spill (viscosity 850 mPa·s, diffusion area approximately 10 m²) occurred on an offshore drilling platform. The mussel-inspired biomimetic sponge absorbent sheets (20×20 cm, 50 sheets in total) of this invention were used for emergency treatment: the absorbent sheets were directly sprinkled onto the oil film surface, and saturation occurred after 5 minutes; the saturated absorbent sheets (magnetically functionalized type) were collected using an unmanned surface vessel equipped with a magnetic recovery device; the collected absorbent sheets were soaked in an alkaline solution (pH=11) for 15 minutes, desorbing 85% of the crude oil; the materials were rinsed with fresh water, dried, and reused. The results showed that the 50 sheets (total weight 750 g) absorbed a total of 31.5 kg of crude oil, recovering 26.8 kg of crude oil, with a material loss of <5%.

[0087] Example 2: Control of Oil Spill Pollution in Nearshore Waters. A nearshore oil pipeline rupture caused a medium-quality crude oil leak. The magnetic nano-adsorbent of this invention was used: magnetic nanoparticles (100nm diameter, 1g / L concentration) were sprayed as an aqueous suspension onto the oil-slicked sea surface; after adsorption for 30 minutes, they were recovered using an electromagnetic recovery vessel (magnetic field strength 0.8T); the recovered particles were desorbed from the crude oil by microwave heating (300W, 2 minutes); the desorbed particles were then surface-repaired and recycled. Calculations show that each kilogram of nano-adsorbent can process 38kg of crude oil, with a recovery cost only 1 / 3 of that of the traditional skimmer method.

[0088] Example 3: Handling Leaks from High-Viscosity Crude Oil Storage Tanks A high-viscosity crude oil (viscosity 1200 mPa·s) leak occurred in a floating oil storage unit (FPSO) tank. The graded porous aerogel blocks of this invention were used: the aerogel was cut into 10×10×5cm blocks (density 0.02 g / cm³, each weighing approximately 10g); these blocks were directly placed at the leak point, and after adsorption saturation, the volume expanded to 12×12×6cm; after manual retrieval, thermal desorption (80℃, 30 min) was performed; the desorbed aerogel was compressed back to its original volume, with a performance retention rate >90%. This aerogel still maintains an adsorption capacity of 45 g / g for ultra-high viscosity crude oil, demonstrating significant advantages under extreme conditions.

[0089] The terms "front," "back," "left," "right," "top," and "bottom" all refer to the figures in the accompanying drawings. Figure 1 Based on the perspective of the observer, the side of the device facing the observer is defined as the front, the left side of the observer is defined as the left, and so on.

[0090] In the description of this invention, it should be understood that the terms "center", "longitudinal", "lateral", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting the scope of protection of this invention.

[0091] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A marine oil sludge adsorbent material based on a mussel-inspired biomimetic structure, characterized in that: It includes a porous substrate (1), a polydopamine interface layer (2), and a metal-polyphenol network (3); The porous substrate (1) serves as a carrier, and its surface and internal pores are sequentially covered with a polydopamine interface layer (2) and a metal-polyphenol network (3). The porous substrate (1) has three-dimensional interconnected channels with a pore size distribution of 50-500 μm and a porosity of not less than 90%; The polydopamine interface layer (2) is formed on the surface and internal channels of the porous substrate (1) by dopamine self-oxidation polymerization, and has a thickness of 10-200 nm. The metal-polyphenol network (3) is formed by the coordination of transition metal ions and plant polyphenols on the polydopamine interface layer (2).

2. A method for preparing a marine oil spill absorbent material based on a mussel-inspired biomimetic structure, the method being used to prepare the marine oil spill absorbent material according to claim 1, characterized in that: Includes the following steps: S1. Pre-treat the porous substrate (1) to obtain a surface-activated porous substrate (1). S2. The pretreated porous substrate (1) is immersed in a buffer solution containing dopamine hydrochloride. Ozone is introduced into the solution using the ozone rapid polymerization method to induce dopamine oxidation polymerization and form a polydopamine interface layer (2) on the surface and internal pores of the substrate. S3. The material obtained in S2 is immersed in a mixed solution containing transition metal ions and plant polyphenols, so that the metal ions coordinate with the polydopamine interface layer (2) and plant polyphenols to form a metal-polyphenol network (3). After washing and drying, the marine oil pollution adsorbent material is obtained.

3. The method for preparing a marine oil sludge adsorbent material based on a mussel biomimetic structure according to claim 2, characterized in that: in, The detailed steps for S2 are as follows: S201. Place the porous substrate (1) into the mounting groove (20). By turning the adjusting rod (23), the adjusting rod (23) drives the ejector pin (24) to move toward the porous substrate (1). Insert the ejector pin (24) into the surface of the substrate to position and fix the porous substrate (1). S202. The lifting cover (12) is lowered by the lifting drive mechanism to form a closed chamber with the reaction container (10). The ozone generator generates ozone and supplies it to the aeration plate (11) through the delivery pipe (14). The ozone is evenly dispersed into microbubbles through the diversion hole (15). S203. The bubbles generated by the peripheral diversion holes (15) rise along the outside of the porous substrate (1), and the bubbles generated by the middle diversion holes (15) directly impact the lower side of the substrate and enter the interior of the substrate through the pores of the substrate, causing the outer surface and internal channels of the porous substrate (1) to form a polydopamine coating. S204. The motor (25) drives the mounting plate (19) and the porous substrate (1) to rotate slowly, disturbing the reaction liquid and breaking the static state. S205. The drive gear (27) is driven to rotate by the motor (28), and the aeration disc (11) is controlled to reciprocate in the reaction vessel (10) by the transmission column (26), intermittently squeezing and releasing the porous substrate (1) to change the internal pore structure of the substrate.

4. A device for preparing marine oil sludge adsorbent material based on mussel biomimetic structure, wherein the device is applied to the preparation method described in claim 3, characterized in that: It includes a reaction vessel (10), an aeration plate (11), and a lifting cover (12). The reaction vessel (10) is equipped with a temperature sensor, a pH sensor and an ozone concentration sensor; a support platform (13) is fixedly connected to the bottom of the reaction vessel (10). The aeration disc (11) is disposed on the surface of the support platform (13); the aeration disc (11) is connected to the conveying pipe (14); a set of flow holes (15) are evenly distributed on the upper side of the aeration disc (11). The lifting cover (12) is connected to a lifting drive mechanism; an annular treatment chamber (16) is fixedly connected to the upper side of the lifting cover (12); the treatment chamber (16) is filled with ozone treatment agent; a set of air inlets (17) are evenly distributed on the bottom of the treatment chamber (16) and the surface of the lifting cover (12); a set of air outlets (18) are evenly distributed on the top of the treatment chamber (16).

5. The apparatus for preparing marine oil sludge adsorbent material based on mussel biomimetic structure according to claim 4, characterized in that: The lifting cover (12) is provided with a mounting plate (19) on its lower side; the mounting plate (19) has a mounting groove (20) at its bottom; a set of ventilation holes (21) are evenly distributed between the top of the mounting groove (20) and the outer side of the mounting plate (19); a set of connecting holes (22) are evenly distributed on the side of the mounting plate (19); an adjusting rod (23) is detachably connected inside the connecting hole (22); a pin (24) is fixedly connected to one end of the adjusting rod (23) near the mounting groove (20).

6. The apparatus for preparing marine oil sludge adsorbent material based on mussel biomimetic structure according to claim 5, characterized in that: The mounting plate (19) is rotatably connected to the lower side of the lifting cover (12); a motor (25) is fixedly connected to the upper side of the lifting cover (12); the motor (25) and the mounting plate (19) are connected by a shaft.

7. The apparatus for preparing marine oil sludge adsorbent material based on mussel biomimetic structure according to claim 6, characterized in that: A transmission column (26) is fixedly connected to the lower side of the aeration disc (11); the transmission column (26) passes through the support platform (13) and the reaction container (10) and slides with them; a set of tooth blocks is provided on the surface of the transmission column (26) and a drive gear (27) is meshed with it; a second motor (28) is fixedly connected to the lower side of the reaction container (10); the second motor (28) and the drive gear (27) are connected by a shaft.

8. The apparatus for preparing marine oil sludge adsorbent material based on mussel biomimetic structure according to claim 7, characterized in that: The upper limit cage (29) and the lower limit cage (30) are fixedly connected to the lower side of the mounting plate (19) and the upper side of the aeration plate (11), respectively, and the diameter of the lower limit cage (30) is larger than that of the upper limit cage (29).

9. The apparatus for preparing marine oil sludge adsorbent material based on mussel biomimetic structure according to claim 5, characterized in that: The processing chamber (16) is equipped with a set of isolation plates (31); the side of the isolation plate (31) is equipped with a set of air guide grooves (32), and the air guide grooves (32) of adjacent isolation plates (31) are staggered.

10. The apparatus for preparing marine oil sludge adsorbent material based on mussel biomimetic structure according to claim 9, characterized in that: A set of permanent magnets (33) are evenly distributed at the top edge of the mounting plate (19); a magnetic block (34) is fixedly connected to the surface of the isolation plate (31) at the corresponding position of the permanent magnet (33).

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