A marine oil spill treatment device with tribo-nano-generator

Abstract

The application discloses a marine oil spill treatment device based on friction nanogenerator, and belongs to the technical field of marine oil spill treatment.The device comprises a buoy, a hydrophobic and oleophilic filter unit communicating inside and outside the buoy, a buffer unit and an oleophobic and hydrophilic filter unit arranged in the buoy, and a power capturing unit.The hydrophobic and oleophilic filter unit is arranged on the peripheral surface of the buoy, and based on the hydrophobic and oleophilic principle, the external marine oil spill is preliminarily filtered and drained into the interior of the buoy.The buffer unit is connected with the outlet of the hydrophobic and oleophilic filter unit, and is used for reducing the flow rate of the oil liquid entering the buoy, so that the oil and water are layered and treated.The oleophobic and hydrophilic filter unit is arranged in the layered water medium, and based on the oleophobic and hydrophilic principle, the water medium in the buoy is secondarily filtered, and the filtered water is discharged from the buoy.Based on the different properties of the oil and water in the marine oil spill, the treatment mode of combining the hydrophobic and oleophilic principle, the oleophobic and hydrophilic principle, and the oil-water layering technology is adopted, and the low-energy-consumption green and environment-friendly oil spill treatment is realized.

Description

Technical Field

[0001] This invention belongs to the field of marine oil spill treatment technology, specifically relating to a marine oil spill treatment device that generates electricity through triboelectric nanotechnology. Background Technology

[0002] During oil exploration, development, storage, transportation, or refining, accidents such as natural disasters or human error can cause oil spills, flowing onto the sea surface and forming oil films of varying thicknesses. This phenomenon is known as an oil spill. The most typical health hazard posed by oil is benzene and its derivatives, which can affect human blood and, with prolonged exposure, increase the incidence of cancer. Due to the flammable and explosive nature of oil, spills pose a threat to both personal and public safety. In the initial stages of an oil spill, or in thicker areas of light crude oil and light refined products, flammable gases may be present; these gases can ignite upon contact with an open flame, causing a fire. Oil spills also harm the marine ecosystem, causing suffocation of marine life, and toxic substances can enter the marine food chain, adversely affecting the marine ecosystem.

[0003] The general steps for handling marine oil spills are as follows: 1) Containment with oil ropes: Several tugboats are used to tow floating oil ropes on the sea surface, confining the leaking crude oil within the ropes and preventing further spread; 2) Pumping oil: The area enclosed by the oil ropes is gradually reduced by moving the tugboats, increasing the thickness of the crude oil on the sea surface as the area decreases. Once the thickness is sufficient, floating oil pumps are used to pump the crude oil to oil tankers for collection and transportation; 3) For the remaining crude oil that cannot be pumped out, chemical decomposition, combustion, and adsorption methods are used. It can be seen from the current methods for handling marine oil spills that they are not only time-consuming and labor-intensive, but also cause further pollution to the marine environment, necessitating a green and efficient marine oil spill treatment device. Summary of the Invention

[0004] The technical problem to be solved:

[0005] To avoid the shortcomings of existing technologies, this invention provides a marine oil spill treatment device based on triboelectric nano-powered generation. Based on the different properties of oil and water in marine oil spills, it adopts a treatment method that combines hydrophobic and oleophilic filtration and oil-water stratification technology, thereby achieving low-energy, green and environmentally friendly oil spill treatment.

[0006] The technical solution of the present invention is: a marine oil spill treatment device for triboelectric nano-power generation, comprising a float, a hydrophobic and oleophilic filter unit connecting the inside and outside of the float, a buffer unit and an oleophobic and hydrophobic filter unit placed inside the float, and an energy harvesting unit.

[0007] The hydrophobic and oleophilic filtration unit is installed on the circumference of the buoy. Based on the principle of hydrophobicity and oleophilicity, it performs preliminary filtration of external marine oil spills and guides the flow into the buoy.

[0008] The buffer unit is connected to the outlet of the hydrophobic and oleophilic filter unit to reduce the flow rate of oil entering the float, which facilitates the stratification of oil and water.

[0009] The oleophobic and hydrophilic filtration unit is located in the stratified water medium. Based on the principle of oleophobicity and hydrophilicity, it performs secondary filtration on the water medium in the float and discharges the filtered water out of the float.

[0010] The energy harvesting unit is used to provide the required electrical energy to the entire device.

[0011] A further technical solution of the present invention is: the outer peripheral surface of the float is provided with multiple inlets, each inlet is surrounded by an appendage, and the shell of the appendage is provided with a hydrophobic and oleophilic filter unit and a first energy capture unit;

[0012] The shell is a cavity structure with openings at both ends. One end of the opening faces outward, and the other end is sealed and fitted to the outer circumference of the float, covering the corresponding float inlet inside.

[0013] The hydrophobic and oleophilic filtration unit is arranged along the lower inner wall of the shell, including a flow pipe, a Fusheng sand at its inlet, and a protective cover; the inlet of the flow pipe is concentrically sealed with the opening on the outside of the shell, and its outlet is sealed and connected with the inlet of the float, with the inlet position higher than the outlet position, so as to realize the diversion of external oil; the protective cover blocks floating objects other than oil from entering the flow channel, and the Fusheng sand performs preliminary filtration of the oil entering the inlet of the flow pipe.

[0014] A further technical solution of the present invention is: the outer opening end of the shell is a loop shape, the inner opening end is a teardrop shape, the upper edges of the two openings and the upper edge of the shell are flush in the horizontal direction, and the lower edges of the two openings and the lower edge of the shell are curved downward in a parabolic shape.

[0015] A further technical solution of the present invention is as follows: the first energy harvesting unit includes an attached power generation platform and PTFE balls. The multi-layer attached power generation platform is arranged horizontally in sequence in the shell along the vertical direction. The attached power generation platform includes a nylon membrane, a copper electrode, and an acrylic resin from top to bottom. Multiple PTFE balls are placed on each attached power generation platform. When the PTFE balls are displaced between the platform and the platform, the PTFE balls generate electrons by friction with the nylon membrane and exhibit negative charge. The nylon membrane loses electrons and becomes positively charged. The copper electrode transports charge and generates current, thus completing triboelectric nano-power generation.

[0016] A further technical solution of the present invention is: the buffer unit is a C-shaped flow guide pipe, which is coaxially arranged inside the float and has multiple overflow holes at the top, forming an annular cavity with the inner wall of the float and fully covering each inlet of the float. The oil flowing in from each flow pipe is gathered in the annular cavity for buffering and deceleration, and then enters the float through the overflow holes to complete the stratification of oil and water in the oil.

[0017] A further technical solution of the present invention is as follows: the oleophobic and hydrophilic filtration unit is located below the float and includes, from the outside to the inside, a filter shell, a PVDF-PES nanofiber layer, a filter inner shell, and a water pump. The top surfaces of the shell and the inner shell are closed structures, and the side walls have several through holes. After stratification, the water at the bottom flows through the through holes of the filter shell, the PVDF-PES nanofiber layer, and the through holes of the filter inner shell in sequence, and is pumped by the water pump to the drain pipe leading to the outside of the float and discharged from the float.

[0018] A further technical solution of the present invention is: the PVDF-PES nanofiber layer is obtained by microwave-assisted in-situ growth of carboxymethyl cyclodextrin-titanium dioxide on a PVDF-PES nanofiber membrane as a substrate, resulting in a superhydrophilic-underwater superoleophobic nanolayer structure.

[0019] A further technical solution of the present invention is: an oil pump is also provided inside the float, and the oil pump's suction port extends into the oil at the top after stratification, and the oil is pumped to the oil discharge pipe leading to the outside of the float for storage.

[0020] A further technical solution of the present invention is: the energy harvesting unit includes a first energy harvesting unit, a second energy harvesting unit, a third energy harvesting unit, and a battery, wherein the second energy harvesting unit is located above the float and has the same structure and power generation principle as the first energy harvesting unit; the third energy harvesting unit includes a photovoltaic panel located at the top of the float for converting solar energy into electrical energy;

[0021] The battery is connected to the first energy harvesting unit, the second energy harvesting unit, and the third energy harvesting unit, respectively, and is used to store the electrical energy generated by the three energy harvesting units and to supply power to the entire device.

[0022] A further technical solution of the present invention is: the float is also equipped with a water-oil interface detector, a warning light and an plexiglass cover; the water-oil interface detector is used to detect the position of the water-oil interface after stratification inside the float;

[0023] The warning light is used to indicate the status of the water-oil interface. When the water-oil interface is located between the oleophobic and hydrophilic filter unit and the oil pump inlet, and the oil level is higher than the oil pump inlet, the warning light is green. In other cases, the warning light emits different lights to indicate the position of water and oil, and the position of water and oil is adjusted by adjusting the rotation speed of the water pump and the oil pump.

[0024] The transparent acrylic cover seals the top of the pontoon, protecting its internal structure, facilitating solar energy acquisition during photovoltaic power generation, and allowing the warning lights to shine through for easy observation.

[0025] Beneficial effects

[0026] The beneficial effects of this invention are as follows: The marine oil spill treatment device based on triboelectric nano-power generation has the following advantages: 1. It solves the problems of large workload and secondary pollution to the marine environment in marine oil spill treatment. 2. Based on triboelectric nano-power generation technology, it efficiently converts the low-frequency motion of ocean waves into electrical energy. 3. It uses hydrophobic and oleophilic materials and oleophobic and hydrophilic materials respectively, which improves the collection efficiency of marine oil spills. 4. It has low manufacturing cost and relatively simple construction steps.

[0027] This invention's hydrophobic and oleophilic filtration unit uses Fusheng sand to absorb and filter oil spills. Fusheng sand is made from aeolian sand deposited in the desert, coated with a hydrophobic and oleophilic mixture of polytetrafluoroethylene (PTFE) and polypropylene. This mixture possesses advantages such as low relative density, high strength, and corrosion resistance, enabling it to filter both water and oil. The PTFE and polypropylene mixture on the outside of the Fusheng sand exhibits both hydrophobic and oleophilic properties. The oleophilic properties allow oil from seawater to pass through, while the hydrophobic properties limit the water flow rate, facilitating the collection of marine oil spills.

[0028] This invention's oleophobic and hydrophilic filtration unit employs a PVDF-PES nanofiber layer for secondary oil filtration. The PVDF-PES nanofiber layer is a nanolayer structure with a suitable pore size, high porosity, and superhydrophilic-underwater superoleophobic properties, formed by microwave-assisted in-situ growth of carboxymethyl cyclodextrin-titanium dioxide on a PVDF-PES nanofiber membrane substrate. The PVDF-PES nanofiber membrane allows water to pass through while preventing oil from returning to the ocean via a water pump due to disturbances or when the water-oil interface is below the water-oil filtration structure.

[0029] The buffer unit of this invention is an annular cavity formed by a C-shaped flow guide channel and the inner wall of the float. It gathers and decelerates the pre-filtered oil, allowing the oil and water in the oil to quickly separate into layers. Without the flow guide channel, fluid with a certain velocity flows directly from the pipe outlet to the center, increasing the mixing degree of water and oil, resulting in an unclear water-oil interface. The oil pump would then extract the water-oil mixture along with the fluid, reducing oil collection efficiency. Furthermore, the flow velocity would act on the water-oil filtration structure, causing damage to the PVDF-PES nanofiber membrane. The flow guide channel allows the inflow to flow along the channel, and the inflow enters the float through multiple annular openings, reducing the water-oil mixing degree at the water-oil interface while preventing impact on the internal structure of the float.

[0030] Preferably, the opening at the outer end of the appendage shell of the present invention is a loop-shaped inlet. The loop-shaped inlet can increase the inflow rate and has a small change in the inflow cross-section, resulting in a more stable inflow. Furthermore, the shape of the appendage shell can also prevent waves from surging up the sea surface. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the overall appearance of the device of the present invention.

[0032] Figure 2This is a schematic cross-sectional view of the device of the present invention.

[0033] Figure 3 This is a cross-sectional view of the inlet flow tube structure of the present invention.

[0034] Figure 4 This is a schematic diagram of the triboelectric nano-power generation principle of the present invention.

[0035] Figure 5 This is a cross-sectional schematic diagram of the float structure of the present invention.

[0036] Figure 6 This is a cross-sectional view of the water-oil filtration structure of the present invention.

[0037] Figure 7 This is a cross-sectional schematic diagram of the flow guiding ring of the present invention.

[0038] Figure 8 This is a cross-sectional view of the floating power generation platform of the present invention.

[0039] Explanation of reference numerals in the attached diagram: 1 is the appendage; 1-1 is the appendage shell; 1-2 is the hydrophobic and oleophilic filter unit; 1-2-1 is the flow tube; 1-2-2 is the Fusheng sand; 1-2-3 is the protective cover; 1-3 is the appendage power generation platform; 1-3-1 is the nylon membrane; 1-3-2 is the copper electrode; 1-3-3 is the acrylic resin; 1-4 is the PTFE ball; 2 is the float; 2-1 is the float structure; 2-1-1 is the float shell; 2-1-2 is the first float platform; 2-1-3 is the second float platform; 2-1- 4 is the third platform of the float, 2-1-5 is the fourth platform of the float, 2-2 is the oleophobic and hydrophilic filter unit, 2-2-1 is the filter shell, 2-2-2 is the PVDF-PES nanofiber layer, 2-2-3 is the filter inner shell, 2-2-4 is the water pump, 2-3 is the battery, 2-4 is the flow guide ring, 2-5 is the oil pump, 2-6 is the water-oil interface detector, 2-7 is the PTFE ball, 2-8 is the float power generation platform, 2-9 is the photovoltaic panel, 2-10 is the warning light, and 2-11 is the plexiglass cover. Detailed Implementation

[0040] The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the invention, and should not be construed as limiting the invention.

[0041] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," and "counterclockwise," 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 limitations on this invention.

[0042] Addressing the shortcomings of existing technologies for treating marine oil spills, such as oil rope containment, oil pump suction, and chemical decomposition, this invention provides a marine oil spill treatment device based on triboelectric nano-power generation. The device includes a float, a hydrophobic and oleophilic filter unit connecting the inside and outside of the float, a buffer unit and an oleophobic-hydrophilic filter unit placed inside the float, and an energy harvesting unit. The hydrophobic-oleophilic filter unit is located on the circumference of the float and performs preliminary filtration of external marine oil spills based on the principle of hydrophobicity and oleophilicity, guiding the flow into the float. The buffer unit is connected to the outlet of the hydrophobic-oleophilic filter unit to reduce the flow rate of oil entering the float, facilitating the stratification of oil and water. The oleophobic-hydrophilic filter unit is located in the stratified water medium and performs secondary filtration of the water medium inside the float based on the principle of hydrophobicity and oleophilicity, discharging the filtered water from the float. The energy harvesting unit provides the necessary electrical energy to the entire device.

[0043] Specifically, the outer circumference of the float has multiple inlets, and each inlet is surrounded by an appendage. The appendage's shell contains a hydrophobic and oleophilic filtration unit and a first energy-capturing unit. The shell is a hollow structure with openings at both ends; one opening faces outwards, and the other opening is sealed to the outer circumference of the float, enclosing the corresponding float inlet. The hydrophobic and oleophilic filtration unit is arranged along the lower inner wall of the shell and includes a flow pipe, a Fusheng sand at its inlet, and a protective cover. The inlet of the flow pipe is concentrically sealed to the outer opening of the shell, and its outlet is sealed to the inlet of the float, with the inlet position higher than the outlet position, thus allowing external oil to flow through. The protective cover prevents floating debris other than oil from entering the flow channel, and the Fusheng sand performs preliminary filtration of the oil entering the flow pipe inlet.

[0044] Specifically, the outer opening of the shell is a loop shape, the inner opening is a teardrop shape, the upper edges of the two openings and the upper edge of the shell are horizontally aligned, and the lower edges of the two openings and the lower edge of the shell are parabolic and curved downwards.

[0045] Specifically, the first energy harvesting unit includes an attached power generation platform and PTFE spheres. The multi-layer attached power generation platform is arranged horizontally in sequence in the shell along the vertical direction. The attached power generation platform includes a nylon membrane, a copper electrode, and acrylic resin from top to bottom. Multiple PTFE spheres are placed on each attached power generation platform. When the PTFE spheres are displaced between themselves and the platform, the PTFE spheres generate electrons through friction with the nylon membrane, exhibiting negative charge. The nylon membrane loses electrons and becomes positively charged. The copper electrode transports the charge, generating current and completing triboelectric nano-power generation.

[0046] Specifically, the buffer unit is a C-shaped flow guide pipe. The flow guide pipe is coaxially arranged inside the float and has multiple overflow holes at the top. It forms an annular cavity with the inner wall of the float and completely covers all the inlets of the float. The oil flowing in from each flow pipe is gathered in the annular cavity for buffering and deceleration, and then enters the float through the overflow holes to complete the stratification of oil and water in the oil.

[0047] Specifically, the oleophobic and hydrophilic filtration unit is located below the float and includes, from the outside to the inside, a filter shell, a PVDF-PES nanofiber layer, a filter inner shell, and a water pump. The top surfaces of the outer shell and the inner shell are closed structures, and the side walls have several through holes. After stratification, the water at the bottom flows through the through holes of the filter shell, the PVDF-PES nanofiber layer, and the through holes of the filter inner shell in sequence, and is pumped by the water pump to the drain pipe leading to the outside of the float before being discharged from the float.

[0048] Specifically, the PVDF-PES nanofiber layer is obtained by microwave-assisted in-situ growth of carboxymethyl cyclodextrin-titanium dioxide on a PVDF-PES nanofiber membrane as a substrate, resulting in a superhydrophilic-underwater superoleophobic nanolayer structure.

[0049] Specifically, an oil pump is also installed inside the pontoon. The oil pump's suction port extends into the oil at the top after stratification, and the oil is pumped to the drain pipe leading to the outside of the pontoon for storage.

[0050] Specifically, the energy harvesting unit includes a first energy harvesting unit, a second energy harvesting unit, a third energy harvesting unit, and a battery. The second energy harvesting unit is located above the float and has the same structure and power generation principle as the first energy harvesting unit. The third energy harvesting unit includes a photovoltaic panel located at the top of the float, which is used to convert solar energy into electrical energy. The battery is connected to the first, second, and third energy harvesting units respectively, and is used to store the electrical energy generated by the three energy harvesting units and to supply power to the entire device.

[0051] Specifically, the float is also equipped with a water-oil interface detector, a warning light, and an acrylic glass cover. The water-oil interface detector is used to detect the position of the water-oil interface after stratification inside the float. The warning light is used to display the status of the water-oil interface. When the water-oil interface is located at the oleophobic-hydrophilic filter unit and the oil pump inlet, and the oil level is higher than the oil pump inlet, the warning light is green. In other cases, the warning light emits different lights to indicate the position and status of water and oil, and the position of water and oil is adjusted by adjusting the rotation speed of the water pump and the oil pump. The acrylic glass cover is transparent, which closes the upper end of the float, protects the internal structure of the float, facilitates the acquisition of solar energy during photovoltaic power generation, and allows the warning light to pass through for easy observation.

[0052] This invention solves the problems of large workload and secondary pollution to the marine environment in marine oil spill treatment, and realizes low-energy, green and environmentally friendly oil spill treatment.

[0053] The above technical solution will be further explained below with reference to the accompanying drawings:

[0054] Reference Figure 1 As shown, this embodiment of a triboelectric nano-powered marine oil spill treatment device includes an appendage 1 and a buoy 2. The appendage 1 consists of 4 to 8 parts, which are welded to the side of the buoy 2. The appendage 1 surrounds the buoy, improving its seakeeping and providing some buoyancy.

[0055] Reference Figure 2 As shown, the appendage 1 includes an appendage shell 1-1, a hydrophobic and oleophilic filter unit 1-2, an appendage power generation platform 1-3, and a PTFE ball 1-4.

[0056] The attached shell 1-1 is a shell with an outer ring-shaped end and an inner teardrop shape. The upper edge of the outer ring-shaped part and the upper edge of the inner teardrop shape are flush, while the lower edge has a parabolic shape. The ring-shaped inlet can increase the inflow rate, and the inflow cross-section changes little, resulting in a more stable inflow. The shape of the attached shell can also prevent waves from surging up the sea surface.

[0057] Reference Figure 2 , 3 As shown, the hydrophobic and oleophilic filter unit 1-2 is located inside the attached housing 1-1 and includes a flow pipe 1-2-1, a Fusheng sand 1-2-2, and a protective cover 1-2-3.

[0058] The outer port of the flow tube 1-2-1 is annular, and the inner port is circular. The flow tube 1-2-1 fits against the lower inner wall of the attachment shell 1-1, extending from the outer port of the attachment shell 1-1 along its lower edge to the inlet of the float 2. The outer port of the flow tube 1-2-1 is concentrically positioned with the outer port of the attachment shell 1-1, facing the water surface during use, allowing marine oil spills to enter the float along the flow tube. A ring-shaped protrusion is provided on the inner wall of the flow tube 1-2-1 for fixing the Fusheng sand 1-2-2. The Fusheng sand is annular, located outside the ring-shaped protrusion of the flow tube, and fits against the inner wall of the flow tube. The raw material of the Fusheng sand is aeolian sand from the desert, coated with a hydrophobic and oleophilic mixture of polytetrafluoroethylene and polypropylene, which has advantages such as low relative density, high strength, and corrosion resistance, and can be used for water and oil filtration. The polytetrafluoroethylene and polypropylene mixture on the outside of Fusheng Sand has hydrophobic and oleophilic properties. The oleophilic properties allow oil in seawater to pass through, while the hydrophobic properties limit the water flow rate, facilitating the collection of marine oil spills.

[0059] The attached shell 1-1 and the flow tube 1-2-1 have complex curved structures and can be manufactured using additive manufacturing technology. The material is a corrosion-resistant, high-strength alloy. The flow tube 1-2-1 is connected to the attached shell 1-1 by welding.

[0060] The protective cover 1-2-3 is a mesh structure with a loop-shaped outer edge, located outside the Fusheng sand 1-2-2. It is used to prevent blockage of the device by floating debris on the ocean surface, while simultaneously securing the Fusheng sand 1-2-2 to the inside. After the Fusheng sand 1-2-2 is placed inside the flow tube 1-2-1, the protective cover 1-2-3 is welded to the outer end of the flow tube 1-2-1.

[0061] Reference Figure 4 As shown, the attached power generation platform 1-3 includes a nylon membrane 1-3-1, a copper electrode 1-3-2, and an acrylic resin 1-3-3. The nylon membrane 1-3-1 is located on the top layer, the copper electrode 1-3-2 is in the middle, and the acrylic resin 1-3-3 is at the bottom. The attached power generation platform 1-3 is installed inside the attached body 1, and consists of 4 to 6 layers, conforming to the curved surfaces of the attached body shell 1-1 and the pipe 1-2-1.

[0062] The PTFE balls 1-4 are polytetrafluoroethylene balls. Multiple PTFE balls 1-4 are placed on each attached power generation platform 1-3. When there is a disturbance, the PTFE balls are displaced between the platform and the platform. The PTFE balls rub against the nylon membrane. The PTFE balls easily gain electrons and become negatively charged, while the nylon membrane loses electrons and becomes positively charged. The copper electrode transports the charge and generates current, thus realizing triboelectric nano-power generation.

[0063] Reference Figure 5As shown, the float 2 includes a float structure 2-1, an oleophobic and hydrophilic filter unit 2-2, a battery 2-3, a flow guide ring 2-4, a water pump 2-5, a water-oil interface detector 2-6, a PTFE ball 2-7, a float power generation platform 2-8, a photovoltaic panel 2-9, a warning light 2-10, and an plexiglass cover 2-11.

[0064] The float structure 2-1 includes a float shell 2-1-1, a first float platform 2-1-2, a second float platform 2-1-3, a third float platform 2-1-4, and a fourth float platform 2-1-5, all made of corrosion-resistant, high-strength alloy material. The float shell 2-1-1 is a cylindrical shell structure, welded to the appendage 1 on its side, and has an opening at its connection to the outlet of the flow pipe 1-2-1. The shape and size of the opening are consistent with the cross-section of the lower outlet of the flow pipe 1-2-1. Similarly, an opening is located at the oil discharge pipe of the oil pump 2-5, fitting flush with the outer wall of the discharge pipe. Both the third float platform 2-1-4 and the fourth float platform 2-1-5 have a circular hole in the center.

[0065] Reference Figure 6 As shown, the oleophobic and hydrophilic filter unit 2-2 includes a filter shell 2-2-1, a PVDF-PES nanofiber layer 2-2-2, a filter inner shell 2-2-3, and a water pump 2-2-4. The oleophobic and hydrophilic filter unit 2-2 is installed on the float three-platform 2-1-4.

[0066] The filter housing 2-2-1 is a cylindrical shell with a sealed top and multiple circular holes on the side to facilitate water flow into the interior of the filter structure.

[0067] The PVDF-PES nanofiber layer 2-2-2 is located inside the filter outer shell 2-2-1 and is wrapped around the side of the filter inner shell 2-2-3. The PVDF-PES nanofiber layer is a microwave-assisted in-situ grown carboxymethyl cyclodextrin-titanium dioxide layer based on a PVDF-PES nanofiber membrane, possessing a nanolayer structure with suitable pore size, high porosity, and superhydrophilic-superoleophobic properties underwater. Water and oil, due to their different densities, form a natural stratified structure inside the float. The oleophobic and hydrophilic filter unit 2-2 is located in the water. The PVDF-PES nanofiber layer allows water to pass through and prevents oil from returning to the ocean via the water pump when disturbed or when the water-oil interface is below the water-oil filter structure.

[0068] The filter inner shell 2-2-3 is also a cylindrical shell with a sealed top and a rectangular opening on the side to facilitate water flow. The filter inner shell is located inside the PVDF-PES nanofiber layer 2-2-2, which is wrapped around the filter inner shell, providing support for the PVDF-PES nanofiber layer 2-2-2.

[0069] The water pump 2-2-4 is a centrifugal pump located in the middle of the oleophobic and hydrophilic filter unit 2-2. The water inlet is opened on the side. The drain pipe passes through the circular holes of the float platform 2-1-4 and the float platform 2-1-5. The water is discharged from the device by the rotation of the turbine blades.

[0070] The storage batteries 2-3 are fan-shaped, numbering 4 to 8, and are located within the third platform 2-1-4 and the fourth platform 2-1-5 of the float, used to store electrical energy from triboelectric nano-generation and photovoltaic generation.

[0071] Reference Figure 7 As shown, the flow guiding channel 2-4 is a C-shaped annular structure located at the lower outlet of the flow pipe 1-2-1, with a loop opening on its upper surface, the opening being located between adjacent flow pipes. The flow guiding channel 2-4 and the inner wall of the float form an annular cavity to buffer the flow velocity of the oil flowing into the float. Without the flow guiding channel, fluid with a certain velocity would flow directly to the middle at the pipe outlet, increasing the mixing degree of water and oil, resulting in an unclear water-oil interface. The oil pump would then extract the water-oil mixture together, reducing the oil collection efficiency. Moreover, a certain flow velocity would act on the water-oil filtration structure, causing damage to the PVDF-PES nanofiber layer. The flow guiding channel allows the inflow to flow along the channel, and the inflow flows into the float through multiple loop openings, reducing the water-oil mixing degree at the water-oil interface, while preventing impact on the internal structure of the float.

[0072] The oil pump 2-5 is a centrifugal pump located below the second platform 2-1-3 of the float. The oil inlet is located at the center of the float 2, extending downwards into the oil layer. The oil discharge pipe of the oil pump 2-5 extends from the opening of the float shell 2-1-1. The oil is drawn from the lower inlet to the discharge pipe by the suction action of the turbine blades, and the discharge pipe is connected to an external floating platform or vessel for storage.

[0073] The water-oil interface detector 2-6 is an immersion detector based on guided wave radar interface monitoring technology. It transmits and receives emitted battery waves, compares the received signal with the pulse signal reflected back from the surface of the measured medium, and calculates the measured distance using the frequency difference between the two to determine the position of the water-oil interface. The water-oil interface detector is located on the lowest power generation platform inside the float. Its lower end is connected to the lowest layer of the float power generation platform 2-8 and the second float platform 2-1-3, and its lowest point is located at the oleophobic and hydrophilic filter unit 2-2, enabling it to measure a large area of ​​the water-oil interface.

[0074] Reference Figure 8As shown, the PTFE balls 2-7 and the power generation platform 2-8 inside the pontoon are made of the same material as the PTFE balls 1-4 and the power generation platform 1-3 in the appendage. Electricity is generated through friction between the PTFE balls and the power generation platform. The power generation platform 2-8 is a circular platform with 4 to 6 layers. Each layer of the power generation platform has multiple PTFE balls 2-7 distributed on it. Adjacent circular platforms are connected at their edges by cylindrical rings, forming a unified structure. The lowest power generation platform is located on the second pontoon platform 2-1-3, and small holes are made on the lowest pontoon power generation platform 2-8 and the second pontoon platform 2-1-3 to allow the lower end of the water-oil interface detector 2-6 to pass through.

[0075] The photovoltaic panels 2-9 are located above the pontoon platform 2-1-2 and cover the entire pontoon platform 2-1-2. The photovoltaic panels utilize the abundant solar energy at sea and convert it into electrical energy.

[0076] The warning light 2-10 is located in the middle of the float platform 2-1-2 and is used to indicate the water-oil interface. When the water-oil interface is between the water-oil filter structure and the oil pump inlet, and the oil level is higher than the oil pump inlet, the warning light is green. In other cases, the warning light emits different lights to indicate the position of water and oil, and the position of water and oil is adjusted by regulating the rotation speed of the water pump and oil pump.

[0077] The acrylic glass cover 2-11 is dome-shaped, enclosing the upper part of the float 2 and protecting the internal structure of the float. The acrylic glass cover is transparent, which facilitates the acquisition of solar energy during photovoltaic power generation, and the light emitted by the warning light can be seen, making it easy to monitor the operating status of the device.

[0078] The assembly sequence of the marine oil spill treatment device using triboelectric nanogenerators in this embodiment is as follows:

[0079] First, assemble appendage 1. Place the Fusheng sand 1-2-2 on the outside of the annular protrusion at the inlet of the flow pipe 1-2-1, and weld the protective cover 1-2-3 to the outer end of the inlet of the flow pipe 1-2-1. This combines the flow pipe 1-2-1, Fusheng sand 1-2-2, and protective cover 1-2-3 to form a hydrophobic and oleophilic filter unit 1-2. Weld the hydrophobic and oleophilic filter unit 1-2 to the appendage shell 1-1, wherein the inlet of the flow pipe 1-2-1 and the outer end of the appendage shell 1-1 are on the same plane, and the flow pipe 1-2-1 extends along the lower edge of the appendage shell 1-1 to the inner end of the appendage shell 1-1. Install the multi-layer appendage power generation platform 1-3 inside the appendage shell 1-1, and place multiple PTFE balls 1-4 on each platform. This completes the assembly of appendage 1. Then, assemble the float 2 in a bottom-up order. Weld the float shell 2-1-1 to the fourth platform 2-1-5. Install the battery 2-3 on the fourth platform 2-1-5. Weld the third platform 2-1-4 above the battery 2-3. Install and fix the water pump 2-2-4 in the middle of the third platform 2-1-4. The drainage pipe of the water pump 2-2-4 passes through the opening between the third platform 2-1-4 and the fourth platform 2-1-5. Wrap the PVDF-PES nanofiber layer 2-2-2 around the side of the filter inner shell 2-2-3 and install it together in the middle of the third platform 2-1-4. Then, put the filter outer shell 2-2-1 onto the PVDF-PES nanofiber layer 2-2-2. Weld the flow guide ring 2-4 to the inner wall of the appendage shell 1-1, and wrap the inlet opening of the appendage shell 1-1 inside. The side with the return annular hole is the upper side. First, install the oil pump 2-5 below the second platform 2-1-3 of the float, and then weld the second platform 2-1-3 to the float shell 2-1-1. During the assembly of the float power generation platform 2-8, first place the oil-water interface detector 2-6 at the bottom layer, and then place multiple PTFE balls 2-7 on each platform layer before assembling each layer. Install the assembled oil-water interface detector 2-6, PTFE balls 2-7, and float power generation platform 2-8 onto the second platform 2-1-3 of the float. Install the first platform 2-1-2 of the float onto the float power generation platform 2-8 and weld it to the float shell 2-1-1. Lay the photovoltaic panels 2-9 on the first platform 2-1-2 of the float, and install the warning light 2-10 in the middle of the first platform 2-1-2. Install the plexiglass cover 2-11 onto the top of the float shell 2-1-1, thus completing the assembly of float 2. Finally, the appendage 1 is welded to the side of the float shell 2-1-1, and the outlet of the flow pipe 1-2-1 is aligned with the side opening of the float shell 2-1-1, so that the appendage 1 and the float 2 form a whole.

[0080] The power generation principle of the marine oil spill treatment device using triboelectric nanogenerators in this embodiment is as follows:

[0081] During operation, the triboelectric nano-powered marine oil spill treatment device is subject to low-frequency vibrations caused by environmental factors such as waves, currents, and wind. The PTFE sphere 1-4 moves on the attached power generation platform 1-3. During this movement, the nylon membrane 1-3-1 loses electrons, while the PTFE sphere gains electrons. The copper electrode 1-3-2 transmits the generated current through a circuit to the battery 2-3. The PTFE sphere 2-7 inside the pontoon and the pontoon power generation platform 2-8 generate current in the same way and store it in the battery 2-3. The photovoltaic panel 2-9 converts solar energy into electrical energy and stores it in the battery 2-3.

[0082] This embodiment describes the marine oil spill treatment principle of a triboelectric nano-powered marine oil spill treatment device.

[0083] During operation, both the water and oil surfaces are located within the inlet section of flow pipe 1-2-1. Under the gravitational potential energy of the water-oil mixture and the suction of the pump, the mixture is drawn from the sea surface into the device. Due to the hydrophobic and oleophilic properties of Fusheng sand 1-2-2, oil is allowed to enter while water is restricted. However, because Fusheng sand 1-2-2 is a porous material, some water will also enter the device, requiring secondary separation of water and oil. The water-oil mixture flows along flow pipe 1-2-1 into guide ring channel 2-4 and then flows inward along the annular opening on the ring channel. Due to the density difference, water and oil naturally stratify. When water pump 2-2-4 pumps water, the PVDF-PES nanofiber layer 2-2-2 in the oleophobic and hydrophilic filter unit 2-2 has oleophobic and hydrophilic properties, allowing water to pass through while preventing oil from returning to the seawater. Oil pump 2-5 then pumps the upper layer of oil to an external floating platform or vessel for oil spill treatment and utilization. The water-oil interface detector 2-6 detects the water and oil levels to determine their positions. When the water-oil interface is located between water pump 2-2-4 and oil pump 2-5, and the oil level is higher than the lower inlet of oil pump 2-2-4, both water pump 2-2-4 and oil pump 2-5 are operating normally, and the warning light 2-10 is green. When the water-oil interface and oil level are in other positions, the rotation speed of water pump 2-2-4 and oil pump 2-5 needs to be adjusted, and the warning light 2-10 will emit different warnings depending on the specific position.

[0084] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention.

Claims

1. A marine oil spill treatment device based on triboelectric nanogenerators, characterized in that: It includes a buoy, a hydrophobic and oleophilic filtration unit connecting the inside and outside of the buoy, a buffer unit and an oleophobic and hydrophobic filtration unit placed inside the buoy, and an energy capture unit; The outer circumference of the float is provided with multiple inlets, and each inlet is surrounded by an appendage. The shell of the appendage is provided with a hydrophobic and oleophilic filter unit and a first energy capture unit. The shell is a cavity structure with two openings. One opening faces outward, and the other opening is sealed and fitted to the outer circumference of the float, covering the corresponding float inlet. The outer opening of the shell is a loop, and the inner opening is teardrop-shaped. The upper edges of the two openings and the upper edge of the shell are horizontally aligned, and the lower edges of the two openings and the lower edge of the shell are parabolic downward curved. The hydrophobic and oleophilic filtration unit is arranged along the lower inner wall of the shell, including a flow tube, a Fusheng sand at its inlet, and a protective cover; the inlet of the flow tube is concentrically sealed with the opening on the outside of the shell, and its outlet is sealed and connected with the inlet of the float, with the inlet position higher than the outlet position, so as to realize the diversion of external oil; the protective cover blocks floating objects other than oil from entering the flow channel, and the Fusheng sand performs preliminary filtration of the oil entering the inlet of the flow tube; The hydrophobic and oleophilic filtration unit is installed on the circumference of the buoy. Based on the principle of hydrophobicity and oleophilicity, it performs preliminary filtration of external marine oil spills and guides the flow into the buoy. The buffer unit is connected to the outlet of the hydrophobic and oleophilic filter unit to reduce the flow rate of oil entering the float, which facilitates the stratification of oil and water. The oleophobic and hydrophilic filtration unit is located in the stratified water medium. Based on the principle of oleophobicity and hydrophilicity, it performs secondary filtration on the water medium in the float and discharges the filtered water out of the float. The energy harvesting unit is used to provide the required electrical energy to the entire device.

2. The marine oil spill treatment device based on triboelectric nanogenerator according to claim 1, characterized in that: The first energy harvesting unit includes an attached power generation platform and PTFE spheres. The multi-layer attached power generation platform is arranged horizontally in sequence in the shell along the vertical direction. The attached power generation platform includes a nylon membrane, a copper electrode, and acrylic resin from top to bottom. Multiple PTFE spheres are placed on each attached power generation platform. When the PTFE spheres are displaced between the platform and the platform, the PTFE spheres generate electrons by friction with the nylon membrane and become negatively charged. The nylon membrane loses electrons and becomes positively charged. The copper electrode transports the charge and generates current, thus completing triboelectric nano-power generation.

3. The marine oil spill treatment device for triboelectric nanogenerators according to claim 1, characterized in that: The buffer unit is a C-shaped flow guide pipe. The flow guide pipe is coaxially arranged inside the pontoon and has multiple overflow holes at the top. It forms an annular cavity with the inner wall of the pontoon and completely covers all the inlets of the pontoon. The oil flowing in from each flow pipe is collected in the annular cavity for buffering and deceleration, and then enters the pontoon through the overflow holes to complete the stratification of oil and water in the oil.

4. The marine oil spill treatment device for triboelectric nano-power generation according to claim 1, characterized in that: The oleophobic and hydrophilic filtration unit is located below the float and includes, from the outside to the inside, a filter shell, a PVDF-PES nanofiber layer, a filter inner shell, and a water pump. The top surfaces of the outer shell and the inner shell are closed structures, and the side walls have several through holes. After stratification, the water at the bottom flows through the through holes of the filter shell, the PVDF-PES nanofiber layer, and the through holes of the filter inner shell in sequence, and is pumped by the water pump to the drain pipe leading to the outside of the float before being discharged from the float.

5. The marine oil spill treatment device for triboelectric nano-power generation according to claim 4, characterized in that: The PVDF-PES nanofiber layer is obtained by microwave-assisted in-situ growth of carboxymethyl cyclodextrin-titanium dioxide on a PVDF-PES nanofiber membrane substrate, resulting in a superhydrophilic-underwater superoleophobic nanolayer structure.

6. A marine oil spill treatment device for triboelectric nanogenerators according to any one of claims 1-5, characterized in that: The pontoon is also equipped with an oil pump. The oil pump's suction port extends into the oil at the top after stratification, and the oil is pumped to the drain pipe leading to the outside of the pontoon for storage.

7. The marine oil spill treatment device for triboelectric nano-power generation according to claim 6, characterized in that: The energy harvesting unit includes a first energy harvesting unit, a second energy harvesting unit, a third energy harvesting unit, and a battery. The second energy harvesting unit is located above the float and has the same structure and power generation principle as the first energy harvesting unit. The third energy harvesting unit includes a photovoltaic panel located at the top of the float, which is used to convert solar energy into electrical energy. The battery is connected to the first energy harvesting unit, the second energy harvesting unit, and the third energy harvesting unit, respectively, and is used to store the electrical energy generated by the three energy harvesting units and to supply power to the entire device.

8. The marine oil spill treatment device for triboelectric nanogenerators according to claim 7, characterized in that: The pontoon is also equipped with a water-oil interface detector, a warning light, and an plexiglass cover; the water-oil interface detector is used to detect the position of the water-oil interface after stratification inside the pontoon. The warning light is used to indicate the status of the water-oil interface. When the water-oil interface is located between the oleophobic and hydrophilic filter unit and the oil pump inlet, and the oil level is higher than the oil pump inlet, the warning light is green. In other cases, the warning light emits different lights to indicate the position of water and oil, and the position of water and oil is adjusted by adjusting the rotation speed of the water pump and the oil pump. The transparent acrylic cover seals the top of the pontoon, protecting its internal structure, facilitating solar energy acquisition during photovoltaic power generation, and allowing the warning lights to shine through for easy observation.

Images