A rotating friction contact electro-catalytic degradation system and method driven by wind energy

Abstract

The application provides a rotating friction contact electro-catalytic degradation system and method driven by wind energy, relates to the technical field of energy and environmental protection, and comprises a wind energy capturing unit, a variable speed transmission unit, a rotating friction catalysis unit, a liquid drop forming unit, a degradation reaction container and a circulating unit, and can be configured with a wind energy storage and transmission assembly. The application generates relative friction between a rotating assembly and a fixed assembly driven by wind energy, generates active oxygen species in situ at a solid-liquid interface, innovatively designs a low-speed / high-speed dual operation mode, forms a solid-liquid-solid three-phase friction interface of liquid drops at a low speed, breaks the liquid drops into micro-liquid drops to strengthen catalysis at a high speed, and the active oxygen generation amount is increased by 3-10 times. The application does not need an external power supply, realizes efficient and deep treatment of organic pollutants in combination with multi-stage and circulating degradation, and is particularly suitable for power supply-free scenes such as fields, remote areas and islands.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, and more specifically to a wind-powered rotating frictional contact electrocatalytic degradation system and method, which is suitable for the green and efficient degradation of organic pollutants such as pesticides, antibiotics, dyes, and surfactants, as well as new pollutants. Background Technology

[0002] In recent years, with the rapid advancement of industrialization and urbanization, large amounts of organic pollutants have been continuously discharged into the aquatic environment. In particular, emerging pollutants such as pesticides, antibiotics, and personal care products are bioaccumulative, persistent, and highly toxic. Even at extremely low concentrations, they pose a serious threat to the balance of ecosystems and human health, and are now frequently detected in drinking water sources in many parts of the world.

[0003] Contact-electro-catalysis (CEC) occurs when two materials with different electron affinities repeatedly come into contact and separate under mechanical agitation. Contact electrification occurs at the interface, causing a high density of charge to accumulate on the catalyst particle surface and forming an extremely strong electric field (up to 10⁻⁶). 8 -10 9 V / m). This strong electric field is sufficient to directly cleave water molecules at the solid-liquid interface to generate hydroxyl radicals (·OH), or to generate superoxide radicals (·O2) by reducing dissolved oxygen. - This process generates highly reactive oxygen species such as hydrogen peroxide (H2O2). These in-situ generated ROS have extremely short lifetimes but extremely strong oxidizing power, efficiently attacking organic pollutant molecules adsorbed on the catalyst surface, degrading them into smaller molecules or mineralizing them into CO2 and H2O. The entire process is driven entirely by mechanical energy (such as stirring, ultrasound, and water flow), requiring no external power source, light irradiation, or chemical oxidants, fundamentally avoiding secondary pollution and high-grade energy consumption, thus becoming a highly promising new green catalytic pathway.

[0004] Micron-sized droplets form 10 due to the large curvature of the gas-liquid interface. 8 ~10 9 A local strong electric field of V / m can activate water molecules to dissociate and generate hydroxyl radicals under normal temperature and pressure conditions without additional catalysts or external oxidants. Hydroxyl radicals are coupled and spontaneously generate hydrogen peroxide. When oxygen and organic compounds such as alcohols and aldehydes coexist in the system, the interfacial electric field can also activate oxygen to generate superoxide and peroxy radicals, which are further generated into organic peroxides such as alkyl hydroperoxides and dialkyl peroxides through chain oxidation.

[0005] Under illumination, photoradiation can excite photogenerated electron-hole pairs on the catalyst surface. These photogenerated charge carriers can effectively suppress the recombination and dissipation of contact charges, while lowering the energy barriers for water molecule splitting and dissolved oxygen reduction, thus forming a synergistic effect with the strong interfacial electric field generated by contact electrocatalysis. Therefore, photo-assisted contact electrocatalysis can significantly increase the levels of hydroxyl radicals (·OH) and superoxide radicals (·O2). - The in-situ production of reactive oxygen species such as α, β, and γ significantly increases the degradation rate of organic pollutants compared to that driven by mechanical means alone.

[0006] Wind energy, as a widely available clean energy source in nature, boasts significant advantages such as abundant reserves, renewability, and zero carbon emissions. If wind energy could be directly coupled with rotating triboelectric contact electrocatalysis technology to construct an integrated self-powered system of "wind energy capture → rotating triboelectric electrification → contact electrocatalytic degradation," the problems of high energy consumption, reliance on external power sources, and difficulty in application to scenarios without electricity in traditional contact electrocatalysis devices could be completely solved. However, there are currently no reports on technologies that directly drive rotating triboelectric contact electrocatalysis to achieve efficient degradation of new pollutants using wind energy, indicating a significant technological gap.

[0007] Most existing contact electrocatalytic devices employ fixed-bed or stirred-bed structures, which suffer from drawbacks such as small frictional contact area, low reactive oxygen generation efficiency, and limited processing capacity. Furthermore, existing devices cannot adaptively adjust their operating modes according to changes in natural wind speed, resulting in low wind energy utilization and unstable degradation effects. Summary of the Invention

[0008] The purpose of this invention is to overcome the above-mentioned defects in the prior art and provide a wind-driven rotating triboelectric contact electrocatalytic degradation system and method. By organically combining wind energy capture technology, rotating triboelectric contact electrocatalytic technology and multi-stage cyclic degradation technology, green, efficient and continuous degradation of organic pollutants can be achieved. It is particularly suitable for scenarios without power supply, such as in the wild, remote areas, and islands.

[0009] To achieve the above-mentioned technical features, the present invention aims to provide a wind-powered rotating triboelectric contact electrocatalytic degradation system, comprising: Wind energy capture unit, variable speed transmission unit, rotary friction catalysis unit, droplet formation unit, degradation reaction vessel and circulation unit; The wind energy capture unit is connected to the transmission unit for capturing natural wind energy and converting it into rotational mechanical energy. The speed transmission unit is connected to the rotary friction catalytic unit and is used to adjust the output speed to adapt to different operating modes of the rotary friction catalytic unit. The rotary friction catalytic unit is located inside the degradation reaction vessel and includes a rotating component and a fixed component arranged coaxially. The rotating component rotates relative to the fixed component under the drive of wind power, and the two form a contact state or a controllable micro-gap state, generating continuous relative rotary friction. The droplet forming unit is arranged in relation to the rotating friction catalytic unit, which is used to quantitatively deliver the pollutant solution to be treated to the surface of the rotating component, and can adapt to different rotation speeds of the rotating component to achieve dual-mode switching between conventional droplet supply and microdroplet breakage. The circulation unit is connected to the outlet of the degradation reaction vessel and the inlet of the droplet forming unit through a pipeline, so as to realize the closed-loop circulation degradation of the polluted solution to be treated. The electrocatalytic degradation system generates a contact electrocatalytic effect at the solid-liquid interface through rotational friction, producing in-situ reactive oxygen species such as hydroxyl radicals, superoxide anion radicals, and hydrogen peroxide, which oxidize and decompose organic pollutant molecules.

[0010] Preferably, the controllable micro-pitch range between the rotating component and the fixed component is 0.1mm-5mm; wherein, in the low-speed rotation mode, contact arrangement or a micro-pitch of 0.1mm-1mm is adopted, and in the high-speed rotation mode, a micro-pitch of 1mm-5mm is adopted.

[0011] Preferably, the surface of the rotating component is loaded with a contact electrocatalytic functional layer, the material of which is selected from one or more of the following: fluoropolymer, polytetrafluoroethylene, polyvinylidene fluoride, fluorinated ethylene propylene copolymer, polydimethylsiloxane, barium titanate, zinc oxide, and titanium dioxide; the contact electrocatalytic functional layer is a continuous and dense thin film structure with a thickness not exceeding 0.15 mm.

[0012] Preferably, the droplet forming unit includes a liquid storage tank, a flow control component, and a liquid outlet structure; the liquid outlet structure is selected from any one of a nozzle, a capillary, a porous liquid distribution head, or a centrifugal liquid ejection structure, wherein the orifice diameter of the nozzle or capillary is in the range of 0.5mm-2mm.

[0013] Preferably, the liquid outlet structure is positioned directly opposite the non-central region of the rotating component; during low-speed rotation, conventional droplets stably adhere to the surface of the rotating component to form a continuous liquid film; during high-speed rotation, conventional droplets are broken into micron-sized droplets with diameters of 50μm-500μm under the combined action of centrifugal force and interfacial shear force.

[0014] Preferably, the transmission unit is an integrated speed-increasing and speed-changing gearbox structure, which can increase the rotational speed of the rotating component through the speed-increasing function at low wind speeds and stabilize the output speed through the speed-changing function at high wind speeds, ensuring that both low-speed and high-speed modes can be stably switched and effective friction catalytic efficiency can be maintained.

[0015] Preferably, the degradation reaction vessel is provided with a multi-stage degradation unit, which adopts a vertical stacking or horizontal series structure, and each stage of the degradation unit is independently equipped with a rotating friction catalytic unit and a droplet forming unit.

[0016] Preferably, the circulation unit is selected from any one of a peristaltic pump, a diaphragm pump, or a centrifugal pump, and has an adjustable flow rate.

[0017] Another aspect of the present invention provides a wind-driven rotary triboelectric contact electrocatalytic degradation method, implemented based on the aforementioned electrocatalytic degradation system, comprising the following steps: S1, Pretreatment of the device: Assemble all components of the device as required, introduce the organic pollutant solution to be treated into the degradation reaction vessel, start the circulation unit, complete the circulation and emptying of the solution in the pipeline and the vessel, and adjust the flow parameters of the droplet forming unit. S2, Dual-mode parameter preset: Based on the local natural wind speed range, preset the critical speed of low-speed rotation mode and high-speed rotation mode, the distance between rotating components and fixed components, the droplet supply flow rate, and the parameters of the contact electrocatalytic functional layer. The optimal combination of working parameters is determined through multiple sets of comparative experiments. S3, Wind-Driven Degradation: The wind energy capture unit is activated, and natural wind energy drives the rotating component to rotate via the variable speed transmission unit. When the wind speed is below the critical wind speed, the device automatically operates in low-speed tribocatalysis mode, where conventional droplets come into contact with the triboelectric interface to generate reactive oxygen species. When the wind speed is above the critical wind speed, the device automatically switches to high-speed tribocatalysis mode, where droplets are broken into microdroplets to enhance the catalytic effect. Reactive oxygen species continuously attack the conjugated double bonds, amino groups, and other active sites of organic pollutants, triggering oxidative decomposition reactions. S4, Deep Recycled Treatment: The incompletely degraded solution is returned to the droplet forming unit through the recycling unit and repeatedly enters the rotating friction catalytic unit for treatment until the pollutant concentration reaches the emission standard, thus completing the degradation treatment.

[0018] Preferably, the optimal operating parameters mentioned in step S2 include: low-speed rotation speed, high-speed rotation speed, component spacing, type of contact electrocatalytic material, thickness of functional layer, droplet supply flow rate, and circulation flow rate.

[0019] Preferably, in step S3, in the low-speed rotation mode, conventional droplets form a solid-liquid-solid three-phase friction interface between the rotating component and the stationary component, generating active oxygen species through direct contact friction; in the high-speed rotation mode, microdroplets undergo interfacial polarization and shear catalysis at the high-speed friction interface, increasing the amount of active oxygen species generated by 3-10 times compared to the low-speed mode.

[0020] The present invention has the following beneficial effects: 1. The device of this invention does not require an external power source and is driven entirely by natural wind energy. It can be widely used in the treatment of organic polluted water bodies in scenarios without power supply, such as in the wild, remote areas, islands, and lake shores, thus solving the pain point of traditional water treatment technologies relying on mains power.

[0021] 2. This invention innovatively proposes a low-speed / high-speed dual operation mode, which can automatically switch operation modes according to changes in natural wind speed. The low-speed mode ensures effective degradation under light wind conditions, while the high-speed mode makes full use of high wind speed conditions to significantly improve degradation efficiency and significantly improve the utilization rate of wind energy.

[0022] 3. In high-speed mode, conventional droplets are broken into micron-sized microdroplets, significantly increasing the solid-liquid contact area. At the same time, the interfacial polarization and shear catalytic effect are significantly enhanced, and the amount of active oxygen species generated is 3-10 times higher than that of traditional contact electrocatalysis technology, resulting in a significant improvement in the degradation rate and removal rate of organic pollutants.

[0023] 4. The present invention adopts a technical solution that combines multi-stage degradation units with cyclic degradation, which can achieve the step-by-step deep degradation of organic pollutants, with stable and reliable treatment effect, and the effluent quality can stably meet the discharge standards.

[0024] 5. The device of this invention has a simple structure, no complex electrical control system, and is easy to manufacture and install. Furthermore, the device does not consume chemical reagents or electricity during operation, resulting in extremely low maintenance costs, making it suitable for large-scale application. Attached Figure Description

[0025] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0026] Figure 1 This is a schematic diagram of the overall structure of the three-stage vertically stacked wind-powered rotating frictional contact electrocatalytic degradation system described in this invention.

[0027] Figure 2 This is a comparison curve of the amount of reactive oxygen species generated at different rotation speeds.

[0028] Figure 3 This is a schematic diagram of the principle verification device of the present invention.

[0029] Figure 4 This is an exploded view of the components of the rotating friction catalytic unit of the present invention.

[0030] Figure 5 This is a cross-sectional view of the rotating friction catalytic unit of the present invention.

[0031] In the diagram: 1. Wind turbine; 2. Speed-increasing gearbox; 3. First acrylic shell; 4. Rotary friction catalytic unit; 5. Third-stage reaction chamber; 6. First water outlet pipe; 7. First water inlet pipe; 8. Peristaltic pump; 9. Sewage droplet; 10. Main shaft; 11. Interstage connecting pipe; 12. Second water outlet pipe; 13. Second water inlet pipe; 14. Pump; 15. Second acrylic shell; 16. Base; 17. Rotary friction reaction disk; 18. PTFE ball; 19. Friction catalytic composite tube assembly; 20. Reaction tank; 21. Servo motor; 22. Light source; 23. First PTFE film; 24. Rotary friction reaction disk; 25. Acrylic cylinder; 26. Second PTFE film; 27. Hole. Detailed Implementation

[0032] The embodiments of the present invention will be further described below with reference to the accompanying drawings.

[0033] Example 1: A wind-powered rotating friction contact electrocatalytic degradation system includes a wind energy capture unit, a variable speed transmission unit, a rotating friction catalytic unit 4, a droplet forming unit, a degradation reaction container, and a circulation unit; the degradation reaction container can be equipped with multiple degradation units and can optionally be equipped with a wind energy storage and transfer unit.

[0034] Specific structure and parameters of each unit: Wind energy capture unit: adopts a three- or five-bladed wind turbine 1 structure, with a diameter of 0.5–2.0m, and is connected to the input end of the variable speed transmission unit through a drive shaft; the wind turbine 1 can adopt a horizontal or vertical axis design, which can flexibly adapt to different wind direction conditions, realize the efficient capture of natural wind energy, and convert wind energy into rotational mechanical energy.

[0035] The variable speed transmission unit adopts an integrated speed-increasing and speed-changing gearbox 2 structure, which is located between the wind energy capture unit and the rotary friction catalytic unit 4. The output end is connected to the rotary friction catalytic unit 4 for transmission. It is used to increase the rotation speed of the rotating component through the speed-increasing function when the wind speed is too low, and to stabilize the speed through the speed-changing function when the wind speed is too high, so as to ensure that the rotary friction catalytic unit 4 can operate stably in both low-speed and high-speed modes and maintain the best degradation efficiency.

[0036] Rotary friction catalytic unit 4: Located inside the degradation reaction vessel, it includes a rotating component and a fixed component arranged coaxially opposite each other. The rotating component is a disc-shaped or cylindrical rotor, and the fixed component is a stator arranged coaxially opposite to the rotor. The two are in contact or have a controllable micro-pitch of 0.1mm-5mm. In low-speed rotation mode, contact arrangement or micro-pitch of 0.1mm-1mm is preferred, and in high-speed rotation mode, micro-pitch of 1mm-5mm is preferred. The rotating component rotates around the main shaft 10 under wind power, forming continuous relative rotational friction with the fixed component.

[0037] The rotating component has a surface-loaded contact electrocatalytic functional layer, or is integrally formed using a contact electrocatalytic material. The contact electrocatalytic material is selected from one or more of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), fluorinated ethylene propylene copolymer (FEP), polydimethylsiloxane (PDMS), barium titanate (BaTiO3), zinc oxide (ZnO), and titanium dioxide (TiO2). When the functional layer is a continuous and dense thin film structure, the thickness does not exceed 0.15 mm, balancing contact electrochemical signal output and interfacial catalytic activity.

[0038] 4. Droplet forming unit: including a liquid storage tank, a flow control component, and a liquid outlet structure; the liquid outlet structure is selected from any one of a nozzle, capillary, porous liquid distribution head, or centrifugal liquid ejection structure, wherein the orifice diameter of the nozzle or capillary is in the range of 0.5mm-2mm; the droplet forming unit is arranged corresponding to the rotating component of the rotating friction catalysis unit 4, and is used to quantitatively deliver the solution to be treated to the surface of the rotating component, and can be adapted to different rotation speeds of the rotating component to realize dual-mode switching of conventional droplet supply and microdroplet breakage - when rotating at low speed, conventional sewage droplets 9 are output, and when rotating at high speed, the sewage droplets 9 are broken into micron-sized microdroplets with a diameter of 50-500μm under the action of high-speed shearing and centrifugal force of the rotating component.

[0039] 5. Multi-stage degradation unit: It includes 2-5 stages of vertically stacked or horizontally connected rotary friction catalytic units 4 (such as the third-stage reaction chamber 5). Each stage of the unit is sealed and connected by an interstage connecting pipe 11. The solution after being degraded by the previous stage rotary friction catalytic unit 4 flows through the subsequent stages of the unit in sequence, realizing the step-by-step deep degradation of organic pollutants and greatly improving the treatment compliance rate.

[0040] 6. Circulation Unit: A peristaltic pump 8, diaphragm pump, or centrifugal pump with adjustable flow rate is used. The first water outlet pipe 6 at the bottom of the degradation reaction vessel is connected to the first water inlet pipe 7 of the droplet forming unit through a connecting pipeline to realize the closed-loop circulation of the solution to be treated. This allows the solution to repeatedly enter the rotating friction catalytic unit 4 for degradation, prolonging the contact time between pollutants and reactive oxygen species and improving degradation efficiency.

[0041] 7. Optional components: Wind energy storage and conversion unit: It uses capacitors or small lithium batteries to store the electrical energy converted from wind energy for a short period of time, and maintains the normal operation of the circulation unit and control system under conditions of no wind or low wind speed, so as to avoid interruption in the degradation process. The degradation reaction vessel is made of a first acrylic shell 3, stainless steel or engineering plastic, and has the characteristics of corrosion resistance, easy processing and good sealing.

[0042] The liquid outlet structure is positioned directly opposite the non-central area of ​​the rotating component. During low-speed rotation, conventional wastewater droplets 9 can stably adhere to the surface of the rotating component to form a continuous liquid film, ensuring the continuity of solid-liquid-solid three-phase contact friction. During high-speed rotation, the conventional wastewater droplets 9 are instantly torn apart and atomized under the dual action of centrifugal force and interfacial shear force, forming uniform micron-sized microdroplets with diameters of 50μm-500μm, significantly increasing the solid-liquid contact area and significantly enhancing the contact electrocatalytic effect.

[0043] Based on the above system, the present invention also provides a wind-driven rotating triboelectric contact electrocatalytic degradation method, comprising the following steps: S1 Unit Pretreatment: Assemble all components of the unit as required and check the sealing of all connections. Pour the organic pollutant solution to be treated into the degradation reaction vessel to the specified level, start the circulation unit, and run for 5-10 minutes to complete the circulation and emptying of the solution in the pipelines and container, removing air from the system. Adjust the flow parameters of the droplet forming unit to ensure that the solution can be uniformly and stably delivered to the surface of the rotating component.

[0044] S2 Dual-Mode Parameter Presets: Based on historical data of local natural wind speeds, the critical rotation speeds for low-speed and high-speed rotation modes are preset. According to the type and concentration of pollutants to be treated, the spacing between the rotating and stationary components, droplet supply flow rate, and parameters of the contact electrocatalytic functional layer are preset. Through multiple sets of comparative experiments, the reactive oxygen species generation and pollutant degradation efficiency under different parameter combinations are measured to determine the optimal operating parameter combination.

[0045] S3 Wind-Driven Degradation: The wind energy capture unit is activated, and natural wind energy drives the rotating component to rotate via the variable speed transmission unit. When the wind speed is lower than the preset critical wind speed, the device automatically operates in low-speed frictional catalysis mode. At this time, the rotating component rotates at a low speed, and the conventional wastewater droplets 9 supplied by the droplet forming unit adhere to the surface of the rotating component, forming a solid-liquid-solid three-phase friction interface with the stationary component, generating active oxygen species through direct contact friction.

[0046] When the wind speed exceeds the preset critical wind speed, the device automatically switches to high-speed tribocatalytic mode. At this time, the rotating component rotates at a high speed, and the conventional wastewater droplets are broken into micron-sized microdroplets under the combined action of centrifugal force and interfacial shear force. The microdroplets undergo intense interfacial polarization and shear catalysis at the high-speed tribocatalytic interface, increasing the generation of reactive oxygen species by 3-10 times compared to the low-speed mode. These reactive oxygen species continuously attack the conjugated double bonds and amino groups of organic pollutant molecules, triggering oxidative decomposition reactions that gradually degrade organic pollutants into smaller organic molecules, ultimately mineralizing them into carbon dioxide and water.

[0047] S4 Deep Recycling Treatment: The incompletely degraded solution at the bottom of the degradation reaction vessel is returned to the droplet forming unit via the recycling unit, and then repeatedly enters the rotating friction catalytic unit 4 for treatment. The concentration of pollutants in the solution is periodically sampled and tested until the pollutant concentration meets the national or local emission standards, at which point the degradation treatment is complete.

[0048] Example 2: See Figure 1 This embodiment provides a three-stage vertically stacked wind-powered rotary friction contact electrocatalytic degradation system, including: a wind energy capture unit, a speed transmission unit, a multi-stage degradation unit, a droplet forming unit, a main shaft 10, a circulation unit, and connecting pipelines.

[0049] The wind energy capture unit includes a wind turbine 1, which adopts a three-bladed horizontal shaft structure and is made of high-strength engineering plastic. It can adapt to different wind direction conditions in the field and convert natural wind energy into rotational mechanical energy.

[0050] The transmission unit is an integrated speed-increasing and speed-changing gearbox 2, located between the impeller 1 and the main shaft 10. The input end of the gearbox 2 is connected to the output shaft of the impeller 1, and the output end is fixedly connected to the main shaft 10. Under low wind speed conditions, the gearbox 2 performs the speed-increasing function, increasing the low speed of the impeller 1 to the speed required for catalytic conversion; under high wind speed conditions, the gearbox 2 performs the speed-changing and speed-stabilizing function, avoiding excessive speed that could lead to overheating of the friction interface and increased wear, thus ensuring stable operation of the system in both low-speed and high-speed modes.

[0051] The multi-stage degradation unit includes a first-stage reaction chamber, a second-stage reaction chamber, and a third-stage reaction chamber 5. Each stage of the reaction chamber has a conical structure that is wider at the top and narrower at the bottom, which facilitates droplet dispersion and microdroplet formation and reduces droplet adhesion to the wall. Each stage of the reaction chamber is equipped with a rotating friction catalytic unit 4, which includes a rotating component and a stationary component. The rotating component is a disc-shaped rotor, coaxially fixed to the main shaft 10, and the rotor surface is loaded with a 0.1 mm thick polytetrafluoroethylene (PTFE) contact electrocatalytic film. The stationary component is an annular stator coaxially arranged with the rotor and fixed to the inner wall of the reaction chamber. A controllable micro-gap is maintained between the stator and the rotor to accommodate different rotation speeds. A first water outlet pipe 6 is provided at the bottom of the first acrylic shell 3 for discharging the mixed liquid after multi-stage degradation.

[0052] The main shaft 10 is a vertically arranged stainless steel drive shaft that runs through the three-stage reaction chamber from top to bottom. Its upper end is connected to the output end of the gearbox 2, and its lower end is fixed to each stage rotor. It can drive the three-stage rotor to rotate synchronously and realize the multi-stage friction catalysis synergistic operation.

[0053] Each droplet forming unit corresponds to a rotating friction catalytic unit 4 and includes a liquid distribution pipe and a nozzle array, with the nozzles positioned directly opposite the non-central region of the rotor. The droplet forming unit is connected to the circulation unit via an interstage connecting pipe 11, enabling dual-mode liquid distribution based on the rotor speed: at low speeds, conventional droplets are output, which stably adhere to the rotor surface to form a continuous liquid film, creating a solid-liquid-solid three-phase friction interface; at high speeds, the conventional droplets are instantly broken into micron-sized microdroplets under the combined action of centrifugal force and interfacial shear force, increasing the solid-liquid contact area and enhancing the contact electrocatalytic effect.

[0054] The circulation unit uses a peristaltic pump 8. The inlet of the peristaltic pump 8 is connected to the first outlet pipe 6, and the outlet is connected to each stage of droplet forming unit through pipelines, forming a closed-loop circulation circuit. The flow rate of the peristaltic pump 8 is adjustable, which can return incompletely degraded wastewater to each stage of rotating friction catalytic unit 4 for repeated treatment, extending the degradation path and improving pollutant removal efficiency.

[0055] During operation, natural wind energy drives the wind turbine 1 to rotate. Mechanical energy is transmitted to the main shaft 10 after being increased or stabilized by the gearbox 2, driving the three-stage rotor to rotate synchronously. The wastewater to be treated is transported to the first inlet pipe 7 by the peristaltic pump 8 and sprayed onto the rotor surface through the nozzle. The rotor and stator rotate and rub against each other, generating active oxygen species (hydroxyl radicals, superoxide anion radicals, hydrogen peroxide) at the solid-liquid interface, which attack the conjugated double bonds, amino groups and other active sites of organic pollutants, triggering oxidation and decomposition reactions. The wastewater flows through the first, second and third stage degradation units in sequence, undergoing progressively deeper degradation. Wastewater that does not meet the standards flows out from the first outlet pipe 6 and is recycled by the peristaltic pump 8 until the pollutant concentration meets the standards, completing the degradation process.

[0056] Example 3: See Figure 3 This embodiment provides a principle verification device, including: a circulating liquid circuit system, a rotating reaction unit, a power drive unit, a reaction tank body, and an optional photosynthesis unit.

[0057] The circulating liquid circuit system consists of a second acrylic shell 15, a second water inlet pipe 13, and a second water outlet pipe 12. One end of the second water inlet pipe 13 and the second water outlet pipe 12 extend into the reaction tank 20 and the friction catalytic composite pipe assembly 19, respectively, and the other end is connected to the upper side wall of the main body of the reaction tank, forming a wastewater circulation loop to maintain the renewal and homogeneous distribution of the reaction liquid during the reaction process.

[0058] The main body of the reaction tank is a trough-shaped structure that is wider at the top and narrower at the bottom, which reduces the adhesion of liquid droplets. The interior is filled with the wastewater reaction liquid to be degraded, and the upper part of the side wall is reserved with inlet and outlet ports to connect with the liquid circuit system.

[0059] Rotary reaction unit: It consists of a rotating friction reaction disk 17 and a friction catalytic composite tube assembly 19 fixed on the rotating friction reaction disk 17. The surface of the rotating friction reaction disk 17 is provided with a PTFE catalytic film. The friction catalytic composite tube assembly 19 is provided with a first PTFE film 23 and PTFE microspheres 18. When the rotating friction reaction disk 17 rotates, it drives the tube body to rotate together, so that the PTFE microspheres 18 inside the tube and the first PTFE film 23 on the tube wall are rubbed and electrified. At the same time, the disk surface realizes droplet dispersion and interfacial catalytic reaction.

[0060] The power drive unit consists of a base 16 and a servo motor 21. The servo motor 21 is fixedly mounted on the base 16, and its output axis passes through the bottom of the reaction tank body and is connected to the center of the rotating friction reaction disk 17, providing it with controllable rotational power.

[0061] Photosynergistic unit: Composed of light source 22, it is located on the upper outer side of the main body of reaction tank 20 and can provide ultraviolet light or simulated sunlight to enhance the degradation effect of contact electrocatalysis.

[0062] During operation, the servo motor 21 drives the rotating friction reaction disk 17 to rotate. Droplets undergo frictional catalysis with the second PTFE film 26 and PTFE microspheres 18 to generate peroxides, which are then ejected through the orifice 27, forming a wastewater circulation loop. Additionally, under high-speed rotation, the ejected droplets are broken into microdroplets by the rotating friction reaction disk 17, and these microdroplets spontaneously generate peroxides on the first PTFE film 23. The light source 22 simulates the synergistic effect of sunlight on contact electrocatalysis, enhancing the degradation effect of contact electrocatalysis.

[0063] Example 4: Example 4-1: The reaction vessel was a 50cm diameter acrylic funnel-shaped container. A motor was connected to the bottom of the rotating friction unit to maintain a fixed rotation speed. 20ml of deionized water was added to the container, and treatment was carried out under the same environmental conditions and at a fixed rotation speed of 800rpm. The reaction times were set to 20min, 40min, 60min, 80min, 100min, and 120min, with samples taken every 20min. The pH of the samples was adjusted to 7.0-8.0 using potassium phosphate buffer solution, and potassium iodide was used as the colorimetric reagent. Oxidation of I in this buffer environment - I2 is generated, and I2 is combined with excess I. - Combine to form I3 - A characteristic absorption peak appears at wavelengths of 350-420 nm, and the absorbance is similar to... The concentration showed a good linear relationship (R²≥0.998) in the range of 0.05-5 mmol / L. The hydrogen peroxide content was indirectly determined by measuring absorbance after the sample had stood for 4 hours.

[0064] Example 4-2: The reaction vessel was a 50cm diameter acrylic funnel-shaped container. 20mL of deionized water and PTFE microspheres were added to the container. The motor was stopped, and the water and PTFE microspheres were brought into contact and rubbed together solely by gravity. Treatment was conducted under the same environmental conditions for 20min, 40min, 60min, 80min, 100min, and 120min, with samples taken every 20min. The absorbance was measured at wavelengths of 350–420nm using the same potassium phosphate-potassium iodide colorimetric method as in Example 1 to indirectly determine the hydrogen peroxide content in the samples.

[0065] Example 4-3: The reaction vessel is an acrylic funnel-shaped container with a diameter of 50cm. The bottom of the rotating friction unit is connected to a motor to fix the rotation speed. 20ml of deionized water is added to the container, and the reaction is carried out under the same environment and at a fixed rotation speed of 200rpm. The reaction time is set to 20min, 40min, 60min, 80min, 100min and 120min respectively, and a sample is taken every 20min.

[0066] Example 4-4: The reaction vessel was an acrylic funnel-shaped container with a diameter of 50 cm. The bottom of the rotating friction unit was connected to a motor to fix the rotation speed. 20 ml of deionized water was added to the container, and the reaction was carried out under the same environment and at a fixed rotation speed of 400 rpm. The reaction time was set to 20 min, 40 min, 60 min, 80 min, 100 min, and 120 min, and samples were taken every 20 min.

[0067] Examples 4-5: The reaction vessel was an acrylic funnel-shaped container with a diameter of 50 cm. The bottom of the rotating friction unit was connected to a motor to fix the rotation speed. 20 ml of deionized water was added to the container, and the reaction was carried out under the same environment and at a fixed rotation speed of 600 rpm. The reaction time was set to 20 min, 40 min, 60 min, 80 min, 100 min, and 120 min, and samples were taken every 20 min.

[0068] Degradation effect such as Figure 2 As shown.

[0069] From Figures 1-2Experimental results show that the rotary friction contact electrocatalytic device designed in this invention, under the conditions of rotor speed of 800 r / min, stator spacing of 0.5 mm, and friction material of PTFE, after a reaction of 120 min, has an absorbance of 1.16 at 350 nm measured by the KI oxidation method (parallel experimental values ​​were 1.20 and 1.13, with an average of 1.16). Under the same conditions, when the rotating component is removed and the solution flows through the friction layer solely by gravity, the absorbance after the same reaction time is only 0.12. The active oxygen yield under rotary friction conditions is approximately 10 times that under conditions without rotary friction, demonstrating that the rotary friction structure has a significant enhancing effect on the contact electrocatalytic efficiency.

[0070] Based on the above experimental results, unless otherwise specified, the basic experimental parameters of this device are set as follows: rotor speed 800 r / min, stator spacing 0.5 mm, friction material PTFE film, nozzle orifice diameter 1 mm, liquid flow rate 100 mL / min, and reaction time 120 min. At this time, the absorbance at 350 nm measured by the KI oxidation method reaches 1.16, indicating the generation of significant reactive oxygen species in the system. This verifies that the wind-powered rotating frictional contact electrocatalytic device provided by this invention can achieve a highly efficient contact electrocatalytic effect during operation.

Claims

1. A wind-powered rotating triboelectric contact electrocatalytic degradation system, characterized in that, include: Wind energy capture unit, variable speed transmission unit, rotary friction catalysis unit, droplet formation unit, degradation reaction vessel and circulation unit; The wind energy capture unit is connected to the transmission unit and is used to capture natural wind energy and convert it into rotational mechanical energy. The speed transmission unit is connected to the rotary friction catalytic unit and is used to adjust the output speed to adapt to different operating modes of the rotary friction catalytic unit. The rotary friction catalytic unit is located inside the degradation reaction vessel and includes a rotating component and a fixed component arranged coaxially. The rotating component rotates relative to the fixed component under the drive of wind power, and the two form a contact state or a controllable micro-gap state, generating continuous relative rotary friction. The droplet forming unit is arranged in relation to the rotating friction catalytic unit, which is used to quantitatively deliver the pollutant solution to be treated to the surface of the rotating component, and can adapt to different rotation speeds of the rotating component to achieve dual-mode switching between conventional droplet supply and microdroplet breakage. The circulation unit is connected to the outlet of the degradation reaction vessel and the inlet of the droplet forming unit through a pipeline, so as to realize the closed-loop circulation degradation of the polluted solution to be treated. The electrocatalytic degradation system generates a contact electrocatalytic effect at the solid-liquid interface through rotational friction, producing in-situ reactive oxygen species such as hydroxyl radicals, superoxide anion radicals, and hydrogen peroxide, which oxidize and decompose organic pollutant molecules.

2. The wind-driven rotary triboelectric contact electrocatalytic degradation system and method according to claim 1, characterized in that: The controllable micro-pitch range between the rotating component and the fixed component is 0.1mm-5mm; wherein, in the low-speed rotation mode, contact arrangement or a micro-pitch of 0.1mm-1mm is adopted, and in the high-speed rotation mode, a micro-pitch of 1mm-5mm is adopted.

3. The wind-driven rotary triboelectric contact electrocatalytic degradation system according to claim 1, characterized in that, The rotating component has a contact electrocatalytic functional layer loaded on its surface. The material of the contact electrocatalytic functional layer is selected from one or more of the following: fluoropolymer, polytetrafluoroethylene, polyvinylidene fluoride, fluorinated ethylene propylene copolymer, polydimethylsiloxane, barium titanate, zinc oxide, and titanium dioxide. The contact electrocatalytic functional layer is a continuous and dense thin film structure with a thickness not exceeding 0.15 mm.

4. The wind-driven rotary triboelectric contact electrocatalytic degradation system according to claim 1, characterized in that, The droplet forming unit includes a liquid storage tank, a flow control component, and a liquid outlet structure; the liquid outlet structure is selected from any one of a nozzle, a capillary, a porous liquid distribution head, or a centrifugal liquid ejection structure, wherein the orifice diameter of the nozzle or capillary is in the range of 0.5mm-2mm.

5. The wind-driven rotary triboelectric contact electrocatalytic degradation system according to claim 4, characterized in that, The liquid outlet structure is positioned directly opposite the non-central area of ​​the rotating component. During low-speed rotation, conventional droplets stably adhere to the surface of the rotating component to form a continuous liquid film. During high-speed rotation, conventional droplets are broken into micron-sized droplets with diameters of 50μm-500μm under the combined action of centrifugal force and interfacial shear force.

6. The wind-driven rotary triboelectric contact electrocatalytic degradation system according to claim 1, characterized in that, The transmission unit is an integrated speed-increasing and speed-changing gearbox structure, which can increase the rotation speed of the rotating component through the speed-increasing function at low wind speeds and stabilize the output speed through the speed-changing function at high wind speeds, ensuring that both low-speed and high-speed modes can be stably switched and effective friction catalytic efficiency can be maintained.

7. The wind-driven rotary triboelectric contact electrocatalytic degradation system according to claim 1, characterized in that, The degradation reaction vessel is equipped with a multi-stage degradation unit, which adopts a vertical stacking or horizontal series structure. Each stage of the degradation unit is independently equipped with a rotating friction catalysis unit and a droplet forming unit.

8. The wind-driven rotary triboelectric contact electrocatalytic degradation system according to claim 1, characterized in that, The circulation unit is selected from any one of a peristaltic pump, a diaphragm pump, or a centrifugal pump, and has an adjustable flow rate.

9. The wind-driven rotary triboelectric contact electrocatalytic degradation system according to claim 1, characterized in that, It also includes a wind energy storage and conversion unit; the wind energy storage and conversion unit is used to store the electrical energy converted from wind energy and maintain the operation of the device when there is no wind or the wind speed is too low.

10. A wind-powered rotating triboelectric contact electrocatalytic degradation method, characterized in that, Based on the electrocatalytic degradation system according to any one of claims 1-9, the process includes the following steps: S1, Pretreatment of the device: Assemble all components of the device as required, introduce the organic pollutant solution to be treated into the degradation reaction vessel, start the circulation unit, complete the circulation and emptying of the solution in the pipeline and the vessel, and adjust the flow parameters of the droplet forming unit. S2, Dual-mode parameter preset: Based on the local natural wind speed range, preset the critical speed of low-speed rotation mode and high-speed rotation mode, the distance between rotating components and fixed components, the droplet supply flow rate, and the parameters of the contact electrocatalytic functional layer, and determine the optimal combination of working parameters through multiple sets of comparative experiments; S3, Wind-Driven Degradation: The wind energy capture unit is activated, and natural wind energy drives the rotating component to rotate via the variable speed transmission unit. When the wind speed is below the critical wind speed, the device automatically operates in low-speed tribocatalysis mode, where conventional droplets come into contact with the triboelectric interface to generate reactive oxygen species. When the wind speed is above the critical wind speed, the device automatically switches to high-speed tribocatalysis mode, where droplets are broken into microdroplets to enhance the catalytic effect. Reactive oxygen species continuously attack the conjugated double bonds, amino groups, and other active sites of organic pollutants, triggering oxidative decomposition reactions. S4, Deep Recycled Treatment: The incompletely degraded solution is returned to the droplet forming unit through the recycling unit and repeatedly enters the rotating friction catalytic unit for treatment until the pollutant concentration reaches the emission standard, thus completing the degradation treatment.

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