Self-breathing electro-catalytic oxidation water treatment device

Abstract

The application is a self-breathing type electro-catalytic oxidation water treatment device, which comprises a float that floats on the water surface; the lower end of the float is provided with an outer cylinder, an iron mesh cylinder, a middle cylinder and an inner cylinder which are sequentially sleeved; the outer cylinder has hydrophobic characteristics; the middle cylinder has hydrophilic characteristics; the inner cylinder forms a positive potential difference under the condition of being electrified, and electrolyzes the water in contact with it to produce oxygen; the lower end of the inner cylinder is provided with an impeller, and the impeller drives the water flow mixed with oxygen to flow downward; the oxygen flows upward from the cavity between the middle cylinder and the outer cylinder; the outer cylinder captures the oxygen to generate hydrogen peroxide, oxidizes the iron mesh cylinder and releases iron ions; the outer cylinder and the middle cylinder form a potential difference under the condition of being electrified, and the positive and negative electrodes between the outer cylinder and the middle cylinder are periodically switched, so that the iron ions are reduced to ferrous ions, and the ferrous ions are activated with the hydrogen peroxide to generate hydroxyl radicals. Through the self-breathing structure, the internal circulation and utilization of oxygen are realized, and the high-energy consumption aeration system required by the traditional electro-Fenton is completely saved.

Description

Technical Field

[0001] This invention relates to the field of water purification technology, specifically a self-breathing electrocatalytic oxidation water treatment device. Background Technology

[0002] Industries such as pharmaceuticals and aquaculture discharge large amounts of wastewater containing toxic, harmful, or persistent organic pollutants into aquatic environments, causing water pollution. Advanced oxidation processes (such as Fenton and Fenton-like reactions) are generally used to generate reactive oxygen species to effectively degrade pollutants and purify the water environment. However, traditional advanced oxidation processes typically rely on the addition of large amounts of chemical reagents (such as H₂O₂ and persulfate), which not only increases operating costs but also requires complex post-treatment processes, thus limiting the practical application of this technology in large-scale wastewater treatment and reuse. Furthermore, traditional Fenton processes often rely on Fe... 2+ The ion-catalyzed conversion of H₂O₂ into hydroxyl radicals (·OH) requires the additional addition of Fe. 2+ It also produces metal sludge, posing a risk of secondary pollution.

[0003] To address the aforementioned issues, a new process has emerged: electro-Fenton technology combined with electrocatalytic two-electron (2e) technology. - The oxygen reduction reaction (ORR) generates H2O2 in situ, which is further electrochemically activated into hydroxyl radicals (·OH) without the need for external H2O2 addition. Only O2 and H2O are required as reactants, making it a promising green water treatment technology. However, the efficiency of H2O2 generation is highly dependent on the concentration of O2 at the cathode surface. O2 has low solubility in water, and the mass transfer rate from the gas phase to the liquid phase and then to the electrode surface is slow. To maintain a sufficient O2 supply, high-energy-consuming aeration is usually required, which not only significantly increases operating energy consumption but may also lead to ineffective decomposition or side reactions of H2O2 during transport. In large-scale wastewater treatment scenarios, aeration energy consumption can account for more than 60% of the total system energy consumption, severely restricting the economic feasibility and engineering application of this technology. Summary of the Invention

[0004] To address the technical problems in the background art, the present invention discloses a self-breathing electrocatalytic oxidation water treatment device.

[0005] The present invention provides a self-breathing electrocatalytic oxidation water treatment device, including a float that floats on the water surface; The lower end of the pontoon is provided with an outer cylinder, a wire mesh cylinder, a middle cylinder and an inner cylinder that extend vertically from the outside to the inside and are connected in sequence. The outer cylinder has hydrophobic properties; The middle tube has hydrophilic properties; When an electric current is applied to the inner cylinder, a positive potential difference is generated, which electrolyzes the water in contact with it to produce oxygen. An impeller is installed at the lower end of the inner cylinder, and the impeller is connected to the drive motor at the upper end of the float via a rotating shaft; the impeller drives the water mixed with oxygen to flow downward; oxygen flows upward from the cavity between the middle cylinder and the outer cylinder. The outer cylinder captures oxygen to generate hydrogen peroxide, which oxidizes the iron mesh cylinder and releases iron ions; When an electric current is applied, a potential difference is formed between the outer cylinder and the middle cylinder, and the positive and negative electrodes between the outer cylinder and the middle cylinder are periodically switched, reducing iron ions to ferrous ions. The ferrous ions are then activated by hydrogen peroxide to generate hydroxyl radicals.

[0006] Furthermore, a flared-mouth-shaped guide tube is provided at the lower end of the inner cylinder.

[0007] Furthermore, the lower end of the guide tube is positioned such that, in vertical projection, the end of the guide tube is located within the cavity between the outer and middle tubes.

[0008] Furthermore, the iron mesh cylinder, the middle cylinder, and the inner cylinder are located below the liquid surface; The upper end of the outer cylinder is above the liquid surface.

[0009] Furthermore, the upper end of the outer cylinder is sealed to the lower end of the float via a sealing gasket.

[0010] Furthermore, the outer cylinder includes a carbon fiber tube; The carbon fiber tube is composited with carbon nanotubes on both the inner and outer sides, giving it hydrophobic properties.

[0011] Furthermore, the middle tube is made of wood; The middle cylinder is carbonized in the absence of oxygen, giving it hydrophilic properties.

[0012] Furthermore, the inner cylinder is made of stainless steel.

[0013] Furthermore, the positive and negative pole switching frequency between the outer and middle cylinders is 8-10 times per minute.

[0014] Furthermore, solar photovoltaic modules and batteries are installed at the upper end of the pontoon.

[0015] The beneficial effects of this invention are: 1. Oxygen is generated in situ by electrolyzing water in the inner cylinder, and a directional water flow is formed by impeller drive, which promotes the active transport of oxygen from the inner cylinder to the outer cylinder, greatly improving the oxygen concentration and mass transfer efficiency on the cathode surface, and effectively overcoming the bottleneck of low oxygen solubility and slow mass transfer in traditional electro-Fenton technology.

[0016] 2. The self-breathing structure enables internal circulation and utilization of oxygen, completely eliminating the need for the high-energy-consuming aeration system required by traditional electric Fenton systems, thus greatly improving the economic efficiency and engineering application feasibility of the technology.

[0017] 3. The hydrophobic outer cylinder acts as a cathode to efficiently capture oxygen and catalyze the two-electron oxygen reduction reaction to generate hydrogen peroxide in situ. At the same time, by periodically switching the electrode polarity of the outer and middle cylinders, the iron ions are recycled and the hydrogen peroxide is electrochemically activated, continuously generating hydroxyl radicals and forming a highly efficient and stable advanced oxidation system.

[0018] 4. No external chemical reagents such as hydrogen peroxide or iron salts are required during the entire process. Water and oxygen are used as reactants only. Furthermore, the generation of iron sludge in the traditional Fenton process is avoided through the slow release of the iron mesh cylinder and the reduction and regeneration of the electrodes, thus eliminating the risk of secondary pollution from the source.

[0019] 5. It can utilize oxygen in water to generate hydroxyl radicals and reduce iron ions in water to ferrous ions, thus achieving iron recycling and higher purification efficiency.

[0020] 6. The device adopts a floating modular design and can be directly deployed in natural water bodies or wastewater ponds without the need for complex infrastructure, resulting in lower costs.

[0021] 7. It consumes only electricity to achieve efficient degradation of pollutants. The overall process is clean and environmentally friendly, which is in line with the development direction of green water treatment technology. Attached Figure Description

[0022] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0023] Figure 1 This is a schematic diagram of the structure of the present invention; Figure 2 This is a top view of the present invention; Figure 3 yes Figure 2 Sectional view of AA; Figure 4 yes Figure 3 Enlarged view of point B in the middle; Figure 5 yes Figure 3 Enlarged view of point C in the middle; In the diagram: 1. Float; 2. Outer cylinder; 3. Mesh cylinder; 4. Middle cylinder; 5. Inner cylinder; 6. Shaft; 7. Drive motor; 8. Sealing gasket; 9. Solar photovoltaic module; 10. Battery; 11. Inner connecting rod; 12. Bearing housing; 13. Bearing; 14. Middle connecting rod; 15. Outer connecting rod; 16. Impeller; 17. First battery; 18. Second battery; 21. Outer mounting ring; 31. Iron mounting ring; 41. Middle mounting ring; 51. Guide Flow tube; 52. Inner mounting ring; 101. First recessed platform; 102. Second recessed platform; 103. First mounting plate; 104. Second mounting plate; 105. Third recessed platform; 106. Third mounting plate; 171. First wire; 181. Second wire; 182. Third wire; 183. Fourth wire; 184. Fifth wire; 185. Second switch; 186. Third switch; 187. Fourth switch; 188. Fifth switch. Detailed Implementation

[0024] The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic diagrams, illustrating only the basic structure of the invention, and therefore only show the components relevant to the invention.

[0025] like Figure 1-5 As shown, the present invention discloses a self-breathing electrocatalytic oxidation water treatment device, including a float 1 floating on the water surface. The lower end of the float 1 is provided with a stepped first recess 101 and a second recess 102, wherein the second recess 102 is higher than the first recess 101.

[0026] The lower end of the pontoon 1 is provided with a vertically extending outer cylinder 2, a wire mesh cylinder 3, a middle cylinder 4, and an inner cylinder 5, which are sequentially nested from the outside to the inside. The specific installation structure is as follows: A second mounting plate 104 is fixed to the surface of the second recessed platform 102 by welding or integral injection molding. The second mounting plate 104 has three layers of threaded holes, each forming a circle with concentric circles of different radii. The inner threaded hole is threaded to the upper end of the inner connecting rod 11. The lower end of the inner connecting rod 11 passes through the inner mounting ring 52 extending radially outward from the upper end of the inner cylinder 5, and is locked in place by a nut threaded to the lower end of the inner mounting ring 52 and connected to the lower end of the inner connecting rod 11. The middle threaded hole is threaded to the upper end of the middle connecting rod 14. The lower end of the middle connecting rod 14 passes through the middle mounting ring 41 extending radially outward from the upper end of the middle cylinder 4, and is locked in place by a nut threaded to the lower end of the middle mounting ring 41 and connected to the lower end of the middle connecting rod 14. The outer threaded hole is threaded to the upper end of the outer connecting rod 15. The lower end of the outer connecting rod 15 passes through the upper end of the iron mesh cylinder 3 and extends radially outward through the iron mounting ring 31. It is then locked and fixed by a nut located at the lower end of the iron mounting ring 31 and threaded to the lower end of the outer connecting rod 15. The inner connecting rod 11, the middle connecting rod 14, the outer connecting rod 15, and the nut threaded to the connecting rod are all made of insulating material; in this embodiment, the material is ceramic. The arrangement of the inner connecting rod 11, the middle connecting rod 14, and the outer connecting rod 15 ensures that the inner cylinder 5, the middle cylinder 4, and the iron mesh cylinder 3 are below the liquid surface.

[0027] A first mounting plate 103 is fixed to the surface of the first recess 101 by welding or integral injection molding. The first mounting plate 103 has four evenly distributed threaded holes. An outer mounting ring 21 extending radially outward is provided at the upper end of the outer cylinder 2. Bolts pass through the outer mounting ring 21 and are threaded into the threaded holes on the first mounting plate 103 to secure the outer cylinder 2. The first recess 101 ensures that the upper end of the outer cylinder 2 is above the liquid surface. A sealing gasket 8 is assumed between the first mounting plate 103 and the outer mounting ring for a sealed connection between the outer cylinder 2 and the float 1.

[0028] The inner cylinder 5, the middle cylinder 4, and the iron mesh cylinder 3 are located below the liquid surface, and under the action of the connecting rod, they form a cavity with the lower end face of the float. The outer cylinder 2 is sealed to the float 1, blocking the outside of the cavity. As a result, when the impeller 16 rotates, the water between the middle cylinder 4 and the inner cylinder 5, and the water between the middle cylinder 4 and the outer cylinder 2, flows upward to the upper side of the inner cylinder 5, then flows downward from the upper side of the inner cylinder 5, and finally flows into the river channel from the lower end of the inner cylinder 5.

[0029] The outer cylinder 2 comprises carbon fiber tubes, which are composited with carbon nanotubes on their inner and outer surfaces through surface grafting, impregnation, or electrophoretic deposition to give them hydrophobic properties. The middle cylinder 4 is made of wood-based carbonized material; in this embodiment, pine wood is used, which is carbonized in the absence of oxygen for 10-20 hours to achieve a hydrophilic surface. The inner cylinder 5 is made of stainless steel.

[0030] A vertically extending shaft 6 is installed inside the middle cylinder 4. The lower end of the shaft 6 extends to the lower end of the middle cylinder 4 and is fitted with an impeller 16; the upper end of the shaft 6 extends above the float 1. The float 1 has a through hole penetrating both the upper and lower sides. A recessed third platform 105 is provided at the upper end of the through hole. A third mounting plate 106 is fixed on the platform of the third platform 105 by welding or integral injection molding. A bearing seat 12 is inserted downward into the through hole and is fixedly connected to the third mounting plate 106. Bearings 13 are arranged vertically and horizontally within the bearing seat 12, and the upper end of the shaft 6 is inserted into the bearing 13. A drive motor 7 (a geared motor) is fixedly installed at the upper end of the float 1. The drive end of the drive motor 7 is fixedly connected to the upper end of the shaft 6, thereby driving the shaft 6 to rotate and causing the impeller 16 to rotate. When the impeller 16 rotates, it drives the water flow downward.

[0031] The upper end of the pontoon 1 is also equipped with a solar photovoltaic module 9, a storage battery 10, and a power source. The solar photovoltaic module 9 converts solar energy into electrical energy to power the power source and the geared motor, and the remaining electricity is used to charge the storage battery 10. When there is no sunlight, the storage battery 10 powers the geared motor and the power source.

[0032] The power supply includes a first battery 17 and a second battery 18 connected in series. In this embodiment, both the first battery 17 and the second battery 18 are 30V. The negative terminal of the first battery 17 is electrically connected to the positive terminal of the second battery 18. The positive terminal of the first battery 17 is electrically connected to the inner cylinder 5 via a first wire 171. A second wire 181 connects the middle cylinder 4 to the positive terminal of the second battery 18, and a third wire 182 connects the middle cylinder 4 to the negative terminal of the second battery 18. A fourth wire 183 connects the outer cylinder 2 to the positive terminal of the second battery 18, and a fifth wire 184 connects the outer cylinder 2 to the negative terminal of the second battery 18. A second switch 185, a third switch 186, a fourth switch 187, and a fifth switch 188 are respectively installed on the second wire 181, the third wire 182, the fourth wire 183, and the fifth wire 184.

[0033] When energized, the inner cylinder 5 generates a potential difference of +60V, which electrolyzes the water in contact with it to produce oxygen. The oxygen generated on the outside of the inner cylinder 5 increases the dissolved oxygen in the water, while the oxygen generated on the inside forms bubbles that flow downwards under the action of the impeller 16. When the bubbles detach from the inner cylinder 5, they enter the area between the middle cylinder 4 and the outer cylinder 2 and float to the surface in this area, generating hydrogen peroxide.

[0034] The second switch 185 and the fifth switch 188 open and close simultaneously, as do the third switch 186 and the fourth switch 187. When the second switch 185 and the fifth switch 188 are open, the third switch 186 and the fourth switch 187 are closed, creating a +30V potential difference between the middle cylinder 4 and the inner cylinder 5. When the second switch 185 and the fifth switch 188 are closed, the third switch 186 and the fourth switch 187 are open, creating a -30V potential difference between the middle cylinder 4 and the outer cylinder 2. By alternately opening and closing the switches, the potential difference between the middle cylinder 4 and the outer cylinder 2 is switched alternately, achieving Fe 2+ and Fe 3+ The potential difference between the inner cylinder 4 and the outer cylinder 2 alternates at a frequency of 8-10 times per minute. The purpose of this setting is: 1. To enhance Fe... 2+ and Fe 3+ 1. Electrochemical cycling; 2. Inhibiting electrode passivation and iron sludge accumulation; 3. Improving the spatial and temporal distribution uniformity of •OH; 4. Extending the lifespan of the iron electrode (iron mesh cylinder 3); 5. Achieving an electro-Fenton system without added iron salts.

[0035] To ensure that bubbles can stably rise from the area between the middle cylinder 4 and the outer cylinder 2, a funnel-shaped guide tube 51 is provided at the lower end of the inner cylinder 5. The diameter of the lower end of the guide tube 51 is larger than the inner diameter of the middle cylinder 4 but smaller than the outer diameter of the outer cylinder 2, so that in the vertical projection, the end of the guide tube 51 is located in the cavity between the outer cylinder 2 and the middle cylinder 4. In this configuration, the guide tube 51 guides the bubbles.

[0036] The working principle of this embodiment is as follows: 1. The outer cylinder 2 serves as an oxygen capture electrode. Utilizing the superhydrophobic microporous structure of this electrode, oxygen generated by the inner cylinder 5 as an anode is efficiently captured and used for the synthesis of hydrogen peroxide (H2O2).

[0037] 2. Under the influence of electricity, the oxygen generated in the inner cylinder 5 moves downward with the water propelled by the impeller 16. After passing through the guide tube 51, the water flow velocity decreases, and the bubbles move upward. Under the guidance of the guide tube 51, they flow into the space between the outer cylinder 2 and the middle cylinder 4. The oxygen is utilized by the outer cylinder 2 to form hydrogen peroxide. The iron mesh cylinder 3 between the outer cylinder 2 and the middle cylinder 4 is slowly oxidized in an oxidizing environment, releasing iron ions. The iron ions move between the outer cylinder 2 and the middle cylinder 4, taking advantage of the hydrophilic properties of the middle cylinder 4 to fully contact the iron ions. During the periodic pulses of the electrode voltage, the iron ions are reduced to ferrous ions. The ferrous ions react with hydrogen peroxide to generate hydroxyl radicals, thus reducing surface iron deposition and achieving periodic self-renewal of the electrodes.

[0038] Therefore, the functions of the three electrodes are: the inner cylinder 5 generates oxygen, the outer cylinder 2 captures and combines oxygen to generate hydrogen peroxide, and the middle cylinder 4 reduces and desorbs iron ions, promoting ferrous ions to participate in the activation of hydrogen peroxide to generate hydroxyl radicals.

[0039] During operation, the power supply to the three coaxial electrodes is turned on, and the impeller 16 is started to make the water flow, thus completing the oxidation of organic matter.

[0040] Compared to existing technologies, the advantages of this embodiment are: 1. Oxygen is generated in situ by electrolyzing water in the inner cylinder 5, and a directional water flow is formed by driving the impeller 16, promoting the active transport of oxygen from the inner cylinder 5 to the outer cylinder 2, significantly improving the oxygen concentration and mass transfer efficiency on the cathode surface, and effectively overcoming the bottlenecks of low oxygen solubility and slow mass transfer in traditional electro-Fenton technology. 2. The internal circulation and utilization of oxygen is achieved through a self-breathing structure, completely eliminating the high-energy-consuming aeration system required by traditional electro-Fenton, greatly improving the economic efficiency and engineering feasibility of the technology. 3. The hydrophobic outer cylinder 2 acts as the cathode to efficiently capture oxygen and catalyze the two-electron oxygen reduction reaction (2e). - The ORR (Organic Oxidation Reduction) process generates hydrogen peroxide in situ. Simultaneously, by periodically switching the electrode polarity between the outer cylinder 2 and the middle cylinder 4, it achieves the cyclic regeneration of iron ions and the electrochemical activation of hydrogen peroxide, continuously generating hydroxyl radicals and forming a highly efficient and stable advanced oxidation system. 4. The entire process requires no external addition of hydrogen peroxide, iron salts, or other chemical reagents; only water and oxygen are used as reactants. Furthermore, the slow release through the iron mesh cylinder 3 and electrode reduction regeneration avoid the generation of iron sludge in traditional Fenton processes, eliminating the risk of secondary pollution at the source. 5. It can utilize oxygen in the water to generate hydroxyl radicals and reduce iron ions in the water to ferrous ions, achieving iron recycling and higher purification efficiency. 6. The device adopts a floating modular design and can be directly deployed in natural water bodies or wastewater ponds, requiring no complex infrastructure and resulting in lower costs. 7. It consumes only electricity, achieving highly efficient degradation of pollutants. The overall process is clean and environmentally friendly, aligning with the development direction of green water treatment technology.

[0041] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A self-breathing electrocatalytic oxidation water treatment device, characterized in that: Including pontoons floating on the water surface (1); The lower end of the pontoon (1) is provided with an outer cylinder (2), an iron mesh cylinder (3), a middle cylinder (4) and an inner cylinder (5) that extend vertically from the outside to the inside and are connected in sequence. The outer cylinder (2) has hydrophobic properties; The middle cylinder (4) has hydrophilic properties; When the inner cylinder (5) is energized, it forms a positive potential difference and electrolyzes the water in contact with it to produce oxygen. An impeller (16) is provided at the lower end of the inner cylinder (5). The impeller (16) is connected to the drive motor (7) at the upper end of the float (1) via a rotating shaft (6). The impeller (16) drives the water mixed with oxygen to flow downward. Oxygen flows upward from the cavity between the middle cylinder (4) and the outer cylinder (2). The outer cylinder (2) captures oxygen to generate hydrogen peroxide, which oxidizes the iron mesh cylinder (3) and releases iron ions; When the outer cylinder (2) and the middle cylinder (4) are energized, a potential difference is formed, and the positive and negative electrodes between the outer cylinder (2) and the middle cylinder (4) are periodically switched to reduce iron ions to ferrous ions. The ferrous ions are activated by hydrogen peroxide to generate hydroxyl radicals.

2. The self-breathing electrocatalytic oxidation water treatment device according to claim 1, characterized in that: The lower end of the inner cylinder (5) is provided with a guide tube (51) with a flared mouth structure.

3. The self-breathing electrocatalytic oxidation water treatment device according to claim 2, characterized in that: The lower end of the guide tube (51) is positioned such that, in vertical projection, the end of the guide tube (51) is located in the cavity between the outer tube (2) and the middle tube (4).

4. The self-breathing electrocatalytic oxidation water treatment device according to claim 1, characterized in that: The iron mesh cylinder (3), the middle cylinder (4) and the inner cylinder (5) are located below the liquid surface; The upper end of the outer cylinder (2) is above the liquid surface.

5. The self-breathing electrocatalytic oxidation water treatment device according to claim 4, characterized in that: The upper end of the outer cylinder (2) is sealed to the lower end of the float (1) through a sealing gasket (8).

6. The self-breathing electrocatalytic oxidation water treatment device according to claim 1, characterized in that: The outer cylinder (2) includes a carbon fiber tube; The carbon fiber tube is composited with carbon nanotubes on both the inner and outer sides, giving it hydrophobic properties.

7. The self-breathing electrocatalytic oxidation water treatment device according to claim 1, characterized in that: The material of the middle cylinder (4) is wood; The middle cylinder (4) is carbonized under oxygen-isolated conditions to give it hydrophilic properties.

8. The self-breathing electrocatalytic oxidation water treatment device according to claim 1, characterized in that: The inner cylinder (5) is made of stainless steel.

9. The self-breathing electrocatalytic oxidation water treatment device according to claim 1, characterized in that: The positive and negative pole switching frequency between the outer cylinder (2) and the middle cylinder (4) is 8-10 times per minute.

10. The self-breathing electrocatalytic oxidation water treatment device according to claim 1, characterized in that: The upper end of the pontoon (1) is equipped with a solar photovoltaic module (9) and a storage battery (10).

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