Method for electrolytic hydrogen production coupled with wastewater oxidation treatment and device therefor

Abstract

The application discloses a method and device for electrolytic hydrogen production coupled with wastewater oxidation treatment. The wastewater raw material is subjected to electrolytic oxidation reaction in a first reaction zone, and then subjected to ozone oxidation and ultraviolet photolysis reaction in a second reaction zone, and circulates in the first reaction zone and the second reaction zone. After the wastewater treated in the second reaction zone meets the electrolytic oxidation or electrolytic hydrogen production requirement of a third reaction zone, the wastewater flows into the third reaction zone for electrolytic oxidation or electrolytic hydrogen production treatment. The application realizes the effect of deep wastewater treatment by combining electrolytic oxidation with ozone oxidation and ultraviolet photolysis, and realizes the detachability of the ultraviolet lamp, thereby greatly prolonging the service life of the wastewater treatment device.

Description

Technical Field

[0001] This invention relates to the field of electrochemical wastewater treatment, specifically to a method and apparatus for treating wastewater by electrolysis coupled with oxidation. Background Technology

[0002] The basic principle of electrochemical oxidation technology is that, under the influence of an external electric field in a specific electrochemical reactor, strong oxidants such as hydroxyl radicals (·OH) are typically generated, which then degrade pollutants in wastewater through chemical reactions, electrochemical processes, or physical processes. Electrochemical oxidation, as an environmentally friendly technology, has been widely researched and applied in the treatment of some recalcitrant pollutants. As a clean treatment process, electrochemical electrolysis is highly flexible and can be used alone or in combination with other treatment methods.

[0003] Electrochemical oxidation does not require the addition of oxidants and can generally be carried out at room temperature and pressure. The reaction process has functions such as degradation, flotation, flocculation, and sterilization. Its advantages include simple operation, strong controllability, economic applicability, mild reaction conditions, no secondary pollution, and minimal environmental impact. However, its disadvantages include low energy efficiency, low electrolysis efficiency, and short electrode lifespan. For different types and levels of organic wastewater with varying degrees of pollution, combining electrochemistry with other water treatment technologies can effectively improve treatment results and reduce energy consumption and costs. Therefore, preliminary treatment is generally performed through electrolytic oxidation, followed by further treatment through ozone reaction and ultraviolet photolysis before discharge.

[0004] Currently, there are two main problems with the treatment of wastewater using electrolytic oxidation combined with ozone and ultraviolet light. First, the wastewater often cannot be treated effectively in a single reaction, and there is also a mixture of treated and fresh wastewater, resulting in incomplete treatment and low efficiency. Second, when combined with ultraviolet photolysis to treat wastewater, the ultraviolet lamps need to be replaced frequently to maintain treatment efficiency, which affects the usability and lifespan of the electrolytic wastewater treatment device.

[0005] Chinese invention CN102863110B discloses an integrated device and method for treating recalcitrant organic wastewater. It utilizes the synergistic effect of coupling between electrochemical catalysis, sonochemical catalysis, photocatalysis, and catalytic ozonation technologies to significantly improve treatment efficiency. However, because its device structure does not employ a partitioned design, fresh wastewater and treated wastewater inevitably mix during the treatment process, leading to reduced treatment efficiency and failing to achieve optimal treatment results.

[0006] Chinese invention CN202010470410.8 discloses a multi-stage internal circulation controllable electrolytic coupling oxidation treatment device for wastewater. This device combines ozone and ultraviolet photolysis with electrolysis to effectively degrade recalcitrant organic matter. However, both the vertical pipe and the ultraviolet lamp are fixed structures, making the device unremovable after the ultraviolet lamp is damaged. Furthermore, the device injects wastewater into a container through a bottom inlet, then into the inner tube through an inlet hole. The wastewater reacts with ozone and undergoes ultraviolet photolysis before flowing out through an outlet pipe. However, because the wastewater initially accumulates in the container after injection, only a portion enters the inner tube for reaction. The reacted liquid then remixes with the wastewater after flowing out of the outlet, resulting in poor treatment efficiency.

[0007] Chinese invention patent CN202010470409.5 discloses an electrolytic coupling oxidation wastewater treatment device that can simultaneously achieve ozone oxidation, ultraviolet photocatalysis, and electrolytic oxidation. Compared with traditional equipment, it has the advantage of simple operation when achieving the same treatment effect. By adding a guide plate inside the container and setting external and internal electrodes respectively, hydrogen and oxygen are produced by electrolysis after the wastewater enters, further realizing the oxidation treatment of wastewater and improving working efficiency. However, it also has the problem of difficulty in replacing ultraviolet lamps. Moreover, the wastewater often does not achieve the desired effect in one reaction. The device only supports the discharge of liquid after one reaction. Due to the guide design of the device, water needs to be continuously injected into the interior for the water to be discharged. This will result in the mixing of wastewater and reaction water, which does not meet the expected environmental protection technology requirements. Summary of the Invention

[0008] The purpose of this invention is to provide a method and apparatus for treating wastewater by electrolysis coupled with oxidation, in order to solve the technical problems of mixing fresh wastewater and treated wastewater in the prior art, and the fact that the ultraviolet lamp cannot be disassembled.

[0009] To achieve the above objectives, the present invention provides a method for treating wastewater by electrolytic hydrogen production coupled with oxidation. The wastewater raw material first undergoes electrolytic oxidation in a first reaction zone, and then undergoes ozone oxidation and ultraviolet photolysis in a second reaction zone. The wastewater circulates between the first and second reaction zones. Once the wastewater treated in the second reaction zone meets the requirements for electrolytic oxidation or electrolytic hydrogen production in the third reaction zone, it flows into the third reaction zone for further electrolytic oxidation or electrolytic hydrogen production.

[0010] The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to the present invention uses wastewater as raw material, which is recalcitrant and highly concentrated sewage. The type of sewage is not specifically limited. Preferably, the wastewater raw material contains one or more of the following: phenols and phenolic derivatives, aromatic amines, halogenated compounds, nitro compounds, hydroxy acid compounds, and reactive dyes.

[0011] The method for treating wastewater by electrolytic hydrogen production coupled with oxidation, as described in this invention, does not specifically limit the current density range during electrolytic oxidation. Those skilled in the art can make conventional adjustments based on the actual wastewater raw materials, treatment conditions, and electrode selection. Preferably, in this invention, electrolytic oxidation is performed in the first and third reaction zones by setting internal and external electrodes. The internal electrode is a stainless steel electrode, and the external electrode is a titanium plate electrode. The current density range is 8-20 mA / cm². 2 In the third reaction zone, hydrogen production can also be carried out by electrolysis. When producing hydrogen by electrolysis, those skilled in the art can determine the current density based on conventional technical knowledge in the field and with reference to the type of electrode selected. This application does not impose any special limitations.

[0012] In the method for treating wastewater by electrolytic hydrogen production coupled with oxidation described in this invention, the concentration range of ozone is not specifically limited during ozone oxidation. Those skilled in the art can make conventional adjustments based on the actual wastewater raw materials and treatment conditions. Preferably, the ozone concentration in the second reaction zone is 10-20 mg / L.

[0013] The method for treating wastewater by electrolytic hydrogen production coupled with oxidation described in this invention does not impose specific limitations on the residence time of wastewater in each reaction zone. Those skilled in the art can make conventional adjustments based on actual treatment conditions. Preferably, the residence time of the wastewater raw material in the first, second, and third reaction zones is 2-20 minutes.

[0014] To achieve the above objectives, the present invention also provides an apparatus for treating wastewater by electrolytic hydrogen production coupled with oxidation, the apparatus comprising a first reaction zone, a second reaction zone, and a third reaction zone, wherein a first electrolytic oxidation device is provided in the first reaction zone, an ozone oxidation and ultraviolet photolysis device is provided in the second reaction zone, and a second electrolytic oxidation device or an electrolytic hydrogen production device is provided in the third reaction zone, wherein the ozone oxidation and ultraviolet photolysis device is provided with a steerable connecting hole for communicating with the first reaction zone or the third reaction zone.

[0015] The device for electrolytic hydrogen production coupled with oxidation to treat wastewater according to the present invention has a detachable ultraviolet photolysis device.

[0016] This invention discloses an electrolytic hydrogen production coupled with oxidation wastewater treatment device, comprising a treatment container. The treatment container has a first reaction zone with a waste liquid inlet pipe on one side and a third reaction zone with a water outlet pipe on the other, with a second reaction zone in the middle. Both the first and second reaction zones are equipped with guide plates connected to the top cover of the treatment container. The guide plates are equipped with aerators and internal electrodes. External electrodes are located on the inner wall of the treatment container. A cylinder and a gas inlet pipe are fixedly connected to the upper surface of the bottom plate of the treatment container corresponding to the second reaction zone. The outlet of the gas inlet pipe is located inside the cylinder, on the side wall of the cylinder on the side of the first reaction zone. The container is provided with an inlet port; the top cover of the processing container corresponding to the second reaction zone is provided with a cover opening, a rotating cover is provided in the cover opening, a tube is provided on the lower surface of the rotating cover, a detachable conduit is provided in the tube, a vertical groove is provided on the inner side wall of the conduit, and a through-hole is provided on the other side wall of the conduit opposite to the groove, one end of a disassembly plate is slidably connected in the groove, and the other end is fixed to the conduit by a cross torsion bar set in the through-hole, a detachable ultraviolet lamp is provided on the lower surface of the disassembly plate, the ultraviolet lamp is located in the conduit, and the lower end of the conduit is located in the cylinder and is sealed to the cylinder.

[0017] The electrolytic hydrogen production coupled with oxidation wastewater treatment device of the present invention has a guide groove on the inner wall of the insert and a slot on the outer wall of the conduit. The guide groove has a vertical abutment and a rotating tube perpendicular to the abutment. A first spring is fixedly connected to the bottom of the guide groove. The first spring is located on one side of the abutment and close to the inner side of the guide groove. One end of a second spring is fixedly connected to the other side surface of the abutment. The other end of the second spring is fixedly connected to a locking block adapted to the slot. A push block is fixedly connected to the top of the first spring. A pull rope is fixedly connected to the top of the push block. The pull rope is wound around the rotating tube and passes through the abutment and the second spring and is fixedly connected to the locking block.

[0018] The electrolytic hydrogen production coupled with oxidation wastewater treatment device of the present invention has a first air bladder at the bottom of the conduit for sealing the conduit and the cylinder.

[0019] The electrolytic hydrogen production coupled oxidation wastewater treatment device of the present invention has a linkage block connected below the cross torsion bar, and a second airbag and a third spring fixedly connected below the linkage block, wherein the second airbag is connected to the first airbag.

[0020] The wastewater treatment device for electrolytic hydrogen production coupled with oxidation according to the present invention has an internal electrode and an external electrode on the waste liquid inlet pipe side as an electrolytic oxidation electrode, and an internal electrode and an external electrode on the outlet pipe side as an electrolytic oxidation electrode or an electrolytic hydrogen production electrode.

[0021] The electrolytic hydrogen production coupled with oxidation wastewater treatment device of the present invention has the liquid inlet located on the lower side wall of the cylinder.

[0022] The electrolytic hydrogen production coupled with oxidation wastewater treatment device of the present invention has an external electrode provided on the side wall of the cylinder.

[0023] In the electrolytic hydrogen production coupled oxidation wastewater treatment device of the present invention, both the waste liquid inlet pipe and the water outlet pipe are located on the upper side wall of the treatment container.

[0024] The wastewater treatment device for electrolytic hydrogen production coupled with oxidation according to the present invention has a drain pipe on the top cover.

[0025] The wastewater treatment device for electrolytic hydrogen production coupled with oxidation according to the present invention has a filter screen installed in the waste liquid inlet pipe for preliminary filtration of the waste liquid.

[0026] The electrolytic hydrogen production coupled with oxidation wastewater treatment device of the present invention has casters on the lower surface of the bottom plate of the treatment container.

[0027] The beneficial effects of this invention are:

[0028] The device of this invention has a small footprint and compact structure, and is suitable for the deep treatment of recalcitrant wastewater, including domestic wastewater and industrial wastewater such as chemical, pharmaceutical, and metallurgical wastewater. Specifically, it has the following advantages:

[0029] 1. The electrolytic hydrogen production coupled with oxidation wastewater treatment device provided by this invention divides the device into three treatment zones: the first treatment zone is for electrolytic oxidation of wastewater, the second treatment zone is for ozone oxidation and ultraviolet photolysis of wastewater, and the third treatment zone is for electrode oxidation or electrolytic hydrogen production of the treated wastewater. The wastewater can be repeatedly circulated between the first and second treatment zones through a detachable and rotatable conduit component and a bayonet design in the second treatment zone, achieving optimal treatment results and avoiding mixing of treated and fresh wastewater.

[0030] 2. The electrolytic hydrogen production coupled oxidation wastewater treatment device provided by the present invention has a hydrogen production function while electrolytically oxidizing wastewater. When the electrode in the third reaction zone is a hydrogen production electrode, the treated liquid entering the third reaction zone can be electrolyzed to produce hydrogen under the action of the electrode.

[0031] 3. The electrolytic hydrogen production coupled oxidation wastewater treatment device provided by the present invention has an overall detachable structure in the second treatment zone, which allows the ultraviolet lamps to be replaced regularly, maintaining the efficiency of ultraviolet photolysis wastewater treatment and extending the service life of the entire device.

[0032] 4. The electrolytic hydrogen production coupled oxidation wastewater treatment device provided by the present invention has a simple structure in the first reaction zone and the third reaction zone. After the entire detachable structure of the second reaction zone is disassembled, the inside of the device can be cleaned easily and conveniently.

[0033] 5. The electrolytic hydrogen production coupled oxidation wastewater treatment device provided by the present invention has an airbag system in the second treatment zone. When the disassembly plate moves downward, it will drive the linkage block to move downward, thereby squeezing the second airbag and inputting the gas inside the second airbag into the first airbag through the air pipe. This will inflate the first airbag and make it contact the inner wall of the cylinder, which can further increase the sealing performance. Attached Figure Description

[0034] Figure 1 This is a schematic diagram of the structure of the electrolytic hydrogen production coupled with oxidation wastewater treatment device of the present invention:

[0035] Figure 2 This is a side view of the catheter described in this invention;

[0036] Figure 3 This is a top view of the catheter described in this invention;

[0037] Figure 4 yes Figure 1 A magnified structural diagram of point A in the middle.

[0038] In the attached figures, the following labels are used:

[0039] 1. Processing container; 2. Cover; 3. Rotating cover; 4. Insert; 5. Guide tube; 6. Slot; 7. Guide groove; 8. Support plate; 9. Rotating tube; 10. First spring; 11. Push block; 12. Pull rope; 13. Second spring; 14. Slot; 15. Slide groove; 16. Slot; 17. Disassembly plate; 18. Cross torsion bar; 19. Ultraviolet lamp; 20. Cylinder; 21. Second airbag; 22. Linkage block; 23. Third spring; 24. Air pipe; 25. First airbag; 26. Gas inlet pipe; 27. Guide plate; 28. Aerator; 29. ​​Internal electrode; 30. External electrode; 31. Waste liquid inlet pipe; 32. Water outlet pipe; 33. Liquid inlet hole; 34. Drain pipe; 35. Casters. Detailed Implementation

[0040] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0041] Figure 1 This is a schematic diagram of the structure of the wastewater treatment device for electrolytic hydrogen production coupled with oxidation according to the present invention. Figure 3This is a top view of the catheter described in this invention. Please refer to... Figure 1 and Figure 3 The electrolytic hydrogen production coupled oxidation wastewater treatment device provided by the present invention includes a treatment container 1. The treatment container 1 has a first reaction zone with a waste liquid inlet pipe 31 on one side and a third reaction zone with a water outlet pipe 32 on the other. A second reaction zone is located in the middle. Both the first and second reaction zones are equipped with guide plates 27 connected to the top cover of the treatment container 1. The guide plates 27 are equipped with aerators 28 and internal electrodes 29. An external electrode 30 is provided on the inner wall of the treatment container 1. A cylinder 20 and a gas inlet pipe 26 are fixedly connected to the upper surface of the bottom plate of the treatment container 1 corresponding to the second reaction zone. The outlet of the gas inlet pipe 26 is located inside the cylinder 20. A liquid inlet hole is provided on the side wall of the cylinder 20 located on the side of the first reaction zone. 33; The top cover of the processing container 1 corresponding to the second reaction zone is provided with a cover opening 2, and a rotating cover 3 is provided in the cover opening 2. A tube 4 is provided on the lower surface of the rotating cover 3. A detachable conduit 5 is provided inside the tube 4. A sliding groove 15 is provided vertically on the inner side wall of the conduit 5. A through-hole 16 is provided on the other side wall of the conduit 5 opposite to the sliding groove 15. One end of a disassembly plate 17 is slidably connected in the sliding groove 15. The other end is fixed to the conduit 5 by a cross torsion bar 18 provided in the through-hole 16. A detachable ultraviolet lamp 19 is provided on the lower surface of the disassembly plate 17. The ultraviolet lamp 19 is located inside the conduit 5. The lower end of the conduit 5 is located inside the cylinder 20 and is sealed to the cylinder 20.

[0042] In this invention, those skilled in the art can routinely adjust the positions of the exposing device 28 and the internal electrode 29 on the guide plate 27 according to the specific shape of the guide plate 27. In a specific embodiment of this invention, the guide plate 27 is elongated, with its bottom end close to the upper surface of the bottom plate of the processing container 1. The internal electrode 29 is located on both sides of the guide plate 27, and the exposing device 28 is located at the bottom of the guide plate 27.

[0043] In this invention, the outer wall of the cylinder 20 is in close contact with the front and rear walls of the treatment container 1, dividing the internal space of the treatment container 1 into a first reaction zone and a third reaction zone. The sizes of the first and third reaction zones can be determined according to actual conditions. The cross-sectional shape of the inner wall of the cylinder 20 is circular so as to form a tight contact with the outer wall of the circular conduit 5. The cross-sectional shape of the outer wall of the cylinder 20 can be any shape, such as rectangular, circular, or elliptical. The liquid inlet 33 on the cylinder 20 only needs to be located below the bottom end of the conduit 5. In a preferred embodiment of this invention, the liquid inlet 33 is close to the upper surface of the bottom plate of the treatment container 1 so that the waste liquid entering the cylinder 20 can fully contact the ozone.

[0044] In this invention, the positions of the waste liquid inlet pipe 31 and the water outlet pipe 32 on the side wall of the treatment container 1 are not specifically limited. In a preferred embodiment of this invention, they are both located on the upper part of the side wall.

[0045] In this invention, the insert 4 can be fixedly connected to the rotating cover 3, or it can be detachably connected to the rotating cover 3. The detachable method between the insert 4 and the conduit 5 is not specifically limited and can be implemented according to conventional detachable structures in the art. In a preferred embodiment of this invention, it is achieved in the following way: Please refer to... Figure 4 The inner wall of the insert 4 is provided with a guide groove 7, and the outer wall of the conduit 5 is provided with a slot 6. The guide groove 7 is provided with a vertical abutment 8 and a rotating tube 9 perpendicular to the abutment. A first spring 10 is fixedly connected to the bottom of the guide groove 7. The first spring 10 is located on one side of the abutment 8 and close to the inner side of the guide groove 7. One end of a second spring 13 is fixedly connected to the other side surface of the abutment 8. The other end of the second spring 13 is fixedly connected to a locking block 14 that is adapted to the slot 6. A push block 11 is fixedly connected to the top of the first spring 10. A pull rope 12 is fixedly connected to the top of the push block 11. The pull rope 12 is wound around the rotating tube 9 and passes through the abutment 8 and the second spring 13 and is fixedly connected to the locking block 14. In use, the user pushes the push block 11 downwards, which in turn squeezes the first spring 10 and retracts the pull rope 12. When the pull rope 12 retracts, it moves the locking block 14 to the left and squeezes the second spring 13. Then the user can insert the tube 5 into the insert 4. After releasing the push block 11, the locking block 14 and the push block 11 are reset by the force of the first spring 10 and the second spring 13. The locking block 14 is inserted into the slot 6 to fix the insert 4 and the tube 5.

[0046] In a preferred embodiment of the present invention, a first airbag 25 is provided at the bottom of the conduit 5, and the outer side of the first airbag 25 contacts the inner wall of the cylinder 30 to achieve a seal between the conduit and the cylinder. In another preferred embodiment, a linkage block 22 is connected below the cross torsion bar 18, and a second airbag 21 and a third spring 23 are fixedly connected below the linkage block 22. The second airbag 212 communicates with the first airbag 25. The second airbag 21 and the first airbag 25 can be directly connected or connected by a connecting device. In a preferred embodiment of the present invention, please refer to... Figure 2 A tube 24 is connected to the lower part of the second airbag 21, and the other end of the tube 24 is connected to the first airbag 25. In use, the cross torsion bar 18 moves the linkage block 22 downward, thereby compressing the second airbag 21 and the third spring 23. Then, the gas inside the second airbag 21 is introduced into the second airbag 25 through the tube 24, causing the second airbag 25 to expand and contact the inside of the cylinder 20 for enhanced sealing.

[0047] In this invention, the internal electrode 29 and external electrode 30 on one side of the wastewater inlet pipe 31 are electrolytic oxidation electrodes used for electrolytic treatment of wastewater, and the internal electrode 29 and external electrode 30 on one side of the outlet pipe 32 are electrolytic oxidation electrodes or electrolytic hydrogen production electrodes used for electrolytic oxidation treatment of wastewater or electrolytic hydrogen production. When used for electrolytic treatment of wastewater, the internal electrode 29 is a stainless steel electrode, and the external electrode 30 is a titanium plate electrode or other electrode materials in the art suitable for electrolytic oxidation of wastewater; when used for electrolytic hydrogen production, both the internal electrode 29 and external electrode 30 are nickel mesh or other electrode materials in the art suitable for electrolytic hydrogen production, and both the internal electrode 29 and external electrode 30 are electrically connected to an external power source.

[0048] In a preferred embodiment of the present invention, an external electrode 30 is provided on the side wall of the cylinder 20. The material of the external electrode 30 on the side wall with the liquid inlet hole 33 is the same as that of the external electrode 30 in the first reaction zone, and the material of the external electrode 30 on the other side is the same as that of the external electrode 30 in the second reaction zone. Both are electrically connected to an external power source.

[0049] In a preferred embodiment of the present invention, the top cover is provided with a drain pipe 34 to facilitate the discharge of gas during the treatment process; the waste liquid inlet pipe 31 is provided with a filter screen for preliminary filtration of the waste liquid; and the bottom plate of the treatment container 1 is provided with casters 35 to facilitate the movement of the device.

[0050] Before the first operation of the device, the detachable components of the second reaction zone are assembled. Assembly can be performed outside the device by inserting the disassembly plate 17 into the slide groove 15. An ultraviolet lamp 19 is detachably connected to the disassembly plate 17. Then, the conduit 5 is fixed: push the push block 11 downward, thereby compressing the first spring 10 and retracting the pull rope 12. When the pull rope 12 retracts, it moves the locking block 14 to the left, compressing the second spring 13. Then, the user can insert the conduit 5 into the insert 4. After releasing the push block 11, the locking block 14 and the push block 11 are reset by the force of the first spring 10 and the second spring 13. The locking block 14 is inserted into the slot 6, thus completing the fixation of the insert 4 and the conduit 5. Then, the cross torsion bar 18 and the disassembly plate 17 are moved downwards. The cross torsion bar 18 moves downwards along the linkage block 22, thereby compressing the second airbag 21 and the third spring 23. The gas inside the second airbag 21 is then introduced into the first airbag 25 through the air tube 24, causing the first airbag 25 to inflate and come into contact with the inside of the cylinder 20, thus reinforcing the seal between the conduit 5 and the cylinder 20. At this point, the entire detachable component in the second reaction zone is installed.

[0051] The internal electrode 29 and the external electrode 30 are electrically connected to an external power source.

[0052] Waste liquid is injected into the first reaction zone through waste liquid inlet pipe 31. Electrolytic oxidation is performed on the waste liquid via internal electrode 29 and external electrode 30. The waste liquid then enters the second reaction zone cylinder 20 through inlet hole 33. Ozone gas is injected through gas inlet pipe 26 to react with the waste liquid, and ultraviolet photolysis occurs in the second reaction zone. The ozone gas is distributed throughout the waste liquid and pushes it upwards. The waste liquid then flows out through slot 16 to the right side of the container and returns to the first reaction zone for further electrolytic oxidation. After multiple cycles of reaction in the first and second reaction zones, rotating the cover 3 rotates the conduit 5, causing slot 16 to face the left side of the container. The liquid, after multiple reactions, enters the third reaction zone, where further electrolytic oxidation and hydrogen production reactions occur. Finally, after electrolytic oxidation, ozone oxidation, and ultraviolet photolysis, the liquid is discharged from the device through outlet pipe 32. Hydrogen produced by electrolysis of water in the third reaction zone is collected and discharged through the outlet pipe of the third reaction zone. When the UV lamp 19 needs to be replaced, the conduit 5 is disassembled. Then, the user rotates the cross torsion bar 18 so that it rotates with the bayonet 16. Then, the disassembly plate 17 is removed upwards to replace the UV lamp 19.

[0053] In use, the device first secures the insert and conduit. One end of the disassembly plate equipped with an ultraviolet lamp is placed in the groove, and the other end is secured by a cross-shaped torsion bar. When the cross-shaped torsion bar rotates downward, it compresses the gas in the second airbag into the first airbag, creating a seal between the cylinder and the conduit. Wastewater is introduced into the first reaction zone through the waste liquid inlet pipe. The inlet waste liquid is guided by the guide plate 27, and the wastewater treatment is further accelerated by the aerator 28. Then, the wastewater flows into the cylinder through the liquid inlet hole. Ozone is introduced into the cylinder through the gas inlet pipe at the bottom of the cylinder for coupled oxidation treatment, and ultraviolet photolysis is performed by the ultraviolet lamp 19.

[0054] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for treating wastewater by electrolytic hydrogen production coupled with oxidation, characterized in that, The wastewater raw material first undergoes electrolytic oxidation in the first reaction zone, and then undergoes ozone oxidation and ultraviolet photolysis in the second reaction zone. The wastewater circulates between the first and second reaction zones. Once the wastewater treated in the second reaction zone meets the requirements for electrolytic oxidation or electrolytic hydrogen production in the third reaction zone, it flows into the third reaction zone for further electrolytic oxidation or electrolytic hydrogen production. The apparatus includes a first reaction zone, a second reaction zone, and a third reaction zone. The first reaction zone is equipped with a first electrolytic oxidation device, the second reaction zone is equipped with an ozone oxidation and ultraviolet photolysis device, and the third reaction zone is equipped with a second electrolytic oxidation device or an electrolytic hydrogen production device. The ozone oxidation and ultraviolet photolysis device is equipped with a steerable communication hole for communicating with the first reaction zone or the third reaction zone. The device specifically includes a processing container. Inside the processing container, there are two sides: a first reaction zone with a waste liquid inlet pipe and a third reaction zone with a water outlet pipe. A second reaction zone is located in the middle. Both the first and second reaction zones are equipped with guide plates connected to the top cover of the processing container. The guide plates are equipped with aerators and internal electrodes. External electrodes are located on the inner wall of the processing container. A cylinder and a gas inlet pipe are fixedly connected to the upper surface of the bottom plate of the processing container corresponding to the second reaction zone. The outlet of the gas inlet pipe is located inside the cylinder. A liquid inlet hole is located on the side wall of the cylinder located on the side of the first reaction zone. The processing container corresponding to the second reaction zone has a cover opening, a rotating cover in the cover opening, an insert on the lower surface of the rotating cover, a detachable conduit inside the insert, a vertical groove on the inner side wall of the conduit, and a through-hole on the other side wall of the conduit opposite the groove, one end of a disassembly plate slidably connected in the groove, the other end of which is fixed to the conduit by a cross torsion bar set in the through-hole, a detachable ultraviolet lamp on the lower surface of the disassembly plate, the ultraviolet lamp being located inside the conduit, and the lower end of the conduit being located inside the cylinder and sealed to the cylinder.

2. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 1, characterized in that, The wastewater raw material contains one or more of the following: phenols and phenolic derivatives, aromatic amines, halogenated compounds, nitro compounds, hydroxy acid compounds, and reactive dyes.

3. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 1, characterized in that, Electrolytic oxidation is performed in the first and third reaction zones by setting internal and external electrodes. The internal electrode is a stainless steel electrode, and the external electrode is a titanium plate electrode. The current density range is 8-20 mA / cm².

4. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 1, characterized in that, The ozone concentration during ozone oxidation in the second reaction zone is 10-20 mg / L.

5. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 1, characterized in that, The residence time of the wastewater raw material in the first reaction zone, the second reaction zone, and the third reaction zone is 2-20 minutes.

6. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 1, characterized in that, The ultraviolet photolysis device has a detachable structure.

7. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 1, characterized in that, The inner wall of the insert is provided with a guide groove, and the outer wall of the conduit is provided with a slot. Inside the guide groove, there is a vertical abutment and a rotating tube perpendicular to the abutment. A first spring is fixedly connected to the bottom of the guide groove. The first spring is located on one side of the abutment and close to the inner side of the guide groove. One end of a second spring is fixedly connected to the other side surface of the abutment. The other end of the second spring is fixedly connected to a locking block that matches the slot. A push block is fixedly connected to the top of the first spring. A pull rope is fixedly connected to the top of the push block. The pull rope is wound around the rotating tube and passes through the abutment and the second spring and is fixedly connected to the locking block.

8. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 7, characterized in that, The bottom of the conduit is provided with a first airbag to achieve a seal between the conduit and the cylinder.

9. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 8, characterized in that, A linkage block is connected below the cross torsion bar, and a second airbag and a third spring are fixedly connected below the linkage block. The second airbag is connected to the first airbag.

10. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 9, characterized in that, The internal and external electrodes on the waste liquid inlet pipe side are electrolytic oxidation electrodes, and the internal and external electrodes on the water outlet pipe side are electrolytic oxidation electrodes or electrolytic hydrogen production electrodes.

11. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 1, characterized in that, The liquid inlet is located on the lower side wall of the cylinder.

12. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 1, characterized in that, External electrodes are provided on the side wall of the cylinder.

13. The method for treating wastewater by electrolytic hydrogen production coupled with oxidation according to claim 1, characterized in that, Both the waste liquid inlet pipe and the water outlet pipe are located on the upper side wall of the treatment container; the top cover is equipped with a drain pipe; the waste liquid inlet pipe is equipped with a filter screen for preliminary filtration of the waste liquid; and the bottom plate of the treatment container is equipped with casters.

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