A method for preparing three-dimensional particles and a low-energy-consumption disc-tube photoelectrocatalytic reactor

Abstract

The present invention discloses a method for preparing three-dimensional particles and a low-energy-consumption disc-tube photoelectrocatalytic reactor, which relates to the technical field of photoelectrocatalytic reactors. The surface of the cathode plate is provided with an upper flow hole. The method for preparing three-dimensional particles and the low-energy-consumption disc-tube photoelectrocatalytic reactor are three-dimensional particles prepared using glass fiber paper as a carrier. The carrier has a porous structure, and the loaded metal oxides and hydroxides are evenly distributed on the surface of the glass fiber carrier, which increases the effective contact with organic molecules and provides better reaction active sites for the system reaction. At the same time, the presence of UV lamps generates transient photogenerated electron-hole pairs on the surface of the semiconductor plate. The holes have strong oxidizing properties and can directly degrade adsorbed pollutants and react with water to generate active oxygen groups such as OH. Photoelectric synergistic catalysis makes · The amount of OH increases significantly. Compared with traditional electrocatalysis, photoelectric synergistic catalysis can save 20% of electricity consumption under the same pollutant removal conditions.

Description

Technical Field

[0001] The present invention relates to the technical field of photoelectrocatalytic reactors, and in particular to a method for preparing three-dimensional particles and a low-energy-consumption disc-tube photoelectrocatalytic reactor. Background Art

[0002] In the 1980s, advanced oxidation technology was developed and is considered to be one of the most effective technologies for removing refractory pollutants from wastewater. This technology generates hydroxyl radicals (·OH), superoxide anions (·O2 - ) and other free radicals, which attack pollutants, causing degradation and mineralization. Photocatalysis faces two major challenges in wastewater treatment: rapid recombination of photogenerated electron-hole pairs, which limits catalytic effectiveness; and photocatalysis generally fails to completely mineralize organic matter. While electrocatalysis can completely mineralize organic matter, energy consumption of 20 to 100 kilowatt-hours per kilogram of COD restricts its large-scale application.

[0003] Anode plate coatings cost as much as 6,000 to 10,000 yuan per square meter. Three-dimensional particle electrodes are typically used to expand the anode plate surface area. However, during continuous operation, existing three-dimensional particle electrodes suffer from a reduction in catalytic sites due to the adsorption and deposition of pollutants on their surfaces. Furthermore, three-dimensional particle electrodes often suffer from the problem of catalytic coating shedding due to a weak bond between the effective catalytic coating and the substrate.

[0004] Therefore, in order to address the problems of weak bonding between the effective catalytic coating and the substrate of the three-dimensional particle electrode, short life of the catalytic coating, easy deposition of organic scale on the three-dimensional particle electrode, and high energy consumption of the electrocatalytic oxidation reactor, a preparation method for a three-dimensional particle electrode with a long catalytic coating life and a low-energy consumption disc-tube photoelectrocatalytic reactor with cross-flow cleaning and descaling effect are proposed. Summary of the Invention

[0005] The present invention provides a method for preparing three-dimensional particles and a low-energy disc-tube photoelectrocatalytic reactor. Glass fiber with a porous structure and a hydrophobic surface is used as a carrier to prepare a three-dimensional particle electrode with a large specific surface area and a tightly integrated catalytic coating and carrier, which greatly increases the active sites of the catalytic reaction. The use of a disc-tube structure allows the fluid to pass tangentially through the surface of the plate in a manner perpendicular to the plate, effectively preventing the scaling of the anode and cathode plates. The arrangement of the anode and cathode plate pores avoids the scaling problem at the gas-liquid interface caused by the long-term accumulation of gas inside the reactor. The three-dimensional particle electrode participates in the electrocatalytic oxidation while also participating in the photocatalytic reaction. The design of the UV lamp longitudinally penetrating the anode and cathode plates allows the UV and electrocatalysis to play a synergistic role in the tubular reaction to the maximum extent, achieving the beneficial effect of significantly reducing the energy consumption of the photoelectrocatalytic operation.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions: a method for preparing three-dimensional particles, the method for preparing three-dimensional particles comprising the following steps:

[0007] The corrugated glass fiber paper was rolled into a honeycomb glass fiber paper with a radius of 20 cm, soaked in 15% silica sol for 15 minutes, microwave-dried for 15 minutes, and calcined in a muffle furnace at 600°C for 8 hours. After cooling, it was cut into two discs with a height of 2 cm, which were designated as discs A and B.

[0008] After mixing 0.5 mol / L FeSO4 solution and 0.1 mol / L SnCl4·5H2O solution, disk A was immersed in the mixture for 1 hour and then dried by microwave for 15 minutes. Then, disk A was immersed in a mixed solution of hydrazine hydrate, NaOH solution, ethylene glycol and water and microwaved for 10 minutes. Then disk A was heat-treated at 900-1200℃ for 1-4 hours in nitrogen protection to obtain three-dimensional particles of Fe3O4-SnO2 / glass fiber disk A.

[0009] 16 mmol Ni(NO3)2·6H2O, 2 mmol VCl3, and 60.0 mmol urea were dissolved in 100 mL methanol and 200 mL water, and ultrasonicated to form a homogeneous solution. Disk B was immersed in the homogeneous solution under ultrasonication for 1 h, microwaved for 10 min, and then heat-treated at 900-1200°C for 1-4 h under nitrogen protection.

[0010] The calcined disk B was placed in 75 mmol CH4N2S dissolved in 300 mL water to form a uniform solution, immersed for 10 min and then calcined at 600 °C;

[0011] At room temperature, in a standard three-electrode system, a platinum mesh electrode was used as the counter electrode, a saturated calomel electrode was used as the reference electrode, and the disc B after double calcination was used as the working electrode for electrodeposition: the electrolyte was 50 mL of a mixed solution of nickel nitrate and nickel acetate, and the molar concentrations of nickel nitrate and nickel acetate were 0.018 mol / L and 0.032 mol / L, respectively. Cyclic voltammetry was used to directly deposit Ni hydroxide in the potential range of -1.1 V to 0 V at a scanning speed of 50 mV / s. After 10 cycles, three-dimensional particles of Ni(OH)2-NF / glass fiber disc B were obtained.

[0012] A and B are loaded into the network framework of three-dimensional particles to obtain three-dimensional particles.

[0013] A low-energy-consumption disc-tube photoelectrocatalytic reactor comprises an upper cathode plate, the surface of which is provided with an upper flow hole, and an upper three-dimensional particle plate is arranged below the upper cathode plate, a reflector is embedded in the interior of the upper three-dimensional particle plate, and an anode plate is arranged below the upper three-dimensional particle plate, the surface of the anode plate is provided with a central flow hole, and a lower three-dimensional particle plate is arranged below the anode plate, a central baffle is embedded in the interior of the lower three-dimensional particle plate, and a lower cathode plate is arranged below the lower three-dimensional particle plate, the surface of the lower cathode plate is provided with a lower flow hole, and exhaust holes are provided at the surface edges of the upper cathode plate, the anode plate, and the lower three-dimensional particle plate, and UV lamps are penetrated into the upper cathode plate, the upper three-dimensional particle plate, the anode plate, the lower three-dimensional particle plate, and the lower cathode plate.

[0014] Furthermore, the interiors of the lower three-dimensional particle plate and the upper three-dimensional particle plate are filled with three-dimensional particles, and the upper cathode plate, anode plate, lower three-dimensional particle plate, upper three-dimensional particle plate, and lower cathode plate are all disc-shaped structures.

[0015] Furthermore, there are four upper flow holes and four lower flow holes respectively, and the upper flow holes are connected to the lower flow holes through the upper three-dimensional particle plate, the central flow hole, and the lower three-dimensional particle plate.

[0016] Furthermore, the upper cathode plate, the lower three-dimensional particle plate, the upper three-dimensional particle plate, the anode plate, and the lower cathode plate are provided with fitting grooves on both sides of the surface, and a torsion spring is provided inside the fitting groove, and the surface of the torsion spring is connected to the electrode sheet, and the upper cathode plate, the anode plate, the lower three-dimensional particle plate, the upper three-dimensional particle plate, and the lower cathode plate are provided with fitting sheets on both sides of the bottom.

[0017] Furthermore, the electrode sheets are elastically connected to the upper cathode plate, the anode plate, and the lower cathode plate respectively through torsion springs, and the electrode sheets form a group of two.

[0018] Furthermore, the upper cathode plate, anode plate, lower three-dimensional particle plate, upper three-dimensional particle plate, and lower cathode plate are stacked, and a tube shell is set on the outside of the upper cathode plate, anode plate, lower three-dimensional particle plate, upper three-dimensional particle plate, and lower cathode plate.

[0019] Furthermore, a spring airbag is provided at the bottom of the inner wall of the tube shell, a placement plate is provided on the top of the spring airbag, and an access pipe is provided on the bottom surface of the tube shell.

[0020] Furthermore, the placement plate and the spring airbag are both ring-shaped structures, and the placement plate is elastically connected to the tube shell through the spring airbag.

[0021] Furthermore, holes are opened on both sides of the tube shell, and an inflatable rubber airbag is set inside the hole. The side of the inflatable rubber airbag is connected to an air pipe, and the inflatable rubber airbag is connected to the spring airbag through the air pipe.

[0022] The present invention provides a method for preparing three-dimensional particles and a low-energy-consumption disc-tube photoelectrocatalytic reactor, which have the following beneficial effects:

[0023] 1. The preparation method of the three-dimensional particles and the low-energy disc-tube photoelectrocatalytic reactor are three-dimensional particles prepared with glass fiber paper as a carrier. The carrier has a porous structure, and the loaded metal oxides and hydroxides are evenly distributed on the surface of the glass fiber carrier, which increases the effective contact with organic molecules and provides better reaction active sites for the system reaction. The flow direction of the sewage is controlled by the reflective plate inside the upper three-dimensional particle plate and the central baffle inside the lower three-dimensional particle plate, so that the sewage can be kept in the upper three-dimensional particle plate and the lower three-dimensional particle plate for as long as possible, thereby prolonging the reaction time and improving the reaction effect.

[0024] 2. The preparation method of the three-dimensional particles and the low-energy disc-tube photoelectrocatalytic reactor, the electrode sheet is rotated out by a torsion spring to facilitate wiring and power supply, which leaves space in the fitting groove. Therefore, when stacked up and down, the fitting sheets on both sides of the bottom of the upper cathode plate, anode plate, lower three-dimensional particle plate, upper three-dimensional particle plate, and lower cathode plate will be embedded in the fitting groove of the lower component, thereby making the upper cathode plate, upper three-dimensional particle plate, anode plate, lower three-dimensional particle plate, and lower cathode plate closely contacted with each other up and down to ensure a stable installation and prevent gaps from forming when stacked up and down, causing sewage to flow out.

[0025] 3. The preparation method of the three-dimensional particles and the low-energy disc-tube photoelectrocatalytic reactor are to install the lower cathode plate, the lower three-dimensional particle plate, the anode plate, the upper three-dimensional particle plate, and the upper cathode plate into the tube shell in sequence. The mounting plate will compress the spring airbag due to the load-bearing, so that the gas inside the spring airbag enters the inflatable rubber airbag along the air pipe. The inflatable rubber airbag will then expand inside the hole groove to seal the gap between the electrode plate and the hole groove to prevent water leakage. When the spring airbag is compressed, the overall height decreases, so that the lower flow hole of the lower cathode plate will be connected to the access pipe, so that the sewage can be discharged along the lower flow hole and the access pipe after the reaction.

[0026] 4. UV light irradiation generates transient photogenerated electron-hole pairs on the surface of the semiconductor plate. Holes have strong oxidizing properties and can directly degrade adsorbed pollutants. They can also react with water to form reactive oxygen groups such as OH. These reactive oxygen groups further oxidize or mineralize pollutants in the solution, creating a synergistic effect with electrocatalytic oxidation, further reducing the energy required to degrade organic matter.

[0027] 5. If the reaction plates are not perforated, bubbles will accumulate between the plates, causing plate scaling and reducing the reaction area. This structure will reduce the treatment efficiency by 40%. Perforating the plates can completely avoid this problem. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a schematic diagram of the explosion structure of a low-energy-consumption disc-tube photoelectrocatalytic reactor of the present invention;

[0029] Figure 2 This is a schematic diagram of the reverse side structure of the upper cathode plate of a low-energy-consumption disc-tube photoelectrocatalytic reactor of the present invention;

[0030] Figure 3 This is a schematic diagram of the internal structure of a shell of a low-energy-consumption disc-tube photoelectrocatalytic reactor according to the present invention;

[0031] Figure 4 A low energy consumption disc tube type photoelectrocatalytic reactor of the present invention Figure 3 A in the middle is an enlarged structural diagram;

[0032] Figure 5 The figure is a schematic diagram of the top view of the tube shell of a low-energy-consumption disc-tube photoelectrocatalytic reactor of the present invention.

[0033] In the figure: 1. Upper cathode plate; 2. Upper flow hole; 3. Upper three-dimensional particle plate; 4. Reflector; 5. Anode plate; 6. Center flow hole; 7. Lower three-dimensional particle plate; 8. Center baffle; 9. Lower cathode plate; 10. Lower flow hole; 11. Fitting groove; 12. Torsion spring; 13. Electrode sheet; 14. Fitting sheet; 15. Tube shell; 16. Spring airbag; 17. Mounting plate; 18. Access pipe; 19. Hole slot; 20. Inflatable rubber airbag; 21. Air pipe; 22. UV lamp; 23. Exhaust hole. DETAILED DESCRIPTION

[0034] The following embodiments of the present invention are described in further detail with reference to the accompanying drawings and examples. The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0035] The present invention provides a technical solution: a method for preparing three-dimensional particles, which comprises the following steps:

[0036] The corrugated glass fiber paper was rolled into a honeycomb glass fiber paper with a radius of 20 cm, soaked in 15% silica sol for 15 minutes, microwave-dried for 15 minutes, and calcined in a muffle furnace at 600°C for 8 hours. After cooling, it was cut into two discs with a height of 2 cm, which were designated as discs A and B.

[0037] After mixing 0.5 mol / L FeSO4 solution and 0.1 mol / L SnCl4·5H2O solution, disk A was immersed in the mixture for 1 hour and then dried by microwave for 15 minutes. Then, disk A was immersed in a mixed solution of hydrazine hydrate, NaOH solution, ethylene glycol and water and microwaved for 10 minutes. Then disk A was heat-treated at 900-1200℃ for 1-4 hours in nitrogen protection to obtain three-dimensional particles of Fe3O4-SnO2 / glass fiber disk A.

[0038] 16 mmol Ni(NO3)2·6H2O, 2 mmol VCl3, and 60.0 mmol urea were dissolved in 100 mL methanol and 200 mL water, and ultrasonicated to form a homogeneous solution. Disk B was immersed in the homogeneous solution under ultrasonication for 1 h, microwaved for 10 min, and then heat-treated at 900-1200°C for 1-4 h under nitrogen protection.

[0039] The calcined disk B was placed in 75 mmol CH4N2S dissolved in 300 mL water to form a uniform solution, immersed for 10 min and then calcined at 600 °C;

[0040] At room temperature, in a standard three-electrode system, a platinum mesh electrode was used as the counter electrode, a saturated calomel electrode was used as the reference electrode, and the disc B after double calcination was used as the working electrode for electrodeposition: the electrolyte was 50 mL of a mixed solution of nickel nitrate and nickel acetate, and the molar concentrations of nickel nitrate and nickel acetate were 0.018 mol / L and 0.032 mol / L, respectively. Cyclic voltammetry was used to directly deposit Ni hydroxide in the potential range of -1.1 V to 0 V at a scanning speed of 50 mV / s. After 10 cycles, three-dimensional particles of Ni(OH)2-NF / glass fiber disc B were obtained.

[0041] A and B are loaded into the network framework of three-dimensional particles to obtain three-dimensional particles.

[0042] like Figure 1-Figure 2As shown, a low-energy consumption disc-tube photoelectrocatalytic reactor comprises an upper cathode plate 1, an upper flow hole 2 is provided on the surface of the upper cathode plate 1, and an upper three-dimensional particle plate 3 is provided below the upper cathode plate 1, a reflector 4 is embedded in the interior of the upper three-dimensional particle plate 3, and an anode plate 5 is provided below the upper three-dimensional particle plate 3, a central flow hole 6 is provided on the surface of the anode plate 5, and a lower three-dimensional particle plate 7 is provided below the anode plate 5, a central flow baffle 8 is embedded in the interior of the lower three-dimensional particle plate 7, and a lower cathode plate 9 is provided below the lower three-dimensional particle plate 7, a lower flow hole 10 is provided on the surface of the lower cathode plate 9, the interior of the lower three-dimensional particle plate 7 and the upper three-dimensional particle plate 3 are filled with three-dimensional particles, and the upper cathode plate 1, the anode plate 5, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3 and the lower cathode plate 9 are provided with a lower flow hole 10 ... three-dimensional particle plate 7 are provided with a lower cathode plate 9, and the lower three-dimensional particle plate 7 and the upper three-dimensional particle plate 3 are filled with three-dimensional particles. The plate 3 and the lower cathode plate 9 are both disc-shaped structures, with four upper flow holes 2 and four lower flow holes 10 respectively. The upper flow hole 2 is connected to the lower flow hole 10 through the upper three-dimensional particle plate 3, the central flow hole 6, and the lower three-dimensional particle plate 7. The upper cathode plate 1, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3, the anode plate 5, and the lower cathode plate 9 are provided with fitting grooves 11 on both sides of the surface, and a torsion spring 12 is provided inside the fitting groove 11. The surface of the torsion spring 12 is connected to an electrode sheet 13. The upper cathode plate 1, the anode plate 5, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3, and the lower cathode plate 9 are provided with fitting sheets 14 on both sides of the bottom. The electrode sheets 13 are elastically connected to the upper cathode plate 1, the anode plate 5, and the lower cathode plate 9 respectively through the torsion spring 12, and the electrode sheets 13 are in groups of two;

[0043] The specific operation is as follows: from top to bottom, the upper cathode plate 1, the upper three-dimensional particle plate 3, the anode plate 5, the lower three-dimensional particle plate 7, and the lower cathode plate 9 are stacked in sequence. When stacking, the electrode sheets 13 on both sides of the upper cathode plate 1, the anode plate 5, and the lower cathode plate 9 are rotated out by the torsion spring 12 to connect the wires and energize them, which leaves space for the fitting groove 11. Therefore, when stacking up and down, the fitting sheets 14 on both sides of the bottom of the upper cathode plate 1, the anode plate 5, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3, and the lower cathode plate 9 will be embedded into The inside of the fitting groove 11 of the lower component, for example, the fitting piece 14 at the bottom of the upper cathode plate 1 will be embedded in the fitting grooves 11 on both sides of the surface of the upper three-dimensional particle plate 3, thereby making the upper cathode plate 1, the upper three-dimensional particle plate 3, the anode plate 5, the lower three-dimensional particle plate 7, and the lower cathode plate 9 closely contact each other up and down to ensure a stable installation and prevent gaps from being generated when stacked up and down so that sewage can flow out. Among them, the surfaces of the upper three-dimensional particle plate 3 and the lower three-dimensional particle plate 7 are both microporous structures to facilitate the entry of sewage;

[0044] The sewage flows into the upper three-dimensional particle plate 3 through the upper flow hole 2 on the surface of the upper cathode plate 1, and enters the lower three-dimensional particle plate 7 along the central flow hole 6 on the surface of the anode plate 5. Finally, the water body flows out along the lower flow hole 10 on the surface of the lower cathode plate 9. After the sewage enters the upper three-dimensional particle plate 3 and the lower three-dimensional particle plate 7, the electrode sheet 13 is connected to the power so that the upper cathode plate 1, the anode plate 5, and the lower cathode plate 9 are energized to perform an electrocatalytic oxidation reaction. At the same time, when the sewage flows through the upper three-dimensional particle plate 3 and the lower three-dimensional particle plate 7, it will pass through the three-dimensional particles inside the two, thereby enhancing the control effect of organic pollutants in the sewage, and the flow direction of the sewage is controlled by the reflector 4 inside the upper three-dimensional particle plate 3 and the central baffle 8 inside the lower three-dimensional particle plate 7, so that the sewage can prolong the time inside the upper three-dimensional particle plate 3 and the lower three-dimensional particle plate 7 as much as possible, thereby prolonging the reaction time to improve the reaction effect.

[0045] like Figure 1 、 Figure 5 As shown, the upper cathode plate 1, the anode plate 5, and the lower cathode plate 9 are provided with exhaust holes at their surface edges, and the upper cathode plate 1, the upper three-dimensional particle plate 3, the anode plate 5, the lower three-dimensional particle plate 7, and the lower cathode plate 9 are provided with UV lamps 22 therein;

[0046] The exhaust hole 23 is used for small hole exhaust. By discharging the exhaust gas, the access area of ​​the three plates can be increased, and the treatment can be effectively improved, and the possibility of scaling between the plates can be effectively reduced. In addition, the assembly gap between the outer diameter of the UV lamp 22 and the inner diameter of the cathode plate reserved hole is 0.5mm, so that only a very small part of the water flow penetrates the plate from the assembly gap, and most of the water flow will move tangentially in the direction perpendicular to the plate. The diameter of the UV lamp 22 is 2cm.

[0047] After adding UV lamp 22, photoelectric synergistic catalysis was tested, and the results were as follows: the amount of OH was greatly increased. Compared with traditional electrocatalysis, under the same pollutant removal conditions, photoelectric synergistic catalysis can save 20% of electricity consumption;

[0048] like Figure 3-Figure 5As shown, the upper cathode plate 1, the anode plate 5, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3, and the lower cathode plate 9 are stacked, and a tube shell 15 is provided on the outside of the upper cathode plate 1, the anode plate 5, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3, and the lower cathode plate 9. A spring airbag 16 is provided at the bottom of the inner wall of the tube shell 15, and a placement plate 17 is provided on the top of the spring airbag 16. An access pipe 18 is provided on the bottom surface of the tube shell 15. The placement plate 17 and the spring airbag 16 are both annular structures, and the placement plate 17 is elastically connected to the tube shell 15 through the spring airbag 16. Holes 19 are provided on both sides of the tube shell 15, and an inflatable rubber airbag 20 is provided inside the hole groove 19. The side of the inflatable rubber airbag 20 is connected to the air supply pipe 21, and the inflatable rubber airbag 20 is connected to the spring airbag 16 through the air supply pipe 21;

[0049] The specific operation is as follows: the lower cathode plate 9 is placed on the surface of the placement tray 17 and pressed down, so that the electrode sheet 13 is screwed out through the hole groove 19 by the torsion spring 12 and exposed to the outside of the tube shell 15 for wiring. The above operation is repeated to install the lower three-dimensional particle plate 7, the anode plate 5, the upper three-dimensional particle plate 3, and the upper cathode plate 1 into the tube shell 15 in sequence. As the upper cathode plate 1, the anode plate 5, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3, and the lower cathode plate 9 are placed, the placement tray 17 will compress the spring airbag 16 due to the load, so that the gas inside the spring airbag 16 enters the inflatable rubber airbag 20 along the air pipe 21. The inflatable rubber airbag 20 therefore expands inside the hole groove 19 to close the gap between the electrode sheet 13 and the hole groove 19 to prevent water leakage;

[0050] Moreover, after the upper cathode plate 1, the anode plate 5, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3, and the lower cathode plate 9 are placed inside the tube shell 15, the spring airbag 16 is compressed and the overall height is lowered, so that the lower flow hole 10 of the lower cathode plate 9 will be plugged into the access pipe 18, so that the sewage can be discharged along the lower flow hole 10 and the access pipe 18 after the reaction;

[0051] When not in working state, the electrode sheet 13 is powered off and enters into a dormant state to reduce energy consumption.

[0052] In summary, if Figure 1-Figure 5As shown, when in use, first the lower cathode plate 9 is placed on the surface of the placement tray 17 and pressed down, so that the electrode sheet 13 is screwed out through the hole slot 19 by the torsion spring 12 and exposed to the outside of the tube shell 15 for wiring, and the above operation is repeated to install the lower three-dimensional particle plate 7, the anode plate 5, the upper three-dimensional particle plate 3, and the upper cathode plate 1 into the tube shell 15 in sequence. As the upper cathode plate 1, the anode plate 5, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3, and the lower cathode plate 9 are placed, the placement tray 17 will compress the spring airbag 16 due to the load, so that the gas inside the spring airbag 16 enters the inside of the inflatable rubber airbag 20 along the air pipe 21. The inflatable rubber airbag 20 therefore expands inside the hole slot 19 to close the gap between the electrode sheet 13 and the hole slot 19 to prevent water from leaking out;

[0053] From top to bottom, an upper cathode plate 1, an upper three-dimensional particle plate 3, an anode plate 5, a lower three-dimensional particle plate 7, and a lower cathode plate 9 are stacked in sequence. When stacked, the electrode sheets 13 on both sides of the upper cathode plate 1, the anode plate 5, and the lower cathode plate 9 are rotated out by the torsion spring 12 so as to connect the wires and energize them, which leaves space for the fitting groove 11. As a result, when stacked up and down, the fitting sheets 14 on both sides of the bottom of the upper cathode plate 1, the anode plate 5, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3, and the lower cathode plate 9 will be embedded in the fitting groove 11 of the lower component. For example, the fitting sheet 14 at the bottom of the upper cathode plate 1 will be embedded in the fitting grooves 11 on both sides of the surface of the upper three-dimensional particle plate 3, thereby making the upper cathode plate 1, the upper three-dimensional particle plate 3, the anode plate 5, the lower three-dimensional particle plate 7, and the lower cathode plate 9 closely contact each other up and down;

[0054] The sewage flows into the upper three-dimensional particle plate 3 through the upper flow hole 2 on the surface of the upper cathode plate 1, and enters the lower three-dimensional particle plate 7 along the central flow hole 6 on the surface of the anode plate 5. Finally, the water body flows out along the lower flow hole 10 on the surface of the lower cathode plate 9. After the sewage enters the upper three-dimensional particle plate 3 and the lower three-dimensional particle plate 7, the electrode sheet 13 is connected to the power so that the upper cathode plate 1, the anode plate 5, and the lower cathode plate 9 are energized to perform an electrocatalytic oxidation reaction. At the same time, when the sewage flows through the upper three-dimensional particle plate 3 and the lower three-dimensional particle plate 7, it will pass through the three-dimensional particles inside the two, thereby enhancing the control effect of organic pollutants in the sewage, and the flow direction of the sewage is controlled by the reflector 4 inside the upper three-dimensional particle plate 3 and the central baffle 8 inside the lower three-dimensional particle plate 7, so that the sewage can prolong the time inside the upper three-dimensional particle plate 3 and the lower three-dimensional particle plate 7 as much as possible, thereby prolonging the reaction time.

[0055] Moreover, after the upper cathode plate 1, the anode plate 5, the lower three-dimensional particle plate 7, the upper three-dimensional particle plate 3, and the lower cathode plate 9 are placed inside the tube shell 15, the spring airbag 16 is compressed and the overall height is lowered, so that the lower flow hole 10 of the lower cathode plate 9 will be connected with the access pipe 18, so that the sewage can be discharged along the lower flow hole 10 and the access pipe 18 after the reaction.

[0056] The embodiments of the present invention are presented for purposes of illustration and description and are not intended to be exhaustive or to limit the invention to the disclosed forms. Many modifications and variations will be apparent to those skilled in the art. The embodiments are chosen and described in order to better illustrate the principles of the invention and its practical application and to enable those skilled in the art to understand the invention and design various embodiments with various modifications as suited for specific applications.

Claims

1. A method for preparing three-dimensional particles, characterized in that: The method for preparing the three-dimensional particles comprises the following steps: The corrugated glass fiber paper was rolled into a honeycomb glass fiber paper with a radius of 20 cm, soaked in 15% silica sol for 15 minutes, microwave-dried for 15 minutes, and calcined in a muffle furnace at 600°C for 8 hours. After cooling, it was cut into two discs with a height of 2 cm, which were designated as discs A and B. After mixing 0.5 mol / L FeSO4 solution and 0.1 mol / L SnCl4·5H2O solution, disk A was immersed in the mixture for 1 hour and then dried by microwave for 15 minutes. Then, disk A was immersed in a mixed solution of hydrazine hydrate, NaOH solution, ethylene glycol and water and microwaved for 10 minutes. Then disk A was heat-treated at 900-1200℃ for 1-4 hours in nitrogen protection to obtain three-dimensional particles of Fe3O4-SnO2 / glass fiber disk A. 16 mmol Ni(NO3)2·6H2O, 2 mmol VCl3, and 60.0 mmol urea were dissolved in 100 mL methanol and 200 mL water, and ultrasonicated to form a homogeneous solution. Disk B was immersed in the homogeneous solution under ultrasonication for 1 h, microwaved for 10 min, and then heat-treated at 900-1200°C for 1-4 h under nitrogen protection. The calcined disk B was placed in 75 mmol CH4N2S dissolved in 300 mL water to form a uniform solution, immersed for 10 min and then calcined at 600 °C; At room temperature, in a standard three-electrode system, a platinum mesh electrode was used as the counter electrode, a saturated calomel electrode was used as the reference electrode, and a twice-calcined disk B was used as the working electrode for electrodeposition: the electrolyte was a 50 mL mixed solution of nickel nitrate and nickel acetate, with molar concentrations of nickel nitrate and nickel acetate of 0.018 mol / L and 0.032 mol / L, respectively. Cyclic voltammetry was used in the potential range of -1.1 V to 0 V at a scan rate of 50 mV / s to directly deposit Ni hydroxide. After 10 cycles, Ni(OH)2-NF / glass fiber disk B three-dimensional particles were obtained. A and B are loaded into the mesh framework of three-dimensional particles to obtain three-dimensional particles, and A and B disks are loaded into a photoelectrocatalytic reactor as three-dimensional particle electrodes.

2. A low-energy-consumption disc-tube photoelectrocatalytic reactor, characterized by: The three-dimensional particle electrode made of the A and B disks according to claim 1 comprises an upper cathode plate (1), an upper flow hole (2) is provided on the surface of the upper cathode plate (1), and an upper three-dimensional particle plate (3) is provided below the upper cathode plate (1), a reflector (4) is embedded in the interior of the upper three-dimensional particle plate (3), and an anode plate (5) is provided below the upper three-dimensional particle plate (3), a central flow hole (6) is provided on the surface of the anode plate (5), and a lower three-dimensional particle plate (7) is provided below the anode plate (5). ), a central baffle (8) is embedded in the interior of the lower three-dimensional particle plate (7), and a lower cathode plate (9) is provided below the lower three-dimensional particle plate (7), a lower flow hole (10) is provided on the surface of the lower cathode plate (9), exhaust holes are provided at the surface edges of the upper cathode plate (1), the anode plate (5), and the lower cathode plate (9), and a UV lamp (22) is provided inside the upper cathode plate (1), the upper three-dimensional particle plate (3), the anode plate (5), the lower three-dimensional particle plate (7), and the lower cathode plate (9).

3. The low-energy-consumption disc-tube photoelectrocatalytic reactor according to claim 2, characterized in that: The interiors of the lower three-dimensional particle plate (7) and the upper three-dimensional particle plate (3) are both filled with three-dimensional particles, and the upper cathode plate (1), the anode plate (5), the lower three-dimensional particle plate (7), the upper three-dimensional particle plate (3), and the lower cathode plate (9) all have a disc-shaped structure.

4. The low-energy-consumption disc-tube photoelectrocatalytic reactor according to claim 2, characterized in that: Four upper flow holes (2) and four lower flow holes (10) are respectively provided, and the upper flow holes (2) are connected to the lower flow holes (10) through the upper three-dimensional particle plate (3), the central flow hole (6), and the lower three-dimensional particle plate (7).

5. The low-energy-consumption disc-tube photoelectrocatalytic reactor according to claim 2, characterized in that: The upper cathode plate (1), the lower three-dimensional particle plate (7), the upper three-dimensional particle plate (3), the anode plate (5), and the lower cathode plate (9) are all provided with fitting grooves (11) on both sides of their surfaces, and a torsion spring (12) is provided inside the fitting groove (11), and the surface of the torsion spring (12) is connected to an electrode sheet (13), and the upper cathode plate (1), the anode plate (5), the lower three-dimensional particle plate (7), the upper three-dimensional particle plate (3), and the lower cathode plate (9) are all provided with fitting sheets (14) on both sides of their bottoms.

6. The low-energy-consumption disc-tube photoelectrocatalytic reactor according to claim 5, characterized in that: The electrode sheets (13) are elastically connected to the upper cathode plate (1), the anode plate (5), and the lower cathode plate (9) respectively through torsion springs (12), and the electrode sheets (13) form a group of two.

7. The low-energy-consumption disc-tube photoelectrocatalytic reactor according to claim 2, characterized in that: The upper cathode plate (1), the anode plate (5), the lower three-dimensional particle plate (7), the upper three-dimensional particle plate (3), and the lower cathode plate (9) are stacked, and a tube shell (15) is provided outside the upper cathode plate (1), the anode plate (5), the lower three-dimensional particle plate (7), the upper three-dimensional particle plate (3), and the lower cathode plate (9).

8. The low-energy-consumption disc-tube photoelectrocatalytic reactor according to claim 7, characterized in that: A spring airbag (16) is provided at the bottom of the inner wall of the tube shell (15), and a placement plate (17) is provided on the top of the spring airbag (16). An access pipe (18) is provided on the bottom surface of the tube shell (15).

9. The low-energy-consumption disc-tube photoelectrocatalytic reactor according to claim 8, characterized in that: The placement plate (17) and the spring airbag (16) are both ring-shaped structures, and the placement plate (17) is elastically connected to the tube shell (15) through the spring airbag (16).

10. The low-energy-consumption disc-tube photoelectrocatalytic reactor according to claim 8, characterized in that: Holes (19) are provided on both sides of the tube shell (15), and an inflatable rubber airbag (20) is provided inside the hole groove (19). The side of the inflatable rubber airbag (20) is connected to an air pipe (21), and the inflatable rubber airbag (20) is connected to the spring airbag (16) through the air pipe (21).

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