Green low-carbon efficient ozone oxidation device

Abstract

The utility model relates to a green low-carbon high-efficiency ozone oxidation device which comprises an ozone reaction tower and at least one group of biofilm formation catalysis components arranged in the tower, and a group of atomization spraying components are arranged above each group of biofilm formation catalysis components at certain intervals; a gas-liquid separator is arranged at the position, close to the tower top, of the ozone reaction tower; ozone is introduced from the bottom of the tower; a water collecting area is further arranged at the tower bottom of the ozone reaction tower, a water outlet pipe is arranged in the water collecting area and is connected with a circulating main pipe and an outer drainage pipe, the circulating main pipe is communicated with a plurality of groups of circulating branch pipes, and each group of circulating branch pipes is correspondingly connected with a group of atomizing spraying components respectively; the circulating main pipe is also communicated with the water inlet; the atomization spraying assembly is used for spraying wastewater to be subjected to ozone treatment downwards in the form of mist liquid drops; the biofilm formation catalysis assembly comprises a plurality of catalysis rods, and the surface of each catalysis rod is coated with an ozone catalyst coating. According to the ozone oxidation device, the ozone utilization rate, the gas-liquid mass transfer coefficient and the oxidation efficiency of ozone on organic matters can be improved, and the effluent quality is ensured.

Description

Technical Field

[0001] This utility model relates to the field of environmental protection technology, specifically to a green, low-carbon, and efficient ozone oxidation device. Background Technology

[0002] Ozone has a high oxidation potential and is a common oxidant. Furthermore, ozone decomposes in water to produce more potent oxidizing agents, such as hydroxyl radicals (·OH), which can effectively remove many recalcitrant organic pollutants through oxidation. Although ozone advanced oxidation technology is widely used and offers advantages such as ease of application, no secondary pollution, and good oxidation effect, technical challenges remain in practical applications, including low ozone utilization and poor wastewater oxidation.

[0003] Currently, bubbling reaction towers (bubbling reaction tanks) and packed reactors are the two main types of ozone oxidation reactors. These reactors primarily improve gas-liquid mass transfer and reaction efficiency by controlling the size of ozone gas bubbles and selecting appropriate packing materials. However, due to the low mass transfer rate of pollutants in a continuous liquid phase, the potential for further improvement in the reaction efficiency of existing reactors is limited. It is necessary to explore novel reaction contact methods to achieve breakthroughs in mass transfer rates and, based on this, develop new high-efficiency reactors to further enhance the effectiveness of ozone oxidation. Utility Model Content

[0004] (a) Technical problems to be solved

[0005] In view of the above-mentioned shortcomings and deficiencies of the prior art, this utility model provides a green, low-carbon and high-efficiency ozone oxidation device. By changing the gas-liquid contact mode, it improves the gas-liquid mass transfer coefficient and the oxidation efficiency of ozone on organic matter, thus solving the problem of low efficiency in the prior art of using ozone to oxidize organic matter in wastewater.

[0006] (II) Technical Solution

[0007] In a first aspect, this utility model provides a green, low-carbon, and highly efficient ozone oxidation device, which includes:

[0008] An ozone reaction tower is provided; at least one set of biofilm catalytic modules is installed inside the ozone reaction tower, and a set of atomizing spray modules is installed above each set of biofilm catalytic modules at a certain distance; a gas-liquid separator is installed near the top of the ozone reaction tower; an ozone recovery pipe is connected to the top of the ozone reaction tower, and the ozone recovered from the top of the tower is introduced into the bottom of the tower through the ozone recovery pipe; a water collection area is also provided at the bottom of the ozone reaction tower, and an outlet pipe is provided in the water collection area. The outlet pipe is connected to a circulation main pipe and an external drainage pipe. The circulation main pipe is connected to several sets of circulation branch pipes, and each set of circulation branch pipes is connected to a set of atomizing spray modules; the circulation main pipe is also connected to the inlet water; the ozone is introduced at a position higher than the liquid level in the water collection area and lower than the bottom biofilm catalytic module.

[0009] The atomizing spray assembly is used to spray the wastewater to be treated by ozone downwards in the form of mist droplets; the attached membrane catalytic assembly includes multiple catalytic rods, each of which is coated with an ozone catalyst coating; the multiple catalytic rods are arranged to form the attached membrane catalytic assembly.

[0010] According to a preferred embodiment of the present invention, the atomizing spray assembly includes a plurality of atomizing nozzles, which are solid conical nozzles that can treat wastewater into droplets with a diameter of 100-1000μm; the catalyst rods have a cross-section that is circular, elliptical, gourd-shaped or droplet-shaped, and the equivalent diameter of each catalyst rod is 1-5cm; the catalyst rods with an elliptical cross-section have their long axis arranged in the vertical direction.

[0011] According to a preferred embodiment of the present invention, the catalytic rods of the attached membrane catalytic module are arranged in two or more layers with interlayer spacing; the single-layer catalytic rods are arranged in parallel with a rod spacing between two catalytic rods; adjacent layers of catalytic rods are staggered, such that one layer of catalytic rods is exactly within the rod spacing of another layer of catalytic rods; or adjacent layers of catalytic rods are crossed, such that one layer of catalytic rods exactly intersects with another layer of catalytic rods. The crossing angle is not limited, but is preferably 15-90 degrees, more preferably 45-90 degrees.

[0012] According to a preferred embodiment of this utility model, three sets of attached biofilm catalytic components and three sets of atomizing spray components are arranged from bottom to top inside the ozone reaction tower; each catalytic rod of the attached biofilm catalytic component is installed and fixed on a mounting bracket on the inner wall of the ozone reaction tower. Preferably, the vertical distance between the uppermost catalytic rod of a single attached biofilm catalytic component and the lower edge of the atomizing nozzle of the corresponding atomizing spray component above it is 15cm-30cm; the single-layer catalytic rods are arranged in parallel and the spacing between two catalytic rods is 3-10 times (preferably 4 times) the diameter of the catalytic rod; the spacing between two layers of catalytic rods is 1-3 times the diameter of the catalytic rod. Preferably, the catalytic rod is made of stainless steel or plastic, and its surface ozone catalyst coating is MnO2.

[0013] According to a preferred embodiment of this utility model, a set of micro-bubbling reaction components is further provided between at least one set of atomizing spray components and a biofilm catalytic component. The micro-bubbling reaction component includes a porous support mesh installed on the inner wall of the ozone reaction tower. A narrowing tube is arranged on the porous support mesh, with flared ends and a narrow middle section. The upper opening of the narrowing tube faces the atomizing nozzle of the atomizing spray component, and the lower opening faces the biofilm catalytic component. The inner wall of the narrowing tube is coated with an organic matter capturing coating and an ozone catalytic coating. The two coatings are alternately arranged in a spot pattern, and there are openings between the narrowing tubes. Ozone introduced from the bottom of the ozone reaction tower reaches the area below the atomizing nozzle through the openings, forming a continuous ozone phase. An enhanced oxidation site is formed inside the narrowing tube. Preferably, the upper end of the narrowing tube is 5-10 cm from the lower edge of the atomizing nozzle of the atomizing spray component, and the lower edge is 1-4 cm from the uppermost catalytic rod of the single set of biofilm catalytic components. The diameter of the narrow section of the narrowing tube is between 0.5-3 cm, and the length of the narrow section is 5-20 cm.

[0014] According to a preferred embodiment of this utility model, each group of circulation branch pipes includes two or more circulation branch pipes, and each circulation branch pipe is connected to at least three atomizing nozzles. Preferably, the flow rate of a single atomizing nozzle is 10-30 L / min (preferably 20 L / min), and the operating pressure is 0.5-1 bar (preferably 0.7 bar). Preferably, each group of circulation branch pipes includes two circulation branch pipes arranged in parallel, and each circulation branch pipe is provided with three atomizing nozzles distributed along the width direction of the ozone reaction tower.

[0015] According to a preferred embodiment of this utility model, the gas-liquid separator comprises a set of inclined corrugated plates, with a spacing of 1-10 mm between adjacent corrugated plates, preferably 1.5-3 mm; the corrugated plates are coated with an ozone catalyst coating. Preferably, the corrugated plates are made of plastic or stainless steel, and the ozone catalyst coating on their surface is MnO2. The ozone catalyst coating on the surface of the corrugated plates has both ozone catalytic and hydrophilic effects, improving the gas-liquid separation effect and the organic matter degradation efficiency.

[0016] According to a preferred embodiment of the present invention, the distance from the bottom of the gas-liquid separator to the upper edge of the atomizing nozzle of the uppermost atomizing spray assembly is 10-15cm, and the distance from the top of the gas-liquid separator to the top of the ozone reaction tower is 25-30cm.

[0017] According to a preferred embodiment of the present invention, the green, low-carbon, and high-efficiency ozone oxidation device further includes an ozone generator located outside the ozone reaction tower; an online ozone detector is installed on the ozone recovery pipe; the online ozone detector is connected to the controller of the ozone generator; when the online ozone detector detects that the ozone concentration in the ozone recovery pipe is insufficient, it controls the ozone generator to turn on to replenish new ozone into the ozone reaction tower.

[0018] According to a preferred embodiment of this utility model, an exhaust fan and a compressor are connected to the ozone recovery pipe. An online ozone detector is located at the front end of the compressor. The exhaust fan extracts the ozone gas collected at the top of the ozone reaction tower, which is then processed by the compressor and introduced into the ozone inlet at the bottom of the ozone reaction tower. The ozone generator introduces ozone into the ozone reaction tower through a vent pipe or combines it with the compressed gas from the compressor and introduces it into the ozone reaction tower together. Alternatively, an online ozone detector can be installed in the middle of the ozone reaction tower. The online ozone detector is connected to the controller of the ozone generator. When the ozone concentration in the ozone reaction tower is detected to be insufficient, the ozone generator is controlled to start to replenish the ozone into the ozone reaction tower. The ozone inlet is located above the liquid level in the water collection area and below the lowest layer of the biofilm catalytic module.

[0019] According to a preferred embodiment of the present invention, the outlet pipe is connected to the main circulation pipe and the external drain pipe via a three-way pipe. The main circulation pipe is connected to the inlet water, and the inlet water continuously supplies the wastewater to be treated. The external drain pipe continuously discharges the treated wastewater. A portion of the water in the collection area is mixed with the inlet water through the main circulation pipe and then sprayed into the ozone reaction tower through the circulation branch pipe and the atomizing spray assembly. Another portion of the water in the collection area is discharged out through the external drain pipe.

[0020] The main circulation pipe is equipped with a pressure gauge, and the connection between the main circulation pipe and each group of circulation branch pipes is equipped with an independent control valve. This allows for the automatic control of all or part of the atomizing spray components in the ozone reaction tower according to the quality of the wastewater to be treated.

[0021] According to a preferred embodiment of the present invention, the top of the ozone reaction tower is equipped with a pressure reducing valve and a pressure gauge, and the pressure is released through the pressure reducing valve when the pressure of the ozone reaction tower exceeds the set value.

[0022] According to a preferred embodiment of this utility model, the ozone reaction tower shell is made of plastic, stainless steel, or fiberglass; or the ozone reaction tower shell is a concrete structure. Preferably, the bottom of the ozone reaction tower is conical to form the water collection area.

[0023] (III) Beneficial Effects

[0024] The technical effects of this utility model are as follows:

[0025] This invention, by incorporating an atomizing spray assembly and introducing ozone at the bottom of the tower, changes the traditional gas-liquid contact method of ozone oxidation compared to existing bubbling reaction towers and packed reactors. It treats ozone as the continuous phase and wastewater as the discontinuous phase, using the atomizing spray assembly to disperse the wastewater into small particles within the continuous ozone gas. This dispersion reduces the particle size of the wastewater, shortens the diffusion path of pollutant molecules from the liquid phase to the gas-liquid interface, and increases the apparent mass transfer rate on the liquid film side of the gas-liquid interface. This green, low-carbon, and highly efficient ozone oxidation device uses the gas phase as the continuous phase while minimizing the particle size of the wastewater (reducing the diffusion path length of pollutant molecules from the liquid phase to the gas-liquid interface), significantly improving the gas-liquid mass transfer coefficient and the gas-liquid interface area. This, in turn, increases the contact probability between ozone molecules and pollutants in the liquid phase, ultimately achieving the goal of increasing the oxidation reaction rate.

[0026] Furthermore, a biofilm catalytic component is installed below the atomizing spray component. The biofilm catalytic component consists of several catalytic rods with an ozone catalytic coating on their surfaces. By utilizing the curved surfaces of these catalytic rods, droplets adhere to the surface of the catalytic rods to form a spreading liquid film, which shortens the diffusion path of ozone molecules into organic molecules in the liquid film. With the help of the ozone catalytic coating on the surface of the catalytic rods, organic molecules in the wastewater are catalytically degraded, thereby improving catalytic efficiency.

[0027] In some embodiments, this invention further includes a set of micro-bubbling reaction components in the atomizing spray assembly and the biofilm catalytic assembly. This slows down the downward movement of wastewater. The atomizing spray assembly sprays fine droplets (100-1000 μm), which react with the continuous ozone phase. Partial degradation of organic matter occurs during this reaction, while the undegraded organic matter falls into the narrowing tube along with the droplets. Ozone gas molecules moving upward from the bottom of the narrowing tube encounter the downward-moving wastewater within the constricted section, causing bubbling. The degradation of organic matter is further enhanced under the catalytic action of the ozone catalytic coating. For larger, more difficult-to-degrade organic molecules, the wastewater flow rate is significantly slowed down in the narrow section, allowing these molecules to be adsorbed by the organic matter-capturing coating within the narrow section. Enhanced degradation occurs under prolonged ozone bubbling. This invention combines two mass transfer methods—continuous gas-phase ozone / atomized wastewater and micro-bubbling—significantly improving ozone utilization efficiency and the degradation effect of ozone on organic matter in wastewater. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the overall structure of the green, low-carbon, and high-efficiency ozone oxidation device in Example 1.

[0029] Figure 2 This is a schematic diagram of the membrane catalytic module and circulation branch pipe in the green, low-carbon, and high-efficiency ozone oxidation device of Example 1.

[0030] Figure 3 This is a schematic diagram of the circulation branch pipe in the green, low-carbon, and high-efficiency ozone oxidation device of Example 1.

[0031] Figure 4 This is a schematic diagram of the green, low-carbon, and high-efficiency ozone oxidation device in Example 2. Detailed Implementation

[0032] To better explain and facilitate understanding of this utility model, the present utility model will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0033] Example 1

[0034] like Figure 1 The diagram shown is a schematic of a preferred embodiment of the green, low-carbon, and high-efficiency ozone oxidation device of this utility model. The device includes an ozone reaction tower, which is generally rectangular (or cylindrical), with a four-sided cone at the bottom to form a water collection area (or a cone). The water collection area is 0.5m high and has a cone angle of 90 degrees. The ozone reaction tower has a total height of 3.5m, a length of 1.5m, and a width of 1m. The ozone reaction tower is completely enclosed, and a pressure reducing valve 9 and a pressure gauge 11-1 are installed at the top. The ozone reaction tower is made of plastic (in other embodiments, it can be stainless steel or concrete). The ozone reaction tower has three sets of biofilm catalytic components 2, spaced apart in the height direction. Atomizing spray components 1 are spaced a certain distance above each set of biofilm catalytic components 2, and a total of three sets of atomizing spray components 1 are installed inside the ozone reaction tower. The atomizing spray assembly 1 includes several atomizing nozzles 101. The flow rate of a single atomizing nozzle 101 is 20L / min, and the operating pressure is 0.7bar. The atomizing nozzle 101 is a solid conical nozzle that can treat wastewater into droplets with a diameter of 100-1000μm.

[0035] The atomizing spray assembly 1 is connected to a circulation branch pipe located outside the ozone reaction tower. The circulation branch pipe is connected to the circulation main pipe, and the lower end of the circulation main pipe is connected to a three-way valve 4. One end of the three-way valve 4 is connected to an external drain pipe 41, and the other end is connected to the ozone reaction tower's outlet pipe 42. A circulation pump 3 is installed on the outlet pipe 42, which is connected to the outlet of the water collection area at the bottom of the ozone reaction tower. The outlet pipe 42, external drain pipe 41, circulation pump 3, circulation main pipe, and circulation branch pipe constitute the wastewater inlet / outlet and circulation device. The circulation main pipe is also connected to the inlet water to be treated, allowing the inlet water and the circulating water at the bottom of the ozone reaction tower to merge and be transported together to the atomizing spray assembly 1 through the circulation branch pipe. A pressure gauge 11-2 is installed on the circulation main pipe, and individual control valves are installed at the connections between the circulation main pipe and each group of circulation branch pipes. These control valves can be used to adjust the number of atomizing spray assemblies 1 operating inside the ozone reaction tower. The outlet pipe 42 is connected to the circulation main pipe and the external drain pipe 41 by a three-way valve 4. The circulation main pipe is connected to the inlet water, and the wastewater to be treated is continuously introduced into the inlet water. The treated wastewater is continuously discharged out through the external drain pipe 41. A portion of the water in the ozone reaction tower's water collection area is mixed with the inlet water through the circulation main pipe and then sprayed into the ozone reaction tower through the circulation branch pipe and the atomizing spray assembly 1. The other portion of the water in the water collection area is discharged out through the external drain pipe 41, thus forming a continuous inlet / outlet ozone advanced oxidation process.

[0036] The biofilm catalytic module 2 includes several catalytic rods 21. The cross-section of the catalytic rods 21 is circular, elliptical, gourd-shaped, or droplet-shaped. If the catalytic rod has an elliptical cross-section, its major axis is arranged vertically. Figure 2 As shown, in this embodiment, the catalyst rod 21 has a circular cross-section with a diameter of 5 cm. The catalyst rods 21 in each attached-film catalytic assembly 2 are distributed in multiple layers, each layer containing several dry catalyst rods 21, which are made of stainless steel. Figure 3 As shown, the top layer has 5 catalyst rods, the second layer has 6, and the third layer has 5. The single-layer catalyst rods are evenly arranged, with a spacing of approximately 4 times the diameter of the catalyst rod; the catalyst rods in adjacent layers are staggered, with a spacing of 2 times the diameter of the catalyst rod. The staggered arrangement refers to... Figure 2 As shown, one layer of catalyst rods is positioned precisely within the spacing between the other two layers. A layer of MnO2 is coated on the surface of the catalyst rod 21, which has ozone catalytic activity. The catalyst rod 21 is mounted and fixed on the mounting bracket 10 on the inner wall of the ozone reaction tower. In this embodiment, the ozone reaction tower is equipped with three sets of catalyst rods, each set constituting a film-attached catalytic assembly 2. The distance between the uppermost catalyst rod of the film-attached catalytic assembly 2 and the lower edge of its upper atomizing nozzle 101 is 18 cm. As the droplets sprayed from the atomizing spray assembly 1 fall, they slide along the curved surface of the catalyst rod 21 and form a liquid film on the surface of the catalyst rod 21. This liquid film is in continuous contact with ozone gas, and because the surface of the catalyst rod 21 has MnO2, it can catalyze the oxidation rate and oxidation intensity of organic matter in wastewater by ozone.

[0037] Combination Figure 3 As shown, since the number of atomizing spray assembly 1 is 3, the number of circulating branch pipes in this embodiment is also 3, and each group of circulating branch pipes contains 2 circulating branch pipes, each of which is equipped with 3 atomizing nozzles 101. The 3 groups of circulating branch pipes are spaced apart in height, each group of circulating branch pipes contains 2 circulating branch pipes, and 3 atomizing nozzles 101 are installed on each circulating branch pipe. The 6 atomizing nozzles 101 form one atomizing spray assembly 1. In this embodiment, the number of atomizing nozzles 101 is 18. Each group of circulating branch pipes is equipped with an independent valve, which can adjust the water inflow of each circulating branch pipe.

[0038] A gas-liquid separator 6 is installed near the top of the ozone reaction tower. The gas-liquid separator 6 consists of a set of inclined corrugated plates made of plastic, with a 2mm gap between adjacent plates. Figure 1 As shown, the corrugated plate is installed with the corrugation extension direction aligned with its tilt direction. A layer of catalyst material, MnO2, is coated on the corrugated plate. The distance from the bottom of the gas-liquid separator 6 to the upper edge of the top atomizing nozzle 101 is 10 cm, and the distance from the top of the gas-liquid separator 6 to the top of the ozone reaction tower is 25 cm.

[0039] An ozone recovery pipe 71 is located at the top of the ozone reaction tower, above the gas-liquid separator 6. An exhaust fan 7 is mounted on the ozone recovery pipe 71 to recycle and reuse the ozone collected at the top of the ozone reaction tower. The lower part of the ozone recovery pipe 71 is connected to a compressor 8, which pressurizes and concentrates the recovered ozone before returning it to the ozone inlet 81 at the bottom of the ozone reaction tower, through which it enters the ozone reaction tower. The ozone inlet 81 is positioned within the ozone reaction tower above the liquid level in the water collection area but below the lowest layer of the biofilm catalytic module 2. An online ozone detector 12 is also installed on the ozone recovery pipe 71, in front of the compressor 8. This detector monitors the ozone concentration in the ozone recovery pipe 71; if the ozone concentration is low, new ozone needs to be added to the ozone reaction tower.

[0040] Specifically, an ozone generator 5 is installed outside the ozone reaction tower, which is connected to the bottom of the ozone reaction tower via a vent pipe 51. Inside the ozone reaction tower, the vent pipe 51 is located between the liquid surface of the water collection area and the bottommost catalytic membrane attachment device 2. The ozone online detector 12 on the ozone recovery pipe 71 is connected to the controller of the ozone generator 5. The controller calculates the amount of fresh ozone that needs to be replenished based on the detection value (concentration) of the ozone online detector 12, combined with the volume of the ozone reaction tower and the set ozone concentration value. Based on the calculation result, the controller controls the ozone generator 5 to work and generate the required amount of ozone. The generated ozone is sent into the ozone reaction tower through the vent pipe 51, or the generated new ozone can be connected to the ozone recovery pipe 71, and the new ozone and the recovered ozone can be combined and compressed together by the compressor 8 to increase the concentration before being introduced into the ozone reaction tower through the ozone inlet 81.

[0041] The processing procedure of the green, low-carbon, and high-efficiency ozone oxidation device in this embodiment is as follows:

[0042] The pH of the effluent from the sand filter is adjusted to between 6.0 and 7.0. It is then connected to the main circulation pipe and merged with the circulating wastewater from the collection area. The wastewater enters the ozone reaction tower through a circulation branch pipe and is dispersed into tiny droplets with a diameter of 100-1000 μm by the atomizing spray assembly 1. Under the combined action of gravity and rising gas, the droplets descend. During this descent, the droplets first come into contact with the continuous ozone atmosphere, where pollutants in the droplets undergo oxidation with ozone molecules and derived hydroxyl radicals, resulting in degradation. Simultaneously, a large number of droplets adhere to the surface of each catalyst rod 21 of the catalytic film attachment device 2, forming a thin liquid film. Pollutants in this liquid film come into contact with the ozone catalyst MnO2 on the surface of the catalyst rod 21, undergoing further oxidation under the catalytic action of the catalyst, resulting in further degradation of the pollutants. The droplets finally fall into the collection area at the bottom of the ozone reaction tower, where they are circulated and sprayed into water mist and oxidized by ozone under the action of the circulation pump 3. The outlet pipe 4 is connected to the circulation pump 3, the outlet end of the circulation pump 3 is connected to the three-way valve 4, the three-way valve 4 is connected to the main circulation pipe, the main circulation pipe is also connected to the inlet water, and the three-way valve 4 is also connected to the external drain pipe 41. Water is continuously supplied to adjust the pH to 6.0-7.0, and water is continuously discharged through the external drain pipe 41. Part of the water in the collection area is discharged, and part of it is diluted with the inlet water and sprayed into the ozone reaction tower as a mist droplets by the circulation branch pipe and the atomizing spray assembly 1.

[0043] Ozone gas generated by ozone generator 5 is introduced from the bottom of the ozone reaction tower. The ozone flow rate is adjustable. The ozone rises from the bottom of the tower, contacting wastewater droplets and the liquid film on the surface of catalyst rod 21 during its ascent. Pollutants in the wastewater react with ozone molecules and derived oxides such as hydroxyl radicals, achieving organic degradation. During its ascent, the gas carries some droplets. This gas-liquid mixture is then separated by gas-liquid separator 6. The separated aqueous phase flows back down along the corrugated plate surface, while the gas continues to rise. The returning liquid wastewater contacts the catalyst MnO2 and ozone on the corrugated plate surface, further oxidizing and degrading the organic matter.

[0044] Ozone-containing gas separated at the top of the ozone reactor is recycled back to the bottom of the reactor via ozone recovery pipe 71, exhaust fan 7, and compressor 8, thus achieving ozone gas recycling and improving ozone utilization efficiency. The exhaust fan 7 and compressor 8 have a flow rate specification of 10 m³ / s. 3 / min. An online ozone detector 12 is installed on the ozone recovery pipe 71. Located at the front end of the compressor 8, the online ozone detector 12 monitors the concentration of recovered ozone in real time. The online ozone detector 12 is also connected to the controller of the ozone generator 5, controlling the start and stop of the ozone generator 5 in real time based on the detected ozone concentration to maintain the ozone gas level inside the ozone reaction tower at a set level, such as 5mg / L-10mg / L. During the operation of the ozone reaction tower, excess gas is discharged through the pressure reducing valve 9 at the top, maintaining the gas pressure inside the ozone reaction tower at 0.1mPa-1.0mPa. Appropriate pressure is beneficial for promoting ozone oxidation efficiency.

[0045] Compared to the conventional bubbling ozone oxidation reaction with wastewater as the continuous phase and ozone as the dispersed phase in a gas-liquid contact mode, this embodiment uses ozone as the continuous phase and wastewater as the dispersed phase, and also sets up a membrane catalytic component 2 composed of an array of catalytic rods 21, forming a gas-liquid-solid three-phase reaction system inside the ozone reaction tower.

[0046] Example 2

[0047] This embodiment is a further improvement on the green, low-carbon, and high-efficiency ozone oxidation device based on Embodiment 1, such as... Figure 4As shown, a micro-bubbling reaction assembly 13 is also provided between the two lower sets of atomizing spray assembly 1 and the biofilm catalytic assembly 2. The micro-bubbling reaction assembly 13 includes a porous support mesh 131 installed on the inner wall of the ozone reaction tower. Some holes in the porous support mesh are fitted with narrow-diameter tubes 132, corresponding to the number of atomizing nozzles 101. Each layer has six narrow-diameter tubes, with flared ends and a narrow middle section. The upper opening of the narrow-diameter tube faces the atomizing nozzles 101 of the atomizing spray assembly 1, and the lower opening faces the biofilm catalytic assembly 2. The inner wall of the narrow-diameter tube 132 is coated with an organic matter capturing coating and an ozone catalytic coating, which are alternately arranged in a spot pattern. There are openings between the narrow-diameter tubes 132, allowing ozone to move from below towards one side of the atomizing spray assembly 1. Ozone introduced from the bottom of the ozone reaction tower reaches the area below the atomizing nozzles 101 through the openings, forming a continuous ozone phase. An enhanced oxidation environment is formed inside the narrow-diameter tube 132. The upper end of the narrowed tube 132 is approximately 5 cm from the lower edge of the atomizing nozzle 101 of the atomizing spray assembly, and the lower edge is 2 cm from the upper edge of the topmost catalytic rod of the single-unit film-coated catalytic assembly; the narrow section of the narrowed tube has a diameter of approximately 2 cm and a length of approximately 7 cm. The ozone catalytic coating can be MnO2, and the organic matter capture coating can be a hydrophobic silane coupling agent (aminopropyltriethoxysilane, APTES) coating; the silane coupling agent is applied at a density of 0.5-1 cm. 2 The irregular spots are sprayed onto the surface of the MnO2 coating. The hydrophilic end of the silane coupling agent is connected to the MnO2, while the hydrophobic end of the silane coupling agent faces outward. They can capture organic molecules in the water.

[0048] This embodiment combines the contact method of continuous ozone gas phase with discontinuous wastewater with the traditional bubbling reaction method by setting up a micro-bubbling reaction component 13. This avoids the rapid fall of recalcitrant organic molecules with water droplets into the collection area. The inner wall of the narrow-diameter pipe 132 is coated with an organic matter capturing coating to retain recalcitrant organic matter, which can further improve the degradation rate of organic matter during one cycle of wastewater. Compared with Embodiment 1, the green, low-carbon, and high-efficiency ozone oxidation device of this embodiment can reduce the COD of wastewater to the set value in a shorter time.

[0049] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this utility model, and are not intended to limit it. Although the utility model has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this utility model.

Claims

1. A green, low-carbon, and high-efficiency ozone oxidation device, characterized in that, include: An ozone reaction tower is provided; at least one set of biofilm catalytic modules is installed inside the ozone reaction tower, and a set of atomizing spray modules is installed above each set of biofilm catalytic modules at a certain distance; a gas-liquid separator is installed near the top of the ozone reaction tower; an ozone recovery pipe is connected to the top of the ozone reaction tower, and the ozone recovered from the top of the tower is introduced into the bottom of the tower through the ozone recovery pipe; a water collection area is also provided at the bottom of the ozone reaction tower, and a water outlet pipe is provided in the water collection area. The water outlet pipe is connected to a circulation main pipe and an external drainage pipe. The circulation main pipe is connected to several sets of circulation branch pipes, and each set of circulation branch pipes is respectively connected to one set of the atomizing spray modules; the circulation main pipe is also connected to the inlet water. The atomizing spray assembly is used to spray the wastewater to be treated by ozone downwards in the form of mist droplets; the attached membrane catalytic assembly includes multiple catalytic rods, each of which is coated with an ozone catalyst coating; the multiple catalytic rods are arranged to form the attached membrane catalytic assembly.

2. The green, low-carbon, and high-efficiency ozone oxidation device according to claim 1, characterized in that, The atomizing spray assembly includes an atomizing nozzle, which is a solid conical nozzle capable of treating wastewater into droplets with a diameter of 100-1000μm; the catalyst rod has a cross-section that is circular, elliptical, gourd-shaped, or droplet-shaped, and the equivalent diameter of each catalyst rod is 1-5cm; the catalyst rod with an elliptical cross-section has its long axis arranged vertically.

3. The green, low-carbon, and high-efficiency ozone oxidation device according to claim 1 or 2, characterized in that, The catalytic rods of the attached membrane catalytic module are arranged in two or more layers with interlayer spacing; the single-layer catalytic rods are arranged in parallel and a rod spacing is formed between the two catalytic rods; the adjacent two layers of catalytic rods are arranged alternately, so that one layer of catalytic rods is exactly located within the rod spacing of another layer of catalytic rods.

4. The green, low-carbon, and high-efficiency ozone oxidation device according to claim 1 or 2, characterized in that, The catalytic rods of the attached membrane catalytic module are arranged in two or more layers with interlayer spacing; the single-layer catalytic rods are arranged in parallel and a rod spacing is formed between the two catalytic rods; the adjacent two layers of catalytic rods are arranged in a cross pattern, so that one layer of catalytic rods exactly intersects with another layer of catalytic rods.

5. The green, low-carbon, and high-efficiency ozone oxidation device according to claim 3, characterized in that, The ozone reaction tower is equipped with three sets of attached biofilm catalytic modules and three sets of atomizing spray modules from bottom to top. Each catalytic rod of the attached biofilm catalytic module is installed and fixed on the mounting bracket on the inner wall of the ozone reaction tower. The vertical distance between the lower edge of the atomizing nozzle of the uppermost catalytic rod of a single attached biofilm catalytic module and the corresponding atomizing spray module above it is 15cm-30cm. The single-layer catalytic rods are arranged in parallel and the spacing between two catalytic rods is 3-10 times the diameter of the catalytic rod. The spacing between two layers of catalytic rods is 1-3 catalytic rod diameters.

6. The green, low-carbon, and high-efficiency ozone oxidation device according to claim 2, characterized in that, Between at least one set of atomizing spray components and a biofilm catalytic component, there is also a set of micro-bubbling reaction components; the micro-bubbling reaction components include a porous support mesh installed on the inner wall of the ozone reaction tower, with a narrowing tube installed on the porous support mesh, the two ends of the narrowing tube being flared and the middle being narrow; the upper opening of the narrowing tube faces the atomizing nozzle of the atomizing spray component, and the lower opening faces the biofilm catalytic component; the inner wall of the narrowing tube is coated with an organic matter capturing coating and an ozone catalytic coating; the two coatings are alternately arranged in a spot pattern, and there are gaps between the narrowing tubes; the diameter of the narrow section is 0.5-3cm, and the length of the narrow section is 5-20cm.

7. The green, low-carbon, and high-efficiency ozone oxidation device according to claim 3, characterized in that, Each set of circulation branch pipes contains two or more circulation branch pipes, and each circulation branch pipe is connected to at least three atomizing nozzles; the flow rate of a single atomizing nozzle is 10-30L / min, and the operating pressure is 0.5-1bar; the atomizing nozzles are distributed along the width of the ozone reaction tower.

8. The green, low-carbon, and high-efficiency ozone oxidation device according to claim 1, characterized in that, The gas-liquid separator consists of a set of inclined corrugated plates with a spacing of 1-10 mm between adjacent corrugated plates, and the corrugated plates are coated with an ozone catalyst coating.

9. The green, low-carbon, and high-efficiency ozone oxidation device according to claim 1, characterized in that, The green, low-carbon, and efficient ozone oxidation device also includes an ozone generator located outside the ozone reaction tower; an online ozone detector on the ozone recovery pipe; the online ozone detector being connected to the controller of the ozone generator; when the online ozone detector detects insufficient ozone concentration in the ozone recovery pipe, it controls the ozone generator to turn on to replenish new ozone into the ozone reaction tower; or an online ozone detector is installed in the middle of the ozone reaction tower, the online ozone detector being connected to the controller of the ozone generator, and when it detects insufficient ozone concentration in the ozone reaction tower, it controls the ozone generator to turn on to replenish new ozone into the ozone reaction tower.

10. The green, low-carbon, and high-efficiency ozone oxidation device according to claim 1, characterized in that, The outlet pipe is connected to the main circulation pipe and the external drain pipe via a T-connector. The main circulation pipe is connected to the inlet water, and the inlet water continuously carries in the wastewater to be treated. The external drain pipe continuously discharges the treated wastewater. A portion of the water in the collection area is mixed with the inlet water through the main circulation pipe and then sprayed into the ozone reaction tower through the circulation branch pipe and the atomizing spray assembly. Another portion of the water in the collection area is discharged out through the external drain pipe.

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