Micro-tubular reactor and system based on modified honeycomb ceramic ozone catalyst

Abstract

The utility model discloses a microtubular reactor and system based on modified honeycomb ceramic ozone catalyst, microtubular reactor includes liquid inlet cylinder, reaction cylinder and liquid outlet cylinder that connect in proper order, liquid inlet cylinder outer end and liquid outlet cylinder outer end are both plugged, liquid inlet cylinder, reaction cylinder and liquid outlet cylinder are communicated in proper order, liquid inlet cylinder outer end and liquid outlet cylinder outer end are sealed. The liquid inlet cylinder, the reaction cylinder and the liquid outlet cylinder form a closed structure, an inner module made of modified honeycomb ceramics is arranged in the reaction cylinder, the liquid inlet cylinder is fixedly connected with a wastewater inlet pipe and an ozone inlet pipe, and the liquid outlet cylinder is connected with an outlet pipe. And the length or the number of the reaction cylinders can be correspondingly adjusted according to actual requirements (such as treatment capacity, treatment speed and treatment effect), so that the reaction device can adapt to different treatment requirements. And the inner module can be replaced, so that the operation cost of the utility model can be reduced.

Description

Technical Field

[0001] This utility model relates to the field of wastewater treatment equipment technology, and in particular to a microtube reactor and system based on a modified honeycomb ceramic ozone catalyst. Background Technology

[0002] In the process of industrialization and urbanization, wastewater often contains a large amount of recalcitrant organic matter. These organic compounds include dyes, pesticides, pharmaceutical intermediates, and synthetic organics, characterized by strong chemical stability and poor biodegradability. Polycyclic aromatic hydrocarbons (PAHs), as a class of organic compounds containing two or more benzene rings, are widely present in the environment, especially in water bodies. They mainly originate from the combustion of fossil fuels such as coal and petroleum, as well as industrial production and processing. Ozone catalytic oxidation technology, as an advanced oxidation technology, utilizes the strong oxidizing properties of ozone and the catalytic effect of a catalyst to decompose recalcitrant PAHs into harmless small molecules, thereby achieving effective pollutant removal. This technology uses ozone as an oxidant, and through the action of a catalyst, decomposes ozone into hydroxyl radicals (·OH) with higher redox potentials, thereby accelerating the decomposition of ozone and the oxidation of organic matter to achieve effective removal of PAHs.

[0003] Furthermore, the strong oxidant hydroxyl radicals (·OH) generated during ozone catalytic oxidation have a short quenching time, resulting in low ozone utilization. While the application of catalysts can improve the low ozone utilization, they present challenges in solid-liquid separation during operation. Additionally, the micron-sized channels of microchannel reactors are prone to clogging, significantly impacting their effectiveness in the catalytic process.

[0004] A microtube reactor is a device that uses microscale channels to carry out chemical reactions. Because the microchannels are extremely small (typically at the micrometer level), the mass transfer efficiency between reactants and products is extremely high.

[0005] Existing microtubular reactors are manufactured using a single piece of honeycomb ceramic and a molded shell, resulting in a fixed processing capacity and efficiency. Furthermore, the processing efficiency and effectiveness of microtubular reactors gradually decrease over time, necessitating replacement of the entire reactor once the required process conditions are not met. Therefore, these microtubular reactors exhibit poor selectivity and high operating costs.

[0006] Patent CN201694885U discloses an ozone catalytic oxidation pollution removal device, including an ozone generator, a water jet injector for introducing water to be treated, an ozone catalytic oxidation reaction tank containing a metal oxide-loaded honeycomb ceramic catalyst occupying 30-50% of the reaction tank volume, and a one-way valve, all connected by pipelines. The patent also provides a wastewater treatment system and a water supply treatment system using the aforementioned ozone catalytic oxidation pollution removal device. This application can effectively oxidize and decompose various toxic, harmful, highly stable, and recalcitrant organic compounds in water, significantly improving water quality, strengthening environmental protection, and safeguarding public health. It achieves high pollution removal efficiency with relatively small investment, making it suitable for large-scale application. However, because the honeycomb ceramic is filled inside the ozone catalytic oxidation reaction tank, its treatment effect and capacity are fixed and cannot be adjusted according to actual conditions. Furthermore, replacing the honeycomb ceramic is very inconvenient.

[0007] Patent CN103395874A discloses an improved structure of a baffled internal circulation biofilm reactor. It includes a reactor body divided into a turbulent flow zone and a biological reaction zone by partitions. The biological reaction zone is further divided into flow channels by at least two small partitions. Honeycomb ceramics are installed between the partitions as a biofilm carrier. This allows for adjustment of the aeration rate according to the wastewater treatment load to control the dissolved oxygen content within the reactor, achieving efficient removal of organic matter, ammonia nitrogen, and total nitrogen from the wastewater. However, the number of honeycomb ceramics used is fixed and cannot be replaced according to actual needs. Utility Model Content

[0008] The technical problem to be solved by this utility model is to provide a microtube reactor and system based on a modified honeycomb ceramic ozone catalyst, in order to solve the problems of poor adaptability and high operating cost of current microtube reactors.

[0009] To solve the above-mentioned technical problems, the technical solution adopted by this utility model is as follows:

[0010] A microtube reactor based on a modified honeycomb ceramic ozone catalyst includes an inlet cylinder, a reaction cylinder, and an outlet cylinder connected in sequence. The outer ends of the inlet cylinder and the outlet cylinder are sealed. The inlet cylinder, reaction cylinder, and outlet cylinder are connected in sequence and form a closed structure. An inner module made of modified honeycomb ceramic is provided inside the reaction cylinder. A wastewater inlet pipe and an ozone inlet pipe are fixedly connected to the inlet cylinder. An outlet pipe is connected to the outlet cylinder.

[0011] Furthermore, the number of reaction cylinders is at least two connected sequentially along the axial direction. The two outer reaction cylinders are connected to the inlet cylinder and the outlet cylinder respectively. The inner modules in each reaction cylinder are several stacked sequentially along the axial direction. Adjacent reaction cylinders, inlet cylinders and corresponding reaction cylinders, and outlet cylinders and corresponding reaction cylinders are all connected by clamps.

[0012] A microtube reaction system based on a modified honeycomb ceramic ozone catalyst is provided. The system employs a microtube reactor based on the modified honeycomb ceramic ozone catalyst described above. The wastewater inlet pipe is connected to a liquid supply main pipe, and the outlet pipe is sequentially connected to a liquid outlet main pipe, a gas-liquid separator, and an ozone digestion tank. The ozone inlet pipe is sequentially connected to an ozone main pipe and an ozone generator.

[0013] Furthermore, at least two supply branch pipes are connected to one end of the main supply pipe, and there are at least two microtube reactors. The number of microtube reactors forms a reactor group with the same number of supply branch pipes. The reactor groups are connected sequentially, and each reactor group corresponds to one supply branch pipe. One end of each supply branch pipe is connected to the main supply pipe, and the other end is connected to the wastewater inlet pipe of the corresponding microtube reactor in the reactor group.

[0014] Furthermore, one end of the liquid outlet main pipe is connected to the gas-liquid separator, and the other end is connected to a liquid outlet branch pipe. The number of liquid outlet branch pipes is the same as that of the liquid supply branch pipes. One end of each liquid outlet branch pipe is connected to the liquid outlet main pipe, and the other end is connected to the outlet pipe of the microtube reactor.

[0015] Furthermore, one end of the main ozone pipe is connected to the ozone generator, and the other end is connected to an ozone branch pipe. The number of ozone branch pipes is the same as that of the liquid supply branch pipes. One end of each ozone branch pipe is connected to the main ozone pipe, and the other end is connected to the ozone inlet pipe of the microtube reactor.

[0016] Furthermore, the outlet pipe of the microtubular reactor in the reactor group and the wastewater inlet pipe of the reactor in the adjacent reactor group are connected by a connecting pipe, and valves are provided on the connecting pipe, the liquid supply branch pipe, the ozone branch pipe and the liquid outlet branch pipe.

[0017] Furthermore, a water tank is connected to the end of the main liquid supply pipe away from the branch liquid supply pipe, and a first water pump and a first flow meter are sequentially installed on the main liquid supply pipe from the water tank to the branch liquid supply pipe.

[0018] The positive effects of this utility model are:

[0019] The microtube reactor includes an inlet cylinder, a reaction cylinder, and an outlet cylinder. An inner module is installed inside the reaction cylinder. The inlet cylinder is connected to a wastewater inlet pipe and an ozone inlet pipe, and the outlet cylinder is connected to an outlet pipe. The inner module is made of modified microtube honeycomb ceramic loaded with a catalyst. The length or number of reaction cylinders can be adjusted according to actual needs (such as throughput, processing speed, and treatment effect), thus adapting this invention to different treatment requirements. The inner module is replaceable, thereby reducing the operating cost of this invention. Microtube reactors can be assembled into reactor groups, connected in series or parallel to increase throughput or treatment effect. Due to the use of integrated molding technology for modified honeycomb ceramic and catalyst, the problems of precision machining and easy clogging of microchannels are improved, achieving efficient ozone utilization with a smaller mass transfer distance in the microtube reactor. This invention achieves complementary advantages by combining honeycomb ceramic, ozone catalyst, and microtube reactor. The honeycomb ceramic is modified, and the catalyst is fixed on the modified honeycomb ceramic with a microporous structure, which is then assembled into a microtube reactor. This invention utilizes microtubes with millimeter-level diameters to reduce mass transfer distance, achieving efficient mass transfer and rapid response, overcoming the low ozone utilization rate problem faced by single ozone catalytic oxidation technologies. Larger pore sizes and a catalyst-ceramic integrated internal module significantly reduce the risk of catalyst detachment and clogging of the pipes, extending its service life. Furthermore, its modular design allows for flexible scale-up production in practical engineering applications. Attached Figure Description

[0020] Figure 1 This is a structural schematic diagram of Example 1;

[0021] Figure 2 This is a schematic diagram of the internal module in Example 1;

[0022] Figure 3 This is a schematic diagram of the arrangement of the internal modules in Embodiment 1;

[0023] Figure 4 This is a structural schematic diagram of Example 2;

[0024] Figure 5 This is a schematic diagram of the structure of Example 3;

[0025] Figure 6 The graph shows the experimental data from Example 3;

[0026] In the picture:

[0027] 1. Wastewater pipe; 2. Water tank; 3. Liquid outlet pipe; 4. Water pump; 5. Main liquid supply pipe; 6. Exhaust gas emission pipe; 7. First flow meter; 8. First valve; 9. First liquid supply branch pipe; 10. Microtubular reactor; 11. Second valve; 12. Second liquid supply branch pipe; 13. Main liquid outlet pipe; 14. First liquid outlet branch pipe; 15. Second liquid outlet branch pipe; 16. Gas-liquid separator; 17. Ozone digestion tank; 18. Internal module; 19. Third valve; 20. Fourth valve; 21. First ozone... 21. Branch pipe; 22. Fifth valve; 23. Sixth valve; 24. Second ozone branch pipe; 25. Second flow meter; 26. Ozone main pipe; 27. Ozone generator; 28. Inlet pipe; 29. ​​Air pump; 30. Connecting pipe; 31. Seventh valve; 32. Wastewater inlet pipe; 33. Ozone inlet pipe; 34. Reaction cylinder; 35. Clamp; 36. Liquid outlet cylinder; 37. Outlet pipe; 38. Liquid inlet cylinder; 39. Liquid supply branch pipe; 40. Liquid outlet branch pipe; 41. Ozone branch pipe; 42. Flange. Detailed Implementation

[0028] Example 1

[0029] like Figures 1 to 3 As shown, a microtubular reactor based on a modified honeycomb ceramic ozone catalyst includes an inlet cylinder 38, a reaction cylinder 34, and an outlet cylinder 36 connected vertically in sequence. The inlet cylinder 38, reaction cylinder 34, and outlet cylinder 36 are all cylindrical and made of polyurethane. The outer ends of the inlet cylinder 38 and the outlet cylinder 36 are sealed. The inlet cylinder 38, reaction cylinder 34, and outlet cylinder 36 are coaxial and sequentially connected, forming a closed structure. An inner module 18 made of modified honeycomb ceramic is disposed inside the reaction cylinder 34, and the inner module 18 is cylindrical in shape. A wastewater inlet pipe 32 is fixedly connected to the top of the inlet cylinder 38, an ozone inlet pipe 33 is fixedly connected to the outer wall of the inlet cylinder 38, and an outlet pipe 37 is connected to the lower end of the outlet cylinder 36.

[0030] The reaction cylinders 34 are two units connected sequentially along the axial direction. Both ends of the reaction cylinder 34, the lower end of the inlet cylinder 38, and the upper end of the outlet cylinder 36 are all flanges 42. The upper reaction cylinder 34 is connected to the inlet cylinder 38, the two reaction cylinders 34 are connected to each other, and the lower reaction cylinder 34 is connected to the outlet cylinder 36 by annular clamps 35 fitted onto the corresponding flanges 42. Each reaction cylinder 34 contains three inner modules 18 stacked sequentially along the axial direction. The inner modules 18 are axially positioned by retaining rings that clamp between two adjacent flanges 42.

[0031] Modified honeycomb ceramics refer to modified honeycomb ceramics whose surface has been modified through physical or chemical methods to improve their properties or functions. Modification treatments can enhance the corrosion resistance, improve the thermal stability, and alter the surface wettability of modified honeycomb ceramics, thereby expanding their application range and improving their performance.

[0032] The modified honeycomb ceramic used in this invention is specifically a catalyst-supported modified microtubular honeycomb ceramic, and its preparation method is as follows:

[0033] 1. Raw material preparation: Cordierite powder and metal salt powder are thoroughly mixed and ground at a mass ratio of 80-100:5-10 to prepare ceramic powder. The ceramic powder is then thoroughly mixed with paraffin wax at a mass ratio of 95-99:1-5 to form a flowable ceramic slurry. The metal salt powder is one or more of the following: magnesium nitrate, manganese nitrate, copper nitrate, zinc nitrate, cobalt nitrate, ferric nitrate, cerium nitrate, magnesium chloride, manganese chloride, copper chloride, zinc chloride, cobalt chloride, ferric chloride, cerium chloride, magnesium sulfate, manganese sulfate, copper sulfate, zinc sulfate, cobalt sulfate, ferric sulfate, cerium sulfate, magnesium acetate, manganese acetate, copper acetate, zinc acetate, cobalt acetate, ferric acetate, and cerium acetate.

[0034] 2. Slurry Casting: Prepare a commercially available cylindrical metal honeycomb ceramic mold with a functional diameter (i.e., inner wall cross-sectional dimension) of 250 mm, a groove width (i.e., honeycomb structure wall thickness) of 0.2 mm, circular openings, and an inner tube diameter of 1 mm. Heat the mixed ceramic slurry to a fluid state, and use an air compressor to force the fluid ceramic slurry into the mold. After slurry casting, allow the ceramic slurry to harden naturally at room temperature for 12 to 24 hours.

[0035] 3. Demolding and Finishing: After the ceramic slurry has fully hardened, a ceramic blank of a certain strength is formed. It is then removed from the mold, and necessary finishing processes are performed on the demolded ceramic blank, such as deburring and reshaping. During the finishing process, the integrity and precision of the blank must be maintained.

[0036] 4. Dewaxing treatment: Calcined Al2O3 powder is used as the adsorbent. The preform is buried in the calcined Al2O3 powder, and the temperature is slowly raised to 80℃ and calcined for 1 hour. Then, the temperature is slowly raised to 300℃ and calcined for 1 hour, followed by a slow increase to 600℃ and calcined for 6 hours. The purpose of this operation is to remove the paraffin wax, which acts as a binder, and to prevent the preform from deforming and cracking due to paraffin wax volatilization during secondary calcination.

[0037] 5. Secondary calcination: After removing the wax-removed blank, calcinate it at 900 to 1200℃ for 12 hours, cool it down and remove it to form inner module 18.

[0038] The reactor is assembled as follows:

[0039] 1. The inner module 18 obtained by the above method is assembled in multiple ways according to production needs, and the assembled string of inner modules 18 is installed in the reaction cylinder 34 made of polyurethane.

[0040] 2. Multiple encapsulated reaction cylinders 34 can be connected in series by clamps 35, and adjacent reaction cylinders 34 can be connected by clamps 35. Then, the first and last reaction cylinders 34 can be connected to the inlet cylinder 38 and the outlet cylinder 36 by clamps 35 respectively to form a microtubular reactor 10.

[0041] The number of reaction cylinders 34 can be adjusted according to actual needs (such as processing volume, processing speed, and processing effect), thus adapting this invention to different processing requirements. The internal module 18 can be replaced, thereby reducing the operating cost of this invention.

[0042] Example 2

[0043] like Figure 4 As shown, a microtubular reaction system based on a modified honeycomb ceramic ozone catalyst is used, employing a microtubular reactor based on a modified honeycomb ceramic ozone catalyst as described in Example 1.

[0044] Two microtubular reactors 10 are arranged side-by-side. The microtubular reaction system also includes a water tank 2. The top of the water tank 2 is connected to a wastewater pipe 1 for injecting wastewater into the water tank 2. A main liquid supply pipe 5 is provided on the water tank 2. One end of the main liquid supply pipe 5 is connected to the bottom of the water tank 2, and the other end is connected to two supply branch pipes 39 via a tee. The two supply branch pipes 39 are a first supply branch pipe 9 connected to the wastewater inlet pipe 32 of the left microtubular reactor 10 and a second supply branch pipe 12 connected to the wastewater inlet pipe 32 of the right microtubular reactor 10. A first valve 8 is provided on the first supply branch pipe 9, and a second valve 11 is provided on the second supply branch pipe 12. A water pump 4 and a first flow meter 7 are sequentially arranged on the main liquid supply pipe 5 from the water tank 2 to the supply branch pipes 39.

[0045] The microtubular reaction system also includes two gas-liquid separators 16 arranged side-by-side and connected in parallel, and an ozone digestion tank 17 connected to the gas outlet at the top of the right-hand gas-liquid separator 16. The ozone digestion tank 17 is connected to a tail gas emission pipe 6 for discharging purified tail gas. The bottoms of the two gas-liquid separators 16 are connected to liquid outlet pipes 3 for sending the treated wastewater to the next stage of wastewater treatment equipment.

[0046] The top of the gas-liquid separator 16 on the left is equipped with a main outlet pipe 13. One end of the main outlet pipe 13 is connected to the top of the gas-liquid separator 16, and the other end is connected to two outlet branch pipes 40 via a tee. The two outlet branch pipes 40 are a first outlet branch pipe 14 connected to the outlet pipe 37 of the microtubular reactor 10 on the left, and a second outlet branch pipe 15 connected to the outlet pipe 37 of the microtubular reactor 10 on the right. The first outlet branch pipe 14 is equipped with a fourth valve 20, and the second outlet branch pipe 15 is equipped with a third valve 19.

[0047] The outlet pipe 37 of the left-hand microtubular reactor 10 and the wastewater inlet pipe 32 of the right-hand microtubular reactor 10 are connected by a connecting pipe 30, which is equipped with a seventh valve 31. The second liquid supply branch pipe 12 is connected to the portion of the connecting pipe 30 located to the right of the seventh valve 31, and the first liquid outlet branch pipe 14 is connected to the portion of the connecting pipe 30 located to the left of the seventh valve 31.

[0048] The microtubular reactor system also includes an ozone generator 27, whose inlet is connected to an inlet pipe 28, and an air pump 29 is mounted on the inlet pipe 28. The ozone generator 27 has a main ozone pipe 26, which is equipped with a second flow meter 25. One end of the main ozone pipe 26 is connected to the outlet of the ozone generator 27, and the other end is connected to two ozone branch pipes 41 via a tee. The two ozone branch pipes 41 are a first ozone branch pipe 21 connected to the ozone inlet pipe 33 of the left-hand microtubular reactor 10, and a second ozone branch pipe 24 connected to the ozone inlet pipe 33 of the right-hand microtubular reactor 10. The first ozone branch pipe 21 is equipped with a fifth valve 22, and the second ozone branch pipe 24 is equipped with a sixth valve 23.

[0049] The seventh valve 31 is closed, and the first valve 8, second valve 11, fourth valve 20, third valve 19, fifth valve 22, and sixth valve 23 are all open. At this time, the two microtube reactors 10 are connected in parallel. When the water pump 4 is running, the sewage in the tank 2 flows sequentially through the main supply pipe 5 into the first supply branch pipe 9 and the second supply branch pipe 12, and then into the two microtube reactors 10 respectively. There, it forms a gas-liquid two-phase system with the ozone delivered to the two microtube reactors 10 by the first ozone branch pipe 21 and the second ozone branch pipe 24. The mixture undergoes catalytic oxidation and decomposition within the inner modules 18 (material of modified honeycomb ceramic loaded with catalyst) of two microtubular reactors 10. The resulting liquid then flows through the first and second effluent branch pipes 14 and 15, respectively, converging into the main effluent pipe 13. From there, it enters two gas-liquid separators 16 for gas-liquid separation. The separated liquid flows through the effluent pipe 3 to the next stage of wastewater treatment equipment. The separated exhaust gas enters the ozone decomposition tank 17. After complete ozone decomposition, the exhaust gas is discharged through the exhaust pipe 6. Connecting the two microtubular reactors 10 in parallel increases the wastewater treatment capacity.

[0050] The seventh valve 31, the first valve 8, the third valve 19, the fifth valve 22, and the sixth valve 23 are all open, while the second valve 11 and the fourth valve 20 are closed. The two microtubular reactors 10 can be operated in series, which can increase the reaction time between ozone and wastewater and make the reaction more complete.

[0051] Example 3

[0052] like Figure 5 As shown, the difference between this embodiment and Embodiment 2 is that:

[0053] There are eight microtubular reactors 10, arranged in groups of four to form two reactor groups, one on the left and one on the right. The microtubular reactors 10 in each reactor group correspond one-to-one. Four connecting pipes 30 are installed between the corresponding pairs of microtubular reactors 10, and four seventh valves 31 are installed on the four connecting pipes 30. The wastewater inlet pipes 32 of the microtubular reactors 10 in the left reactor group are all connected to the first supply branch pipe 9 via valves. The outlet pipes 37 of the microtubular reactors 10 in the left reactor group are all connected to the first outlet branch pipe 14. The ozone inlet pipes 33 of the microtubular reactors 10 in the left reactor group are all connected to the first ozone branch pipe 21 via valves.

[0054] The wastewater inlet pipes 32 of the microtubular reactor 10 in the reactor group on the right are all connected to the second liquid supply branch pipe 12 through valves. The outlet pipes 37 of the microtubular reactor 10 in the reactor group on the right are all connected to the second liquid outlet branch pipe 15. The ozone inlet pipes 33 of the microtubular reactor 10 in the reactor group on the right are all connected to the second ozone branch pipe 24 through valves.

[0055] In this embodiment, by adjusting the opening and closing states of the seventh valve 31, the first valve 8, the second valve 11, the fourth valve 20, and the third valve 19, the two reactor groups can be operated in series or in parallel to cope with different operating conditions. The number of microtubular reactors 10 put into operation can be adjusted according to the operating requirements by changing the opening and closing states of the valves in the wastewater inlet pipe 32 and the ozone inlet pipe 33.

[0056] With continuous operation of the treatment process, the catalyst loaded on the modified honeycomb ceramic inevitably faces problems such as detachment, poisoning, and deactivation. Regular maintenance and replacement of the inner module 18 are required during use to ensure purification efficiency. By installing valves at the wastewater inlet pipe 32, ozone inlet pipe 33, and outlet pipe 37, the corresponding valves can be closed, allowing for maintenance or replacement of the microtubular reactor 10 without affecting production. Furthermore, by opening or closing the corresponding valves, the number of microtubular reactors 10 in operation can be adjusted to meet the requirements of actual working conditions.

[0057] The following shows the processing results of this embodiment in the experiment:

[0058] The experimental water was used in a discontinuous flow. The total effective volume of the microtube reactor 10 was 300 ml, and the water residence time in the microtube reactor 10 was 30 min. Ozone was generated by an oxygen source through an ozone generator 27, and the ozone flux was controlled at 4 mg / min by a second flow meter 25. The simulated polluted wastewater was a 100 mg / L m-cresol solution.

[0059] like Figure 6 As shown, the TOC removal was measured after 30 minutes of reaction. The pollutant mineralization after treatment by the reaction system reached 71%, which was 40% and 30% higher than that of ozonation alone and conventional honeycomb ceramic catalytic ozonation systems, respectively. The formulations of the honeycomb ceramics used in the qualitative analysis experiment are as follows: the unmodified honeycomb ceramics have a metal phase ratio of 37% Al2O3, 13% MgO, and 50% SiO2; the Mn-modified honeycomb ceramics in this embodiment have a cordierite metal phase ratio of 33% Al2O3, 12% MgO, 45% SiO2, 3% MnO2, 4% Mn2O3, and 4% Mn3O4; and the Fe / Mn-modified honeycomb ceramics in this patent have a cordierite metal phase ratio of 33% Al2O3, 12% MgO, 45% SiO2, 1% MnO2, 2% Mn2O3, 2% Mn3O4, 1% Fe2O3, 1% Fe3O4, 2% MnFe2O4, and 1% MnFeO3.

[0060] The above-described embodiments are detailed and specific, illustrating preferred embodiments of the present utility model. They are only used to illustrate the technical ideas and features of the present utility model, with the aim of enabling those skilled in the art to understand the content of the present utility model and implement it accordingly. However, they are not limited to the present utility model, and the patent scope of the present utility model cannot be limited by this embodiment alone. That is, any equivalent changes or modifications made to the spirit disclosed in the present utility model, without departing from the structure of the present utility model, such as local improvements within the system and modifications or transformations between subsystems, are still within the patent scope of the present utility model.

Claims

1. A micro-tubular reactor based on a modified honeycomb ceramic ozone catalyst, characterized in that, It comprises a liquid inlet cylinder (38), a reaction cylinder (34) and a liquid outlet cylinder (36) connected in sequence, the outer ends of the liquid inlet cylinder (38) and the liquid outlet cylinder (36) are blocked, the liquid inlet cylinder (38), the reaction cylinder (34) and the liquid outlet cylinder (36) are communicated in sequence, the liquid inlet cylinder (38), the reaction cylinder (34) and the liquid outlet cylinder (36) form a closed structure, the reaction cylinder (34) is provided with an inner module (18) made of modified honeycomb ceramic, the liquid inlet cylinder (38) is fixedly connected with a wastewater inlet pipe (32) and an ozone inlet pipe (33), and the liquid outlet cylinder (36) is connected with an outlet pipe (37).

2. A micro-tubular reactor based on modified honeycomb ceramic ozone catalyst according to claim 1, characterized in that, The number of the reaction cylinders (34) is at least two connected in sequence along the axial direction, the outer two reaction cylinders (34) are connected with the liquid inlet cylinder (38) and the liquid outlet cylinder (36) respectively, and the inner module (18) in each reaction cylinder (34) is a plurality of modules stacked in sequence along the axial direction, and the adjacent reaction cylinders (34), the liquid inlet cylinder (38) and the corresponding reaction cylinder (34), and the liquid outlet cylinder (36) and the corresponding reaction cylinder (34) are connected through a clamp (35).

3. A micro-tubular reactor system based on modified honeycomb ceramic ozone catalyst characterized in that, The micro-tube reactor based on the modified honeycomb ceramic ozone catalyst of claim 1 or 2, the wastewater inlet pipe (32) is connected with a liquid supply main pipe (5), the outlet pipe (37) is connected in sequence with a liquid outlet main pipe (13), a gas-liquid separation tank (16) and an ozone digestion tank (17), and the ozone inlet pipe (33) is connected in sequence with an ozone main pipe (26) and an ozone generator (27).

4. A micro-tubular reaction system based on a modified honeycomb ceramic ozone catalyst according to claim 3, characterized in that, The liquid supply main pipe (5) is connected with at least two liquid supply branch pipes (39) at one end, and there are at least two micro-tube reactors (10), the micro-tube reactors (10) form a reactor group with the same number as the number of the liquid supply branch pipes (39), the reactor groups are connected in sequence, each reactor group corresponds to a liquid supply branch pipe (39), one end of the liquid supply branch pipe (39) is connected with the liquid supply main pipe (5), and the other end is connected with the wastewater inlet pipe of the micro-tube reactor (10) in the corresponding reactor group.

5. A micro-tubular reaction system based on a modified honeycomb ceramic ozone catalyst according to claim 4, characterized in that, The liquid outlet main pipe (13) is connected with the gas-liquid separation tank (16) at one end, and is connected with a liquid outlet branch pipe (40) at the other end, the number of the liquid outlet branch pipe (40) is the same as that of the liquid supply branch pipe (39), one end of the liquid outlet branch pipe (40) is connected with the liquid outlet main pipe (13), and the other end is connected with the outlet pipe (37) of the micro-tube reactor (10).

6. A micro-tubular reaction system based on a modified honeycomb ceramic ozone catalyst according to claim 5, characterized in that, The ozone main pipe (26) is connected with the ozone generator (27) at one end, and is connected with an ozone branch pipe (41) at the other end, the number of the ozone branch pipe (41) is the same as that of the liquid supply branch pipe (39), one end of the ozone branch pipe (41) is connected with the ozone main pipe (26), and the other end is connected with the ozone inlet pipe (33) of the micro-tube reactor (10).

7. A micro-tubular reaction system based on a modified honeycomb ceramic ozone catalyst according to claim 6, characterized in that, The outlet pipe (37) of the micro-tube reactor (10) in the reactor group is connected with the wastewater inlet pipe (32) of the reactor in the adjacent reactor group through a communication pipe (30), and valves are arranged on the communication pipe (30), the liquid supply branch pipe (39), the ozone branch pipe (41) and the liquid outlet branch pipe (40).

8. A micro-tubular reaction system based on a modified honeycomb ceramic ozone catalyst according to claim 3, characterized in that, The water tank (2) is connected to the distal end of the liquid supply main pipe (5) away from the liquid supply branch pipe (39), and the first water pump (4) and the first flow meter (7) are arranged on the liquid supply main pipe (5) in sequence from the water tank (2) to the liquid supply branch pipe (39).

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