Fluidized bed catalytic ozonation-biochemical coupling treatment device

Abstract

A fluidized bed catalytic ozonation-biochemical coupling treatment device comprises an ozone catalyst fluidization expansion unit, an ozone oxidation unit and a biological membrane unit, the ozone oxidation unit and the biological membrane unit are used for being matched with each other, a catalyst is arranged in the ozone oxidation unit, and biological filler is arranged in the biological membrane unit; the ozone catalyst fluidization expansion unit comprises an internal reflux unit and an external reflux unit, the internal reflux unit is arranged on the side wall of the ozone oxidation unit, and the external reflux unit is connected between the ozone oxidation unit and the biological membrane unit; a water inlet ozone adding unit is connected to the bottom of the ozone oxidation unit, a three-phase separator is mounted at the middle upper part in the ozone oxidation unit, and an ozone tail gas destroying unit is connected to the top of the ozone oxidation unit. The utility model aims to overcome the problems of low ozone utilization rate, complex system structure, large occupied area, low treatment efficiency and the like in the prior art, and realizes efficient, stable and economical advanced sewage treatment, especially removal of refractory organics and chromaticity.

Description

TECHNICAL FIELD

[0001] The utility model relates to industrial wastewater advanced treatment technical field especially a fluidized bed ozone catalytic oxidation-biochemical coupling treatment device. BACKGROUND

[0002] With the rapid development of industrialization and urbanization, water pollution problems are becoming increasingly serious, and higher requirements are put forward for wastewater treatment technology. Although the traditional biological treatment method has remarkable effect in removing organic pollutants, it has limited effect on the removal of some refractory organic matter and colority. Therefore, seeking more efficient and more environmentally friendly advanced wastewater treatment technology has become a research hotspot.

[0003] The simple ozone oxidation process has problems such as low ozone utilization rate and incomplete mineralization. The catalytic ozone oxidation technology can significantly improve the oxidation capacity and utilization efficiency of ozone by introducing catalysts. The biofilm method is a biological treatment technology that uses attached microorganisms to degrade pollutants, which has the advantages of high biomass and strong resistance to impact load. The ozone catalytic oxidation-biochemical coupling process combining ozone catalytic oxidation and membrane biological treatment method can improve the overall COD removal rate and reduce the ozone dosage.

[0004] However, the ozone catalytic oxidation device using ozone catalyst fixed bed reactor coupled with the biofilm device still has the following problems:

[0005] (1) The ozone utilization efficiency is not high, resulting in high treatment cost;

[0006] (2) The system structure is complex and the land area is large, which is not conducive to engineering application and promotion;

[0007] (3) The fixed bed reactor is easy to produce local blockage, affecting the long-term operation stability;

[0008] (4) Limited adaptability to water quality and load fluctuations.

[0009] Fluidized bed technology has the characteristics of good mass transfer effect and high reaction efficiency, which can reduce the catalyst required for ozone catalytic oxidation, and does not need to backwash the ozone catalytic oxidation reactor, and is widely used in chemical and environmental protection fields. The application of fluidized bed technology in ozone catalytic oxidation process can reduce the amount of catalyst required, and does not need to backwash the reactor, which is beneficial to improve the overall performance and economy of the system.

[0010] Chinese patent application 202422136700.5 discloses a three-phase ozone biological fluidized bed, which is provided with a support layer, a supporting layer, a biological fluidized layer, a labyrinth biological carrier separator and a three-phase separator from bottom to top inside the main body of the fluidized bed. The reactor realizes the cooperation and combination of ozone advanced oxidation, hydrodynamic cavitation, ozone catalytic oxidation and biological action. The frequency of the control circulating pump is controlled to stabilize the expansion rate of the fluidized bed, and the influence of the change of the water inflow and the water load is reduced. At the same time, the biological carrier separator is arranged between the fluidized layer and the three-phase separator, and the separation effect of the activated carbon carrier particles and the gas and water is further strengthened under the premise of stable expansion rate of the fluidized layer, so as to prevent the activated carbon carrier from flowing out of the reactor with water. However, the patent is not a coupling system of fluidized bed ozone and independent biological membrane reactor, and there may be limitations when treating high-concentration or complex component sewage.

[0011] At present, the coupling of fluidized bed ozone catalytic oxidation technology and independent biological membrane reactor is still less, and such a coupling system is expected to overcome the shortcomings of the prior art and realize more efficient and stable sewage deep treatment. However, how to design a compact, high-efficiency and adaptable fluidized bed ozone catalytic oxidation-biological membrane coupling sewage deep treatment device is still a technical problem to be solved. Utility model content

[0012] The technical problem to be solved by the utility model is to provide a fluidized bed ozone catalytic oxidation-biological coupling treatment device aiming at the shortcomings of the prior art, so as to overcome the problems of low ozone utilization rate, complex system structure, large floor area and low treatment efficiency in the prior art, realize efficient, stable and economic sewage deep treatment, and especially remove refractory organic matter and colority.

[0013] The technical problem to be solved by the utility model is solved through the following technical scheme. The utility model is a fluidized bed ozone catalytic oxidation-biological coupling treatment device, which comprises an ozone catalyst fluidized expansion unit, an ozone oxidation unit and a biological membrane unit for mutual cooperation, the ozone oxidation unit is internally provided with a catalyst, and the biological membrane unit is internally provided with biological filler; the ozone catalyst fluidized expansion unit comprises an internal reflux unit and an external reflux unit, the internal reflux unit is arranged on the side wall of the ozone oxidation unit, and the external reflux unit is connected between the ozone oxidation unit and the biological membrane unit; the ozone oxidation unit is connected with a water inlet ozone adding unit at the bottom, a three-phase separator is installed in the middle upper part of the ozone oxidation unit, and an ozone tail gas destruction unit is connected with the top of the ozone oxidation unit.

[0014] The technical problems to be solved by the utility model also can be further realized through following technical scheme, for the fluidized bed ozone catalytic oxidation-biochemical coupling treatment device described above, the ozone oxidation unit and the biofilm unit are concentric cylinder structure, and the ozone oxidation unit is located in the inner layer.

[0015] The technical problems to be solved by the utility model also can be further realized through following technical scheme, for the fluidized bed ozone catalytic oxidation-biochemical coupling treatment device described above, the ozone oxidation unit and the biofilm unit are left and right structure.

[0016] The technical problems to be solved by the utility model also can be further realized through following technical scheme, for the fluidized bed ozone catalytic oxidation-biochemical coupling treatment device described above, the three-phase separator includes the conical separator body and the flow guide plate arranged up and down, the flow guide channel is formed between the flow guide plate and the conical separator body, the gas outlet and the liquid outlet are arranged at the top of the conical separator body, the gas outlet is communicated with the ozone tail gas destruction unit, and the liquid outlet is communicated with the biofilm unit.

[0017] The technical problems to be solved by the utility model also can be further realized through following technical scheme, for the fluidized bed ozone catalytic oxidation-biochemical coupling treatment device described above, the three-phase separator is located at the 1 / 2~2 / 3 height position of the ozone oxidation unit.

[0018] The technical problems to be solved by the utility model also can be further realized through following technical scheme, for the fluidized bed ozone catalytic oxidation-biochemical coupling treatment device described above, the inner reflux unit includes the inner variable frequency circulating pump and the inner reflux ozone adding unit that are sequentially connected, the inner reflux water inlet that is communicated with the inner reflux unit is arranged on the ozone oxidation unit above the three-phase separator, and the inner reflux water outlet that is communicated with the inner reflux unit is arranged at the bottom of the ozone oxidation unit.

[0019] The technical problems to be solved by the utility model also can be further realized through following technical scheme, for the fluidized bed ozone catalytic oxidation-biochemical coupling treatment device described above, the outer reflux unit includes the outer variable frequency circulating pump and the Venturi ozone dissolved gas unit that are sequentially connected, the outer reflux water outlet that is communicated with the outer reflux unit is arranged at the bottom of the ozone oxidation unit, and the outer reflux water inlet that is communicated with the outer reflux unit is arranged at the bottom of the biofilm unit.

[0020] The technical problems to be solved by the utility model also can be further realized through following technical scheme, for the fluidized bed ozone catalytic oxidation-biochemical coupling treatment device described above, the ozone tail gas destruction unit includes the tail gas collecting pipe, the gas-liquid separation tank and the tail gas destroyer.

[0021] The technical problems solved by the utility model further can be further realized through the following technical solutions, for the fluidized bed ozone catalytic oxidation-biochemical coupling treatment device, the diameter of the catalyst is 1.5~2.5mm, the specific gravity is 1.4~1.8g / cm 3 , the filling amount of the catalyst is 10%~12% of the effective volume of the ozone oxidation unit, the internal reflux ratio of the ozone oxidation unit is 3~5, and the external reflux ratio is 1~2; the height-diameter ratio of the ozone oxidation unit is 4.5~16:1.

[0022] The technical problems solved by the utility model further can be further realized through the following technical solutions, for the fluidized bed ozone catalytic oxidation-biochemical coupling treatment device, the bottom of the ozone oxidation unit is further provided with a water distribution and air distribution unit for cooperating with the water inlet ozone adding unit, the internal reflux unit and the external reflux unit, and the water distribution and air distribution unit is arranged in a spiral upward mode; the bottom of the biological membrane unit is further provided with an aeration unit and a backwashing unit.

[0023] Compared with the prior art, the utility model has the advantages of:

[0024] 1. High-efficiency ozone utilization: the fluidized bed structure significantly improves the utilization efficiency of ozone, and the ozone dosage is only 0.8~1.5mgO3 / mgCOD, which is reduced by 30-50% compared with the traditional process, and the treatment cost is greatly reduced;

[0025] 2. Compact structure: the concentric cylindrical structure design reduces the area occupied by the device by about 40%, which is beneficial to engineering application and popularization;

[0026] 3. Strong impact resistance: the fluidized bed structure and the design of the three-phase separator enhance the impact load resistance of the system, and the device can stably treat sewage with a COD concentration of 80~400mg / L, and has strong adaptability;

[0027] 4. High running stability: the real-time optimization and adjustment of the process parameters are realized, the stability of the treatment effect is ensured, and the system running stability is improved by about 20%;

[0028] 5. Reduced catalyst usage: the fluidized bed structure reduces the usage of catalyst;

[0029] 6. Long service life of catalyst: the fluidized bed structure reduces the carbon deposition and passivation of the catalyst, prolongs the service life of the catalyst, and reduces the operation and maintenance cost;

[0030] 7. Low energy consumption: through optimization design and intelligent control, the overall energy consumption of the system is reduced by about 25% compared with the traditional process. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 It is a structural schematic view of the utility model.

[0032] Figure 2 Another structural schematic view of the utility model;

[0033] Figure 3 The structural schematic view of the three-phase separator of the utility model;

[0034] Figure 4 The structural schematic view of the inner and outer reflux units of the utility model;

[0035] Figure 5 The structural top view of Figure 1 ;

[0036] Figure 6 The structural top view of Figure 2 . DETAILED DESCRIPTION

[0037] In order to make the purpose, technical scheme and advantages of the embodiments of the utility model clearer, the technical scheme in the embodiments of the utility model will be described clearly and completely below in combination with the drawings of the utility model. Obviously, the described embodiments are part of the embodiments of the utility model, rather than all the embodiments. Based on the embodiments in the utility model, all other embodiments obtained by the person skilled in the art without creative labor fall within the protection scope of the utility model.

[0038] Referring to Figures 1-6 , a fluidized bed ozone catalytic oxidation-biochemical coupling treatment device, comprising an ozone catalyst fluidization expansion unit, an ozone oxidation unit 100 and a biofilm unit 200 for mutual cooperation, the ozone oxidation unit 100 is used for providing a fluidization and expansion environment of the catalyst, and the catalyst 106 is built-in, preferably, the catalyst 106 is a spherical alumina supported catalyst, the diameter is 1.5-2.5mm, the specific gravity is 1.4-1.8g / cm 3 , and the filling amount of the catalyst 106 is 10%-12% of the effective volume of the ozone oxidation unit 100; the biofilm unit 200 is built-in biological filler 201, which is used for biodegradation of organic matter in wastewater, preferably, the biofilm unit 200 is built-in MBBR filler, biological rope filler or polyurethane biological filler 201; the biofilm unit 200 is closely matched with the ozone oxidation unit 100 to form a coupling treatment system;

[0039] Specifically:

[0040] The height-diameter ratio of the ozone oxidation unit 100 is 4.5-16:1, the ozone oxidation unit 100 and the biofilm unit 200 are concentric cylindrical structures, and the ozone oxidation unit 100 is located in the inner layer, or the ozone oxidation unit 100 and the biofilm unit 200 are left-right structures.

[0041] An inlet water ozone adding unit 300A is connected to the bottom of the ozone oxidation unit 100, for adding ozone while the inlet water is input, and the ozone dosage is 0.8-1.5 mgO3 / mgCOD; a three-phase separator 101 is installed in the middle and upper part of the ozone oxidation unit 100, for separating gas, liquid and solid particles, avoiding the loss and blockage of the catalyst, preferably, the three-phase separator 101 is located at the 1 / 2-2 / 3 height position of the ozone oxidation unit 100, and the three-phase separator 101 comprises a conical separator body 102 and a flow guide plate 105 arranged in a top and bottom manner, a flow guide channel is formed between the flow guide plate 105 and the conical separator body 102, a gas outlet 103 and a liquid outlet 104 are arranged at the top of the conical separator body 102, the gas outlet 103 is communicated with an ozone tail gas destruction unit 500, and the liquid outlet 104 is communicated with a biofilm unit 200.

[0042] An ozone tail gas destruction unit 500 is connected to the top of the ozone oxidation unit 100, specifically, the ozone tail gas destruction unit 500 comprises a tail gas collecting pipe, a gas-liquid separation tank and a tail gas destroyer;

[0043] The ozone catalyst fluidization expansion unit comprises an inner reflux unit 400B and an outer reflux unit 400C, which ensures the sufficient treatment of the sewage and the effective utilization of the catalyst, the inner reflux unit 400B is arranged on the side wall of the ozone oxidation unit 100, and the outer reflux unit 400C is connected between the ozone oxidation unit 100 and the biofilm unit 200, preferably:

[0044] The inner reflux unit 400B comprises an inner variable frequency circulating pump 402B and an inner reflux ozone adding unit 300B arranged in sequence, an inner reflux inlet 401B communicated with the inner reflux unit 400B is arranged on the ozone oxidation unit 100 above the three-phase separator 101, and an inner reflux outlet 403B communicated with the inner reflux unit 400B is arranged at the bottom of the ozone oxidation unit 100, so that the inner reflux ratio of the ozone oxidation unit 100 is 3-5;

[0045] The outer reflux unit 400C comprises an outer variable frequency circulating pump 402C and a Venturi ozone dissolved gas unit 300C arranged in sequence, an outer reflux inlet 401C communicated with the outer reflux unit 400C is arranged at the bottom of the ozone oxidation unit 100, and an outer reflux outlet 403C communicated with the outer reflux unit 400C is arranged at the bottom of the biofilm unit 200, so that the outer reflux ratio of the ozone oxidation unit 100 is 1-2;

[0046] At the bottom of the ozone oxidation unit 100, a water and air distribution unit 404 is also installed for cooperation with the water inlet ozone adding unit 300A, the internal reflux unit 400B and the external reflux unit 400C, the water and air distribution unit is arranged in a spiral ascending manner, the water and air distribution unit 404 is provided with a water inlet and outlet, the internal reflux outlet 403B and the external reflux outlet 403C are arranged on the water and air distribution unit 404, and at the bottom of the biofilm unit 200, an aeration unit and a backwashing unit are also installed for maintaining the activity of the biofilm and preventing clogging.

[0047] In summary, the ozone catalytic oxidation unit comprises an ozone jet adding unit and a fluidized bed ozone reactor, the fluidized bed ozone reactor comprises a cyclone water and air distribution unit, a reaction zone, a three-phase separator 101, a water outlet device, a circulating device and an ozone tail gas destruction unit 500, the cyclone water and air distribution unit comprises a water inlet and a cyclone water distributor, the reaction zone is internally provided with an ozone catalyst bed, the three-phase separator 101 comprises a sedimentation zone, a reflux gap and a gas collecting chamber, the water outlet device comprises a water collecting tank and a water outlet weir plate, the circulating device comprises internal circulation and external circulation of the ozone oxidation unit 100, and the ozone tail gas destruction unit 500 is connected to the gas chamber of the reactor through a pipeline.

[0048] The flow rate of the reaction zone in the ozone oxidation unit 100 is 4 m / h-10 m / h, and the flow rate of the sedimentation zone is 0.8 m / h; the three-phase separator 101 is an integrated three-phase separator 101 or a split three-phase separator 101, the inclination angle of the inclined plate of the integrated three-phase separator 101 ranges from 55° to 60°, the cover between the reflecting plate and the gap of the split three-phase separator 101 is preferably 100 mm-200 mm, the gap speed is less than or equal to 2 m / h, the height of the sedimentation zone is greater than 1 m, a triangular weir should be additionally arranged on the water collecting tank, the water head on the weir should be greater than 25 mm, the water level is preferably at the 1 / 2 position of the teeth of the triangular weir, and the water outlet weir load is less than 1.7 L / (s·m); the external circulation and the internal circulation are both realized by pressurization of a water pump, and the reflux ratio is determined according to the upflow velocity.

[0049] The biofilm unit 200 has, from bottom to top, a water outlet, an aeration unit or a stirring device (selected according to the function), a reflux pipeline, filler, a flowmeter arranged on the reflux pipeline, and a water outlet weir plate arranged on the water outlet, and the overflow load is designed to be 2.0 L / (s·m)-3.0 L / (s·m).

[0050] In actual use, the device is integrally prepared from carbon steel material, and the inner wall is provided with a corrosion-resistant layer; the hydraulic retention time of the ozone oxidation unit 100 is 0.5-1 h, the hydraulic retention time of the biofilm unit 200 is 3-5 h, and the device is suitable for treating sewage with an inlet water COD concentration of 60-500 mg / L.

[0051] Secondly, an intelligent control unit (including a controller and a display) can be provided for real-time monitoring and adjustment of ozone dosage, internal and external reflux ratio, dissolved oxygen concentration and hydraulic retention time.

[0052] The core principle of the present application is to combine fluidized bed ozone catalytic oxidation technology with biofilm treatment technology, to realize synergistic effect of the two technologies through optimized structure design and process parameters, specifically:

[0053] (1) Fluidized bed ozone catalytic oxidation: through fluidized bed technology, the contact area of catalyst with sewage and ozone is increased, the mass transfer efficiency and reaction rate are improved, at the same time, the fluidized state can prevent carbon deposition and passivation on the surface of the catalyst, prolong the service life of the catalyst, reduce the amount of catalyst used, and reduce the investment;

[0054] (2) Biofilm treatment: MBBR fillers, biological rope fillers or polyurethane fillers and other non-filter biological fillers provide a large specific surface area of biological attachment sites, forming high-activity and high-concentration biofilms, enhancing the biological degradation capacity;

[0055] (3) Concentric cylindrical structure: by placing the ozone oxidation unit in the inner layer and the biofilm unit in the outer layer, a compact space layout is realized, and the hydraulic conditions and mass transfer process are optimized;

[0056] (4) Three-phase separator: through the optimized design of the three-phase separator, efficient separation of gas-liquid-solid is realized, ensuring effective reflux of the catalyst and stable operation of the system;

[0057] (5) Internal and external reflux units: by adjusting the internal and external reflux ratio, effective coupling of ozone oxidation and biological treatment is realized, and the impact load capacity is improved;

[0058] (6) Intelligent control unit: by real-time monitoring and adjustment of key parameters, the optimal operating state of the system under different water quality conditions is ensured.

[0059] The present application realizes effective coupling of ozone catalytic oxidation and biofilm treatment, has the advantages of high treatment efficiency, high ozone utilization rate, small land occupation, strong impact load capacity, etc., and the removal rates of COD and colority in the effluent are ≥85% and ≥80%, respectively.

[0060] Example 1: A fluidized bed ozone catalytic oxidation-biofilm coupled wastewater advanced treatment device, comprising an ozone oxidation unit, a biofilm unit, an ozone dosage unit, an internal reflux unit, an external reflux unit, a three-phase separator, an ozone tail gas destruction unit;

[0061] The ozone oxidation unit and the biofilm unit adopt a concentric cylindrical structure, the ozone oxidation unit is located in the inner layer, the height-diameter ratio of the ozone oxidation unit is 5:1, the inner diameter is 1 m, and the height is 5 m; the ozone oxidation unit is internally provided with a spherical alumina supported catalyst, the diameter is 2 mm, the specific gravity is 1.6 g / cm 3 , and the filling amount is 11% of the effective volume of the ozone oxidation unit;

[0062] The biofilm unit is internally provided with polyurethane sponge biological filler, is provided with an aeration unit and a backwashing unit, the outer diameter of the biofilm unit is 1.5 m, and the height is 5 m;

[0063] The ozone dosage of the ozone dosing unit is 1.2 mg O3 / mg COD. The internal reflux ratio of the internal reflux unit is 3.0, and the external reflux ratio of the external reflux unit is 1.5;

[0064] The three-phase separator is located at the position of 2 / 3 of the height of the ozone oxidation unit, and comprises a conical separator body, a gas outlet, a liquid outlet and a flow guide plate;

[0065] The processing capacity of the device is 100 m³ / d, which is suitable for treating wastewater with an influent COD concentration of 200 mg / L, the hydraulic retention time of the ozone oxidation unit is 1.5 h, and the hydraulic retention time of the biofilm unit is 4 h.

[0066] The experimental results show that after the device runs for 30 days, the removal rate of effluent COD reaches 88%, and the removal rate of colority reaches 85%; the system runs stably, and has strong anti-shock load capacity; when the influent COD concentration suddenly increases to 300 mg / L, the effluent quality can still remain stable.

[0067] Embodiment 2: The device structure is the same as that of embodiment 1, but some parameters are adjusted:

[0068] The height-diameter ratio of the ozone oxidation unit is 5.5:1, the inner diameter is 0.8 m, the height is 4.4 m, the diameter of the catalyst is 1.8 mm, and the specific gravity is 1.5 g / cm 3 , and the filling amount is 10% of the effective volume of the ozone oxidation unit;

[0069] The outer diameter of the biofilm unit is 1.2 m, and the height is 4.4 m;

[0070] The ozone dosage is 1.0 mg O3 / mg COD; the internal reflux ratio is 2.8, and the external reflux ratio is 1.4;

[0071] The processing capacity of the device is 80 m³ / d, which is suitable for treating wastewater with an influent COD concentration of 150 mg / L; the hydraulic retention time of the ozone oxidation unit is 1.2 h, and the hydraulic retention time of the biofilm unit is 3.5 h;

[0072] The experimental results show that after the device is operated for 30 days, the removal rate of the effluent COD reaches 86%, and the removal rate of the colority reaches 82%. The system is stable in operation, and the energy consumption is reduced by about 10% compared with Example 1.

[0073] In order to verify the superiority of the present application, the following comparative experiments are set up:

[0074] Comparative Example 1: traditional fixed-bed ozone catalytic oxidation + biological filter process

[0075] A conventional fixed-bed ozone catalytic oxidation reactor and an independent biological filter are used, and the treatment capacity and the influent water quality are the same as those of Example 1.

[0076] Comparative Example 2: traditional non-fixed-bed ozone oxidation + biological contact oxidation process

[0077] A conventional non-fixed-bed ozone oxidation reactor and an independent biological contact oxidation tank are used, and the treatment capacity and the influent water quality are the same as those of Example 1.

[0078] Comparison of test results:

[0079] .

Claims

1. A fluidized bed ozone catalytic oxidation-biochemical coupling treatment device, characterized in that: The ozone catalyst fluidized expansion unit, the ozone oxidation unit and the biofilm unit are matched with each other, the ozone oxidation unit is internally provided with a catalyst, and the biofilm unit is internally provided with biological filler.

2. The fluidized bed ozone catalytic oxidation-biochemical coupling treatment device according to claim 1, characterized in that: The ozone oxidation unit and the biofilm unit are in a concentric cylinder structure, and the ozone oxidation unit is located in the inner layer.

3. The fluidized bed ozone catalytic oxidation-biochemical coupling treatment device according to claim 1, characterized in that: The ozone oxidation unit and the biofilm unit are in a left-right structure.

4. The fluidized bed ozone catalytic oxidation-biochemical coupling treatment device according to claim 1, characterized in that: The three-phase separator comprises a conical separator body and a guide plate arranged in an upper and lower mode, a guide channel is formed between the guide plate and the conical separator body, a gas outlet and a liquid outlet are arranged at the top of the conical separator body, the gas outlet is communicated with the ozone tail gas destruction unit, and the liquid outlet is communicated with the biofilm unit.

5. The fluidized bed ozone catalytic oxidation-biochemical coupling treatment device according to claim 1 or 4, characterized in that: The three-phase separator is located at a position of 1 / 2-2 / 3 of the height of the ozone oxidation unit.

6. The fluidized bed ozone catalytic oxidation-biochemical coupling treatment device according to claim 1, characterized in that: The inner reflux unit comprises an inner variable frequency circulating pump and an inner reflux ozone adding unit which are sequentially connected and arranged, an inner reflux water inlet which is communicated with the inner reflux unit is arranged on the ozone oxidation unit above the three-phase separator, and an inner reflux water outlet which is communicated with the inner reflux unit is arranged at the bottom of the ozone oxidation unit.

7. The fluidized bed ozonation-catalytic oxidation-biochemical coupling treatment device according to claim 1 or 6, characterized in that: The outer reflux unit comprises an outer variable frequency circulating pump and a Venturi ozone gas dissolving unit which are sequentially connected and arranged, an outer reflux water outlet which is communicated with the outer reflux unit is arranged at the bottom of the ozone oxidation unit, and an outer reflux water inlet which is communicated with the outer reflux unit is arranged at the bottom of the biofilm unit.

8. The fluidized bed ozone catalytic oxidation-biochemical coupling treatment device according to claim 1, characterized in that: The ozone tail gas destruction unit comprises a tail gas collecting pipe, a gas-liquid separation tank and a tail gas destroyer.

9. The fluidized bed ozone catalytic oxidation-biochemical coupling treatment device according to claim 1, characterized in that: The diameter of the catalyst is 1.5-2.5mm, and the specific gravity is 1.4-1.8g / cm 3 The filling amount of the catalyst is 10-12% of the effective volume of the ozone oxidation unit, the internal reflux ratio of the ozone oxidation unit is 3-5, the external reflux ratio is 1-2, and the height-diameter ratio of the ozone oxidation unit is 4.5-16:

1.

10. The fluidized bed ozone catalytic oxidation-biochemical coupling treatment device according to claim 1, characterized in that: A water distribution and gas distribution unit which is matched with the water inlet ozone adding unit, the inner reflux unit and the outer reflux unit is further arranged at the bottom of the ozone oxidation unit, and the water distribution and gas distribution unit is arranged in a spiral upward mode; an aeration unit and a backwashing unit are further arranged at the bottom of the biofilm unit.

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