A heterogeneous ozone catalytic oxidation treatment system and method based on internal component reinforced internal circulation fluidization

Abstract

The present invention discloses a heterogeneous ozone catalytic oxidation treatment system and method based on internal component-enhanced internal circulation fluidization, comprising a catalytic oxidation unit, a water inlet unit, an ozone generating unit, an air supply unit, an in-situ regeneration and cleaning unit, and a gas-liquid reflux unit; the water inlet unit, the ozone generating unit, the air supply unit, the in-situ regeneration and cleaning unit, and the gas-liquid reflux unit are connected to the catalytic oxidation unit, and an ultrasonic cavitation unit is provided in the catalytic oxidation unit; the catalytic oxidation unit comprises a fluidized bed; the fluidized bed comprises an outer shell, and a carrier distribution device, a multiple-circulation internal circulation device, a top flow guide component, and a labyrinth-type carrier separation device are provided in the outer shell. The present invention organically combines the internal circulation fluidized bed technology with the heterogeneous ozone catalytic oxidation technology, and performs structural optimization and strengthening, effectively improving the ozone reaction rate and utilization rate during heterogeneous ozone catalytic oxidation treatment, ensuring the stability and efficiency of the catalyst operation, and improving the water treatment effluent effect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of sewage treatment, and particularly relates to a heterogeneous ozone catalytic oxidation treatment system and method based on internal member reinforced internal circulation fluidization. BACKGROUND

[0002] The circulating water system of a thermal power plant using urban reclaimed water as a supplementary water source produces a large amount of circulating blowdown water after circulation, which is complex in composition, poor in biodegradability and difficult to biodegrade, and has a greater environmental hazard. After investigation, the existing circulating blowdown water pretreatment process mostly adopts a "pretreatment + membrane desalination" process to treat the wastewater for turbidity removal, hardness removal and salt removal before reuse. However, the coagulation and clarification softening pretreatment process has limited removal capacity for refractory organic matter, and the over-standard organic pollutants will inevitably adversely affect the normal operation of the subsequent ultrafiltration and reverse osmosis membrane treatment system. Therefore, on the basis of the existing process, a new wastewater pretreatment technology needs to be found to better and efficiently remove organic matter from blowdown water.

[0003] Advanced oxidation technology can use the generated hydroxyl radicals to rapidly mineralize organic pollutants or improve the biodegradability of wastewater, and has many advantages such as fast reaction speed, wide adaptability, strong oxidation capacity and the like. As a typical advanced oxidation process, the addition of a catalyst promotes the decomposition of ozone to produce active substances (hydroxyl radicals, superoxide radicals and singlet oxygen, etc.) with stronger catalytic capacity, and has no selectivity, greatly improving the treatment capacity and ozone utilization rate of the technology. Compared with other advanced oxidation technologies, the oxidation rate is fast, the organic matter mineralization rate is high, there is no secondary pollution, and there are also synergistic removal benefits such as color removal, deodorization, sterilization and disinfection. The technology is widely used in petrochemical, papermaking, printing and dyeing industries, but relatively less in the power industry.

[0004] In the heterogeneous ozone catalytic oxidation technology, the adaptability, activity and stability, durability of the catalyst and the mass transfer efficiency of the reactor have a greater impact on the treatment effect, energy consumption level and operating cost of the entire treatment system. At present, the heterogeneous ozone catalytic oxidation technology mostly adopts a fixed bed oxidation tower (oxidation tank) process, and the following problems exist in actual application: The mass transfer efficiency is low and is easily affected by suspended solids in the wastewater, causing waste of ozone. SS, extracellular polymeric substances (EPS), microbial floc and microbial metabolites in the wastewater can react with O3, reducing the O3 and hydroxyl radicals available for COD removal, thereby reducing the COD removal rate of the wastewater, the ozone utilization efficiency, and increasing the ozone consumption and operating cost. The loss of active components due to catalyst abrasion easily causes secondary pollution and pipeline blockage, and the surface is easily contaminated and deposited with organic matter (extracellular polymeric substances) and inorganic matter (inorganic salt deposition), which seriously makes the activity of the catalyst rapidly decrease or even deactivate, affecting the catalytic performance and thus the treatment effect of catalytic oxidation. The catalyst filling amount is large, and the proportion is as high as more than 50% of the reactor volume, the service life is about 3-5 years, the failed catalyst is difficult to handle as a hazardous waste, and the disposal cost is high. In actual operation, methods such as frequent backwashing, setting multiple treatment stages, and increasing coagulation and sedimentation pretreatment processes are often used to reduce the influence on the ozone catalytic oxidation reaction and slow down the decline in treatment capacity, but these methods inevitably increase the operation and maintenance burden, limiting the popularization and application of the technology in water treatment. SUMMARY

[0005] The present application solves the problems of low three-phase mass transfer efficiency, weak resistance to water quality and quantity fluctuations, easy accumulation and hardening of pollutants on the surface of the catalyst, excessive catalyst dosage, and high operation and disposal costs of the existing fixed-bed heterogeneous ozone catalytic oxidation process reactor, and aims to provide a heterogeneous ozone catalytic oxidation treatment system and method based on internal member reinforced internal circulation fluidization, which realizes efficient and stable, low-cost treatment of municipal reclaimed water, circulating water and sewage by internal member reinforcement and efficiency enhancement, and promotes the popularization and application of the internal circulation fluidized heterogeneous ozone catalytic oxidation treatment technology.

[0006] To achieve the above-mentioned purpose, the following technical solutions are adopted in the present application:

[0007] A heterogeneous ozone catalytic oxidation treatment system based on internal member reinforced internal circulation fluidization, comprising a catalytic oxidation unit, a water inlet unit, an ozone generation unit, a gas supply unit, an ultrasonic cavitation unit, an in-situ regeneration and cleaning unit, and a gas-liquid reflux unit.

[0008] The water inlet unit, the ozone generation unit, the gas supply unit, the in-situ regeneration and cleaning unit, and the gas-liquid reflux unit are connected to the catalytic oxidation unit, and the ultrasonic cavitation unit is arranged in the catalytic oxidation unit.

[0009] The catalytic oxidation unit comprises a fluidized bed; the fluidized bed comprises a shell, and the shell is provided with a carrier distribution device, a multiple loop internal circulation device, a top flow guide member, and a labyrinth carrier separation device.

[0010] The present application further improves that the shell comprises a lower cylinder, a straight cylinder section and an upper cylinder connected in series; the lower cylinder and the lower end of the straight cylinder section are connected through a tapered horn pipe, the upper cylinder and the upper end of the straight cylinder section are connected through a gradually expanding horn pipe, the lower cylinder is elliptical, the straight cylinder section and the upper cylinder are cylindrical, the upper part of the upper cylinder is closed, the tapered horn pipe is provided with a carrier distribution device inside, and the carrier distribution device is connected to the upper part of the lower cylinder; the upper part of the carrier distribution device is provided with a multiple loop internal circulation device inside the straight cylinder section; and the upper part of the multiple loop internal circulation device is provided with a top flow guide member inside the straight cylinder section.

[0011] The further improvement of the present application is that a labyrinth carrier separation device is arranged in the straight cylinder section at the upper part of the top flow guide member; and an ultrasonic cavitation unit is arranged on the outer wall of the straight cylinder section and the area above the top flow guide member.

[0012] The further improvement of the present application is that the bottom of the lower cylinder is provided with a water inlet and a backflow water inlet, the sidewall of the lower cylinder is provided with an ozone gas inlet and a catalytic oxidation unit, the top of the upper cylinder is provided with a tail gas discharge port, the sidewall of the upper cylinder is provided with a water outlet, a backflow port and a drainage and residue discharge port; and an umbrella-shaped gas collecting cover is arranged inside the upper cylinder, which is in communication with the tail gas discharge port.

[0013] The further improvement of the present application is that the ratio of the height of the shell to the diameter of the straight cylinder section is: the ratio of the multiple loop internal circulation device to the diameter of the straight cylinder section is 0.6-0.7:1, the angle between the gradually tapered horn tube and the horizontal direction is 45°-70°, the angle between the gradually expanded horn tube and the horizontal direction is 45°-60°, the vertical distance between the lower end of the multiple loop internal circulation device and the carrier distribution device is 0.15-0.3 times the diameter of the straight cylinder section, the vertical distance between the upper end of the multiple loop internal circulation device and the water outlet is 0.8-1.2 times the diameter of the straight cylinder section, the diameter of the lower cylinder is the same as that of the multiple loop internal circulation device and they are on the same axis; and the ratio of the diameter of the upper cylinder to the diameter of the straight cylinder section is 1.2-1.3:1.

[0014] The further improvement of the present application is that the labyrinth carrier separation device is composed of reflection cones arranged in the height direction in a longitudinal and horizontal alternating manner, the top end is flush with the lower end of the gradually expanded horn tube, and the bottom end is arranged at intervals with the top end of the top flow guide member.

[0015] The further improvement of the present application is that the carrier distribution device includes a gas distribution device, a water distribution device and a double-layer carrier distribution plate, the double-layer carrier distribution plate is arranged between the lower cylinder and the straight cylinder section, the middle space of the double-layer carrier distribution plate is connected with the catalytic oxidation unit, the water distribution device penetrates the upper and lower layers of the double-layer carrier distribution plate, and the water distribution device is communicated with the inside of the lower cylinder and the straight cylinder section; the gas distribution device is connected with the upper layer of the double-layer carrier distribution plate, and the gas distribution device is connected with the straight cylinder section and the hollow space of the double-layer carrier distribution plate; the angle between the flow channel of the gas distribution device and the horizontal direction is 45°-60°, and the flow channel is located above the horizontal direction; and the angle between the flow channel of the water distribution device and the horizontal direction is 30°-45°, and the flow channel is located below the horizontal direction.

[0016] The further improvement of the present application is that the water inlet unit includes a connected dissolved gas pressurizing pump and a water inlet flowmeter, and the outlet of the water inlet flowmeter is connected with the water inlet of the catalytic oxidation unit.

[0017] The ozone generation unit includes a connected ozone generator, ozone concentration instrument and gas flowmeter, and the outlet of the gas flowmeter is connected with the catalytic oxidation unit.

[0018] The air supply unit comprises a fan and an air inlet flow meter connected to each other, and the outlet of the air inlet flow meter is connected to the catalytic oxidation unit.

[0019] The ultrasonic cavitation unit comprises an ultrasonic generator and a plurality of ultrasonic transducers connected to each other, the ultrasonic transducers are uniformly arranged along the outer wall of the straight cylinder section in the circumferential direction, the frequency is 30-40 kHz, and the power is 0.5-1 kW.

[0020] The in-situ regeneration and cleaning unit comprises a regeneration and cleaning pump, and the outlet of the regeneration and cleaning pump is connected to the catalytic oxidation unit.

[0021] The gas-liquid reflux unit comprises a water production external circulation reflux system and a tail gas external reflux system, the water production external circulation reflux system comprises a reflux pump, the inlet and outlet of the reflux pump are connected to the catalytic oxidation unit, and the tail gas external reflux system comprises a tail gas reflux pipeline, one end of the tail gas reflux pipeline is connected to the catalytic oxidation unit.

[0022] A heterogeneous ozone catalytic oxidation treatment method based on internal component reinforced internal circulation fluidization comprises the following steps:

[0023] The ozone gas prepared by the ozone generation unit, the air of the air supply unit and the to-be-treated refractory organic wastewater are transported into the catalytic oxidation unit, and catalytic oxidation reaction occurs between the ozone and the fluidized bed catalyst, so that the organic pollutants in the to-be-treated organic wastewater are preliminarily degraded; the ultrasonic cavitation unit at the upper part of the fluidized bed performs ultrasonic cavitation synergism, ozone reinforced oxidation reaction occurs, and the preliminarily degraded organic matter is further reinforced, and then part of the produced water enters the catalytic oxidation unit through the gas-liquid reflux unit to remove the pollutants in depth.

[0024] Compared with the prior art, the method has the following beneficial effects:

[0025] In the application, the internal circulation fluidized bed technology and the heterogeneous ozone catalytic oxidation technology are organically combined by arranging the multiple internal circulation devices and the top flow guide component in the fluidized bed, and the structure is optimized and strengthened, so that the ozone reaction rate and utilization of the heterogeneous ozone catalytic oxidation treatment system are effectively improved, the stability and efficiency of the catalyst are reliably ensured, the water treatment effluent effect is improved, the consumption of ozone and catalyst is saved, the operation and maintenance cost is significantly reduced, and the application can be better applied to different concentration organic wastewater treatment scenes such as power plant circulating water sewage, circulating water supplement water and desulfurization wastewater, and the problems of low gas-liquid-solid three-phase mass transfer efficiency, easy pollution of incoming water SS, organic matter and inorganic matter, large catalyst dosage and high operation and disposal cost of the traditional heterogeneous ozone catalytic oxidation technology are solved.

[0026] Further, the application proposes an internal circulation fluidized bed based on internal component reinforcement, on the basis of optimization of the main body configuration structure, fine arrangement of the carrier distribution device (water and air distribution device), multiple loop internal circulation device, top flow guide component, labyrinth carrier separation device, and loading of low-density millimeter-level high-performance catalysts that are easy to fluidize, to strengthen the circulating fluidization process of the fluidized bed, achieve a fully uniform and stable fluidization effect, and improve the gas-liquid-solid mass transfer efficiency; the surface of the fluidized catalyst is subjected to high-frequency disturbance by gas and liquid to achieve real-time interface update, greatly slowing down the deposition, hardening, and deactivation of pollutants; at the same time, the loss of catalyst with high-speed water and gas flow is reduced or avoided, and good treatment effect can be ensured even in the case of severe water quality and quantity fluctuations, and the water quality and quantity impact resistance is strong.

[0027] Further, in the application, by setting an ultrasonic cavitation unit, a water inlet unit, a gas-liquid reflux unit, and a gas supply unit, based on the ultrasonic cavitation and water-gas external circulation reflux synergistic method, the gas-liquid contact area and reaction time are increased, and the treatment effect is improved; by setting an in-situ regeneration cleaning unit, based on the in-situ regeneration and skimming method, the operation is optimized, the catalyst surface in the catalytic oxidation unit is kept clean and efficient for a long time, and the service life of the catalyst is prolonged. The multiple high-efficiency reinforcement methods in the application work together to improve the utilization efficiency of ozone, maintain the long-term use of catalysts, save energy and reduce consumption, and the use cost is low. The treatment cost of the application is lower than that of traditional heterogeneous ozone catalytic oxidation process, and the economic benefit is good.

[0028] Further, the labyrinth carrier separation device is set to help the fluidized bed catalyst to fall back and avoid being discharged with the water and gas flow, causing waste and secondary pollution.

[0029] Further, the ultrasonic cavitation unit is arranged in the area above the straight cylinder segment outer wall and the top flow guide component, for cavitation of the circulating fluidization escape gas into micron-sized bubbles, delaying the rising, improving the interface contact, and strengthening the ozone oxidation effect.

[0030] Further, the umbrella-shaped gas collecting hood is set to help the gas in the liquid phase to be quickly and completely separated, reducing the risk of environmental pollution caused by the overflow of ozone with the water flow.

[0031] Further, the included angle between the gradually expanding horn pipe and the horizontal direction is 45°~60°, so that the water and gas flow state at this position is smoothly transitioned, and the accumulation of carriers is also avoided.

[0032] Furthermore, the vertical distance between the lower end of the multiple-circulation internal circulation device and the carrier distribution device is 0.15~0.3 times the diameter of the straight cylinder section, to prevent the spacing from being too narrow to form circulation or too large to cause carrier accumulation at the bottom; the vertical distance between the upper end of the multiple-circulation internal circulation device and the water outlet is 0.8~1.2 times the diameter of the straight cylinder section, to ensure the upper circulation flow effect and circulation speed and provide the space required for ultrasonic cavitation; the lower cylinder has the same diameter as the multiple-circulation internal circulation devices 1-3 and is on the same axis, which is convenient for gathering and collecting the water flow flowing out of the carrier distribution device, and can suck in the circulating and descending gas-liquid flow to promote the circulation flow speed; the ratio of the upper cylinder diameter to the straight cylinder diameter is 1.2~1.3:1, which provides a larger space for gas-liquid-solid separation. At the same time, the flow rate in this area slows down, which is convenient for a small amount of carriers carried out with the water flow to sink and fall back. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 is a process flow chart of the system of the present invention;

[0034] Figure 2 This is a schematic diagram of the structure of the internal component-enhanced internal circulation fluidized heterogeneous ozone catalytic oxidation device;

[0035] Figure 3 is a top view of the carrier distribution plate;

[0036] Figure 4 This is the main view of the carrier distribution plate;

[0037] Figure 5 This is the main view of the multiple circulation internal circulation device;

[0038] Figure 6 A top view of the top flow guide member;

[0039] Figure 7 This is the main view of the top guide component;

[0040] Figure 8 It is a schematic diagram of the structure of a labyrinth-type carrier separation device;

[0041] In the figure, 1-catalytic oxidation unit, 1-1-outer shell, 1-2-carrier distribution device, 1-3-multiple loop internal circulation device, 1-4-top flow guide member, 1-5-labyrinth carrier separation device, 1-6-fluidized bed catalyst, 1-1-1-lower cylinder, 1-1-2-straight cylinder section, 1-1-3-upper cylinder, 1-1-4-water inlet, 1-1-5-water outlet, 1-1-6-ozone gas inlet, 1-1-7-air inlet, 1-1-8-reflux port, 1-1-9-reflux water inlet, 1-1-10-tail gas discharge port, 1-1-11-drainage and deslagging port, 1-2-1-air distribution device, 1-2-2-water distribution device, 1-2-3-double-layer carrier distribution plate, 2-1-dissolved gas pressurizing pump, 2-2-water inlet flowmeter, 3-1-ozone generator, 3-2-ozone concentration meter, 3-3-gas flowmeter, 4-1-fan, 4-2-air inlet flowmeter, 5-regeneration and cleaning pump, 6-reflux pump, 7-1-ultrasonic generator, 7-2-ultrasonic vibrator, 8-tail gas reflux pipeline. DETAILED DESCRIPTION

[0042] In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to the accompanying drawings. The preferred embodiments of the present application are shown in the drawings. However, the present application can be realized in various different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that the disclosure of the present application can be more thoroughly and completely understood.

[0043] In addition, the elements in the present application are referred to as "fixed to" or "provided on" another element, which can be directly on another element or can have a middle element. When an element is considered to be "connected" to another element, it can be directly connected to another element or can have a middle element. The terms "vertical", "horizontal", "left", "right" and the like used herein are only for illustrative purposes and do not represent the only embodiment.

[0044] The present application organically combines the internal circulation fluidized bed technology with the heterogeneous ozone catalytic oxidation technology, and strengthens the structure for efficiency, solves the problems of low three-phase mass transfer efficiency, large catalyst consumption and easy deactivation, high operation and disposal cost of the existing fixed bed, effectively improves the ozone reaction rate and utilization rate of the heterogeneous ozone catalytic oxidation reaction system, reliably ensures the operation stability and high efficiency of the catalyst, significantly improves the effluent water quality, significantly improves the anti-water quality and quantity fluctuation ability, reduces the cost and increases the efficiency, and realizes the efficient and low-cost operation of wastewater.

[0045] Reference Figures 1-8The application discloses a heterogeneous ozone catalytic oxidation treatment system based on internal component reinforced internal circulation fluidization, which comprises a catalytic oxidation unit 1, a water inlet unit, an ozone generation unit, an air supply unit, an ultrasonic cavitation unit, an in-situ regeneration cleaning unit and a gas-liquid reflux unit.

[0046] Wherein, referring to Figure 1 and Figure 2 , the catalytic oxidation unit 1 comprises a heterogeneous ozone catalytic oxidation internal circulation fluidized bed, a fluidized bed catalyst 1-6 is arranged in the fluidized bed, and the fluidized bed catalyst 1-6 provides a catalytic oxidation reaction site for ozone and organic matters. The main structure of the fluidized bed comprises an outer shell 1-1, a carrier distribution device 1-2, a multiple loop internal circulation device 1-3, a top flow guide component 1-4 and a labyrinth carrier separation device 1-5. Specifically, the outer shell 1-1 comprises a lower cylinder 1-1-1, a straight cylinder segment 1-1-2, an upper cylinder 1-1-3 and related interfaces, the lower cylinder 1-1-1 is connected with the lower end of the straight cylinder segment 1-1-2 through a converging bellmouth pipe, the upper cylinder 1-1-3 is connected with the upper end of the straight cylinder segment 1-1-2 through a diverging bellmouth pipe, the lower cylinder 1-1-1 is in an elliptical shape, the straight cylinder segment 1-1-2 and the upper cylinder 1-1-3 are in a cylindrical shape, the upper part of the upper cylinder 1-1-3 is closed, four vertical support circular pipes are uniformly arranged on the outer wall of the converging bellmouth pipe along the circumferential direction, and the outermost circular pipe is located on the same vertical line as the outer wall of the straight cylinder segment 1-1-2; the lower cylinder 1-1-1 is used for uniformly distributing water, the straight cylinder segment 1-1-2 is a main reaction zone and is divided into a catalytic oxidation section and an ultrasonic cavitation synergistic ozone oxidation section from bottom to top, and the upper cylinder 1-1-3 is used for gas-liquid-solid three-phase separation. Referring to Figure 5 , the carrier distribution device 1-2 is arranged in the converging bellmouth pipe, the carrier distribution plate 1-2 is connected with the upper part of the lower cylinder 1-1-1, and the carrier distribution device 1-2 is used for uniformly distributing water and air and avoiding the phenomena of deflection and short flow; referring to Figure 6 , the multiple loop internal circulation device 1-3 is arranged in the upper part of the carrier distribution device 1-2 and the straight cylinder segment 1-1-2 and is used for guiding the main reaction zone to form a good and stable circulating flow state; the top flow guide component 1-4 is arranged in the upper part of the multiple loop internal circulation device 1-3 and the straight cylinder segment 1-1-2 and is used for assisting the circulation of gas-liquid-solid three phases; the labyrinth carrier separation device 1-5 is arranged in the upper part of the top flow guide component 1-4 and the straight cylinder segment 1-1-2 and is used for assisting the fluidized bed catalyst to fall back and avoiding flowing out with water and air, thereby causing waste and secondary pollution; the ultrasonic cavitation unit is arranged in the region above the outer wall of the straight cylinder segment 1-1-2 and the top flow guide component 1-4 and is used for cavitating the circulating fluidization escape gas into micron-sized bubbles, delaying the rising, improving the interface contact and strengthening the ozone oxidation effect.

[0047] Further, the lower cylinder 1-1-1 is provided with a water inlet 1-1-4 and a backflow water inlet 1-1-9 at the bottom, and is provided with an ozone inlet 1-1-6 and an air inlet 1-1-7 at the sidewall; the upper cylinder 1-1-3 is provided with a tail gas discharge port 1-1-10 at the top, and is provided with a water outlet 1-1-5, a backflow port 1-1-8 and a drainage and deslagging port 1-1-11 at the sidewall. Preferably, the upper cylinder 1-1-3 is internally provided with an umbrella-shaped gas collecting cover, which is in the shape of an inverted cone and is internally hollowed out, and which is in communication with the tail gas discharge port 1-1-10. The umbrella-shaped gas collecting cover helps to quickly and completely separate the gas in the liquid phase, and reduces the risk of environmental pollution caused by the overflow of ozone with the water flow.

[0048] Preferably, the ratio of the height of the shell 1-1 to the diameter of the straight cylinder segment 1-1-2 is 4-10:1, which facilitates the formation of a circulating flow state and avoids the carrier from being washed out with the water flow; the ratio of the diameter of the multiple loop internal circulation device 1-3 to the diameter of the straight cylinder segment 1-1-2 is 0.6-0.7:1, which facilitates the formation of a good circulating flow state; the angle between the tapered horn pipe and the horizontal direction is 45°-70°, and the angle between the flared horn pipe and the horizontal direction is 45°-60°, which makes the water and gas flow state at this position smoothly transition, and also avoids the accumulation of the carrier; the vertical distance between the lower end of the multiple loop internal circulation device 1-3 and the carrier distribution device 1-2 is 0.15-0.3 times the diameter of the straight cylinder segment 1-1-2, which prevents the distance from being too narrow to form a circulation or the distance from being too large to cause the carrier to accumulate at the bottom; the vertical distance between the upper end of the multiple loop internal circulation device 1-3 and the water outlet 1-1-5 is 0.8-1.2 times the diameter of the straight cylinder segment, which ensures the upper circulating flow effect and circulating speed and provides the space required for ultrasonic cavitation; the lower cylinder 1-1-1 and the multiple loop internal circulation device 1-3 have the same diameter and are on the same axis, which facilitates the collection of the water and gas flow out of the carrier distribution device, and enables the circulation of the descending backflow of the gas-liquid flow, thereby promoting the circulating flow speed; the ratio of the diameter of the upper cylinder 1-1-3 to the diameter of the straight cylinder segment 1-1-2 is 1.2-1.3:1, which provides a larger space for gas-liquid-solid separation, and at the same time slows down the flow rate in this area, thereby facilitating the sinking and falling of a small amount of carrier carried out with the water flow. Preferably, the hydraulic retention time of the fluidized bed is 0.5-1 h, which can be determined according to the wastewater quality through a small test.

[0049] Preferably, referring to Figure 7The top flow guide member 1-4 is mushroom-shaped in the circumferential direction, the upper part is semi-spherical, and the lower part is an inner buckle conical type. The radius (r) of the semi-spherical type is 0.6-0.8 times the radius of the multiple loop internal circulation device 1-3, and the vertical distance between the top flow guide member 1-4 and the upper end of the multiple loop internal circulation device 1-3 is 0.6-1 times the radius (r). The lower rotary structure of the top flow guide member guides the circulating flow rate of the three-phase mixture to change direction, so that the flow field flow direction is regular and unified, the overall circulation efficiency of the flow field is improved, the kinetic energy dissipation is reduced, and the solid phase can be effectively avoided. The upper part of the flow guide member can prevent the accumulation of fluid mixture, so that the carrier lifted up can smoothly slide along the wall.

[0050] Preferably, the labyrinth carrier separation device 1-5 is composed of flow reflection cones arranged in the vertical direction in turn, the top end is flush with the lower end of the gradually expanding horn pipe, and the vertical distance between the bottom end and the top end of the top flow guide member 1-4 is 200-400 mm; see Figure 8 The labyrinth carrier separation device 1-5 is arranged with 3-5 layers of flow reflection cones, the top angle (ß) of each layer of reflection cone is 45-90°, the reflection cone distance (a) is 1-2 cm, the reflection cone bottom width (b) is 2-4 times the reflection cone distance, and the distance (h) between adjacent two layers of reflection cones is 5-10 cm. The labyrinth carrier separation device 1-5 can effectively block and fall back the fluidized catalyst that breaks away from the circulating flow, greatly reducing the possibility of being washed away with water flow. At the same time, due to the fact that the reflection cone itself occupies part of the flow passage area, the flow rate of the mixed fluid can be increased, and the reflection cone blocking effect can make the micron-sized bubble water-gas mixture after ultrasonic cavitation move irregularly along the reflection cone turn-back, form high-frequency disturbance to the sewage, strengthen the degree of turbulent flow, and make the molecules collide more frequently. At the same time, the cutting of the cone angle makes the bubbles break and the diameter decrease again. The high flow rate, high frequency gas-liquid intensified disturbance effect makes the ozone dissolve sufficiently, the gas-liquid mass transfer efficiency is improved, and the ozone oxidation treatment effect is improved.

[0051] Preferably, see Figure 3 and Figure 4The carrier distribution device 1-2 comprises a gas distribution device 1-2-1, a water distribution device 1-2-2 and a double-layer carrier distribution plate 1-2-3. The double-layer carrier distribution plate 1-2-3 is hollow in the center and separates the lower cylinder 1-1-1 from the straight cylinder segment 1-1-2. The middle space of the double-layer carrier distribution plate 1-2-3 is connected to the ozone inlet pipe 1-1-6 and the air inlet pipe 1-1-7. The water distribution device 1-2-2 penetrates the upper and lower layers of the double-layer carrier distribution plate 1-2-3 and is in communication with the inside of the lower cylinder 1-1-1 and the straight cylinder segment 1-1-2. The gas distribution device 1-2-1 is connected to the upper layer of the double-layer carrier distribution plate 1-2-3 and is connected to the hollow space of the straight cylinder segment 1-1-2 and the double-layer carrier distribution plate 1-2-3. The water and gas are uniformly distributed in different spaces without interference, ensuring uniform water and gas distribution. The water distribution device 1-2-2 and the gas distribution device 1-2-1 are alternately and uniformly distributed along the diameter direction and are connected to the reserved interfaces of the double-layer carrier distribution plate 1-2-3 by threads, ensuring that the water and gas flow is close to plug flow and avoiding the concentration of air along the central position, which can cause air to gather in the center of the fluidized bed and form a bubbling bed and other low-efficiency devices. The flow channel of the gas distribution device 1-2-1 forms an angle of 45°-60° with the horizontal direction, and the horizontal direction is above 45°-60°. The slightly outwardly sprayed gas flow reduces the agglomeration of the gas flow, so that the gas holdup rate of each region of the main reactor is consistent. The flow channel of the water distribution device 1-2-2 forms an angle of 30°-45° with the horizontal direction, and the horizontal direction is below 30°-45°. This effectively prevents the entry of small fluidized bed carriers and prevents the clogging of the water distribution device and the backflow of the catalyst to the lower cylinder. Preferably, the water distribution device 1-2-2 and the gas distribution device 1-2-1 are made of titanium alloy material.

[0052] Preferably, the multiple loop internal circulation device 1-3 is multi-segmented, each segment has a length (s) of 150-300 mm, and a loop gap length (d) of 20-50 mm. The number of loops is determined according to the length of the multiple loop internal circulation device, the length of each segment and the loop gap length. The gas-liquid forms a local loop from the upper and lower gaps, shortens the circulation path and time, and is beneficial to the mixing of gas-liquid-solid three phases, strengthens the fluid mixing mechanism, and is beneficial to improving the overall oxygen transfer efficiency and reducing the aeration energy consumption.

[0053] Preferably, the fluidized bed catalyst 1-6 is a flexible supported copper-manganese composite oxide catalyst (Mn / Cu-Al2O3 catalyst). The catalyst carrier is aluminum silicate fiber, which is light and soft. The active components are MnO2 and CuO metal oxides, which are prepared by impregnation and calcination. The density is close to 1, the particle size is 0.15-0.25 mm, the specific surface area is large, the mechanical strength is high, the internal pore channel is regular, the pore volume is large, the adaptability is good, and the efficiency is stable.

[0054] Further, the water inlet unit comprises a dissolved gas pressurizing pump 2-1 and a water inlet flow meter 2-2 connected in sequence, the inlet of the dissolved gas pressurizing pump 2-1 is connected to the pipeline for extracting raw water to be treated, and the outlet of the water inlet flow meter 2-2 is connected to the water inlet 1-1-4 of the catalytic oxidation unit 1 through the pipeline. Preferably, the dissolved gas pressurizing pump 2-1 has a frequency regulation function, which can adjust the water inlet flow in real time according to the needs. The water inlet flow meter is used to control the ozone dosage and air supply of the ozone generation unit and air supply unit.

[0055] Further, the ozone generation unit comprises an ozone generator 3-1, an ozone concentration instrument 3-2 and a gas flow meter 3-3 connected in sequence, the inlet of the ozone generator 3-1 is connected to the oxygen preparation device, the outlet of the gas flow meter 3-3 is connected to the ozone inlet 1-1-6 of the catalytic oxidation unit 1 through the pipeline, and the ozone generator 3-1 is used to prepare ozone gas of a certain concentration for the catalytic unit. According to the O / C ratio obtained by experiments, the ozone dosage is accurately calculated and controlled by the ozone concentration instrument 3-2, the gas flow meter 3-3 and the water inlet flow meter 2-2, and then the preparation amount of the ozone generator 3-1 is controlled.

[0056] Further, the air supply unit comprises a fan 4-1 and an air inlet flow meter 4-2 connected in sequence, the outlet of the air inlet flow meter 4-2 is connected to the air inlet 1-1-7 of the catalytic oxidation unit 1 through the pipeline, and the fan is used to provide appropriate air for the catalytic unit. According to the gas-water ratio required by the circulating fluidization obtained by experiments, the air volume is accurately calculated and controlled by the air inlet flow meter 4-2 and the water inlet flow meter 2-2, so as to ensure a good and stable circulating fluidization state. Preferably, the fan 4-1 also serves as a backwashing air supply device, which provides the required air volume and air pressure for backwashing of the catalytic oxidation unit 1, thereby saving investment and land occupation.

[0057] Further, the ultrasonic cavitation unit comprises an ultrasonic wave generator 7-1 and an ultrasonic wave vibrator 7-2 connected in sequence. The middle position of the height of the gradual expansion horn tube to the top flow guide member 1-4 is the arrangement area of the ultrasonic cavitation synergistic reaction section, and the ultrasonic wave vibrator 7-2 is uniformly arranged in 4 groups along the outer wall of the straight cylinder section 1-1-2 in the circumferential direction, with a frequency of 30-40 kHz and a power of 0.5-1 kW. In this area, ultrasonic synergistic ozone oxidation reaction occurs, the overflow bubbles are controlled in microns by using ultrasonic cavitation effect, the gas-liquid interface area is increased, the ozone reaction time is prolonged, the gas-liquid mass transfer efficiency and ozone utilization rate are improved, and the removal of residual organic matter is strengthened.

[0058] Further, the in-situ regeneration cleaning unit comprises a regeneration cleaning pump 5, the inlet end of the regeneration cleaning pump 5 is connected with the cleaning chemical tank and the clean water tank through pipelines, and the outlet end is connected with the backflow water inlet 1-1-9 of the catalytic oxidation unit 1 through a pipeline, the regeneration cleaning pump is used when the catalytic oxidation unit is regenerated and cleaned, when the treatment efficiency cannot be effectively recovered by the conventional backwashing, the required cleaning chemical liquid is supplied according to the cleaning steps, the internal deep dirt and the surface deposits of the catalyst are thoroughly removed through pickling and alkaline cleaning, and the initial catalytic performance is recovered. Preferably, the regeneration cleaning pump 5 is used as the backwashing water supply equipment, and provides the required water amount for the catalytic oxidation unit 1 during backwashing, thereby saving investment and land occupation.

[0059] Further, the gas-liquid backflow unit comprises a water production external circulation backflow system and a tail gas external backflow system, the water production external circulation backflow system comprises a backflow pump 6, the inlet end of the backflow pump 6 is connected with the backflow port 1-1-8 of the catalytic oxidation unit 1 through a pipeline, and the outlet end of the backflow pump 6 is connected with the backflow water inlet 1-1-9 of the catalytic oxidation unit 1 through a pipeline, part of the produced water is backflowed to the water inlet end of the catalytic unit for reaction again, and the residual pollutants are deeply removed; the tail gas external backflow system comprises a tail gas backflow pipeline 8, one end of the tail gas backflow pipeline 8 is connected with the tail gas discharge port 1-1-10 of the catalytic oxidation unit 1, and the other end is connected with the inlet end of the dissolved gas pressurizing pump 2-1, the tail gas is backflowed to the inlet end of the dissolved gas pressurizing pump and is sucked and lifted into the catalytic unit for reuse, without the need of additionally arranging a tail gas collection and destruction device, while the ozone preparation amount and the fan air supply amount can be reduced, thereby saving investment and energy saving and consumption reduction. Preferably, the backflow pump 6 has a frequency conversion adjustment function, and the backflow amount can be adjusted according to the components of the organic pollutants, the difficulty of degradation and the water outlet requirement.

[0060] The application provides a heterogeneous ozone catalytic oxidation treatment method based on internal member reinforced internal circulation flow, which comprises the following steps:

[0061] S1. The to-be-treated refractory organic wastewater is lifted by the metering of the water inlet unit dissolved gas pressurizing pump 2-1 and then enters the catalytic oxidation unit 1, and flows through the catalytic oxidation section and the ultrasonic cavitation enhanced ozone oxidation section from bottom to top. In the lower part of the internal circulating fluidized bed, the organic matter, ozone and fluidized bed catalyst 1-6 undergo adsorption, surface coordination complexation and hydroxyl radical oxidation, consume ozone, decompose organic matter, and preliminarily degrade the organic pollutants in the to-be-treated organic wastewater. In this area, the fluidized bed carrier is fluidized under the action of gas stripping force and water flow force, and the catalyst particles collide and rub with each other. The refractory pollutants, inorganic salts and inorganic crystals adsorbed on the surface of the catalyst fall off from the surface of the catalyst under the action of the shearing force of gas and water and the friction force generated by the collision of the catalyst with each other, so that the interface of the catalyst is updated in real time, the stability of the catalyst in the long-term use process is ensured, the catalyst deactivation phenomenon and the catalyst caking phenomenon are avoided, and the water quality impact resistance is strong. In the upper part of the internal circulating fluidized bed, the ozone enhanced oxidation reaction occurs through ultrasonic cavitation enhancement, and the preliminarily degraded organic matter is further treated. Then, a part of the produced water is transported into the catalytic oxidation unit 1 by the backflow unit backflow pump 6 to remove the pollutants in depth, and the remaining part of the produced water is directly discharged or subjected to post-treatment. The remaining undissolved oxygen, air and a small amount of unreacted ozone mixed gas are collected by the tail gas backflow unit backflow pipeline 8 and then sent to the inlet of the water inlet unit dissolved gas pressurizing pump 2-1 for reuse;

[0062] S2: The ozone generator 3-1 in the ozone generation unit generates a proper amount of ozone gas and sends it into the catalytic oxidation unit 1 to supply the required amount of ozone for the catalytic oxidation reaction in step S1. The air fan 4-1 in the gas supply unit sends a proper amount of air into the catalytic oxidation unit 1 to form a uniform and stable circulating fluidized state in the catalytic oxidation unit 1 in step S1. The ultrasonic wave generator 7-1 in the ultrasonic cavitation unit adjusts the ultrasonic wave frequency emission and controls the ultrasonic wave power to control the bubble particle size of the ultrasonic cavitation enhanced ozone oxidation reaction system in step S1 to be in the micron level, increase the gas-liquid phase interface area, prolong the residence time and improve the ozone utilization rate.

[0063] S3: During the operation of the catalytic oxidation unit 1 in step S1, the suspended solids and surfactants and other substances wrapped and carried by the bubbles continuously accumulate and thicken on the water surface. The slag and scum are removed by periodically opening the slag and water discharge door 1-1-11 located at the upper part of the upper cylinder 1-1-3, and the water quality of the effluent and the long-term surface cleanliness of the catalyst are improved.

[0064] S4: After the catalytic oxidation unit 1 in step S1 is operated for several days, the catalyst surface is slightly contaminated, the system is stopped and the conventional backwashing is performed. The air fan 4-1 in the gas supply unit and the regeneration cleaning pump 5 in the regeneration cleaning unit supply the required water and gas for backwashing. The backwashing mode adopts gas washing-gas and water washing-water washing to realize the complete stripping and removal of the catalyst surface layer pollutants.

[0065] S5: After the catalytic oxidation unit 1 in step S1 runs for several months, the catalyst surface is seriously contaminated, and the effluent water quality is significantly deteriorated. The system is shut down for regeneration cleaning. The regeneration liquid required for regeneration, the regeneration gas is supplied by the air supply unit fan 4-1 and the regeneration cleaning unit regeneration cleaning pump 5. The regeneration mode adopts emptying-liquid feeding-gas washing-soaking-circulation-water washing. The deep dirt inside the catalyst is effectively removed in time, the initial catalytic efficiency is restored, the service life is prolonged, and the energy consumption and operation and maintenance cost are greatly reduced.

[0066] Further, the fluidized bed catalyst 1-6 in step S1 is filled with 20-50 g / L; the ratio of ozone dosage to organic matter content in wastewater (O / C ratio) in step S2 is 0.6-1:1, and the gas-water ratio is 1-3:1; the gas flushing intensity in step S3 is 10 L / m 2 ·s, and the water washing intensity is 8 L / m 2 ·s; the regeneration liquid in step S5 includes hydrochloric acid with a mass concentration of 31%, sodium hydroxide with a mass concentration of 30%, and sodium hypochlorite with a mass concentration of 10%. The regeneration liquid preparation includes two parts. One part is to dilute hydrochloric acid with a mass concentration of 31% to a mass concentration of 0.2%, and the other part is a mixed solution after dilution of a solution containing sodium hydroxide and sodium hypochlorite. The mass concentration of sodium hydroxide in the mixed solution is 0.1%, and the mass concentration of sodium hypochlorite is 0.2%. When hydrochloric acid is used for regeneration cleaning, the pH is controlled to be 2-3, and when the mixed solution of sodium hydroxide and sodium hypochlorite is used for regeneration cleaning, the pH is controlled to be 11-12.

[0067] Example 1

[0068] 1. The average COD concentration of the circulating water blowdown water in a certain thermal power plant is 60-100 mg / L. The non-homogeneous ozone catalytic oxidation treatment system based on internal member reinforced internal circulation fluidization of the present application is added between the filtration and ultrafiltration. The system has a single set of water treatment capacity of 100 m 3 / h, the hydraulic retention time of the catalytic fluidized bed is 30 min, the Mn / Cu-Al2O3 catalyst with a diameter of 0.15 mm is used, the filling amount is 50 g / L, the air source is used to prepare ozone, the ozone concentration is 15 mg / L; the height-diameter ratio of the internal circulation catalytic fluidized bed is 4:1, the diameter ratio of the multiple circulation internal circulation device to the straight cylinder section is 0.7, the angle between the gradually tapered horn pipe and the horizontal is 60°, the angle between the gradually expanded horn pipe and the horizontal is 45°, the vertical distance between the lower end of the multiple circulation internal circulation device and the carrier distribution device is 0.2 times the diameter of the straight cylinder section, the vertical distance between the upper end of the multiple circulation internal circulation device and the water outlet is 1 times the diameter of the straight cylinder section, the diameter ratio of the upper cylinder body to the straight cylinder section is 1.2 times, the radius (r) of the top flow guide member is 0.6 times the radius of the multiple circulation internal circulation device, and the vertical distance between the top flow guide member and the upper end of the multiple circulation internal circulation device is 0.6 times the radius (r); the labyrinth gas-liquid disturbance device is arranged in three layers around the reflection cone, each layer of the reflection cone has a top angle of 90°, the horizontal distance between adjacent reflection cones is 1 cm, the bottom surface width of the reflection cone is 2 cm, and the distance between adjacent two layers of the reflection cone is 5 cm; the gas distribution device flow channel has an upward angle of 45° with the horizontal, and the water distribution device flow channel has a downward angle of 30° with the horizontal; the length of each section of the multiple circulation internal circulation device is 200 mm, and the circulation gap length is 20 mm; the backflow water amount is 20%. The water quality indexes of the influent and effluent are shown in the following table 1:

[0069] Table 1 Water quality indexes of influent and effluent

[0070]

[0071] Comparative Example 1

[0072] The traditional fixed bed ozone catalytic oxidation process system is used, the Mn / Cu-Al2O3 catalyst with a diameter of 3-5 mm is used, and the filling amount is 50 g / L. Comparative Example 1 is compared with Example 1, that is, under the same influent water quality, water amount, reaction time, ozone concentration and dosage, and other operating parameter conditions, the COD concentration of the influent and effluent is monitored, and is shown in Table 2.

[0073] Table 2 Water quality indexes of influent and effluent of the traditional fixed bed ozone catalytic oxidation treatment process system

[0074]

[0075] From the table 1, table 2, the application based on the internal member strengthens the non-homogeneous ozone catalytic oxidation treatment system of internal circulation fluidization, compared with the traditional fixed bed ozone catalytic oxidation treatment process system, the average COD removal rate is increased by 16.5%, and the ozone utilization rate is increased by 21%, which shows that the application is better than the traditional fixed bed process, mainly because the fluidized bed catalyst has larger external surface area and average pore size, and provides more active sites, which is more conducive to the adsorption and oxidation of organic matter and the conversion and utilization of ozone. At the same time, the circulating flow state increases the contact probability of pollutants, ozone and active sites, and has higher three-phase mass transfer efficiency than the traditional fixed bed.

[0076] Comparative example 2

[0077] The traditional fixed bed ozone catalytic oxidation process system is used, the Mn / Cu-Al2O3 catalyst with a diameter of 3-5mm is used, and the fluidized bed filling amount is 50g / L. Compared with example 1 of the application, under the same water quality, water quantity, reaction time, ozone concentration and dosage, etc. Operating parameter conditions, the fixed bed catalyst dosage is changed to achieve similar COD concentration of effluent as the target, and the results are shown in table 3.

[0078] Table 3 water quality indexes of traditional fixed bed ozone catalytic oxidation treatment process system

[0079]

[0080] From the table 1, table 3, the application based on the internal member strengthens the non-homogeneous ozone catalytic oxidation treatment system of internal circulation fluidization, compared with the traditional fixed bed ozone catalytic oxidation treatment process system, the fixed bed catalyst usage is 6.8 times that of the fluidized bed to achieve the same COD removal effect, which shows that the application can greatly reduce the usage of catalyst in the ozone catalytic oxidation process compared with the traditional fixed bed process. It is estimated that the application can save 70% of the purchase cost of catalyst.

[0081] The application proposes an internal circulating fluidized bed based on the fine layout of internal components such as carrier distribution devices, multiple loop internal circulation devices, top flow guide components, and labyrinth carrier separation devices, which strengthens the circulating flow state, improves mass transfer, and realizes real-time interface update on the catalyst surface through high-frequency gas-liquid disturbance, prolongs the service life, and improves the resistance to water quality and quantity impact. The application proposes a method for increasing the gas-liquid contact area and reaction time based on ultrasonic cavitation and water-gas external circulation reflux to improve the treatment effect; and a system and method for in-situ regeneration, defoaming and skimming of residues to optimize operation and ensure long-term clean and efficient catalyst. The application combines the internal circulating fluidized bed technology with the heterogeneous ozone catalytic oxidation technology, effectively improves the ozone utilization rate of the reaction system, reliably ensures the long-term use of the catalyst, significantly improves the water treatment effluent effect, greatly reduces the consumption of ozone and catalyst, saves operation and disposal costs, and can be well applied to different concentration organic wastewater treatment scenarios such as power plant circulating water and blowdown water, circulating water makeup water, and desulfurization wastewater.

[0082] The above only describes the best embodiments of the application, but cannot be understood as limiting the claims. The application is not limited to the above embodiments, and the specific structure allows changes. Any changes made within the protection scope of the independent claims of the application are within the protection scope of the application.

[0083] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

Claims

1. A heterogeneous ozone catalytic oxidation treatment system based on internal components to enhance internal circulation fluidization, characterized in that: It includes a catalytic oxidation unit (1), a water inlet unit, an ozone generating unit, an air supply unit, an ultrasonic cavitation unit, an in-situ regeneration cleaning unit and a gas-liquid reflux unit; The water inlet unit, the ozone generating unit, the air supply unit, the in-situ regeneration and cleaning unit, and the gas-liquid reflux unit are connected to the catalytic oxidation unit (1), and an ultrasonic cavitation unit is provided in the catalytic oxidation unit (1); The catalytic oxidation unit (1) includes a fluidized bed; the fluidized bed includes an outer shell (1-1), and the outer shell (1-1) is provided with a carrier distribution device (1-2), a multiple loop internal circulation device (1-3), a top flow guide component (1-4) and a labyrinth-type carrier separation device (1-5); The outer shell (1-1) includes a connected lower cylinder (1-1-1), a straight section (1-1-2) and an upper cylinder (1-1-3); the lower end of the lower cylinder (1-1-1) and the straight section (1-1-2) are connected through a gradually contracting trumpet tube, and the upper cylinder (1-1-3) and the upper end of the straight section (1-1-2) are connected through a gradually expanding trumpet tube; the lower cylinder (1-1-1) is elliptical, and the straight section (1-1-2) and the upper cylinder (1-1-3) are cylindrical. The upper part of the upper cylinder (1-1-3) is closed, a carrier distribution device (1-2) is provided inside the tapered bell tube, and the carrier distribution device (1-2) is connected to the upper part of the lower cylinder (1-1-1); a multiple-circulation internal circulation device (1-3) is provided on the upper part of the carrier distribution device (1-2) and in the straight cylinder section (1-1-2); a top flow guide component (1-4) is provided on the upper part of the multiple-circulation internal circulation device (1-3) and in the straight cylinder section (1-1-2); The multiple loop internal circulation device (1-3) is a multi-stage type; The top flow-guiding component (1-4) is mushroom-shaped along the circumferential direction, with the upper portion being semi-spherical and the lower portion being inward-conical; The labyrinth-type carrier separation device (1-5) is composed of reflection cones that are alternately arranged vertically, horizontally and horizontally in the height direction, with the top end flush with the bottom end of the gradually expanding trumpet tube and the bottom end spaced apart from the top end of the top guide member (1-4); The carrier distribution device (1-2) includes an air distribution device (1-2-1), a water distribution device (1-2-2) and a double-layer carrier distribution plate (1-2-3). The double-layer carrier distribution plate (1-2-3) is arranged between the lower cylinder (1-1-1) and the straight cylinder section (1-1-2). The middle space of the double-layer carrier distribution plate (1-2-3) is connected to the catalytic oxidation unit (1). The water distribution device (1-2-2) passes through the upper and lower plates of the double-layer carrier distribution plate (1-2-3). The water distribution device (1-2-2) is connected to the lower cylinder (1 -1-1) is connected to the interior of the straight-tube section (1-1-2); the air distribution device (1-2-1) is connected to the upper plate of the double-layer carrier distribution plate (1-2-3), and the air distribution device (1-2-1) is connected to the hollow space of the straight-tube section (1-1-2) and the double-layer carrier distribution plate (1-2-3); the flow channel of the air distribution device (1-2-1) is at an angle of 45°~60° to the horizontal direction and is located above the horizontal direction, and the flow channel of the water distribution device (1-2-2) is at an angle of 30°~45° to the horizontal direction and is located below the horizontal direction.

2. The heterogeneous ozone catalytic oxidation treatment system based on internal component-enhanced internal circulation fluidization according to claim 1 is characterized in that: A labyrinth-type carrier separation device (1-5) is provided in the straight cylinder section (1-1-2) located above the top flow-guiding component (1-4); and an ultrasonic cavitation unit is provided on the outer wall of the straight cylinder section (1-1-2) and in the area above the top flow-guiding component (1-4).

3. The heterogeneous ozone catalytic oxidation treatment system based on internal component-enhanced internal circulation fluidization according to claim 1 is characterized in that: A water inlet (1-1-4) and a return water inlet (1-1-9) are provided at the bottom of the lower cylinder (1-1-1); an ozone air inlet (1-1-6) and a catalytic oxidation unit (1) are provided on the side wall of the lower cylinder (1-1-1); a tail gas discharge port (1-1-10) is provided on the top of the upper cylinder (1-1-3); a water outlet (1-1-5), a return port (1-1-8) and a water discharge and slag discharge port (1-1-11) are provided on the side wall of the upper cylinder (1-1-3); an umbrella-shaped gas collecting hood is provided inside the upper cylinder (1-1-3); and the umbrella-shaped gas collecting hood is connected to the inside of the tail gas discharge port (1-1-10).

4. The heterogeneous ozone catalytic oxidation treatment system based on internal component-enhanced internal circulation fluidization according to claim 1 is characterized in that: The ratio of the height of the shell (1-1) to the diameter of the straight section (1-1-2) is (4~10):(1), the diameter ratio of the multiple circulation internal circulation device (1-3) to the straight section (1-1-2) is 0.6~0.7:1, the angle between the tapered bell tube and the horizontal direction is 45°~70°, the angle between the tapered bell tube and the horizontal direction is 45°~60°, the lower end of the multiple circulation internal circulation device (1-3) is vertical to the double-layer carrier distribution plate (1-2-3) The vertical spacing is 0.15~0.3 times the diameter of the straight cylinder section (1-1-2); the vertical spacing between the upper end of the multiple-circulation internal circulation device (1-3) and the water outlet (1-1-5) is 0.8~1.2 times the diameter of the straight cylinder section; the lower cylinder (1-1-1) and the multiple-circulation internal circulation device (1-3) have the same diameter and are located on the same axis; the ratio of the diameter of the upper cylinder (1-1-3) to the diameter of the straight cylinder section (1-1-2) is 1.2~1.3:

1.

5. The heterogeneous ozone catalytic oxidation treatment system based on internal component-enhanced internal circulation fluidization according to claim 1 is characterized in that: The water inlet unit includes a dissolved air pressure pump (2-1) and a water inlet flow meter (2-2) connected to each other, and the outlet of the water inlet flow meter (2-2) is connected to the water inlet (1-1-4) of the catalytic oxidation unit (1); The ozone generating unit includes an ozone generator (3-1), an ozone concentration meter (3-2) and a gas flow meter (3-3) connected to each other, and the outlet of the gas flow meter (3-3) is connected to the catalytic oxidation unit (1); The air supply unit comprises a connected fan (4-1) and an air intake flow meter (4-2), and the outlet of the air intake flow meter (4-2) is connected to the catalytic oxidation unit (1).

6. The heterogeneous ozone catalytic oxidation treatment system based on internal component-enhanced internal circulation fluidization according to claim 1 is characterized in that: The ultrasonic cavitation unit includes a connected ultrasonic generator (7-1) and a plurality of ultrasonic vibrators (7-2); the ultrasonic vibrators (7-2) are evenly arranged along the circumferential direction of the outer wall of the straight cylinder section (1-1-2), with a frequency of 30-40 kHz and a power of 0.5-1 kW; The in-situ regeneration cleaning unit comprises a regeneration cleaning pump (5), and the outlet of the regeneration cleaning pump (5) is connected to the catalytic oxidation unit (1); The gas-liquid reflux unit includes a water production external circulation reflux system and a tail gas external reflux system. The water production external circulation reflux system includes a reflux pump (6), the inlet of the reflux pump (6) and the outlet of the reflux pump (6) are connected to the catalytic oxidation unit (1); the tail gas external reflux system includes a tail gas reflux pipeline (8), one end of the tail gas reflux pipeline (8) is connected to the catalytic oxidation unit (1).

7. A heterogeneous ozone catalytic oxidation treatment method based on internal components to enhance internal circulation fluidization based on the system according to any of claims 1 to 6, characterized in that: The following steps are involved: The ozone gas produced by the ozone generation unit, the air from the air supply unit, and the hard-to-degrade organic wastewater to be treated are transported to the catalytic oxidation unit (1) to undergo a catalytic oxidation reaction with the fluidized bed catalyst to initially degrade the organic pollutants in the organic wastewater to be treated; ultrasonic cavitation enhancement is carried out in the ultrasonic cavitation unit on the upper part of the fluidized bed to produce an ozone-enhanced oxidation reaction to further enhance the treatment of the initially degraded organic matter; then a portion of the produced water enters the catalytic oxidation unit (1) through the gas-liquid reflux unit to deeply remove the pollutants.

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