A device and method for simultaneously dissolving and intensifying catalytic ozone oxidation reaction

Abstract

A device and method for simultaneous solvent-catalyst-enhanced catalytic ozone oxidation reaction are disclosed. The reaction device includes a simultaneous solvent-catalyst reaction chamber and a post-solution catalytic enhancement reaction chamber, which are connected by a flange. The post-solution catalytic enhancement reaction chamber has a sieve plate and a backwash inlet at its bottom. The simultaneous solvent-catalyst reaction chamber can achieve internal circulation and is equipped with an inlet pipe, an annular water distribution system, a guide cylinder, a simultaneous solvent-catalyst catalyst, a separation cone, a collection cone, and a drain outlet. The post-solution catalytic enhancement reaction chamber includes a multi-stage baffle first unit cylinder, a post-solution catalytic enhancement catalyst, a second unit cylinder, a water outlet, and a tail gas outlet. The device also includes a flange and a base. This invention combines a special reaction structure design, using an ejector to achieve gas-liquid mixing, and further cutting it through the annular water and gas distribution system of the ejector to enhance dissolved gas efficiency; it rationally partitions the reactor, optimizes the internal space, selects the optimal catalyst particle size, and enhances mass transfer between the gas, liquid, and solid phases to achieve simultaneous solvent-catalyst-enhanced and post-solution catalytic enhancement; it reduces the amount of catalyst added, lowers energy consumption, enhances the reaction rate, improves ozone utilization, and saves costs.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, specifically to a solvent-catalyst simultaneous enhanced catalytic ozone oxidation reactor and method. Background Technology

[0002] In recent years, with increasingly stringent wastewater discharge standards, the development of efficient and low-cost advanced wastewater treatment technologies has become increasingly important. Catalytic ozone oxidation technology, as an ideal wastewater treatment technology, has been widely used in wastewater treatment. Currently, the most commonly used catalytic ozone oxidation reactors have relatively simple structures, but suffer from problems such as uneven aeration, low ozone utilization, high catalyst dosage, and poor catalytic effect.

[0003] Improving water and gas distribution methods, optimizing the internal spatial structure of the reactor, enhancing the gas-liquid-solid three-phase mass transfer efficiency, increasing ozone utilization, reducing energy consumption, and broadening the application scope of catalytic ozone oxidation technology necessitates the research and development of a high-performance catalytic ozone oxidation reactor. Therefore, a catalytic ozone oxidation device and method capable of solving the aforementioned problems is currently needed. Summary of the Invention

[0004] The purpose of this invention is to provide a solvent-catalyst simultaneously enhanced catalytic ozone oxidation reactor and method, which enhances the dissolved gas efficiency and ozone utilization rate of catalytic ozone oxidation. This objective can be achieved through the following technical solutions.

[0005] A solvent-catalyst-enhanced catalytic ozone oxidation reactor includes a solvent-catalyst-simultaneous reaction chamber and a post-solution catalytic enhancement reaction chamber, connected by a flange with a support layer in the middle. The solvent-catalyst-simultaneous reaction chamber, from bottom to top, comprises a collection cone, an annular jet water and gas distribution system, a guide cylinder, a separation cone, and a solvent-catalyst-simultaneous catalyst. The post-solution catalytic enhancement reaction chamber includes a multi-stage baffle unit, a backwash inlet, an outlet, and a post-solution catalytic enhancement catalyst. The bottom of the collection cone is fixedly connected to the inner wall of the solvent-catalyst-simultaneous reaction chamber, and the bottom is equipped with an annular water and gas distribution system. A drain outlet is located on the side wall of the collection cone and connected to the outer wall of the solvent-catalyst-simultaneous reaction chamber. The bottom of the collection cone is equipped with an annular water and gas distribution system, and the side wall of the collection cone is equipped with a drain outlet and connected to the outer wall of the rapid mixing catalytic reaction chamber.

[0006] The annular jet water and air distribution system consists of a primary jet and a secondary jet. The primary jet is connected in series with the water and air inlet pipe and the secondary jet. The secondary jet consists of multiple (3-6) ordinary jets connected in series in a ring. Wastewater and ozone flow into the secondary jet through the primary jet, where they are further mixed and cut before entering the guide tube.

[0007] The guide tube is welded to the center of the solvent-catalyst synchronous reaction chamber via a bracket. The lower end of the guide tube is 3-8 cm away from the collecting cone, and the upper end of the guide tube is 10-30 cm away from the separating cone.

[0008] The separation cone is a hollow frustum-shaped cone, with its center aligned with the center of the post-dissolution catalytic enhancement reaction chamber. Its top is fixedly connected to the support layer, and a sieve plate is installed at the top opening.

[0009] The solvent-catalyst co-catalyst can be an ozone catalyst with a particle size between 0.5-2 mm, supported by activated carbon, zeolite, ceramsite, molecular sieve, γ-Al2O3, etc., and loaded or doped with one or more transition metal components.

[0010] The post-dissolution catalytic enhancement reaction chamber is provided with a backwash water inlet at the bottom, a water outlet on the upper side wall, and a tail gas outlet at the top.

[0011] The multi-stage baffle unit cylinder is a series of concentric cylinders arranged at fixed intervals, with the opening at the center of the lower support layer of the post-dissolution catalytic enhancement reaction chamber and the center of the separation cone as the center. The bottom of the first unit cylinder, located near the center, is welded to the support layer. A 3-5cm gap is reserved between the top of the first unit cylinder and the top of the reactor to ensure that the catalyst overflows upward into the second unit cylinder. The top of the second unit cylinder is welded to the top of the reactor, and a 3-5cm gap is reserved between the bottom of the second unit cylinder and the second support layer to ensure that the catalyst flows downward into the third unit cylinder. The arrangement of the unit cylinders is similar. Post-dissolution catalytic enhancement catalyst is added between each unit cylinder.

[0012] The post-solution catalytic enhancement catalyst can be selected with a particle size between 3-8 mm, using activated carbon, zeolite, ceramsite, molecular sieve, γ-Al2O3, etc. as supports, and loaded or doped with one or more transition metal components.

[0013] Furthermore, the materials used for the structure of the solvent-catalyst synchronous reaction chamber, the post-solution catalytic enhancement reaction chamber, and each of the reaction chambers can be 316L stainless steel.

[0014] Furthermore, the tail gas outlet of the post-dissolution catalytic enhancement reaction chamber can be connected to a tail gas destroyer, or connected to a polytetrafluoroethylene pipe to collect unused ozone and re-enter the reactor for recycling.

[0015] Furthermore, the post-dissolution catalytic enhancement reaction chamber unit can be set in two or more units, depending on the actual situation.

[0016] Furthermore, the transition metal catalyst supported or doped by the solvent-catalyst co-catalyst may be selected from at least one of titanium, cobalt, lanthanum and cerium.

[0017] Furthermore, the transition metal catalyst supported or doped on the post-solution catalytic enhancement catalyst may be selected from at least one of iron, manganese, copper, and nickel.

[0018] Furthermore, the catalytic ozone oxidation reaction device also includes an ozone generator, the ozone generator's inlet end being connected to an air source, an oxygen-enriched source, or a liquid oxygen source unit, and the ozone generator's outlet end being connected to an ozone concentration analyzer.

[0019] Furthermore, the ozone concentration analyzer is located between the ozone generator and the catalytic ozone oxidation reaction device.

[0020] In some embodiments of the present invention, the method for preparing the solvent-catalyst co-catalyst includes:

[0021] (1) Activation pretreatment of catalyst support in solvent-catalyst synchronous reaction chamber: Mix 0.5-2.0 mol / L KOH activator with activated carbon at a mass ratio of (0.1-1):1. After constant temperature shaking at 15-40℃ for 1-6 h, place it in a forced-air drying oven at 105℃ for 2-12 h, and then transfer it to a muffle furnace at 600-800℃ for 90 min for later use;

[0022] (2) Co-Ce bimetallic component loading: Co(NO3)2·6H2O and Ce(NO3)3·6H2O were mixed at a molar ratio of 1:1 to prepare 0.3-1.2 mol / L Co(NO3)2·6H2O and Ce(NO3)3·6H2O mixture as impregnation solution for composite loading component. The above impregnation solution was mixed with activated carbon at a mass ratio of (0.1-1):1 for 6-24 h. The deposit was dried and then calcined in a muffle furnace at 400-800℃ for 2 h to obtain Co-Ce / activated carbon.

[0023] (3) Molding: Co-Ce / activated carbon, bentonite, neutral silica sol and Fe2O3 are mixed in a ratio of 3:2.5:4:0.5 and placed in a granulator. Add an appropriate amount of water to granulate and shape. After standing at room temperature for 24 hours, transfer to a muffle furnace and calcine at 200-500℃ for 120 minutes. Cool naturally to room temperature to obtain the solvent-catalyst synchronous catalyst.

[0024] In some embodiments of the present invention, the preparation method of the post-solution catalytic enhancement catalyst includes:

[0025] (1) Pretreatment of spherical activated carbon support: 0.5-2.0 mol / L C6H 12 O6 and spherical activated carbon are mixed at a mass ratio of (0.1-1):1. After constant temperature shaking at 15-40℃ for 6 hours, the mixture is placed in a forced-air drying oven and dried at 105℃ for 12 hours. Then, it is transferred to a tube furnace and calcined at 600-800℃ under a nitrogen atmosphere for 90 minutes for later use.

[0026] (2) Fe-Mn bimetallic impregnation: Fe(NO3)3·9H2O and Mn(NO3)2 are prepared in a molar ratio of 1:1 to prepare a 0.3-1.2 mol / L Fe(NO3)3·9H2O and Mn(NO3)2 mixture as the impregnation solution of the composite loading component; the above impregnation solution is impregnated with pretreated spherical activated carbon at a mass ratio of (0.1-1):1 for 6-24 h, and after standing at room temperature for 24 h, it is transferred to a tube furnace at 200-800℃ under a nitrogen atmosphere for 2 h, and then naturally cooled to room temperature to obtain the dissolved catalytic enhancement catalyst.

[0027] In another aspect of the invention, a method for catalytic oxidation of wastewater using the reaction apparatus described above is provided. The method includes the following steps:

[0028] (1) The ozone generated by the ozone generator flows into the ozone concentration analyzer through the pipeline, and then flows into the first jet in the annular jet water and gas distribution system after passing through the concentration analyzer.

[0029] (2) The wastewater to be treated flows into the primary jet injector through the wastewater lift pump and wastewater pipe;

[0030] (3) The ozone gas and sewage are mixed in the first-stage jet injector to obtain a first-stage gas-water mixture;

[0031] (4) The primary gas-water mixture is fed into the secondary jet in the annular water and gas distribution system through a pipeline, and after further mixing and cutting, it forms a secondary gas-water mixture, which then enters the solvent-catalyst synchronous reaction chamber.

[0032] (5) The secondary gas-water mixture is fully mixed and contacted with the solvent-catalyst synchronous reaction chamber. Under the action of the guide tube, the gas-liquid-solid three-phase mass transfer effect is enhanced, and some pollutants in the wastewater are removed. The effluent from the solvent-catalyst synchronous reaction chamber enters the post-solution catalytic enhancement reaction chamber through the sieve plate.

[0033] (6) The secondary gas-water mixture enters the first unit cylinder of the post-dissolution catalytic enhancement reaction chamber. Under the action of pressure difference, the secondary gas-water mixture entering the first unit cylinder reacts fully with the post-dissolution catalytic enhancement catalyst and then enters the second unit cylinder. This process is repeated until it enters the water outlet unit.

[0034] (7) After the treatment is completed, the effluent from the post-dissolution catalytic enhancement reaction chamber is discharged from the reactor through the drain outlet.

[0035] According to the embodiments of the present invention, the method for catalytic oxidation of wastewater employs the above-mentioned reaction unit, which enables wastewater to undergo multi-stage catalytic oxidation in the reaction unit under the synergistic effect of ozone and ozone catalyst, generating highly reactive oxygen species. At the same time, it enhances the gas-liquid-solid three-phase mass transfer rate, increases the amount of highly reactive oxygen species generated, and improves the utilization efficiency of ozone. Through multi-stage catalysis, the deep treatment performance of wastewater is enhanced, and the effluent quality of the reaction device is improved, resulting in good economic and environmental benefits.

[0036] Compared with the prior art, the present invention has the following advantages:

[0037] (1) The present invention sets up an annular jet water and gas distribution system, which achieves preliminary gas-liquid mixing through a first-stage jet nozzle, and further cuts it through a second-stage jet nozzle to fully mix the gas and liquid, thereby enhancing the dissolved gas efficiency and ozone utilization rate.

[0038] (2) By setting up a solvent-catalyst synchronous reaction chamber and using a flow guide tube and separation cone, the present invention achieves full mixing of the three phases and separation of the two phases, efficiently performs preliminary catalytic oxidation and degradation of wastewater, with a short hydraulic retention time and lower cost;

[0039] (3) This invention sets up a post-dissolution catalytic enhancement reaction chamber, rationally partitions and optimizes the internal structure through a multi-stage baffle unit cylinder, reuses the catalyst and ozone for catalytic oxidation reaction, reuses the ozone in the water, further enhances the gas-liquid-solid three-phase mass transfer efficiency, and further enhances the degradation of wastewater.

[0040] (4) The present invention achieves a higher catalytic effect by adding a catalyst that matches the reaction chamber to different reaction chambers and by optimizing the catalyst particle size and the active component loaded according to the reaction characteristics of different regions;

[0041] (5) This invention enhances the reaction rate, reduces energy consumption, and improves the efficiency of catalytic ozone reaction by simultaneously treating the solvent and catalyst and enhancing the post-solution catalysis. Attached Figure Description

[0042] Figure 1 This is a schematic diagram of a reactor structure according to an embodiment of the present invention;

[0043] Figure 2 This is a schematic diagram of the structure of a solvent-catalyst synchronous reaction chamber according to an embodiment of the present invention;

[0044] Figure 3 This is a schematic diagram of the structure of a post-solution catalytic enhancement catalyst according to an embodiment of the present invention;

[0045] Figure 4 This is a schematic diagram of a ring-shaped water and air distribution system according to an embodiment of the present invention. Detailed Implementation

[0046] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0047] Example 1: 0.5 mol / L KOH was used as an activator and mixed with activated carbon powder at a mass ratio of 1:1. After constant temperature shaking at 25°C for 2 hours, it was placed in a forced-air drying oven and dried at 105°C for 2 hours. Then, it was transferred to a muffle furnace and activated at 600°C for 90 minutes. After cooling to room temperature, it was placed in a 0.3 mol / L mixture of Co(NO3)2·6H2O and Ce(NO3)3·6H2O at a molar ratio of 1:1. The mixture was then impregnated with activated carbon at a mass ratio of 1:1 for 6 hours. The deposit was dried and then calcined in a muffle furnace at 400°C for 2 hours to obtain Co-Ce / activated carbon. Co-Ce / activated carbon, bentonite, neutral silica sol, and Fe2O3 were mixed in a ratio of 3:2.5:4:0.5 and placed in a granulator. An appropriate amount of water was added to granulate the mixture. After standing at room temperature for 24 hours, the mixture was transferred to a muffle furnace and calcined at 200°C for 120 minutes. The mixture was then naturally cooled to room temperature to obtain a solvent-catalyst co-catalyst.

[0048] 0.5 mol / L C6H 12 O6 and spherical activated carbon were mixed at a mass ratio of 1:1. After constant temperature shaking at 25℃ for 6 hours, the mixture was placed in a forced-air drying oven and dried at 105℃ for 12 hours. Then, it was transferred to a tube furnace and calcined at 600℃ under a nitrogen atmosphere for 90 minutes. After cooling to room temperature, it was placed in a 0.3 mol / L mixture of Cu(NO3)2·3H2O and Mn(NO3)2 at a molar ratio of 1:1 and impregnated at a mass ratio of 1:1 for 6 hours. After standing at room temperature for 24 hours, it was transferred to a tube furnace and impregnated at 400℃ under a nitrogen atmosphere for 2 hours. After naturally cooling to room temperature, the dissolved catalyst was obtained.

[0049] The two catalysts mentioned above are respectively added to the catalytic ozone oxidation reactor (e.g.) Figure 1In the two catalytic reaction chambers shown, the circulating water from a chemical plant was treated. The water quality characteristics were: COD=104 mg / L, pH=8.19, conductivity=5812 μs / cm. The treated water entered the first-stage jet pump through a booster pump. Ozone was generated by the ozone generator and then entered the first-stage jet pump through the negative pressure generated by the first-stage jet pump of the annular water and gas distribution system (1-2) to form a gas-liquid mixture. It entered the second-stage jet pump through the inlet pipe (1-1). After being evenly distributed by the annular water and gas distribution system (1-2), it entered the guide tube (1-3) in the solvent-catalyst synchronous reaction chamber (1) to form an upflow zone. The gas-liquid mixture was fully mixed and contacted with the solvent-catalyst synchronous catalyst (1-4). When it reached the separation cone (1-5), the gas-liquid mixture... The gas and liquid mixture flows down to the collection cone (1-6) outside the guide tube, forming an internal circulation. As the gas-liquid mixture continuously enters, it passes through the sieve plate (2-1) at the flange (2) and enters the first unit cylinder (3-1) of the post-dissolution catalytic enhancement reaction chamber (3). Under the action of pressure difference, the gas-liquid mixture entering the first unit cylinder reacts fully with the post-dissolution catalytic enhancement catalyst (3-2) and then enters the second unit cylinder (3-3). This process is repeated until it enters the outlet (3-4). The remaining tail gas is discharged through the tail gas outlet (3-5). After treatment by this simultaneous enhanced catalytic ozone oxidation reaction device, the COD is 27.2 mg / L, pH is 8.23, conductivity is 4120 μs / cm, and ozone utilization rate is 96.18%. Under the same operating conditions as in Example 1, a commercially available tower reactor filled with a commercially available ozone catalyst was used. After treatment, the effluent COD was 53.8 mg / L, pH was 8.20, conductivity was 5620 μs / cm, and ozone utilization was 72.36%. The effect was lower than that of the original reactor, but the treatment effect was improved by 25.58% and the ozone utilization was improved by 23.82% compared to a commercially available tower reactor filled with a commercially available ozone catalyst.

[0050] Example 2: 1.5 mol / L KOH was used as an activator and mixed with activated carbon powder at a mass ratio of 1:1. After constant temperature shaking at 30°C for 4 hours, it was placed in a forced-air drying oven and dried at 105°C for 2 hours. Then, it was transferred to a muffle furnace and activated at 650°C for 90 minutes. After cooling to room temperature, it was placed in a 0.6 mol / L mixture of Co(NO3)2·6H2O and Ce(NO3)3·6H2O at a molar ratio of 1:1. The mixture was then impregnated with activated carbon at a mass ratio of 1:1 for 6 hours. The deposit was dried and then calcined in a muffle furnace at 400°C for 2 hours to obtain Co-Ce / activated carbon. Co-Ce / activated carbon, bentonite, neutral silica sol, and Fe2O3 were mixed in a ratio of 3:2.5:4:0.5 and placed in a granulator. An appropriate amount of water was added to granulate the mixture. After standing at room temperature for 24 hours, the mixture was transferred to a muffle furnace and calcined at 400℃ for 120 minutes. The mixture was then naturally cooled to room temperature to obtain a solvent-catalyst synergistic catalyst.

[0051] 1.0 mol / L C6H 12 O6 and γ-Al2O3 were mixed at a mass ratio of 1:1. After being shaken at 25℃ for 6 hours, the mixture was dried in a forced-air drying oven at 105℃ for 12 hours. Then, it was transferred to a tube furnace and calcined at 600℃ under a nitrogen atmosphere for 90 minutes. After cooling to room temperature, it was immersed in a 0.6 mol / L mixture of Cu(NO3)2·3H2O and Mn(NO3)2 at a molar ratio of 1:1 for 6 hours. After standing at room temperature for 24 hours, it was transferred to a tube furnace and calcined at 600℃ under a nitrogen atmosphere for 2 hours. After naturally cooling to room temperature, the dissolved catalyst was obtained.

[0052] The two catalysts mentioned above are respectively added to a solvent-catalyst-enhanced catalytic ozone oxidation reactor (e.g.) Figure 1 In the two catalytic reaction chambers (shown), effluent from a pharmaceutical factory's biochemical tank was treated using a quartz sand media filter. The effluent COD was 64 mg / L. Following the operating steps in Example 1, the wastewater was treated using this solvent-catalyst-enhanced catalytic ozone oxidation reactor, resulting in a COD of 21.6 mg / L and an ozone utilization rate of 97.45%. Under the same operating conditions as in Example 2, a commercially available tower reactor filled with a commercially available ozone catalyst was used. After treatment, the effluent COD was 46.4 mg / L, and the ozone utilization rate was 67.45%. The effect was lower than that of this reactor, but the treatment effect was improved by 38.75% and the ozone utilization rate was improved by 30% compared to the commercially available tower reactor filled with a commercially available ozone catalyst.

[0053] Example 3: The catalyst prepared under the conditions described in Example 2 was selected as the typical catalyst. Electroplating wastewater with a COD of 147 mg / L was selected as the actual wastewater. The wastewater was treated according to the operating steps in Example 1. After treatment by this solvent-catalyst simultaneous enhanced catalytic ozone oxidation reactor, the COD was 42.6 mg / L, and the ozone utilization rate was 98.37%. Under the same operating conditions as in Example 3, a commercially available tower reactor filled with a commercially available ozone catalyst was used. After treatment, the effluent COD was 64.9 mg / L, and the ozone utilization rate was 81.45%. The effect was lower than that of this reactor, but the treatment effect was improved by 15.17% and the ozone utilization rate was improved by 16.92% compared to the commercially available tower reactor filled with a commercially available ozone catalyst.

[0054] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A solvent-catalyst simultaneously enhanced catalytic ozone oxidation reactor, characterized in that, include: The solvent-catalyst synchronous reaction chamber (1) and the post-solution catalytic enhancement reaction chamber (3) are connected by a flange (2). The bottom of the post-solution catalytic enhancement reaction chamber (3) is provided with a sieve plate (2-1) and a backwash water inlet (2-2). The solvent-catalyst synchronous reaction chamber (1) is provided with a water inlet pipe (1-1), an annular water and gas distribution system (1-2), a guide tube (1-3), a solvent-catalyst synchronous catalyst (1-4), a separation cone (1-5), a collection cone (1-6), and a drain outlet (1-7). The guide tube (1-3) is fixed in the center of the solvent-catalyst synchronous reaction chamber (1) by a bracket. The lower end of the guide tube (1-3) is connected to the collection cone. (1-6) Maintain a distance of 3-8cm, and the upper end of the guide tube (1-3) maintains a distance of 10-30cm from the separation cone (1-5); the separation cone (1-5) is a hollow truncated cone, its top is fixedly connected to the support layer, and a sieve plate is installed at the top opening; the annular water and gas distribution system (1-2) is composed of a primary jet ejector and a secondary jet ejector connected in series, the primary jet ejector is connected in series with the water and gas inlet pipe and the secondary jet ejector, and the secondary jet ejector is composed of 3-6 ordinary jet ejectors connected in series in a ring; the solvent-catalyst synchronous reaction chamber (1) is filled with a solvent-catalyst synchronous catalyst (1-4), and the solvent-catalyst synchronous catalyst... The particle size of the catalyst (1-4) is 0.5-2 mm, and its support is selected from activated carbon, zeolite, ceramsite, molecular sieve or γ-Al2O3, and at least one of cobalt and cerium is supported or doped; the post-dissolution catalytic enhancement reaction chamber (3) includes a multi-stage baffle first unit cylinder (3-1), a post-dissolution catalytic enhancement catalyst (3-2), a second unit cylinder (3-3), a water outlet (3-4), and a tail gas outlet (3-5); the post-dissolution catalytic enhancement reaction chamber (3) is filled with a post-dissolution catalytic enhancement catalyst (3-2), the particle size of the post-dissolution catalytic enhancement catalyst (3-2) is 3-8 mm, and its support is selected from activated carbon, zeolite, ceramsite, molecular sieve or γ-Al2O3, and at least one of cobalt and cerium is supported or doped; Zeolite, ceramsite, molecular sieve or γ-Al2O3, supported or doped with one or more of iron, manganese, copper and nickel; the first unit cylinder (3-1) and the second unit cylinder (3-3) are concentric cylindrical structures: the bottom of the first unit cylinder (3-1) is welded to the support layer, and the top is reserved with a 3-5cm gap from the top of the reactor; the top of the second unit cylinder (3-3) is welded to the top of the reactor, and the bottom is reserved with a 3-5cm gap from the support layer; the post-dissolution catalytic enhancement catalyst (3-2) is added between the first unit cylinder (3-1) and the second unit cylinder (3-3); the device is also equipped with a base (5).

2. The solvent-catalyst simultaneous enhanced catalytic ozone oxidation reactor according to claim 1, characterized in that, The solvent-catalyst co-catalysts (1-4) are prepared by the following method: (1) Mix 0.5-2.0 mol / L KOH activator with activated carbon at a mass ratio of (0.1-1):1, keep at a constant temperature of 15-40℃ for 1-6 h, dry in a 105℃ forced-air drying oven for 2-12 h, and then transfer to a muffle furnace to activate at 600-800℃ for 90 min for later use; (2) Prepare a 0.3-1.2 mol / L mixture of Co(NO3)2·6H2O and Ce(NO3)3·6H2O in a molar ratio of 1:1 as the impregnation solution. Impregnate the activated carbon with the impregnation solution at a mass ratio of (0.1-1):1 for 6-24 hours. After drying the deposit, calcine it in a muffle furnace at 400-800℃ for 2 hours to obtain Co-Ce / activated carbon. (3) Mix Co-Ce / activated carbon with bentonite, neutral silica sol and Fe2O3 in a ratio of 3:2.5:4:0.5 and place them in a granulator. Add water to granulate and shape. After standing at room temperature for 24 hours, transfer to a muffle furnace and calcine at 200-500℃ for 120 minutes. Cool naturally to obtain the final product.

3. The solvent-catalyst simultaneous enhanced catalytic ozone oxidation reactor according to claim 1, characterized in that, The post-solution catalytic enhancement catalyst (3-2) is prepared by the following method: (1) Add 0.5-2.0 mol / L C6H 12 O6 and spherical activated carbon are mixed at a mass ratio of (0.1-1):1, and then the mixture is kept at a constant temperature of 15-40℃ and shaken for 6 hours. After drying in a forced-air drying oven at 105℃ for 12 hours, it is then transferred to a tube furnace and calcined in a nitrogen atmosphere at 600-800℃ for 90 minutes for later use. (2) Take Fe(NO3)3·9H2O and Mn(NO3)2 and prepare a 0.3-1.2 mol / L mixture in a molar ratio of 1:1 as the impregnation solution. Impregnate the pretreated spherical activated carbon with the impregnation solution at a mass ratio of (0.1-1):1 for 6-24 hours. After standing at room temperature for 24 hours, transfer it to a tube furnace and calcine it at 200-800℃ under a nitrogen atmosphere for 2 hours. After natural cooling, the product is obtained.

4. A method for wastewater treatment using the reaction apparatus according to any one of claims 1-3, characterized in that, Includes the following steps: (1) The wastewater to be treated is introduced into the first-stage jet of the annular water and gas distribution system (1-2) through the inlet pipe (1-1). At the same time, ozone enters the first-stage jet through the negative pressure generated by the first-stage jet to form a gas-liquid mixture. The gas-liquid mixture flows into the second-stage jet through the pipeline for further cutting and mixing. (2) The gas-liquid mixture obtained in step (1) is introduced into the solvent-catalyst synchronous reaction chamber (1) and mixed and contacted with the solvent-catalyst synchronous catalyst (1-4) under the action of the guide tube (1-3) to carry out a preliminary catalytic oxidation reaction; (3) The mixed fluid obtained in step (2) is passed through the sieve plate (2-1) into the post-dissolution catalytic enhancement reaction chamber (3), and flows through the first unit cylinder (3-1) and the second unit cylinder (3-3) in sequence, and reacts with the post-dissolution catalytic enhancement catalyst (3-2) therein; (4) Collect the treated water discharged through the outlet (3-4).

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