Device and method for synchronously strengthening catalytic ozonation reaction by dissolving and catalyzing

Abstract

The invention relates to a device and a method for a dissolution-catalysis synchronous enhanced catalytic ozonation reaction, the reaction device comprises a dissolution-catalysis synchronous reaction chamber and an after-dissolution catalysis enhanced reaction chamber, the two chambers are connected by a flange, and the bottom of the after-dissolution catalysis enhanced reaction chamber is provided with a sieve plate and a backwashing water inlet; the dissolution-catalysis synchronous reaction chamber can realize internal circulation and is provided with a water inlet pipe, an annular water distribution system, a guide cylinder, a dissolution-catalysis synchronous catalyst, a separation cone barrel, a collection cone barrel and a sewage draining exit; the after-dissolution catalysis enhancement reaction chamber comprises a multi-stage baffling first unit cylinder, an after-dissolution catalysis enhancement catalyst, a second unit cylinder, a water outlet and a tail gas exhaust port; the device is also provided with a flange, a base and the like. According to the invention, a special reaction structure design is combined, the jet device is adopted to realize gas-liquid mixing, and the jet device is used for further cutting through an annular water and gas distribution system, so that the gas dissolving efficiency is enhanced; the reactor is reasonably partitioned, the internal space is optimized, the particle size of the catalyst is optimized, mass transfer among gas, liquid and solid phases is enhanced, and dissolution and catalysis synchronization and after-dissolution catalysis enhancement are realized; the catalyst dosage is reduced, the energy consumption is reduced, the reaction rate is enhanced, the ozone utilization rate is improved, and the cost is saved.

Description

Technical Field

[0001] The invention relates to the technical field of wastewater treatment, and in particular to a device and method for a solution-catalyst synchronous enhanced catalytic ozone oxidation reaction. Background Art

[0002] In recent years, with the increasingly stringent sewage discharge standards, the development of efficient and low-cost wastewater deep treatment technology has become increasingly important. Catalytic ozone oxidation technology has been widely used in sewage treatment as an ideal wastewater treatment technology. At present, the most commonly used catalytic ozone oxidation reactor has a relatively simple structure, and has problems such as uneven aeration, low ozone utilization, high catalyst dosage and poor catalytic effect.

[0003] It is urgent to improve the water and gas distribution method, optimize the internal space structure of the reactor, improve the gas-liquid-solid three-phase mass transfer efficiency, improve ozone utilization, reduce energy consumption, broaden the application scope of catalytic ozone oxidation technology, and research and develop catalytic ozone oxidation reactors with excellent performance. Therefore, a catalytic ozone oxidation device and method that can solve the above problems is needed. Summary of the invention

[0004] The purpose of the present invention is to provide a device and method for simultaneously strengthening catalytic ozone oxidation reaction by dissolving and catalyzing, and to utilize the device and method to strengthen the dissolving gas efficiency and ozone utilization rate of catalytic ozone oxidation. The purpose of the present invention can be achieved through the following technical solutions.

[0005] A dissolution-catalyst synchronous enhanced catalytic ozone oxidation reaction device comprises a dissolution-catalyst synchronous reaction chamber and a post-dissolution catalytic enhancement reaction chamber, which are connected by a flange, and a supporting layer is provided in the middle of the flange. The dissolution-catalyst synchronous reaction chamber is provided with a collecting cone barrel, an annular jet water and air distribution system, a guide tube, a separation cone barrel and a dissolution-catalyst synchronous catalyst from bottom to top; the post-dissolution catalytic enhancement reaction chamber comprises a multi-stage baffle unit tube, a backwash water inlet, a water outlet and a post-dissolution catalytic enhancement catalyst. The bottom of the collecting cone barrel is fixedly connected to the inner wall of the dissolution-catalyst synchronous reaction chamber, and an annular water and air distribution system is provided at the bottom, and a sewage outlet is provided on the side wall, which is connected to the outer wall of the dissolution-catalyst synchronous reaction chamber. The bottom of the collecting cone barrel is provided with an annular water and air distribution system, and a sewage outlet is provided on the side wall of the collecting cone barrel, which is connected to the outer wall of the rapid mixing catalytic reaction chamber.

[0006] The annular jet water and air distribution system is composed of a primary ejector and a secondary ejector. The primary ejector is connected in series with the water and air inlet pipe and the secondary ejector. The secondary ejector is composed of a plurality of (3-6) common ejectors connected in series in an annular arrangement. Wastewater and ozone flow through the primary ejector into the secondary ejector, and are further mixed and cut before entering the guide tube.

[0007] The guide tube is welded at the center of the dissolution-catalysis synchronous reaction chamber through a bracket, the lower end of the guide tube is 3-8 cm away from the collecting cone barrel, and the upper end of the guide tube is 10-30 cm away from the separation cone barrel.

[0008] The separation cone barrel is a hollow frustum, the center of which is consistent with the center of the post-dissolution catalytic enhancement reaction chamber, the top is fixedly connected to the supporting layer, and a sieve plate is installed at the top opening.

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

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

[0011] The multi-stage baffle unit tube is a plurality of groups of concentric cylinders arranged at fixed intervals with the opening provided at the lower supporting layer of the post-dissolution catalytic enhanced catalytic reaction chamber and the center of the separation cone barrel as the center of the circle, the bottom of the first unit tube of the inner circle arranged close to the center of the circle is welded to the supporting layer, a 3-5 cm gap is reserved between the top of the first unit tube and the top of the reactor so that it can overflow upward in the first unit tube to the second unit tube, the top of the second unit tube is welded to the top of the reactor, a 3-5 cm gap is reserved between the bottom of the second unit tube and the second supporting layer so that it can flow downward in the second unit tube to the third unit tube, and the arrangement of the unit tubes is similar, and the post-dissolution catalytic enhanced catalyst is added to the gap between each unit tube.

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

[0013] Furthermore, the simultaneous dissolution and catalysis reaction chamber, the post-dissolution catalytic enhancement reaction chamber, and the internal structural materials of each reaction chamber thereof can be made of 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 tube to collect unused ozone and re-enter the reactor for recycling.

[0015] Furthermore, two or more post-dissolution catalytic enhancement reaction chamber unit cylinders may be provided according to actual conditions.

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

[0017] Furthermore, the transition metal catalyst supported or doped by the post-dissolution catalytic enhancement catalyst can 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 air inlet end of the ozone generator is connected to an air source, an oxygen-rich source or a liquid oxygen source unit, and the air outlet end of the ozone generator is connected to an ozone concentration analyzer.

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

[0020] In some embodiments of the present invention, the method for preparing the simultaneous dissolution-catalysis catalyst comprises:

[0021] (1) Catalyst carrier activation pretreatment in the solution-catalyst synchronous reaction chamber: Mix 0.5-2.0 mol / L KOH activator and activated carbon in a mass ratio of (0.1-1): 1. After constant temperature oscillation at 15-40°C for 1-6 hours, place it in a forced air drying oven at 105°C for 2-12 hours, and then transfer it to a muffle furnace at 600-800°C for activation for 90 minutes for use;

[0022] (2) Co-Ce bimetallic component loading: Co (NO3)2·6H2O and Ce (NO3)3·6H2O are prepared in a molar ratio of 1:1 to prepare a 0.3-1.2 mol / L Co (NO3)2·6H2O, Ce (NO3)3·6H2O mixed solution as the impregnation solution of the composite loading component, and the impregnation solution is mixed with activated carbon at a mass ratio of (0.1-1): 1 for 6-24 h. After drying the sediment, it is transferred to a muffle furnace and calcined at 400-800 ° C for 2 h to obtain Co-Ce / activated carbon;

[0023] (3) Molding: Mix Co-Ce / activated carbon with bentonite, neutral silica sol and Fe2O3 in a ratio of 3:2.5:4:0.5 and place in a granulator. Add appropriate amount of water to form granules. 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 a solution-catalyzed synchronous catalyst.

[0024] In some embodiments of the present invention, the method for preparing the post-dissolution catalytic enhancement catalyst comprises:

[0025] (1) Pretreatment of spherical activated carbon carrier: 0.5-2.0 mol / L C6H 12 O6 and spherical activated carbon are mixed in a mass ratio of (0.1-1): 1. After constant temperature oscillation at 15-40℃ for 6 hours, it is placed in a blast drying oven at 105℃ for 12 hours, and then transferred to a tube furnace for calcination at 600-800℃ in a nitrogen atmosphere for 90 minutes for 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, Mn (NO3)2 mixed solution as the impregnation solution of the composite loading component; the above impregnation solution is impregnated with the pretreated spherical activated carbon in a mass ratio of (0.1-1): 1 for 6-24 h, and then placed at room temperature for 24 h, transferred to a tubular furnace at 200-800 ° C in a nitrogen atmosphere for 2 h, and naturally cooled to room temperature to obtain a post-dissolution catalytic enhanced catalyst.

[0027] In another aspect of the present invention, the present invention provides a method for catalytically oxidizing wastewater using the above-mentioned reaction device. The method comprises the following steps:

[0028] (1) The ozone produced by the ozone generator flows into the ozone concentration analyzer through a pipeline, and then flows into the first-stage ejector in the annular jet water and gas distribution system after passing through the concentration analyzer;

[0029] (2) The sewage to be treated flows into the primary ejector through the sewage pipe via the sewage lifting pump;

[0030] (3) The ozone gas and sewage are mixed in the primary ejector to obtain a primary gas-water mixture;

[0031] (4) The primary gas-water mixture is passed through a pipeline into a secondary ejector in the annular water and gas distribution system, and is further mixed and cut to form a secondary gas-water mixture, which then enters a solution-catalyst synchronous reaction chamber;

[0032] (5) The secondary gas-water mixture is fully mixed and contacted with the dissolution-catalysis synchronous catalyst in the dissolution-catalysis synchronous reaction chamber, and the gas-liquid-solid three-phase mass transfer effect is enhanced under the action of the guide tube, thereby removing part of the pollutants in the sewage, and the effluent from the dissolution-catalysis synchronous reaction chamber enters the post-dissolution catalytic enhancement reaction chamber through the sieve plate;

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

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

[0035] According to the method for catalytic oxidation of sewage in an embodiment of the present invention, the above-mentioned reaction unit is used to cause the sewage to undergo multi-stage catalytic oxidation in the reaction unit under the synergistic action of ozone and ozone catalyst to generate highly active oxygen substances, while enhancing the gas-liquid-solid three-phase mass transfer rate, increasing the amount of highly active oxidizing substances generated, and improving the utilization efficiency of ozone. The deep treatment performance of sewage is enhanced through multi-stage catalysis, and the effluent water quality of the reaction device is improved, which has 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, realizes preliminary gas-liquid mixing through the first-stage ejector, and further cuts it in the second-stage ejector to make the gas and liquid fully mixed, thereby enhancing the efficiency of gas dissolution and the utilization rate of ozone;

[0038] (2) The present invention achieves full mixing of three phases and separation of two phases by setting up a dissolution-catalysis synchronous reaction chamber and using a guide tube, a separation cone, etc., so as to efficiently carry out preliminary catalytic oxidation degradation of sewage, shorten the hydraulic retention time, and reduce the cost;

[0039] (3) The present invention provides a post-dissolution catalytic enhancement reaction chamber, rationally partitions and optimizes the internal structure through a multi-stage baffle unit tube, recycles the catalyst and ozone for catalytic oxidation reaction, reuses the ozone in the water, and further enhances the gas-liquid-solid three-phase mass transfer efficiency, thereby further enhancing the degradation of sewage;

[0040] (4) The present invention achieves a higher catalytic effect with less catalyst addition by adding catalysts matching different reaction chambers and optimizing the catalyst particle size and the active components loaded according to the reaction characteristics of different regions;

[0041] (5) The present invention enhances the reaction rate, reduces energy consumption, and improves the efficiency of catalytic ozone reaction by synergistic treatment of simultaneous dissolution and catalysis and post-dissolution catalysis. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0043] Figure 2 is a schematic structural diagram of a dissolution-catalysis synchronous reaction chamber according to an embodiment of the present invention;

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

[0045] Figure 4 It is a schematic structural diagram of an annular water and air distribution system according to an embodiment of the present invention. DETAILED DESCRIPTION

[0046] Embodiments of the present invention are described in detail below, and examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to be used to explain the present invention, but should not be understood 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 oscillation at 25°C for 2 hours, it was placed in a blast drying oven at 105°C for 2 hours, and then transferred to a muffle furnace for activation at 600°C for 90 minutes. After cooling to room temperature, it was placed in a 0.3 mol / L mixed solution of Co (NO3)2·6H2O and Ce (NO3)3·6H2O in a molar ratio of 1:1, and impregnated for 6 hours according to the mass ratio of the impregnation solution to the activated carbon of 1:1. After drying the sediment, it was transferred to a muffle furnace and calcined at 400°C for 2 hours to obtain Co-Ce / activated carbon. Co-Ce / activated carbon was mixed with bentonite, neutral silica sol and Fe2O3 in a ratio of 3:2.5:4:0.5 and placed in a granulator. An appropriate amount of water was added to form granules. 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 naturally cooled to room temperature to obtain a solution-catalyzed synchronous 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 oscillation at 25°C for 6 hours, it was placed in a blast drying oven at 105°C for 12 hours, and then transferred to a tube furnace for calcination at 600°C in a nitrogen atmosphere for 90 minutes. After cooling to room temperature, it was placed in a 0.3 mol / L mixed solution of Cu (NO3)2·3H2O and Mn (NO3)2 at a molar ratio of 1:1, and immersed for 6 hours at a mass ratio of 1:1. After standing at room temperature for 24 hours, it was transferred to a tube furnace at 400°C in a nitrogen atmosphere for 2 hours, and naturally cooled to room temperature to obtain a post-dissolution catalytic enhancement catalyst.

[0049] The above two catalysts are added into the catalytic ozone oxidation reaction device (such as Figure 1The circulating water discharged from a chemical plant is taken for treatment in two catalytic reaction chambers (shown in FIG. 1 ), and the water quality characteristics are as follows: COD = 104 mg / L, pH = 8.19, and conductivity = 5812 μs / cm. The treated water enters the first-stage ejector through a lift pump. After being generated by the ozone generator, the ozone enters the first-stage ejector through the negative pressure generated by the first-stage ejector of the annular water and gas distribution system (1-2) to form a gas-liquid mixture. The ozone enters the second-stage ejector through the water inlet pipe (1-1). After being evenly distributed with water and gas by the annular water and gas distribution system (1-2), the ozone enters the guide tube (1-3) in the solution-catalysis synchronous reaction chamber (1) to form an upflow zone. The gas-liquid mixture is fully mixed and contacted with the solution-catalysis synchronous catalyst (1-4). When the gas-liquid mixture reaches the separation cone barrel (1-5), the gas-liquid mixture is The catalyst forms a downward flow outside the guide tube to the collecting cone barrel (1-6), thereby forming an internal circulation form. As the gas-liquid mixture continues to enter, it enters the first unit tube (3-1) in the post-dissolution catalytic enhancement reaction chamber (3) through the sieve plate (2-1) provided at the flange (2). Under the action of the pressure difference, the gas-water mixture entering the first unit tube fully reacts with the post-dissolution catalytic enhancement catalyst (3-2) and then enters the second unit tube (3-3), and reciprocates until it enters the water outlet (3-4). The remaining tail gas is discharged through the tail gas outlet (3-5). After being treated by the present dissolution-catalysis synchronous enhanced catalytic ozone oxidation reaction device, COD=27.2mg / L, pH=8.23, conductivity=4120 μs / cm, and ozone utilization rate is 96.18%. Under the same operating conditions as in Example 1, a commercially available tower reactor was used to fill a commercially available ozone catalyst. 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 present reactor, and the treatment effect was 25.58% higher than that of the commercially available tower reactor filled with a commercially available ozone catalyst, and the ozone utilization was 23.82% higher.

[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 oscillation at 30°C for 4 hours, it was placed in a blast drying oven at 105°C for 2 hours, and then transferred to a muffle furnace for activation at 650°C for 90 minutes. After cooling to room temperature, it was placed in a 0.6 mol / L mixed solution of Co (NO3)2·6H2O and Ce (NO3)3·6H2O in a molar ratio of 1:1, and the impregnation liquid and activated carbon were impregnated for 6 hours at a mass ratio of 1:1. After the sediment was dried, it was transferred to a muffle furnace and calcined at 400°C for 2 hours to obtain Co-Ce / activated carbon. Co-Ce / activated carbon was mixed with bentonite, neutral silica sol and Fe2O3 in a ratio of 3:2.5:4:0.5 and placed in a granulator. An appropriate amount of water was added to form granules. After standing at room temperature for 24 hours, the mixture was transferred to a muffle furnace and calcined at 400°C for 120 minutes. The mixture was naturally cooled to room temperature to obtain a solution-catalyzed synchronous catalyst.

[0051] 1.0 mol / L C6H 12 O6 and γ-Al2O3 are mixed at a mass ratio of 1: 1. After constant temperature oscillation at 25°C for 6 hours, it is placed in a blast drying oven at 105°C for 12 hours, and then transferred to a tube furnace for calcination at 600°C in a nitrogen atmosphere for 90 minutes. After cooling to room temperature, it is placed in a 0.6 mol / L mixed solution of Cu (NO3)2·3H2O and Mn (NO3)2 at a molar ratio of 1:1, and immersed for 6 hours at a mass ratio of 1:1. After standing at room temperature for 24 hours, it is transferred to a tube furnace at 600°C in a nitrogen atmosphere for 2 hours, and naturally cooled to room temperature to obtain a post-dissolution catalytic enhancement catalyst.

[0052] The above two catalysts are added into the solution-catalyst synchronous enhanced catalytic ozone oxidation reaction device (such as Figure 1 In the two catalytic reaction chambers (shown in FIG. 1 ), the effluent from a biochemical pool of a pharmaceutical factory was treated after passing through a quartz sand medium filter. The effluent COD was 64 mg / L. The wastewater was treated according to the operating steps in Example 1. After being treated by the present dissolution-catalyzed synchronous enhanced catalytic ozone oxidation reaction device, the COD was 21.6 mg / L, and the ozone utilization rate was 97.45%. Under the same operating conditions as Example 2, a commercially available tower reactor was filled with a commercially available ozone catalyst. After treatment, the effluent COD was 46.4 mg / L, and the ozone utilization rate was 67.45%. The effect is lower than that of the present reactor, and the treatment effect is improved by 38.75% and the ozone utilization rate is improved by 30% compared with the commercially available tower reactor filled with a commercially available ozone catalyst.

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

[0054] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A solvent-catalyzed simultaneous enhanced catalytic ozone oxidation reaction device characterized by: include: A dissolution-catalysis synchronous reaction chamber (1) and a post-dissolution catalytic enhancement reaction chamber (3), the two chambers are connected by a flange (2), and a sieve plate (2-1) and a backwash water inlet (2-2) are provided at the bottom of the post-dissolution catalytic enhancement reaction chamber (3); the dissolution-catalysis synchronous reaction chamber (1) can realize internal circulation, and the dissolution-catalysis synchronous reaction chamber (1) is provided with a water inlet pipe (1-1), an annular water and air distribution system (1-2), a guide tube (1-3), a dissolution-catalysis synchronous catalyst (1-4) separation cone barrel (1-5), a collection cone barrel (1-6) and a sewage outlet (1-7); the post-dissolution catalytic enhancement reaction chamber (3) comprises a multi-stage baffled first unit barrel (3-1), a post-dissolution catalytic enhancement catalyst (3-2), a second unit barrel (3-3), a water outlet (3-4), and an exhaust gas outlet (3-5); the device is also provided with a flange (4) and a base (5), etc.

2. The solvent-catalyzed simultaneous enhanced catalytic ozone oxidation reaction device according to claim 1 is characterized in that: The first-stage ejector is connected in series with the water and air inlet pipe and the second-stage ejector. The second-stage ejector is composed of multiple (3-6) ordinary ejectors connected in series in a ring shape. The wastewater and ozone flow into the second-stage ejector through the first-stage ejector, and are further mixed and cut before entering the guide tube.

3. The solvent-catalyzed simultaneous enhanced catalytic ozone oxidation reaction device according to claim 1, characterized in that: The dissolution-catalysis synchronous reaction chamber is filled with a dissolution-catalysis synchronous catalyst, the catalyst particle size is between 0.5-2 mm, and activated carbon, zeolite, ceramsite, molecular sieve, γ-Al2O3, etc. are used as carriers, and one or more transition metal components among titanium, cobalt, lanthanum and cerium are loaded or doped.

4. The solvent-catalyzed simultaneous enhanced catalytic ozone oxidation reaction device according to claim 1, characterized in that: The post-dissolution catalytic enhancement reaction chamber is filled with a post-dissolution catalytic enhancement catalyst, the catalyst particle size is between 3-8 mm, activated carbon, zeolite, ceramsite, molecular sieve, γ-Al2O3, etc. are used as carriers, and one or more transition metal components of iron, manganese, copper and nickel are loaded or doped.

5. The solvent-catalyzed simultaneous enhanced catalytic ozone oxidation reaction device according to claim 1, characterized in that: The post-dissolution catalytic enhancement reaction chamber is provided with a multi-stage baffle unit tube, and a post-dissolution catalytic enhancement catalyst is added between each unit tube.

6. The solvent-catalyzed simultaneous enhanced catalytic ozone oxidation reaction device according to claim 3, characterized in that: The method for preparing the simultaneous dissolution-catalysis catalyst comprises: (1) Pretreatment of catalyst carrier activation by simultaneous solvent-catalyst: Mix 0.5-2.0 mol / L KOH activator and activated carbon in a mass ratio of (0.1-1):

1. After constant temperature oscillation at 15-40°C for 1-6 hours, place it in a forced air drying oven at 105°C for 2-12 hours, and then transfer it to a muffle furnace at 600-800°C for activation for 90 minutes for use; (2) Co-Ce bimetallic component loading: Co (NO3)2·6H2O and Ce (NO3)3·6H2O are prepared in a molar ratio of 1:1 to prepare 0.3-1.2 mol / L Co (NO3)2·6H2O and Ce (NO3)3·6H2O mixed solution as the impregnation solution of the composite loading component. The impregnation solution and activated carbon are impregnated at a mass ratio of (0.1-1): 1 for 6-24 h. After the sediment is dried, it is transferred to a muffle furnace and calcined at 400-800 °C for 2 h to obtain Co-Ce / activated carbon. (3) Molding: Mix Co-Ce / activated carbon with bentonite, neutral silica sol and Fe2O3 in a ratio of 3:2.5:4:0.5 and place in a granulator. Add appropriate amount of water to form granules. 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 a solution-catalyzed synchronous catalyst.

7. The solvent-catalyzed simultaneous enhanced catalytic ozone oxidation reaction device according to claim 4, characterized in that: The method for preparing the post-dissolution catalytic enhancement catalyst comprises: (1) Pretreatment of spherical activated carbon carrier: 0.5-2.0 mol / L C6H 12 O6 and spherical activated carbon are mixed in a mass ratio of (0.1-1):

1. After constant temperature oscillation at 15-40℃ for 6 hours, it is placed in a forced air drying oven at 105℃ for 12 hours, and then transferred to a tubular furnace for calcination at 600-800℃ in a nitrogen atmosphere for 90 minutes for use; (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, Mn (NO3)2 mixed solution as the impregnation solution of the composite loading component; the above impregnation solution is impregnated with the pretreated spherical activated carbon in a mass ratio of (0.1-1): 1 for 6-24 h, and then placed at room temperature for 24 h, transferred to a tubular furnace at 200-800 ° C in a nitrogen atmosphere for 2 h, and naturally cooled to room temperature to obtain a post-dissolution catalytic enhanced catalyst.

8. The method for treating wastewater by using the solvent-catalyzed simultaneous enhanced catalytic ozone oxidation reaction device according to claim 1, characterized in that: include: (1) The treated water enters the first-stage ejector of the annular water and gas distribution system through a lifting pump. The ozone enters the first-stage ejector through the negative pressure generated by the first-stage ejector to form a gas-liquid mixture. The gas-liquid mixture flows into the second-stage ejector through a pipeline for further cutting and mixing, so that the gas and liquid are fully mixed, thereby enhancing the efficiency of gas dissolution and the utilization rate of ozone. (2) The guide tube in the solution-catalysis synchronous reaction chamber forms an upflow zone, and the gas-liquid mixture is fully mixed and contacted with the solution-catalysis synchronous catalyst. When the gas-liquid mixture rises to the separation cone, a downflow zone is formed outside the guide tube to the collection cone, thereby forming an internal circulation, achieving full mixing of the three phases and separation of the two phases, and efficiently performing preliminary catalytic oxidation degradation of the sewage; (3) The post-dissolution catalytic enhancement reaction chamber is equipped with a multi-stage baffled unit tube to rationally partition and optimize the internal structure. The gas-water mixture passes through the first unit tube and the second unit tube in turn, and repeatedly and fully contacts and reacts with the post-dissolution catalytic enhancement catalyst therein in multiple stages, thereby realizing partitioned addition of the catalyst, enhancing the specific catalytic efficiency, and achieving the effect of adding a small amount of catalyst and high efficiency.

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