Quasi-suspended spherical catalyst, preparation method thereof and catalytic ozonation system

Abstract

The invention belongs to the technical field of sewage treatment, and particularly relates to a quasi-suspended spherical catalyst, a preparation method thereof and a catalytic ozonation system. The quasi-suspended spherical catalyst comprises a concrete catalytic material substrate and fly ash floating beads, the concrete catalytic material substrate comprises copper nitrate, cerous nitrate, manganese chloride and ferric nitrate, the volume ratio of the concrete catalytic material substrate to the fly ash floating beads is 1: 1-1: 9, and the fly ash floating beads are mixed and distributed in the concrete catalytic material substrate. The concrete catalytic material substrate is a sphere with the particle size of 1-10 mm. The quasi-suspended spherical catalyst adopts a concrete cementing process without calcination, inorganic hollow fly ash floating bead solid waste recycling aggregate is synchronously mixed, the cost is lower, fly ash floating beads regulate and control the catalyst density to realize homogeneous spherical catalyst distribution, the application catalytic effect is better, the quasi-suspended spherical catalyst is coupled with a micro-nano bubble ozonation process, and the application range is wider. The reaction tank is lower in manufacturing cost, the dissolved air backflow water amount is smaller, and the system is more energy-saving.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage treatment systems, and in particular relates to a quasi-suspended spherical catalyst and a preparation method thereof, and an ozone catalytic oxidation system. Background Art

[0002] Industrial wastewater often contains complex and difficult-to-degrade organic components. Ozone oxidation treatment is an effective way to remove them. Because the ozone oxidation process has no secondary pollution, it is widely used in wastewater treatment. In order to improve the efficiency of ozone oxidation of organic matter, the efficiency of catalytic ozone to produce hydroxyl radicals during the reaction process can be improved. At present, the use of catalysts to catalyze ozone can effectively promote the generation of hydroxyl radicals generated by ozone. Therefore, the ozone catalytic oxidation technology using catalysts has become an efficient process for industrial wastewater treatment, but the process system still has room for improvement. For example, the jet dissolution mode and dissolution efficiency of ozone need to be further improved, the catalyst preparation cost needs to be further reduced, the reactor structure needs to be further simplified to reduce the cost, the catalyst scaling problem needs to be further solved, and the collaborative energy saving and efficiency improvement of the catalyst and the process system needs to be further optimized. Therefore, the development of low-cost and efficient catalysts and efficient ozone catalytic oxidation systems has become a research hotspot in industrial water treatment.

[0003] In the prior art, invention patent CN118698590 provides a catalyst prepared by molecular sieve, which is prepared by high-cost, high-energy consumption methods such as impregnation, alkali precipitation, and calcination of molecular sieve particles. The catalyst cost is high, and the density of the catalyst particles is large. A large disturbance kinetic energy is required to better catalyze the ozone oxidation process. The catalyst needs to be optimized. Invention patent CN117699950A provides an ozone catalytic oxidation system based on high-frequency cutting of water vapor and dissolved gas and a method of use. A gas compression pump is used in the process flow to pressurize the ozone gas. The pressurization of ozone gas alone will cause the gas to heat up and the ozone to attenuate, resulting in a low ozone benefit rate in the system, and the ozone dissolving method needs to be improved. Invention patent CN118561407A provides an ozone nano-micro bubble sewage treatment system and a sewage treatment method thereof, which improves the ozone addition efficiency by adding micro-nano bubbles, but sets a dissolved air pump for dissolved air pressurization, causing subsequent reactors to be in a high-pressure state. There is a problem of safe use of the pressure tank after the process is scaled up, and the above technical solutions have not made improvements and adaptations to the catalyst and the applied system. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a quasi-suspended spherical catalyst and a preparation method thereof, and an ozone catalytic oxidation system. The present invention combines a quasi-suspended homogeneous spherical catalyst with an ozone micro-nano bubble dissolving gas process. When the micro-nano bubbles adhere to the surface of the spherical catalyst or flush the surface of the spherical catalyst, they can block the attachment of the flocculant remaining in the previous process to a certain extent, and can inhibit the problem of catalytic fouling failure.

[0005] In order to achieve the above technical objectives, the technical solution adopted by the embodiment of the present invention is: In the first aspect, an embodiment of the present invention provides a quasi-suspended spherical catalyst, which includes a concrete catalytic material matrix and fly ash floating beads, wherein the concrete catalytic material matrix includes copper nitrate, cerium nitrate, manganese chloride and ferric nitrate, and the volume ratio of the concrete catalytic material matrix to the fly ash floating beads is 1:1-1:9, and the fly ash floating beads are mixed and distributed inside the concrete catalytic material matrix, and the concrete catalytic material matrix is ​​spherical with a particle size of 1-10 mm.

[0006] In a second aspect, an embodiment of the present invention provides a method for preparing the quasi-suspended spherical catalyst according to the first aspect, comprising the following steps: Step S1, preparation of concrete catalytic material matrix: copper nitrate, cerium nitrate, manganese chloride and ferric nitrate are dissolved according to the metal ion molar concentration of 1-5:1-5:1-5:1-5 to prepare a catalytic component mixed solution, sodium hydroxide solution is added to the mixed solution until the pH value of the mixed solution rises to 7-12, the mixed solution is re-stirred every 10-90 minutes and sodium hydroxide solution is added to adjust the pH value to 7-12, after repeating 1-10 times, the slurry containing the active catalytic component is added into the concrete dry powder and starts to mix, and water is added and mixed simultaneously until the preparation of concrete slurry is completed, that is, the concrete catalytic material matrix; Step S2: Mix the prepared concrete catalytic material matrix and fly ash floating beads in a volume ratio of 1:1-1:9, and perform inverted mold granulation to control the particle diameter to 1-10 mm and the overall wet density of the particles to 1-1.05 g / cm 3 The mass fraction of the catalytic component iron in the particles is controlled between 0.05% and 5%. After the particles are dried, solidified and cured, the quasi-suspended spherical catalyst is prepared.

[0007] In a third aspect, an embodiment of the present invention provides an ozone catalytic oxidation system, including an ozone catalytic oxidation reaction tank, an oxygen station, a water-cooled ozone generator, and a gas-liquid booster pump; The ozone catalytic oxidation reaction tank is filled with the quasi-suspended spherical catalyst described in the first aspect, the bottom of the side wall of the ozone catalytic oxidation reaction tank is connected to a water inlet pipe, and the top of the side wall is provided with a water outlet pipe, part of the water outlet of the water outlet pipe is returned to the gas-liquid booster pump through the tail water return pipe, and the water outlet of the gas-liquid booster pump enters the ozone catalytic oxidation reaction tank through a secondary cutter; The oxygen station is connected to the water-cooled ozone generator through a pipeline, the water-cooled ozone generator is connected to the gas-liquid booster pump through a pipeline, and the gas-liquid booster pump is connected to the secondary cutter through a pipeline.

[0008] Furthermore, the ozone catalytic oxidation reaction tank is cylindrical, a flexible supporting layer is provided inside the ozone catalytic oxidation reaction tank, and the quasi-suspended spherical catalyst is loaded on the flexible supporting layer.

[0009] Furthermore, the upper part of the flexible supporting layer is arranged 10-50 cm above the bottom of the ozone catalytic oxidation reaction tank and fixed on the inner wall of the ozone catalytic oxidation reaction tank, and the bottom of the flexible supporting layer is in contact with the bottom of the ozone catalytic oxidation reaction tank.

[0010] Furthermore, the flexible supporting layer is made of a stainless steel wire mesh, and the mesh area of ​​the stainless steel wire mesh is larger than the bottom area thereof.

[0011] Furthermore, the water inlet pipe is connected to the bottom of the side wall of the ozone catalytic oxidation reaction tank at an angle along the tangent direction of the bottom edge.

[0012] Furthermore, the ratio of the water inflow of the tailwater return pipe to the water inflow of the water inlet pipe is controlled between 0.1-1.

[0013] Furthermore, the secondary cutter is arranged at the bottom of the ozone catalytic oxidation reaction tank, and the size of the bubbles cut by the secondary cutter is 0.1-10 microns.

[0014] Furthermore, the ozone catalytic oxidation system is used in the process of deep treatment of industrial wastewater including printing and dyeing wastewater to remove organic pollutants.

[0015] The technical solution provided by the embodiment of the present invention has the following beneficial effects: 1. The present invention adopts concrete granulation to prepare spherical catalysts. Alkali precipitation slurry containing active catalytic components is directly mixed into concrete. After concrete bonding, the particles can achieve higher strength without high-temperature calcination. The non-calcination process is more low-carbon and energy-saving, and the manufacturing cost is lower.

[0016] 2. The premixed alkali precipitation slurry method makes the catalytic active components evenly distributed in the internal and external structures of the spherical concrete particles. Different from the surface-loaded catalytic components, the spherical catalyst of the present invention has effective catalytic components in both the internal and external structures. Even if the surface is worn, it can continue to be effectively used, and the spherical catalyst has a longer life cycle.

[0017] 3. Using fly ash beads as part of the aggregate to prepare spherical catalysts is a resource utilization of coal-fired waste, which has environmental benefits. As a hollow inorganic glass microsphere, the beads have good stability such as anti-oxidation. The mixing ratio of fly ash beads is relatively large, which can effectively reduce the manufacturing cost of the catalyst and has good economic benefits. At the same time, the main chemical components of fly ash beads are SiO 2 、Al 2 O 3 , Fe 3 O 4 Etc., have abundant surface hydroxyl groups, which can significantly promote the catalytic ozone oxidation to produce hydroxyl radicals; after further loading active catalytic components such as Cu, Ce, Mn, and Fe, the yield of hydroxyl radicals is further improved, thereby promoting the oxidative removal of difficult-to-degrade pollutants in wastewater.

[0018] 4. When spherical catalysts are granulated, the density is adjusted by mixing a certain proportion of fly ash beads, so that the density of the particles is reduced and a quasi-suspended state is achieved. The quasi-suspended spherical catalyst is easier to expand in the catalyst bed in the reactor and is more evenly dispersed in the sewage. It is a homogeneously distributed catalyst with better ozone catalytic oxidation effect, which is a beneficial innovative improvement for the adaptation of spherical catalysts to reactors.

[0019] 5. In the catalytic oxidation process, since a quasi-suspended spherical catalyst with homogeneous distribution is used in the catalytic oxidation tank body, the supporting layer can be simplified to a flexible supporting layer. The incoming water can push the flexible supporting layer upward, leaving a mixing space for the incoming water and the dissolved air water. The flexible supporting layer can greatly reduce the construction cost of the supporting structure of the ozone catalytic oxidation tank body.

[0020] 6. A secondary cutter is used in the process system. The secondary cutter has the function of further cutting and dispersing ozone bubbles, making the ozone micro-nano bubbles entering the ozone catalytic oxidation reaction pool richer and more stable, prolonging the reaction time between ozone and pollutants and between ozone and catalysts, and significantly improving the utilization efficiency of ozone. In addition, the area from the secondary cutter to the gas-liquid booster pump is a high-pressure area, and the outlet of the secondary cutter enters the atmospheric pressure to release the ozone-dissolved water containing ozone micro-nano bubbles. The ozone catalytic oxidation reaction pool does not need to be operated under pressure, thus simplifying and optimizing the process of ozone catalytic oxidation.

[0021] 7. The quasi-suspended homogeneous spherical catalyst is combined with the ozone micro-nano bubble dissolution process. When the micro-nano bubbles adhere to the surface of the spherical catalyst or flush the surface of the spherical catalyst, they can to a certain extent block the attachment of the flocculant remaining in the previous process, and inhibit the problem of catalytic scaling and failure. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a cross-sectional view of the quasi-suspended spherical catalyst in Example 1 of the present invention.

[0023] Figure 2 This is a SEM image of the quasi-suspended spherical catalyst in Example 1 of the present invention.

[0024] Figure 3 Schematic diagram of the structure of the ozone catalytic oxidation system in Example 2 of the present invention.

[0025] Figure 4 for Figure 3 The effect diagram of the ozone catalytic oxidation system in treating printing and dyeing wastewater.

[0026] Explanation of the reference numerals: 1-quasi-suspended spherical catalyst; 11-concrete catalytic material matrix; 12-fly ash floating beads; 2-ozone catalytic oxidation reaction tank; 3-flexible supporting layer; 4-water inlet pipe; 5-water outlet pipe; 6-tail water return pipe; 7-oxygen station; 8-water-cooled ozone generator; 9-gas-liquid booster pump; 10-secondary cutter. DETAILED DESCRIPTION

[0027] In the description of the present invention, it is necessary to understand that the directions or positional relationships indicated by directional words such as "inside, outside", "up, down", "left, right", etc. are usually based on the directions or positional relationships shown in the drawings. They are only for the convenience of describing the present invention and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the device or element referred to must have a specific direction or be constructed and operated in a specific direction. Therefore, they cannot be understood as limiting the scope of protection of the present invention.

[0028] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0029] Example 1 like Figure 1As shown, a quasi-suspended spherical catalyst includes a concrete catalytic material matrix 11 and fly ash floating beads 12. The volume ratio of the concrete catalytic material matrix 11 to the fly ash floating beads 12 is 1:2. The concrete catalytic material matrix 11 includes copper nitrate, cerium nitrate, manganese chloride and ferric nitrate. The fly ash floating beads 12 are mixed and distributed inside the concrete catalytic material matrix 11. The concrete catalytic material matrix 11 is spherical with a particle size of 10 mm.

[0030] The preparation of the above-mentioned quasi-suspended spherical catalyst comprises the following steps: Step S1, preparation of concrete catalytic material matrix 11: copper nitrate, cerium nitrate, manganese chloride and ferric nitrate are dissolved in a metal ion molar concentration of 1:1:1:1 to prepare a catalytic component mixed solution, sodium hydroxide solution is added to the mixed solution until the pH value of the mixed solution reaches 9, the mixed solution is stirred again every 30 minutes and sodium hydroxide solution is added to adjust the pH value to 9, after repeating 3-5 times, the slurry containing active catalytic components is added into the concrete dry powder and starts to mix, and water is added and mixed simultaneously until the concrete slurry is prepared, that is, the concrete catalytic material matrix 11; Step S2: Mix the prepared concrete catalytic material matrix 11 and the fly ash floating beads 12 in a volume ratio of 1:2, and perform inverted mold granulation to control the particle diameter to 10 mm and the overall wet density of the particles to 1.05 g / cm 3 , the mass fraction of the catalytic component iron in the particles is controlled to be 5%, and after the particles are dried, solidified and cured, the quasi-suspended spherical catalyst 1 is prepared. Figure 2 shown.

[0031] Example 2 like Figure 3 As shown, an ozone catalytic oxidation system includes a quasi-suspended spherical catalyst 1, an ozone catalytic oxidation reaction tank 2, a flexible supporting layer 3, a water inlet pipe 4, a water outlet pipe 5, a tail water return pipe 6, an oxygen station 7, a water-cooled ozone generator 8, a gas-liquid booster pump 9 and a secondary cutter 10.

[0032] The ozone catalytic oxidation reaction tank 2 is filled with a quasi-suspended spherical catalyst 1, the bottom of the side wall of the ozone catalytic oxidation reaction tank 2 is connected to a water inlet pipe 4, and the top of the side wall is provided with a water outlet pipe 5. Part of the water outlet of the water outlet pipe 5 flows back to the gas-liquid booster pump 9 through the tail water return pipe 6, and the water outlet of the gas-liquid booster pump 9 enters the ozone catalytic oxidation reaction tank 2 through the secondary cutter 10; The oxygen station 7 is connected to the water-cooled ozone generator 8 through a pipeline, the water-cooled ozone generator 8 is connected to the gas-liquid booster pump 9 through a pipeline, and the gas-liquid booster pump 9 is connected to the secondary cutter 10 through a pipeline.

[0033] The ozone catalytic oxidation reaction pool 2 is cylindrical, and a flexible supporting layer 3 is arranged inside the ozone catalytic oxidation reaction pool 2. The flexible supporting layer 3 is arranged in the ozone catalytic oxidation reaction pool 2 at a distance of 50 cm from the bottom of the pool, and the periphery is fixed on the inner wall of the ozone catalytic oxidation reaction pool 2. The quasi-suspended spherical catalyst 1 is loaded above the flexible supporting layer 3.

[0034] The ozone catalytic oxidation reaction tank 2 is cylindrical, and a flexible supporting layer 3 is arranged inside the ozone catalytic oxidation reaction tank 2 , and the quasi-suspended spherical catalyst 1 is loaded on the flexible supporting layer 3 .

[0035] The upper part of the flexible supporting layer 3 is arranged 10-50cm above the bottom of the ozone catalytic oxidation reaction pool 2, and is fixed on the inner wall of the ozone catalytic oxidation reaction pool 2, and the bottom of the flexible supporting layer 3 is in contact with the bottom of the ozone catalytic oxidation reaction pool 2. As an embodiment, the flexible supporting layer 3 adopts a stainless steel wire mesh, the mesh area of ​​the stainless steel wire mesh is larger than its bottom area, and the bottom of the stainless steel wire mesh is in contact with the bottom of the ozone catalytic oxidation reaction pool 2. Specifically, the flexible supporting layer 3 is in the shape of a net bag, and the mouth is fixed on the inner wall of the ozone catalytic oxidation reaction pool 2, 50cm away from the bottom of the pool, and the bottom falls to the bottom of the ozone catalytic oxidation reaction pool 2 under its own gravity. Therefore, the supporting layer does not need to support the weight of the quasi-suspended spherical catalyst 1 after drainage alone, and its structural strength can be greatly reduced, which can simplify the construction of the reaction pool and reduce the construction cost of the process system.

[0036] The water inlet pipe 4 is connected to the bottom of the side wall of the ozone catalytic oxidation reaction tank 2 at an access angle along the tangent direction of the bottom circle. The secondary cutter 10 is arranged at the bottom of the ozone catalytic oxidation reaction tank 2. The sewage raw water entering tangentially can form a vortex mixing and enter the dissolved air water dissolved with ozone from the secondary cutter 10 at the bottom of the ozone catalytic oxidation reaction tank 2. The sewage mixed with ozone immediately contacts the upper spherical catalyst, and the catalytic oxidation effect can be further improved.

[0037] The ratio of the water inlet volume of the tail water return pipe 6 to the water inlet volume of the water inlet pipe 4 is controlled between 0.1-1, the flow rate of the tail water return pipe 6 is reduced, and the dissolved gas concentration is increased, which can reduce the return water volume and thus reduce energy consumption.

[0038] Example 3 The application of the above-mentioned ozone catalytic oxidation system is applied to the removal of organic pollutants in the printing and dyeing wastewater deep treatment unit, and includes the following steps: (1) loading the quasi-spherical suspended catalyst 1 into the ozone catalytic oxidation reaction tank 2, and loading the quasi-spherical suspended catalyst 1 to half the height of the ozone catalytic oxidation reaction tank 2; (2) After biochemical treatment, the printing and dyeing wastewater enters the ozone catalytic oxidation reaction tank 2 from the water inlet pipe 4. Since the water inlet pipe 4 is connected to the bottom of the side wall of the ozone catalytic oxidation reaction tank 2 at an angle along the tangent direction of the bottom circle, the sewage entering tangentially can form a vortex. When the inlet water fills the bottom of the ozone catalytic oxidation reaction tank 2, the flexible support layer 3 and the quasi-suspended spherical catalyst 1 thereon are both supported. When the sewage fills the entire ozone catalytic oxidation reaction tank 2, the bed of the quasi-suspended spherical catalyst 1 begins to expand due to the water passing through the gaps. Since the density of the quasi-suspended spherical catalyst 1 is close to that of water, it can be suspended and evenly dispersed in the entire ozone catalytic oxidation reaction tank 2 at a certain sewage cross-sectional flow rate. Compared with the entire liquid-solid two-phase system, the quasi-suspended spherical catalyst 1 presents a quasi-homogeneous distribution effect, which is conducive to improving the catalytic oxidation effect. After the inlet water fills the ozone catalytic oxidation reaction tank 2, it will overflow from the water outlet pipe 5; (3) Turn on the gas-liquid booster pump 9, the water-cooled ozone generator 8 and the oxygen station 7 in sequence. The oxygen from the oxygen station 7 enters the water-cooled ozone generator 8 to generate high-concentration (concentration of 120-170 mg / L) ozone gas. The gas-liquid booster pump 9 is a cutting pump. It simultaneously sucks in the sewage connected to the outlet pipe 5 and the high-concentration ozone gas connected to the water-cooled ozone generator 8 in the tail water return pipe 6 and mixes them to form a high-pressure gas-water mixture (pressure of 0.2-0.8 MPa). The high-pressure gas-water mixture reaches the secondary cutter 10 along the pipeline. Under the action of the secondary cutter 10, the high-pressure gas-water mixture releases dissolved water full of bubbles (diameter of 0.1-10 microns) of micro-nano bubbles at normal pressure and enters the ozone generator. At the bottom of the oxygen catalytic oxidation reaction pool 2, the ozone gas intake is controlled, and the ozone concentration of the dissolved water is not less than 20 mg / L. Since the flexible supporting layer 3 is supported, an area without the quasi-suspended spherical catalyst 1 is separated from the bottom of the ozone catalytic oxidation reaction pool 2. Under the swirling action of the water inlet pipe 1, the inlet water and the dissolved water containing ozone in this area can be quickly mixed, and the sewage mixed with dissolved and micro-nano bubble ozone immediately enters the area with the spherical catalyst. The surface of the quasi-homogeneously dispersed spherical catalyst can promote the dissolved and micro-nano bubble ozone in contact with it to generate hydroxyl free radicals to oxidize the difficult-to-degrade organic matter in the sewage under the action of the catalytic components, so as to achieve the purpose of removing organic pollutants in the sewage.

[0039] The flexible support layer 3 is made of a stainless steel wire mesh, the mesh area of ​​which is larger than the bottom area, and the bottom of which is in contact with the bottom of the ozone catalytic oxidation reaction tank 2. When water is passed, the flexible support layer 3 is supported together with the quasi-suspended spherical catalyst 1, so that the flexible support layer 3 does not need to support the weight of the catalyst after drainage alone, and its structural strength can be greatly reduced, which can simplify the construction of the reaction tank and reduce the construction cost of the process system.

[0040] The ratio of the water flow rate of the tailwater return pipe 6 to the water flow rate of the water inlet pipe 4 is controlled between 0.1 and 1. The return water flow rate of the tailwater return pipe 6 is reduced, and the concentration of dissolved ozone is increased, so that the process system can reduce the return water volume and thus reduce energy consumption.

[0041] Combining the quasi-suspended, quasi-homogeneously distributed spherical catalyst particles with the ozone micro-nano bubble dissolved gas process, the micro-nano bubbles attached to the surface of the spherical catalyst or flushing the surface of the spherical catalyst can to a certain extent block the attachment of flocculants remaining in the previous process, thereby inhibiting problems such as catalytic scaling and failure.

[0042] After a period of operation, the quasi-suspended spherical catalyst and the ozone catalytic oxidation system containing the same operated stably. Sampling monitoring showed that the COD removal rate was 38-48%, and the effluent COD index was stable below the local emission standard limit of 40 mg / L, achieving good treatment effect. The 12 treatment effect test data of the embodiment are shown below Figure 4 .

[0043] Finally, it should be noted that the above specific implementation methods are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to examples, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the spirit and scope of the technical solution of the present invention, which should be included in the scope of the claims of the present invention.

Claims

1. A quasi-suspended spherical catalyst, characterized in that: The quasi-suspended spherical catalyst (1) comprises a concrete catalytic material matrix (11) and fly ash floating beads (12); the concrete catalytic material matrix (11) comprises copper nitrate, cerium nitrate, manganese chloride and iron nitrate; the volume ratio of the concrete catalytic material matrix (11) to the fly ash floating beads (12) is 1:1-1:9; the fly ash floating beads (12) are mixed and distributed inside the concrete catalytic material matrix (11); and the concrete catalytic material matrix (11) is spherical with a particle size of 1-10 mm.

2. The method for preparing the quasi-suspended spherical catalyst according to claim 1, characterized in that: The following steps are involved: Step S1, preparation of a concrete catalytic material matrix (11): copper nitrate, cerium nitrate, manganese chloride and ferric nitrate are dissolved in a metal ion molar concentration of 1-5:1-5:1-5:1-5 to prepare a catalytic component mixed solution, sodium hydroxide solution is added to the mixed solution until the pH value of the mixed solution rises to 7-12, the mixed solution is stirred again every 10-90 minutes and sodium hydroxide solution is added to adjust the pH value to 7-12, after repeating 1-10 times, the slurry containing the active catalytic components is added into the concrete dry powder and mixing is started, and water is added and mixed simultaneously until the preparation of the concrete slurry is completed, that is, the concrete catalytic material matrix (11); Step S2: Mix the prepared concrete catalytic material matrix (11) and the fly ash floating beads (12) in a volume ratio of 1:1-1:9, and perform inverted molding to granulate the particles, control the particle diameter to be 1-10 mm, and control the overall wet density of the particles to be 1-1.05 g / cm 3 The mass fraction of the catalytic component iron in the particles is controlled between 0.05% and 5%. After the particles are dried, solidified and cured, the quasi-suspended spherical catalyst (1) is prepared.

3. An ozone catalytic oxidation system, characterized in that: It comprises an ozone catalytic oxidation reaction pool (2), an oxygen station (7), a water-cooled ozone generator (8) and a gas-liquid booster pump (9); The ozone catalytic oxidation reaction tank (2) is filled with the quasi-suspended spherical catalyst (1) according to claim 1, the bottom of the side wall of the ozone catalytic oxidation reaction tank (2) is connected to a water inlet pipe (4), and the top of the side wall is provided with a water outlet pipe (5), part of the water outlet of the water outlet pipe (5) is returned to the gas-liquid booster pump (9) through the tail water return pipe (6), and the water outlet of the gas-liquid booster pump (9) enters the ozone catalytic oxidation reaction tank (2) through a secondary cutter (10); The oxygen station (7) is connected to the water-cooled ozone generator (8) via a pipeline, the water-cooled ozone generator (8) is connected to the gas-liquid booster pump (9) via a pipeline, and the gas-liquid booster pump (9) is connected to the secondary cutter (10) via a pipeline.

4. The ozone catalytic oxidation system according to claim 3, characterized in that: The ozone catalytic oxidation reaction tank (2) is cylindrical, a flexible supporting layer (3) is provided inside the ozone catalytic oxidation reaction tank (2), and the quasi-suspended spherical catalyst (1) is loaded on the flexible supporting layer (3).

5. The ozone catalytic oxidation system according to claim 3, characterized in that: The upper part of the flexible supporting layer (3) is arranged 10-50 cm above the bottom of the ozone catalytic oxidation reaction pool (2) and is fixed on the inner wall of the ozone catalytic oxidation reaction pool (2), and the bottom of the flexible supporting layer (3) is in contact with the bottom of the ozone catalytic oxidation reaction pool (2).

6. The ozone catalytic oxidation system according to claim 4 or 5, characterized in that: The flexible supporting layer (3) is made of a stainless steel wire mesh, the mesh area of ​​the stainless steel wire mesh being larger than the bottom area thereof.

7. The ozone catalytic oxidation system according to claim 3, characterized in that: The water inlet pipe (4) is connected to the bottom of the side wall of the ozone catalytic oxidation reaction tank (2) at an angle along the tangent direction of the bottom edge circumference.

8. The ozone catalytic oxidation system according to claim 3, characterized in that: The ratio of the water inflow of the tailwater return pipe (6) to the water inflow of the water inlet pipe (4) is controlled between 0.1 and 1.

9. The ozone catalytic oxidation system according to claim 3, characterized in that: The secondary cutter (10) is arranged at the bottom of the ozone catalytic oxidation reaction pool (2), and the size of the bubbles cut by the secondary cutter is 0.1-10 micrometers.

10. The ozone catalytic oxidation system according to claim 3, characterized in that: The ozone catalytic oxidation system is used in the process of deep treatment of industrial wastewater including printing and dyeing wastewater to remove organic pollutants.

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