Ozone catalyst as well as preparation method and application thereof

Abstract

The invention discloses an ozone catalyst and a preparation method and application thereof, and belongs to the field of wastewater treatment.The preparation method comprises the following steps that aromatic organic small molecules containing heteroatoms are subjected to a coupling reaction under the action of the catalyst in an adsorption polymerization mode to generate an aromatic heteroatom polymer, and the aromatic heteroatom polymer is obtained; the surface of the styrene type porous microsphere resin is coated with the coating liquid; then dipping in an aqueous solution containing a metal salt A and a metal salt B, and carrying out metal ion loading; and finally, carrying out reduction reaction on the metal ion coordinated composite resin to obtain the metal monatomic composite resin material. The ozone catalyst disclosed by the invention is used for carrying out ozone catalytic oxidation treatment on organic wastewater, and the highest removal rate of bisphenol A can reach 87.6%.

Description

Technical Field

[0001] The invention belongs to the field of wastewater treatment, and in particular relates to an ozone catalyst and a preparation method and application thereof. Background Art

[0002] Ozone has been increasingly valued in wastewater treatment for its strong oxidizing power (second only to fluorine and ·OH), fast reaction speed, no sludge and secondary pollution, and ability to improve the biodegradability of water. However, using ozone alone to treat wastewater has disadvantages such as low ozone utilization, insufficient oxidizing power, low ozone content, and poor treatment effect. Compared with single ozonation, catalytic ozone oxidation generates hydroxyl radicals with stronger oxidizing power, has a faster reaction rate, low selectivity, and can decompose organic matter more thoroughly.

[0003] At present, heterogeneous catalysts used in ozone catalytic oxidation can be divided into three types of catalysts: activated carbon catalysts, metal oxide catalysts, and supported catalysts. Activated carbon has abundant active sites, large specific surface area, strong adsorption capacity, and the catalytic oxidation system formed with ozone has the characteristics of strong degradation ability, no metal ion dissolution, good stability, etc. However, activated carbon has low compressive strength and is easy to break when the turbulence degree in the reaction is large, which limits its industrial application. The hydroxyl groups on the surface of metal oxides are the active sites of the reaction. Generally, multi-component metal oxides are superior to single-component metal oxides because of their large number of hydroxyl groups and wide applicability. The metal oxide catalyst has a low specific surface area, the surface properties are easy to change, and the active components are easy to leach, making the catalytic effect less than ideal. Supported catalysts are active components or additives loaded on carriers. The carrier can not only improve the mechanical strength but also provide active centers for the catalytic reaction, but the catalytic degradation ability of existing supported catalysts still needs to be improved. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the above background technology, provide an ozone catalyst and a preparation method and application thereof, and improve the removal rate of organic pollutants.

[0005] In order to solve the above technical problems, the technical solution proposed by the present invention is: A method for preparing an ozone catalyst comprises the following steps: (1) Through adsorption polymerization, aromatic organic small molecules containing heteroatoms undergo coupling reaction under the action of a catalyst to generate aromatic heteroatom polymers, which are then coated on the surface of styrene-based porous microsphere resins to obtain porous microsphere resins coated with aromatic heteroatom polymers; The aromatic organic small molecules containing heteroatoms include one or any combination of pyrrole, thiophene, and furan; (2) Immersing the porous microsphere resin coated with the aromatic heteroatom polymer in an aqueous solution containing metal salt A and metal salt B to load the metal ions and obtain a composite resin coordinated with metal ions; the metal salt A is one or both of ferric sulfate and manganese sulfate, and the metal salt B is one or any combination of palladium chloride, silver nitrate, chloroauric acid, and platinum chloride; (3) The metal ion coordinated composite resin is subjected to a reduction reaction to obtain a metal single atom composite resin material, namely the ozone catalyst.

[0006] As a further improvement, the amount of the aromatic organic small molecules containing heteroatoms is 1-5% of the mass of the styrene porous microsphere resin.

[0007] As a further improvement, the catalyst in step (1) is one or any combination of ferric chloride, ammonium persulfate, and sodium persulfate.

[0008] As a further improvement, the reaction temperature of step (1) is 50-80°C.

[0009] As a further improvement, in step (2), the amount of the metal salt A is 1-5% of the mass of the styrene porous microsphere resin, and the amount of the metal salt B is 1-5% of the mass of the styrene porous microsphere resin.

[0010] As a further improvement, the impregnation temperature in step (2) is 60-80°C.

[0011] As a further improvement, the reducing agent used in the reduction reaction in step (3) is one or any combination of sodium borohydride, lithium aluminum tetrahydride, and diisobutylaluminum hydride.

[0012] As a further improvement, the temperature of the reduction reaction in step (3) is 40-60°C.

[0013] The present invention provides an ozone catalyst, which is prepared by adopting the preparation method.

[0014] The present invention also provides an application of the ozone catalyst in ozone catalytic oxidation treatment of organic wastewater.

[0015] Compared with the prior art, the present invention has the following beneficial effects: The present invention uses styrene porous microsphere resin as raw material for modification and modification, firstly, through the mode of adsorption polymerization, aromatic small molecules containing heteroatoms are subjected to coupling reaction under the catalysis of a catalyst to generate porous microsphere resin coated with aromatic heteroatom polymer, and the medium polar and polar resins have good adsorption capacity for organic matter, can enrich organic matter, and increase the contact efficiency between oxidizing species and organic pollutants. Aromatic heteroatom polymers have abundant delocalized electrons, which can better excite ozone to rapidly produce a large number of hydroxyl radicals, and the introduction of heteroatoms also provides a large number of adsorption sites for the next step of metal ion compounding. The porous microsphere resin coated with aromatic heteroatom polymer is loaded with transition metal ions and noble metal ions to obtain a porous microsphere resin coated with aromatic heteroatom polymer coordinated by metal ions, and then the metal ion coordinated composite resin is subjected to reduction reaction to obtain a resin material composited with metal single atoms, which is an ozone catalyst. The reduced metal ions become noble metals and transition metal single atom catalysts, which can synergistically excite the catalytic activity of ozone, and improve the oxidation capacity and utilization rate of ozone.

[0016] When in use, the catalyst is directly loaded into the ozone reactor to carry out ozone catalytic oxidation treatment on organic wastewater. Taking bisphenol A as the simulated organic wastewater, the removal rate of bisphenol A can reach up to 87.6% after ozone catalytic treatment. DETAILED DESCRIPTION

[0017] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and carefully in combination with preferred embodiments below, but the protection scope of the present invention is not limited to the following specific embodiments.

[0018] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0019] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0020] In some specific embodiments, the method for preparing the ozone catalyst of the present invention comprises the following steps: (1) Through adsorption polymerization, aromatic organic small molecules containing heteroatoms undergo coupling reaction under the action of a catalyst to generate aromatic heteroatom polymers, which are then coated on the surface of styrene-based porous microsphere resins to obtain porous microsphere resins coated with aromatic heteroatom polymers.

[0021] In some embodiments, the styrene porous microsphere resin may be a polystyrene porous microsphere resin, which may be polar or medium polar, with a particle size of 0.5-5 mm. It is dried before use at a drying temperature of 80-120°C.

[0022] In some embodiments, the aromatic organic small molecule containing heteroatoms can be one or any combination of pyrrole, thiophene, and furan. The amount of the aromatic organic small molecule containing heteroatoms is 1-5% of the mass of the porous microsphere resin.

[0023] In some embodiments, the catalyst used is one or any combination of ferric chloride, ammonium persulfate, and sodium persulfate. The amount of the catalyst used is 0.1-0.5% of the mass of the porous microsphere resin.

[0024] In some embodiments, the reaction solvent is anhydrous ethanol, and the amount thereof is 2-4 times the mass of the porous microsphere resin. The reaction temperature is 50-80° C., and the reaction time is 12-24 hours.

[0025] The coupling mechanism of this step: the aromatic organic small molecules containing heteroatoms are first protonated under the action of the catalyst. The protonated intermediates tend to polymerize due to instability, and undergo carbon-carbon coupling reactions to generate protonated coupling products. Then the intermediates are deprotonated to generate polymers. The mechanism is as follows:

[0026] When R is N, it is the polymerization of pyrrole, when R is O, it is the polymerization of furan, and when R is S, it is the polymerization of thiophene.

[0027] (2) The porous microsphere resin coated with the aromatic heteroatom polymer is immersed in an aqueous solution containing metal salt A and metal salt B to load metal ions (including transition metal ions and noble metal ions) to obtain a metal ion coordinated composite resin.

[0028] In some embodiments, the metal salt A can be one or both of ferric sulfate and manganese sulfate, the metal salt B can be one or any combination of palladium chloride, silver nitrate, chloroauric acid, and platinum chloride, the amount of metal salt A is 1-5% of the mass of the porous microsphere resin, the amount of metal salt B is 1-5% of the mass of the porous microsphere resin, and the total concentration of the metal salt aqueous solution is 5-10%.

[0029] In some embodiments, the immersion time is 4-8 hours and the immersion temperature is 60-80° C. Then filter, wash and dry.

[0030] (3) The metal ion coordinated composite resin is subjected to a reduction reaction to obtain a metal single atom composite resin material, namely the ozone catalyst.

[0031] In some embodiments, the reducing agent used in the reduction reaction is one or any combination of sodium borohydride, lithium aluminum tetrahydride, and diisobutylaluminum hydride, and the amount of the reducing agent is 10-20% of the mass of the porous microsphere resin.

[0032] In some embodiments, the solvent used for reduction is methanol, the reduction temperature is 40-60°C, and the reduction time is 6-8h. After the reaction is completed, the mixture is filtered, washed, and vacuum dried. Preferably, the vacuum drying temperature is 80-120°C and the drying time is 12h.

[0033] Since low-valence reducing substances are more likely to activate ozone, metal atoms have a lower valence than metal ions and have certain reducing properties, so their catalytic effect is better.

[0034] When in use, the catalyst of the present invention is directly loaded into an ozone reactor, and ozone is introduced to perform ozone catalytic oxidation treatment on organic wastewater, which can be used to treat organic wastewater containing bisphenol A, chlorobenzene, nitrobenzene, etc.

[0035] In this system, ozone will be catalyzed to produce a large number of strong oxidizing active species such as superoxide free radicals and hydroxyl free radicals. The active free radicals first attack the benzene ring structure of bisphenol A to break the bonds of bisphenol A to generate small organic molecules, which are further oxidized by hydroxyl free radicals into carbon dioxide and water.

[0036] In the following embodiments, the medium polar styrene porous microsphere resin adopts the D113 macroporous weakly acidic cation exchange resin produced by Langfang Senate Chemical Co., Ltd., and the polar styrene porous microsphere resin adopts the D001 macroporous strongly acidic cation exchange resin produced by Langfang Senate Chemical Co., Ltd.

[0037] The ozone concentration and flow rate in the following examples and comparative examples are the same.

[0038] Example 1 1kg of medium polar styrene porous microsphere resin with a particle size of 2mm was placed in a 100℃ forced air drying oven for 12h for drying and standby use. 10g of pyrrole, 10g of thiophene and 1g of ammonium persulfate were dissolved in 2kg of anhydrous ethanol to prepare a solution. The dried resin was poured into the above solution, heated to 60℃ for reaction for 24h, and filtered after the reaction to obtain porous microsphere resin coated with aromatic heteroatom polymer. 10g of ferric sulfate, 10g of manganese sulfate and 10g of platinum chloride were prepared into a 5% aqueous solution and heated to 60℃. The above-obtained resin was poured into a metal salt solution and soaked for 8h, then the excess solution was filtered out and washed with ethanol. The washed composite was dried at 100℃ for 12h. Pour the dried composite into 2 kg of anhydrous methanol, heat to 50°C, slowly add 100 g of sodium borohydride in batches, and continue the reaction for 6 hours after the sodium borohydride is completely added. After the reaction is completed, filter and wash with methanol. Dry the washed product at 100°C for 12 hours to obtain the ozone oxidation catalyst.

[0039] The catalyst was loaded into an ozone reactor, a 100.0 mg / L bisphenol A aqueous solution was poured into the reactor, and ozone was introduced by aeration for 60 minutes. After the reaction, the bisphenol A content was 12.4 mg / L, and the removal rate was 87.6%.

[0040] Example 2 1kg of medium polar styrene porous microsphere resin with a particle size of 2mm was placed in a 100℃ forced air drying oven for 12h for drying and standby use. 10g of furan, 10g of thiophene and 1g of ammonium persulfate were dissolved in 2kg of anhydrous ethanol to prepare a solution. The dried resin was poured into the above solution, heated to 60℃ for reaction for 24h, and filtered after the reaction to obtain porous microsphere resin coated with aromatic heteroatom polymer. 10g of ferric sulfate, 10g of manganese sulfate and 10g of platinum chloride were prepared into a 5% aqueous solution and heated to 60℃. The above-obtained resin was poured into a metal salt solution and soaked for 8h, then the excess solution was filtered out and washed with ethanol. The washed composite was dried at 100℃ for 12h. Pour the dried composite into 2 kg of anhydrous methanol, heat to 50°C, slowly add 100 g of sodium borohydride in batches, and continue the reaction for 6 hours after the sodium borohydride is completely added. After the reaction is completed, filter and wash with methanol. Dry the washed product at 100°C for 12 hours to obtain the ozone oxidation catalyst.

[0041] The catalyst was loaded into an ozone reactor, a bisphenol A aqueous solution with a concentration of 100.0 mg / L was poured into the reactor, and ozone was introduced by aeration for 60 minutes. After the reaction, the bisphenol A content was 14.6 mg / L and the removal rate was 85.4%.

[0042] Example 3 1kg of medium polar styrene porous microsphere resin with a particle size of 2mm was placed in a 100℃ blast drying oven for 12h for drying and standby use. 10g of pyrrole, 10g of thiophene and 1g of ammonium persulfate were dissolved in 2kg of anhydrous ethanol to prepare a solution. The dried resin was poured into the above solution, heated to 60℃ for reaction for 24h, and filtered after the reaction to obtain a porous microsphere resin coated with an aromatic heteroatom polymer. 20g of manganese sulfate and 10g of platinum chloride were prepared into a 5% aqueous solution and heated to 60℃. The resin obtained above was poured into a metal salt solution and soaked for 8h, then the excess solution was filtered out and washed with ethanol. The washed composite was dried at 100℃ for 12h. The dried composite was poured into 2kg of anhydrous methanol, heated to 50℃, and 100g of sodium borohydride was slowly added in batches. After the sodium borohydride was completely added, the reaction continued for 6h. After the reaction was completed, it was filtered and washed with methanol. The washed product was dried at 100℃ for 12h to obtain an ozone oxidation catalyst.

[0043] The catalyst was loaded into an ozone reactor, a 100.0 mg / L bisphenol A aqueous solution was poured into the reactor, and ozone was introduced by aeration for 60 minutes. After the reaction, the bisphenol A content was 13.9 mg / L, and the removal rate was 86.1%.

[0044] Example 4 1kg of medium polar styrene porous microsphere resin with a particle size of 2mm was placed in a 100℃ forced air drying oven for 12h for drying and standby use. 10g of pyrrole, 10g of thiophene and 1g of ammonium persulfate were dissolved in 2kg of anhydrous ethanol to prepare a solution. The dried resin was poured into the above solution, heated to 60℃ for reaction for 24h, and filtered after the reaction to obtain porous microsphere resin coated with aromatic heteroatom polymer. 10g of ferric sulfate, 10g of manganese sulfate and 10g of palladium chloride were prepared into a 5% aqueous solution and heated to 60℃. The above-obtained resin was poured into a metal salt solution and soaked for 8h, then the excess solution was filtered out and washed with ethanol. The washed composite was dried at 100℃ for 12h. Pour the dried composite into 2 kg of anhydrous methanol, heat to 50°C, slowly add 100 g of sodium borohydride in batches, and continue the reaction for 6 hours after the sodium borohydride is completely added. After the reaction is completed, filter and wash with methanol. Dry the washed product at 100°C for 12 hours to obtain the ozone oxidation catalyst.

[0045] The catalyst was loaded into an ozone reactor, a 100.0 mg / L bisphenol A aqueous solution was poured into the reactor, and ozone was introduced by aeration for 60 minutes. After the reaction, the bisphenol A content was 16.8 mg / L, and the removal rate was 83.2%.

[0046] Comparative Example 1 1kg of medium polar styrene porous microsphere resin with a particle size of 2mm was placed in a 100℃ forced air drying oven for 12h for drying and standby use, without coating with aromatic heteroatom polymer. 10g of ferric sulfate, 10g of manganese sulfate, and 10g of platinum chloride were prepared into a 5% aqueous solution and heated to 60℃. The resin obtained above was poured into the metal salt solution and soaked for 8h, then the excess solution was filtered out and washed with ethanol. The washed composite was dried at 100℃ for 12h. The dried composite was poured into 2kg of anhydrous methanol, heated to 50℃, and 100g of sodium borohydride was slowly added in batches. After the sodium borohydride was completely added, the reaction was continued for 6h. After the reaction was completed, it was filtered and washed with methanol. The washed product was dried at 100℃ for 12h to obtain an ozone oxidation catalyst.

[0047] The catalyst was loaded into an ozone reactor, a 100.0 mg / L bisphenol A aqueous solution was poured into the reactor, and ozone was introduced by aeration for 60 minutes. After the reaction, the bisphenol A content was 42.8 mg / L, and the removal rate was 57.2%.

[0048] Comparative Example 2 1kg of medium polar styrene porous microsphere resin with a particle size of 2mm was placed in a 100℃ forced air drying oven for 12h for drying and used for standby use. 10g of pyrrole, 10g of thiophene and 1g of ammonium persulfate were dissolved in 2kg of anhydrous ethanol to prepare a solution. The dried resin was poured into the above solution, heated to 60℃ for reaction for 24h, and filtered after the reaction to obtain porous microsphere resin coated with aromatic heteroatom polymer. Without metal compounding, an ozone oxidation catalyst was obtained.

[0049] The catalyst was loaded into an ozone reactor, a 100.0 mg / L bisphenol A aqueous solution was poured into the reactor, and ozone was introduced by aeration for 60 minutes. After the reaction, the bisphenol A content was 58.4 mg / L, and the removal rate was 41.6%.

[0050] Comparative Example 3 1kg of medium polar styrene porous microsphere resin with a particle size of 2mm was placed in a 100℃ forced air drying oven for 12h for drying and standby use. 10g of pyrrole, 10g of thiophene and 1g of ammonium persulfate were dissolved in 2kg of anhydrous ethanol to prepare a solution. The dried resin was poured into the above solution, heated to 60℃ for reaction for 24h, and filtered after the reaction to obtain porous microsphere resin coated with aromatic heteroatom polymer. 10g of ferric sulfate, 10g of manganese sulfate and 10g of platinum chloride were prepared into a 5% aqueous solution and heated to 60℃. The above-obtained resin was poured into a metal salt solution and soaked for 8h, then the excess solution was filtered out and washed with ethanol. The washed composite was dried at 100℃ for 12h.

[0051] The metal ions were directly loaded into the ozone reactor without reduction. A bisphenol A aqueous solution with a concentration of 100.0 mg / L was poured into the reactor, and ozone was introduced by aeration for 60 minutes. After the reaction, the bisphenol A content was 38.8 mg / L and the removal rate was 61.2%.

[0052] Comparative Example 4 1kg of medium polar styrene porous microsphere resin with a particle size of 2mm was placed in a 100℃ blast drying oven for 12h for drying and standby use. 10g of pyrrole, 10g of thiophene and 1g of ammonium persulfate were dissolved in 2kg of anhydrous ethanol to prepare a solution. The dried resin was poured into the above solution, heated to 60℃ for reaction for 24h, and filtered after the reaction to obtain a porous microsphere resin coated with an aromatic heteroatom polymer. Only 20g of manganese sulfate metal salt was added to prepare a 5% aqueous solution and heated to 60℃. The resin obtained above was poured into the metal salt solution and soaked for 8h, then the excess solution was filtered out and washed with ethanol. The washed composite was dried at 100℃ for 12h. The dried composite was poured into 2kg of anhydrous methanol, heated to 50℃, and 100g of sodium borohydride was slowly added in batches. After the sodium borohydride was completely added, the reaction continued for 6h. After the reaction was completed, it was filtered and washed with methanol. The washed product was dried at 100℃ for 12h to obtain an ozone oxidation catalyst.

[0053] The catalyst was loaded into an ozone reactor, a bisphenol A aqueous solution with a concentration of 100.0 mg / L was poured into the reactor, and ozone was introduced by aeration for 60 minutes. After the reaction, the bisphenol A content was 24.6 mg / L and the removal rate was 75.4%.

[0054] Comparative Example 5 1kg of medium polar styrene porous microsphere resin with a particle size of 2mm was placed in a 100℃ blast drying oven for 12h for drying and standby use. 10g of pyrrole, 10g of thiophene and 1g of ammonium persulfate were dissolved in 2kg of anhydrous ethanol to prepare a solution. The dried resin was poured into the above solution, heated to 60℃ for reaction for 24h, and filtered after the reaction to obtain a porous microsphere resin coated with an aromatic heteroatom polymer. Only 10g of platinum chloride metal salt was added to prepare a 5% aqueous solution and heated to 60℃. The resin obtained above was poured into the metal salt solution and soaked for 8h, then the excess solution was filtered out and washed with ethanol. The washed composite was dried at 100℃ for 12h. The dried composite was poured into 2kg of anhydrous methanol, heated to 50℃, and 100g of sodium borohydride was slowly added in batches. After the sodium borohydride was completely added, the reaction continued for 6h. After the reaction was completed, it was filtered and washed with methanol. The washed product was dried at 100℃ for 12h to obtain an ozone oxidation catalyst.

[0055] The catalyst was loaded into an ozone reactor, a bisphenol A aqueous solution with a concentration of 100.0 mg / L was poured into the reactor, and ozone was introduced by aeration for 60 minutes. After the reaction, the bisphenol A content was 21.7 mg / L and the removal rate was 78.3%.

[0056] The above is only a preferred embodiment of the present invention and does not limit the present invention in any form. Therefore, any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the content of the technical solution of the present invention shall fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing an ozone catalyst, characterized in that: The steps include: (1) Through adsorption polymerization, aromatic organic small molecules containing heteroatoms undergo coupling reaction under the action of a catalyst to generate aromatic heteroatom polymers, which are then coated on the surface of styrene-based porous microsphere resins to obtain porous microsphere resins coated with aromatic heteroatom polymers; The aromatic organic small molecules containing heteroatoms include one or any combination of pyrrole, thiophene, and furan; (2) Immersing the porous microsphere resin coated with the aromatic heteroatom polymer in an aqueous solution containing metal salt A and metal salt B to load the metal ions and obtain a composite resin coordinated with metal ions; the metal salt A is one or both of ferric sulfate and manganese sulfate, and the metal salt B is one or any combination of palladium chloride, silver nitrate, chloroauric acid, and platinum chloride; (3) The metal ion coordinated composite resin is subjected to a reduction reaction to obtain a metal single atom composite resin material, namely the ozone catalyst.

2. The method for preparing an ozone catalyst according to claim 1, characterized in that: The amount of the aromatic organic small molecules containing heteroatoms is 1-5% of the mass of the styrene porous microsphere resin.

3. The method for preparing an ozone catalyst according to claim 1, characterized in that: The catalyst in step (1) is one or any combination of ferric chloride, ammonium persulfate, and sodium persulfate.

4. The method for preparing an ozone catalyst according to any one of claims 1 to 3, characterized in that: The reaction temperature of step (1) is 50-80°C.

5. The method for preparing an ozone catalyst according to any one of claims 1 to 3, characterized in that: In step (2), the amount of metal salt A is 1-5% of the mass of the styrene porous microsphere resin, and the amount of metal salt B is 1-5% of the mass of the styrene porous microsphere resin.

6. The method for preparing an ozone catalyst according to any one of claims 1 to 3, characterized in that: The immersion temperature in step (2) is 60-80°C.

7. The method for preparing an ozone catalyst according to any one of claims 1 to 3, characterized in that: The reducing agent used in the reduction reaction of step (3) is one or any combination of sodium borohydride, lithium aluminum tetrahydride, and diisobutylaluminum hydride.

8. The method for preparing an ozone catalyst according to any one of claims 1 to 3, characterized in that: The temperature of the reduction reaction in step (3) is 40-60°C.

9. An ozone catalyst, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the ozone catalyst according to claim 9 in ozone catalytic oxidation treatment of organic wastewater.

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