An ozone catalyst, its preparation method and application

Abstract

The present invention discloses an ozone catalyst, a preparation method thereof and an application thereof, belonging to the field of wastewater treatment, which comprises the following steps: through an adsorption polymerization method, aromatic organic small molecules containing heteroatoms undergo a coupling reaction under the action of a catalyst to generate an aromatic heteroatom polymer, which is coated on the surface of a styrene-based porous microsphere resin; then it is impregnated in an aqueous solution containing metal salt A and metal salt B for loading metal ions; finally, the composite resin coordinated with metal ions is subjected to a reduction reaction to obtain a resin material with single metal atoms composite. The ozone catalyst of the present invention is used for ozone catalytic oxidation treatment of organic wastewater, and the highest removal rate of bisphenol A can reach 87.6%.

Description

Technical Field

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

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

[0003] Currently, the heterogeneous catalysts applied to catalytic ozonation can be divided into three types: activated carbon catalysts, metal oxide catalysts, and supported catalysts. Activated carbon has rich active sites, a large specific surface area, strong adsorption ability, and has characteristics such as strong degradation ability, no metal ion dissolution, and good stability when forming a catalytic oxidation system with ozone. However, activated carbon has low compressive strength and is prone to breakage when the turbulence degree in the reaction is relatively large, which limits its industrial application. The hydroxyl groups present on the surface of metal oxides are the active sites of the reaction. Usually, multi-component metal oxides are superior to single-component metal oxides because they have more hydroxyl groups and wide applicability. Metal oxide catalysts have a relatively low specific surface area, the surface properties are easily changed, and the active components are easily leached out, resulting in an unsatisfactory catalytic effect. Supported catalysts are to load active components or additives on the carrier. The carrier can not only improve the mechanical strength but also provide active centers for the catalytic reaction. However, 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 above-mentioned deficiencies and defects in the background art, and provide an ozone catalyst, a preparation method thereof, and an application thereof, so as to improve the removal rate of organic pollutants.

[0005] To solve the above technical problem, the technical solution proposed by the present invention is as follows:

[0006] A preparation method of an ozone catalyst includes the following steps:

[0007] (1) By means of adsorption polymerization, an aromatic organic small molecule containing a heteroatom undergoes a coupling reaction under the action of a catalyst to generate an aromatic heteroatom polymer, which is coated on the surface of a styrene-based porous microsphere resin to obtain a porous microsphere resin coated with an aromatic heteroatom polymer;

[0008] The aromatic organic small molecule containing a heteroatom includes one or any combination of pyrrole, thiophene, and furan;

[0009] (2) Immerse the porous microsphere resin coated with aromatic heteroatom polymer in an aqueous solution containing metal salt A and metal salt B for metal ion loading to 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;

[0010] (3) Carry out a reduction reaction on the composite resin coordinated with metal ions to obtain a resin material composite with single metal atoms, that is, the ozone catalyst.

[0011] As a further improvement, the dosage of the aromatic organic small molecule containing heteroatoms is 1-5% of the mass of the styrene-based porous microsphere resin.

[0012] As a further improvement, the catalyst in step (1) is one or any combination of ferric chloride, ammonium persulfate, and sodium persulfate.

[0013] As a further improvement, the reaction temperature in step (1) is 50-80 °C.

[0014] As a further improvement, the dosage of metal salt A in step (2) is 1-5% of the mass of the styrene-based porous microsphere resin, and the dosage of metal salt B is 1-5% of the mass of the styrene-based porous microsphere resin.

[0015] As a further improvement, the impregnation temperature in step (2) is 60-80 °C.

[0016] 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 hydride, and diisobutylaluminum hydride.

[0017] As a further improvement, the temperature of the reduction reaction in step (3) is 40-60 °C.

[0018] An ozone catalyst provided by the present invention is prepared by the described preparation method.

[0019] The present invention also provides an application of the ozone catalyst in the catalytic oxidation treatment of organic wastewater by ozone.

[0020] Compared with the prior art, the beneficial effects of the present invention are:

[0021] The present invention modifies and modifies styrene-based porous microsphere resin as a raw material. First, through the method of adsorption polymerization, aromatic small molecules containing heteroatoms undergo a coupling reaction under the catalysis of a catalyst to generate a porous microsphere resin coated with an aromatic heteroatom polymer. Medium-polarity and polar resins have good adsorption capacity for organic substances, which can enrich organic substances and increase the contact efficiency between oxidation species and organic pollutants. The aromatic heteroatom polymer has abundant delocalized electrons, which can better stimulate ozone to rapidly generate a large amount of hydroxyl radicals. At the same time, the introduction of heteroatoms also provides a large number of adsorption sites for the next-step complexation of metal ions. The porous microsphere resin coated with an aromatic heteroatom polymer is loaded with transition metal ions and noble metal ions to obtain a porous microsphere resin coated with a metal ion-coordinated aromatic heteroatom polymer. Then, the metal ion-coordinated composite resin is subjected to a reduction reaction to obtain a resin material composite with metal single atoms, which is the ozone catalyst. The reduced metal ions become noble metal and transition metal single-atom catalysts, which can synergistically stimulate the catalytic activity of ozone and improve the oxidation ability and utilization rate of ozone.

[0022] When in use, the catalyst is directly loaded into an ozone reactor to carry out ozone catalytic oxidation treatment on organic wastewater. Using bisphenol A as the simulated organic wastewater, the removal rate of bisphenol A can reach up to 87.6% after ozone catalytic treatment. Detailed implementation mode

[0023] To facilitate the understanding of the present invention, the following will describe the present invention more comprehensively and meticulously in combination with preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.

[0024] Unless otherwise defined, all professional terms used hereinafter have the same meaning as commonly 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 protection scope of the present invention.

[0025] Unless otherwise specifically stated, various raw materials, reagents, instruments, and equipment used in the present invention can be obtained through market purchase or can be prepared by existing methods.

[0026] In some specific implementation modes, the preparation method of the ozone catalyst of the present invention includes the following steps:

[0027] (1) Through the method of adsorption polymerization, aromatic organic small molecules containing heteroatoms undergo a coupling reaction under the action of a catalyst to generate an aromatic heteroatom polymer, which is coated on the surface of styrene-based porous microsphere resin to obtain a porous microsphere resin coated with an aromatic heteroatom polymer.

[0028] In some embodiments, the styrene-based porous microsphere resin can be a polystyrene porous microsphere resin, which can be polar or medium polar, with a particle size of 0.5 - 5 mm. Before use, it is dried, and the drying temperature is 80 - 120 °C.

[0029] In some embodiments, the heteroatom-containing aromatic organic small molecule can be one or any combination of pyrrole, thiophene, and furan. The amount of the heteroatom-containing aromatic organic small molecule used is 1 - 5% of the mass of the porous microsphere resin.

[0030] 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.

[0031] In some embodiments, the reaction solvent is absolute ethanol, and its amount 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 h.

[0032] The coupling mechanism of this step: The heteroatom-containing aromatic organic small molecule is first protonated under the action of the catalyst. Due to instability, the protonated intermediate has a polymerization tendency to undergo a carbon-carbon coupling reaction to form a protonated coupling product, and then the intermediate product is deprotonated to form a polymer. The mechanism is as follows:

[0033]

[0034] When R is N, it is the polymerization of pyrrole; when R is O, it is the polymerization of furan; when R is S, it is the polymerization of thiophene.

[0035] (2) Immerse the porous microsphere resin coated with the aromatic heteroatom polymer in an aqueous solution containing metal salt A and metal salt B for loading metal ions (including transition metal ions and noble metal ions) to obtain a metal ion-coordinated composite resin.

[0036] In some embodiments, the metal salt A can be one or two of ferric sulfate and manganese sulfate, and the metal salt B can be one or any combination of palladium chloride, silver nitrate, chloroauric acid, and platinum chloride. The amount of the metal salt A used is 1 - 5% of the mass of the porous microsphere resin, the amount of the metal salt B used is 1 - 5% of the mass of the porous microsphere resin, and the total concentration of the metal salt aqueous solution is 5 - 10%.

[0037] In some embodiments, the impregnation time is 4 - 8 h, and the impregnation temperature is 60 - 80 °C. Then, it is filtered, washed, and dried.

[0038] (3) Carry out a reduction reaction on the metal ion-coordinated composite resin to obtain a resin material with single metal atoms composite, that is, the ozone catalyst.

[0039] In some embodiments, the reducing agent used in the reduction reaction is one or any combination of sodium borohydride, lithium aluminum hydride, and diisobutylaluminum hydride, and the dosage of the reducing agent is 10-20% of the mass of the porous microsphere resin.

[0040] In some embodiments, the solvent used for reduction is methanol, the reduction temperature is 40-60 °C, and the reduction time is 6-8 h. After the reaction is completed, filtration and washing are carried out, and vacuum drying treatment is performed. Preferably, the temperature of the vacuum drying treatment is 80-120 °C, and the drying time is 12 h.

[0041] Since substances with low-valence reducibility can more easily activate ozone, metal single atoms have a lower valence than metal ions and have a certain reducibility, so their catalytic effect is better.

[0042] During use, the catalyst of the present invention is directly loaded into the ozone reactor, and ozone is introduced to perform ozone catalytic oxidation treatment on the organic wastewater, which can be used for the treatment of organic wastewater containing bisphenol A, chlorobenzene, nitrobenzene, etc.

[0043] In this system, ozone will be catalyzed to generate a large amount of strongly oxidizing active species such as superoxide radicals and hydroxyl radicals. The active radicals first attack the benzene ring structure of bisphenol A to break the bond of bisphenol A to generate organic small molecules, and the organic small molecules are further oxidized by hydroxyl radicals to carbon dioxide and water.

[0044] In the following examples, the medium-polarity styrene-based porous microsphere resin is the D113 macroporous weakly acidic cation exchange resin of Langfang Sunnat Chemical Co., Ltd., and the polar styrene-based porous microsphere resin is the D001 macroporous strongly acidic cation exchange resin of Langfang Sunnat Chemical Co., Ltd.

[0045] In the following examples and comparative examples, the ozone concentration and flow rate introduced are the same.

[0046] Example 1

[0047] Put 1 kg of medium-polarity styrene-based porous microsphere resin with a particle size of 2 mm in a blast drying oven at 100 °C for 12 h for drying treatment and reserve for use. Separately, dissolve 10 g of pyrrole, 10 g of thiophene, and 1 g of ammonium persulfate in 2 kg of absolute ethanol to form a solution. Pour the dried resin into the above solution, raise the temperature to 60 °C and react for 24 h. After the reaction, filter to obtain porous microsphere resin coated with aromatic heteroatom polymer. Take 10 g of ferric sulfate, 10 g of manganese sulfate, and 10 g of platinum chloride to prepare a 5% aqueous solution and raise the temperature to 60 °C. Pour the resin obtained above into the metal salt solution and soak for 8 h, then filter off the excess solution and wash with ethanol. The washed composite is dried at 100 °C for 12 h. Pour the dried composite into 2 kg of absolute methanol, raise the temperature to 50 °C, and slowly add 100 g of sodium borohydride in batches. After the complete addition of sodium borohydride, continue to react for 6 h. After the reaction, filter and wash with methanol. Dry the washed product at 100 °C for 12 h to obtain the ozone oxidation catalyst.

[0048] Load the catalyst into an ozone reactor, pour a 100.0 mg / L aqueous bisphenol A solution into the reactor, and introduce ozone by aeration for 60 min. After the reaction, the content of bisphenol A is 12.4 mg / L, and the removal rate is 87.6%.

[0049] Example 2

[0050] Put 1 kg of medium-polarity styrene-based porous microsphere resin with a particle size of 2 mm in a blast drying oven at 100 °C for 12 h for drying treatment and reserve for use. Separately, dissolve 10 g of furan, 10 g of thiophene, and 1 g of ammonium persulfate in 2 kg of absolute ethanol to form a solution. Pour the dried resin into the above solution, raise the temperature to 60 °C and react for 24 h. After the reaction, filter to obtain porous microsphere resin coated with aromatic heteroatom polymer. Take 10 g of ferric sulfate, 10 g of manganese sulfate, and 10 g of platinum chloride to prepare a 5% aqueous solution and raise the temperature to 60 °C. Pour the resin obtained above into the metal salt solution and soak for 8 h, then filter off the excess solution and wash with ethanol. The washed composite is dried at 100 °C for 12 h. Pour the dried composite into 2 kg of absolute methanol, raise the temperature to 50 °C, and slowly add 100 g of sodium borohydride in batches. After the complete addition of sodium borohydride, continue to react for 6 h. After the reaction, filter and wash with methanol. Dry the washed product at 100 °C for 12 h to obtain the ozone oxidation catalyst.

[0051] Load the catalyst into an ozone reactor, pour a 100.0 mg / L aqueous bisphenol A solution into the reactor, and introduce ozone by aeration for 60 min. After the reaction, the content of bisphenol A is 14.6 mg / L, and the removal rate is 85.4%.

[0052] Example 3

[0053] Put 1 kg of medium-polarity styrene-based porous microsphere resin with a particle size of 2 mm in a blast drying oven at 100 °C for 12 h for drying treatment and reserve for use. Separately, dissolve 10 g of pyrrole, 10 g of thiophene, and 1 g of ammonium persulfate in 2 kg of absolute ethanol to form a solution. Pour the dried resin into the above solution, heat up to 60 °C and react for 24 h. After the reaction is completed, filter to obtain porous microsphere resin coated with aromatic heteroatom polymer. Take 20 g of manganese sulfate and 10 g of platinum chloride to prepare a 5% aqueous solution and heat up to 60 °C. Pour the resin obtained above into the metal salt solution and soak for 8 h, then filter off the excess solution and wash with ethanol. The washed composite is dried at 100 °C for 12 h. Pour the dried composite into 2 kg of absolute methanol, heat up to 50 °C, and slowly add 100 g of sodium borohydride in batches. After the addition of sodium borohydride is complete, continue to react for 6 h. After the reaction is completed, filter and wash with methanol. The washed product is dried at 100 °C for 12 h to obtain the ozone oxidation catalyst.

[0054] Load the catalyst into an ozone reactor, pour a 100.0 mg / L aqueous solution of bisphenol A into the reactor, and introduce ozone by aeration for 60 min. After the reaction is completed, the content of bisphenol A is 13.9 mg / L, and the removal rate is 86.1%.

[0055] Example 4

[0056] Put 1 kg of medium-polarity styrene-based porous microsphere resin with a particle size of 2 mm in a blast drying oven at 100 °C for 12 h for drying treatment and reserve for use. Separately, dissolve 10 g of pyrrole, 10 g of thiophene, and 1 g of ammonium persulfate in 2 kg of absolute ethanol to form a solution. Pour the dried resin into the above solution, heat up to 60 °C and react for 24 h. After the reaction is completed, filter to obtain porous microsphere resin coated with aromatic heteroatom polymer. Take 10 g of ferric sulfate, 10 g of manganese sulfate, and 10 g of palladium chloride to prepare a 5% aqueous solution and heat up to 60 °C. Pour the resin obtained above into the metal salt solution and soak for 8 h, then filter off the excess solution and wash with ethanol. The washed composite is dried at 100 °C for 12 h. Pour the dried composite into 2 kg of absolute methanol, heat up to 50 °C, and slowly add 100 g of sodium borohydride in batches. After the addition of sodium borohydride is complete, continue to react for 6 h. After the reaction is completed, filter and wash with methanol. The washed product is dried at 100 °C for 12 h to obtain the ozone oxidation catalyst.

[0057] Load the catalyst into an ozone reactor, pour a 100.0 mg / L aqueous solution of bisphenol A into the reactor, and introduce ozone by aeration for 60 min. After the reaction is completed, the content of bisphenol A is 16.8 mg / L, and the removal rate is 83.2%.

[0058] Comparative Example 1

[0059] 1 kg of medium-polarity styrene-based porous microsphere resin with a particle size of 2 mm was placed in a blast drying oven at 100 °C for 12 h for drying treatment and standby, without coating with aromatic heteroatom polymer. 10 g of ferric sulfate, 10 g of manganese sulfate, and 10 g of platinum chloride were prepared into a 5% aqueous solution and heated to 60 °C. The resin obtained above was poured into the metal salt solution and soaked for 8 h, then the excess solution was filtered off and washed with ethanol. The washed composite was dried at 100 °C for 12 h. The dried composite was poured into 2 kg of anhydrous methanol, heated to 50 °C, and 100 g of sodium borohydride was slowly added in batches. After the complete addition of sodium borohydride, the reaction continued for 6 h. After the reaction, it was filtered and washed with methanol. The washed product was dried at 100 °C for 12 h to obtain the ozone oxidation catalyst.

[0060] The catalyst was loaded into an ozone reactor, and an aqueous solution of bisphenol A with a concentration of 100.0 mg / L was poured into the reactor, and ozone was introduced by aeration for 60 min. After the reaction, the content of bisphenol A was 42.8 mg / L, and the removal rate was 57.2%.

[0061] Comparative Example 2

[0062] 1 kg of medium-polarity styrene-based porous microsphere resin with a particle size of 2 mm was placed in a blast drying oven at 100 °C for 12 h for drying treatment and standby. Another 10 g of pyrrole, 10 g of thiophene, and 1 g of ammonium persulfate were dissolved in 2 kg of anhydrous ethanol to form a solution. The dried resin was poured into the above solution, heated to 60 °C and reacted for 24 h. After the reaction, filtration was carried out to obtain the porous microsphere resin coated with aromatic heteroatom polymer. Without metal composite, the ozone oxidation catalyst was obtained.

[0063] The catalyst was loaded into an ozone reactor, and an aqueous solution of bisphenol A with a concentration of 100.0 mg / L was poured into the reactor, and ozone was introduced by aeration for 60 min. After the reaction, the content of bisphenol A was 58.4 mg / L, and the removal rate was 41.6%.

[0064] Comparative Example 3

[0065] 1 kg of medium-polarity styrene-based porous microsphere resin with a particle size of 2 mm was placed in a 100 °C forced-air drying oven for 12 h for drying treatment and reserved for use. Another 10 g of pyrrole, 10 g of thiophene, and 1 g of ammonium persulfate were dissolved in 2 kg of absolute ethanol to prepare a solution. The dried resin was poured into the above solution, and the temperature was raised to 60 °C for reaction for 24 h. After the reaction, filtration was carried out to obtain porous microsphere resin coated with aromatic heteroatom polymer. 10 g of ferric sulfate, 10 g of manganese sulfate, and 10 g of platinum chloride were prepared into a 5% aqueous solution and the temperature was raised to 60 °C. The resin obtained above was poured into the metal salt solution and soaked for 8 h, then the excess solution was filtered off and washed with ethanol. The washed composite was dried at 100 °C for 12 h.

[0066] Without reducing the metal ions, it was directly loaded into an ozone reactor. An aqueous bisphenol A solution with a concentration of 100.0 mg / L was poured into the reactor, and ozone was introduced by aeration for reaction for 60 min. After the reaction, the content of bisphenol A was 38.8 mg / L, and the removal rate was 61.2%.

[0067] Comparative Example 4

[0068] 1 kg of medium-polarity styrene-based porous microsphere resin with a particle size of 2 mm was placed in a 100 °C forced-air drying oven for 12 h for drying treatment and reserved for use. Another 10 g of pyrrole, 10 g of thiophene, and 1 g of ammonium persulfate were dissolved in 2 kg of absolute ethanol to prepare a solution. The dried resin was poured into the above solution, and the temperature was raised to 60 °C for reaction for 24 h. After the reaction, filtration was carried out to obtain porous microsphere resin coated with aromatic heteroatom polymer. Only 20 g of manganese sulfate metal salt was added to prepare a 5% aqueous solution and the temperature was raised to 60 °C. The resin obtained above was poured into the metal salt solution and soaked for 8 h, then the excess solution was filtered off and washed with ethanol. The washed composite was dried at 100 °C for 12 h. The dried composite was poured into 2 kg of absolute methanol, and the temperature was raised to 50 °C. 100 g of sodium borohydride was slowly added in batches. After the complete addition of sodium borohydride, the reaction continued for 6 h. After the reaction, filtration was carried out and washed with methanol. The washed product was dried at 100 °C for 12 h to obtain the ozone oxidation catalyst.

[0069] The catalyst was loaded into an ozone reactor. An aqueous bisphenol A solution with a concentration of 100.0 mg / L was poured into the reactor, and ozone was introduced by aeration for reaction for 60 min. After the reaction, the content of bisphenol A was 24.6 mg / L, and the removal rate was 75.4%.

[0070] Comparative Example 5

[0071] 1 kg of medium-polarity styrene-based porous microsphere resin with a particle size of 2 mm was placed in a 100 °C forced-air drying oven for 12 h for drying treatment and standby. Another 10 g of pyrrole, 10 g of thiophene, and 1 g of ammonium persulfate were dissolved in 2 kg of absolute ethanol to prepare a solution. The dried resin was poured into the above solution, and the temperature was raised to 60 °C for reaction for 24 h. After the reaction, filtration was carried out to obtain porous microsphere resin coated with aromatic heteroatom polymer. Only 10 g of platinum chloride metal salt was prepared into a 5% aqueous solution and the temperature was raised to 60 °C. The resin obtained above was poured into the metal salt solution and soaked for 8 h, then the excess solution was filtered off and washed with ethanol. The washed composite was dried at 100 °C for 12 h. The dried composite was poured into 2 kg of absolute methanol, the temperature was raised to 50 °C, and 100 g of sodium borohydride was slowly added in batches. After the complete addition of sodium borohydride, the reaction continued for 6 h. After the reaction, filtration was carried out and washed with methanol. The washed product was dried at 100 °C for 12 h to obtain the ozone oxidation catalyst.

[0072] The catalyst was loaded into an ozone reactor, and an aqueous solution of bisphenol A with a concentration of 100.0 mg / L was poured into the reactor, and ozone was introduced by aeration for reaction for 60 min. After the reaction, the content of bisphenol A was 21.7 mg / L, and the removal rate was 78.3%.

[0073] The above is only a preferred embodiment of the present invention and does not impose any form of limitation on the present invention. Therefore, any simple modification, equivalent change, and modification made to the above embodiments based on the technical essence of the present invention without departing from the technical solution of the present invention shall fall within the scope of protection of the technical solution of the present invention.

Claims

1. Application of an ozone catalyst in the treatment of organic wastewater by ozone catalytic oxidation, characterized in that The ozone catalyst is prepared by the following steps: (1) Through the way of adsorption polymerization, the aromatic organic small molecules containing heteroatoms undergo a coupling reaction under the action of a catalyst to generate an aromatic heteroatom polymer, which is coated on the surface of the styrene-based porous microsphere resin to obtain a porous microsphere resin coated with an aromatic heteroatom polymer; The aromatic organic small molecules containing heteroatoms include one or any combination of pyrrole, thiophene, and furan; (2) The porous microsphere resin coated with an aromatic heteroatom polymer is impregnated in an aqueous solution containing metal salt A and metal salt B for loading metal ions to obtain a composite resin coordinated with metal ions; The metal salt A is one or two 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 composite resin coordinated with metal ions is subjected to a reduction reaction to obtain a resin material composite with metal single atoms, that is, the ozone catalyst.

2. The application according to claim 1, characterized in that, The dosage of the aromatic organic small molecules containing heteroatoms is 1-5% of the mass of the styrene-based porous microsphere resin.

3. The application according to claim 1, wherein The catalyst in step (1) is one or any combination of ferric chloride, ammonium persulfate, and sodium persulfate.

4. The application according to any one of claims 1 to 3, characterized in that, The reaction temperature in step (1) is 50-80 °C.

5. The application according to any one of claims 1 to 3, characterized in that, The dosage of the metal salt A in step (2) is 1-5% of the mass of the styrene-based porous microsphere resin, and the dosage of the metal salt B is 1-5% of the mass of the styrene-based porous microsphere resin.

6. The application according to any one of claims 1 to 3, characterized in that The impregnation temperature in step (2) is 60-80 °C.

7. The application according to any one of claims 1 to 3, characterized in that, The reducing agent used in the reduction reaction in step (3) is one or any combination of sodium borohydride, lithium aluminum hydride, and diisobutylaluminum hydride.

8. The application 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.

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