Preparation method and application of macroporous resin supported Fenton-like catalyst

Abstract

The invention relates to the technical field of chemical catalytic materials, and discloses a preparation method and application of a macroporous resin supported Fenton-like catalyst, 5-aminosalicylic acid, p-nitrobenzaldehyde and the like are used as reaction raw materials to obtain amino Schiff base salicylic acid, chloromethylated macroporous phenolic resin reacts with the amino Schiff base salicylic acid and is chelated and adsorbed with Fe < 2 + >, and the macroporous resin supported Fenton-like catalyst is obtained. The macroporous resin loaded Fenton-like catalyst is obtained, so that the transfer and surface reaction of H2O2 and organic matter molecules are facilitated, and more. OH is further generated to catalyze the degradation of phenol; the problem that a traditional Fenton catalyst is narrow in pH range is solved, and wide pH adaptability is achieved; after the macroporous resin supported Fenton-like catalyst is used for many times, the Fe < 2 + > dissolution rate is low, and the reaction activity is good; generated. OH can oxidize and degrade H2S and NH3 molecules, hydrogen sulfide and ammonia gas generated in industrial production and farms are eliminated, and air is purified.

Description

Technical Field

[0001] The invention relates to the technical field of chemical catalytic materials, and in particular to a preparation method and application of a macroporous resin-supported Fenton-type catalyst. Background Art

[0002] With the rapid development of social economy and science and technology, the pollution of water environment by pollutants is becoming more and more serious. Organic matter is one of the main pollutants causing water pollution. Phenolic compounds among pollutants are widely present in petrochemical, textile, dye, pharmaceutical and other industries, resulting in a large amount of phenol and its derivatives in industrial wastewater. In addition, almost all industrial production will produce industrial tail gas. Untreated industrial tail gas contains harmful and odorous gases such as hydrogen sulfide and ammonia. Direct discharge will cause major air pollution problems. As an advanced oxidation technology, Fenton catalysis has attracted much attention in the field of organic wastewater treatment because of its advantages such as simple reaction device, mild reaction conditions and low operating cost. Homogeneous catalysts have high catalytic activity for Fenton reaction, but there are many problems in homogeneous Fenton system, such as H 2 O 2 There is a certain risk in the transportation of Fe 3+ Reduction to Fe 2+ The slow rate, narrow optimum pH range, and large amount of iron-containing sludge produced limit the application of the homogeneous Fenton method.

[0003] Heterogeneous Fenton catalysis mainly utilizes Fe 2+ Catalytic H 2 O 2 The hydroxyl radicals (·OH) are decomposed to form hydroxyl radicals (·OH), which oxidize and decompose the target pollutants, thus realizing the separation and reuse of solid catalysts. In particular, the porous carrier-supported heterogeneous Fenton catalysis can effectively combine the adsorption performance of the porous carrier with the high reactivity of the nanocatalytic particles, and is becoming an important research direction in advanced oxidation technology. Although the supported Fenton catalysis has made significant progress, there are still some shortcomings in this technology, such as large catalyst dosage, H 2 O 2 Due to the large dosage, poor catalyst stability and short life, its application in industry is still subject to certain limitations.

[0004] The commonly used Fenton catalyst carrier in the existing wastewater treatment technology is porous carbon, which has the advantages of large specific surface area and good adsorption performance. However, due to the weak interaction between activated carbon and metal, the active components are easily dissolved, which is not conducive to the reuse of materials. Chelating resin has the advantages of large adsorption capacity and the ability to release chelated metal ions under appropriate conditions, and is increasingly widely used for the capture and separation of metal ions. However, the traditional iron oxide heterogeneous Fenton catalyst has a large specific surface energy and is easy to agglomerate, and cannot fully utilize the active sites on the catalyst surface, which is not conducive to the degradation of phenol. The present invention aims to introduce chelating groups into macroporous phenolic resins, utilize their rich pore structure and chelating groups, and significantly improve the Fe 2+ loading efficiency and degradation rate of organic pollutants. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art, provide a preparation method and application of a macroporous resin-supported Fenton-type catalyst, and improve the Fe 2+ loading efficiency and degradation rate of organic matter.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] A method for preparing a macroporous resin-supported Fenton-type catalyst comprises the following steps:

[0008] (1) Add macroporous phenolic resin and acetone to a reaction flask equipped with a dropping funnel, stir evenly, add zinc chloride, drop 1,4-dichloromethoxybutane, react at 50-65° C. for 5-10 hours, disperse in deionized water, stand overnight, filter, wash with ethanol and deionized water, and dry to obtain chloromethylated macroporous phenolic resin.

[0009] (2) Add chloromethylated macroporous phenolic resin and N,N-dimethylformamide to a reaction flask equipped with a reflux condenser, stir evenly, and add the structural formula The amino Schiff base salicylic acid is stirred for reaction. After the reaction is completed, it is filtered, washed with ethanol and acetone, and dried to obtain a macroporous chelating phenolic resin.

[0010] (3) Adding a macroporous chelating phenolic resin and deionized water into a reaction flask, adding a ferrous sulfate aqueous solution with a mass fraction of 15-25%, reacting at a temperature of 20-35° C. and a rotation speed of 100-150 r / min for 12-24 hours, filtering, washing with deionized water and ethanol alternately, and drying to obtain a macroporous resin-supported Fenton-type catalyst.

[0011] Preferably, in step (1), the ratio of macroporous phenolic resin, acetone, zinc chloride and 1,4-dichloromethoxybutane is 1 g: (10-30) mL: (0.3-0.8) g: (2.5-6) ​​g.

[0012] Preferably, in step (2), the ratio of chloromethylated phenolic resin, N,N-dimethylformamide, and amino Schiff base salicylic acid is 1 g: (15-30) mL: (0.8-2) g.

[0013] Preferably, in step (2), the reaction temperature is 80-110° C. and the reaction time is 24-48 h.

[0014] Preferably, the mass concentration of the macroporous chelating phenolic resin in step (3) is 0.5-2.5 g / L.

[0015] Preferably, the preparation method of amino Schiff base salicylic acid in step (2) comprises the following steps:

[0016] Step S1, add 5-aminosalicylic acid and methanol to a reaction flask equipped with a reflux condenser, stir evenly, add p-nitrobenzaldehyde, react at 60-80°C for 2-5h, cool to room temperature, filter and dry to obtain nitrosalic acid. The preparation reaction formula is as follows:

[0017]

[0018] Step S2: Add nitroschiff base salicylic acid and ethanol to a reaction flask, stir evenly, add sodium dithionite, react at 45-60° C. for 2-4 hours, filter, wash with deionized water, and recrystallize with ethanol to obtain amino Schiff base salicylic acid. The preparation reaction formula is as follows:

[0019]

[0020] Preferably, in step S1, the ratio of 5-aminosalicylic acid, methanol, and p-nitrobenzaldehyde is 1 g: (10-20) mL: (1.05-1.2) g.

[0021] Preferably, in step S2, the ratio of nitro-Schiff base salicylic acid, ethanol, and sodium dithionite is 1 g: (25-40) mL: (3-4.2) g.

[0022] Preferably, the macroporous resin-supported Fenton-type catalyst is used in the degradation of organic pollutants.

[0023] By adopting the above technical solution, the beneficial effects of the present invention are:

[0024] The invention uses 5-aminosalicylic acid, p-nitrobenzaldehyde, sodium dithionite and the like as reaction raw materials to prepare amino Schiff base salicylic acid with a bifunctional chelating group, and uses chloromethylated macroporous phenolic resin to undergo grafting reaction to obtain macroporous chelating phenolic resin, and then reacts with Fe 2+ Chelating adsorption is produced to obtain a macroporous resin-supported Fenton-type catalyst, and the method is simple and has strong feasibility.

[0025] (1) Macroporous phenolic resin has a rich pore structure, large pore size and specific surface area, and can adsorb Fe 2+ Amino Schiff base salicylic acid has Schiff base and salicylic acid chelate groups, where the Schiff base can react with Fe 2+ Electrostatic coordination occurs, increasing Fe 2+ adsorption; salicylic acid has carboxyl and hydroxy bidentate coordination groups, which can bind Fe 2+ The prepared macroporous chelating phenolic resin has strong coordination and chelation effects, forming a stable six-membered chelate ring. The chelation and coordination work together to make the prepared macroporous chelating phenolic resin have strong coordination and chelation effects on Fe 2+ It exhibits strong adsorption behavior, providing favorable conditions for subsequently improving the degradation rate of organic pollutants.

[0026] (2) The surface structure of the macroporous resin-supported Fenton-type catalyst is loose and porous, with high adsorption capacity. It also contains chelating groups and macroporous structures, which are very effective for Fe 2+ It has good adsorption and chelation effect, which is beneficial to H 2 O 2 Molecular and organic molecular transport and surface reaction can be 2 O 2 The contact is complete, thereby generating more hydroxyl radicals (·OH), catalyzing the degradation of phenol; in addition, it overcomes the problem of narrow pH range of traditional Fenton catalysts and has a wide pH adaptability; after repeated use of macroporous resin-supported Fenton catalysts, Fe 2+ The dissolution rate is low, the reaction activity is good, and the service life is long.

[0027] (3) Fe in macroporous resin-supported Fenton-type catalysts 2+ Can catalyze H 2 O 2 Produces Fe 3+ and ·OH, the mechanism is Fe 2+ +H 2 O 2 →Fe 3+ + OH+HO - The generated OH can oxidize and degrade H 2 S and NH 3 The molecule, whose mechanism is H 2 S+·OH→H 2 O+S→SO2 +H 2 O; NH 3 +·OH→H 2 O+N 2 ; It can eliminate hydrogen sulfide and ammonia produced by industrial production and farms, and can be effectively used to treat gaseous pollutants, purify the air, and reduce harmful and odorous gases produced in industrial production. DETAILED DESCRIPTION

[0028] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] Preparation method of macroporous phenolic resin: add 240mL of distilled water, 60mL of tetraethyl orthosilicate, and 60mL of 25% polyacrylic acid into a three-necked flask, stir evenly, adjust the pH to 1 with hydrochloric acid to form a stable O / W type emulsified system, slowly add 40mL of synthesized phenolic resin prepolymer, heat to 80°C, keep warm for 0.5h, then add 6g of hexamethylenetetramine and 0.9g of resorcinol, adjust the pH of the reaction system to 1 with 6mol / L hydrochloric acid, heat to 90°C and react for 4.5h, then filter, wash with deionized water and ethanol to obtain macroporous phenolic resin.

[0030] Example 1

[0031] (1) Add 35 g of 5-aminosalicylic acid and 560 mL of methanol to a reaction flask equipped with a reflux condenser, stir evenly, add 39.2 g of p-nitrobenzaldehyde, react at 70° C. for 4 h, cool to room temperature, filter and dry to obtain nitroschiff base salicylic acid.

[0032] (2) Add 30 g of nitroschiff base salicylic acid and 950 mL of ethanol into a reaction flask, stir evenly, add 105 g of sodium dithionite, react at 55° C. for 3 h, filter, wash with deionized water, and recrystallize with ethanol to obtain amino Schiff base salicylic acid.

[0033] (3) Add 25 g of macroporous phenolic resin and 450 mL of acetone to a reaction flask equipped with a dropping funnel, stir evenly, add 15 g of zinc chloride, add 80 g of 1,4-dichloromethoxybutane dropwise, react at 60° C. for 8 h, disperse in deionized water, let stand overnight, filter, wash with ethanol and deionized water, and dry to obtain chloromethylated macroporous phenolic resin.

[0034] (4) Add 18 g of chloromethylated macroporous phenolic resin and 450 mL of N,N-dimethylformamide to a reaction flask equipped with a reflux condenser, stir evenly, add 27 g of amino Schiff base salicylic acid, react at 100 °C for 32 h, filter, wash with ethanol and acetone, and dry to obtain a macroporous chelating phenolic resin.

[0035] Example 2

[0036] (1) Add 60 g of 5-aminosalicylic acid and 600 mL of methanol to a reaction flask equipped with a reflux condenser, stir evenly, add 63 g of p-nitrobenzaldehyde, react at 80° C. for 2 h, cool to room temperature, filter and dry to obtain nitroschiff base salicylic acid.

[0037] (2) Add 50 g of nitroschiff base salicylic acid and 1250 mL of ethanol into a reaction flask, stir evenly, add 150 g of sodium dithionite, react at 60° C. for 2 h, filter, wash with deionized water, and recrystallize with ethanol to obtain amino Schiff base salicylic acid.

[0038] (3) Add 45 g of macroporous phenolic resin and 450 mL of acetone to a reaction flask equipped with a dropping funnel, stir evenly, add 13.5 g of zinc chloride, add 112.5 g of 1,4-dichloromethoxybutane dropwise, react at 65° C. for 5 h, disperse in deionized water, let stand overnight, filter, wash with ethanol and deionized water, and dry to obtain chloromethylated macroporous phenolic resin.

[0039] (4) Add 32 g of chloromethylated macroporous phenolic resin and 480 mL of N,N-dimethylformamide to a reaction flask equipped with a reflux condenser, stir evenly, add 25.6 g of amino Schiff base salicylic acid, react at 110° C. for 24 h, filter, wash with ethanol and acetone, and dry to obtain a macroporous chelating phenolic resin.

[0040] Example 3

[0041] (1) Add 25 g of 5-aminosalicylic acid and 500 mL of methanol to a reaction flask equipped with a reflux condenser, stir evenly, add 30 g of p-nitrobenzaldehyde, react at 60° C. for 5 h, cool to room temperature, filter and dry to obtain nitroschiff base salicylic acid.

[0042] (2) Add 20 g of nitroschiff base salicylic acid and 800 mL of ethanol into a reaction flask, stir evenly, add 84 g of sodium dithionite, react at 45 °C for 4 h, filter, wash with deionized water, and recrystallize with ethanol to obtain amino Schiff base salicylic acid.

[0043] (3) Add 15 g of macroporous phenolic resin and 450 mL of acetone to a reaction flask equipped with a dropping funnel, stir evenly, add 12 g of zinc chloride, dropwise add 90 g of 1,4-dichloromethoxybutane, react at 50° C. for 10 h, disperse in deionized water, stand overnight, filter, wash with ethanol and deionized water, and dry to obtain chloromethylated macroporous phenolic resin.

[0044] (4) Add 12 g of chloromethylated macroporous phenolic resin and 360 mL of N,N-dimethylformamide to a reaction flask equipped with a reflux condenser, stir evenly, add 24 g of amino Schiff base salicylic acid, react at 105 °C for 36 h, filter, wash with ethanol and acetone, and dry to obtain a macroporous chelating phenolic resin.

[0045] Comparative Example 1

[0046] Add 25 g of macroporous phenolic resin and 450 mL of acetone to a reaction flask equipped with a dropping funnel, stir evenly, add 15 g of zinc chloride, add 80 g of 1,4-dichloromethoxybutane dropwise, react at 60 ° C for 8 h, disperse in deionized water, stand overnight, filter, wash with ethanol and deionized water, and dry to obtain chloromethylated macroporous phenolic resin.

[0047] Adsorption test: prepare a ferrous sulfate solution with a mass concentration of 0.01 mol / L, and transfer 30 mL of chromium into four stoppered conical flasks, add 0.1 g of the phenolic resin prepared in the example and the comparative example respectively, oscillate at a constant temperature under nitrogen to reach adsorption equilibrium, stand for separation, and determine the Fe content in the supernatant. 2+ The equilibrium concentration of ions, then the adsorption amount = V(C 0 -C e )×56 / m, where V is the volume of the solution (mL), C 0 It is Fe 2+ Initial concentration of ions (mol / L), C e It is Fe 2+ The equilibrium concentration of the ions (mol / L), m is the mass of the phenolic resin (g), and the molar mass of the Fe atom is 56 g / mol.

[0048] Table 1 Adsorption test

[0049] Adsorption capacity (mg / g) Example 1 184.4 Example 2 133.8 Example 3 205.6 Comparative Example 1 82.1

[0050] The test results in the table above show that after amino Schiff base salicylic acid is grafted onto the surface of chloromethylated macroporous phenolic resin, the macroporous chelating phenolic resin has a strong affinity for Fe 2+ The adsorption capacity of the macroporous phenolic resin was significantly improved, and the adsorption capacity in Example 3 was 205.6 mg / g. This is because the macroporous phenolic resin has a rich pore structure, a large pore size and a large specific surface area, which can adsorb Fe 2+On the other hand, the grafted amino Schiff base salicylic acid has Schiff base and salicylic acid chelate groups, wherein the Schiff base can react with Fe 2+ Electrostatic coordination occurs, increasing Fe 2+ Salicylic acid has carboxyl and hydroxy bidentate coordination groups, which can bind Fe 2+ The prepared macroporous chelating phenolic resin has strong coordination and chelation effects, forming a stable six-membered chelate ring. The chelation and coordination work together to make the prepared macroporous chelating phenolic resin have strong coordination and chelation effects on Fe 2+ It exhibits strong adsorption behavior, providing favorable conditions for subsequently improving the degradation rate of organic pollutants.

[0051] Example 4

[0052] Add macroporous chelating phenolic resin (prepared in Example 3) and deionized water into a reaction flask, configure the macroporous chelating phenolic resin to a mass concentration of 0.5 g / L, then add 20% by mass ferrous sulfate aqueous solution, react for 16 hours at a temperature of 25° C. and a rotation speed of 120 r / min, filter, wash alternately with deionized water and ethanol, and obtain a macroporous resin-supported Fenton catalyst after drying.

[0053] Example 5

[0054] Add macroporous chelating phenolic resin (prepared in Example 3) and deionized water into a reaction flask, configure the macroporous chelating phenolic resin to a mass concentration of 1 g / L, then add a 15% mass fraction of ferrous sulfate aqueous solution, react for 12 hours at a temperature of 35° C. and a rotation speed of 150 r / min, filter, wash alternately with deionized water and ethanol, and obtain a macroporous resin-supported Fenton catalyst after drying.

[0055] Example 6

[0056] Add macroporous chelating phenolic resin (prepared in Example 3) and deionized water into a reaction flask, configure the macroporous chelating phenolic resin to a mass concentration of 1.5 g / L, then add 25% by mass ferrous sulfate aqueous solution, react at a temperature of 20° C. and a rotation speed of 100 r / min for 24 h, filter, wash alternately with deionized water and ethanol, and obtain a macroporous resin-supported Fenton catalyst after drying.

[0057] Example 7

[0058] Add macroporous chelating phenolic resin (prepared in Example 3) and deionized water into a reaction flask, configure the macroporous chelating phenolic resin to a mass concentration of 2 g / L, then add 20% by mass ferrous sulfate aqueous solution, react at a temperature of 30° C. and a rotation speed of 140 r / min for 16 h, filter, wash alternately with deionized water and ethanol, and obtain a macroporous resin-supported Fenton catalyst after drying.

[0059] Example 8

[0060] Add macroporous chelating phenolic resin (prepared in Example 3) and deionized water into a reaction flask, configure the macroporous chelating phenolic resin to a mass concentration of 2.5 g / L, then add 25% by mass ferrous sulfate aqueous solution, react at a temperature of 35° C. and a rotation speed of 140 r / min for 24 h, filter, wash alternately with deionized water and ethanol, and obtain a macroporous resin-supported Fenton catalyst after drying.

[0061] Comparative Example 2

[0062] Add a macroporous chelating phenolic resin (prepared by Comparative Example 1) and deionized water into a reaction flask, configure the macroporous chelating phenolic resin to a mass concentration of 0.5 g / L, then add a 20% mass fraction of ferrous sulfate aqueous solution, react for 16 hours at a temperature of 25° C. and a rotation speed of 120 r / min, filter, wash alternately with deionized water and ethanol, and obtain a macroporous resin-supported Fenton catalyst after drying.

[0063] Phenol degradation rate test: 50 mL of 100 mg / L phenol solution was added to the reactor, and the pH was adjusted to 3.1-10.7. Then, 2 mL of 100 mg / L H 2 O 2 and 0.1 g of macroporous resin-supported Fenton-like catalyst, stirred at 25°C for a while, and the 4-aminoantipyrine method was used. The visible spectrophotometer was used at λ max =Measure the absorbance before and after photodegradation at 510nm, and calculate the phenol degradation rate. The phenol degradation rate η = (C 0 -C t ) / C 0 × 100%, where C 0 is the initial mass concentration of phenol (mg / L), C t They are the mass concentrations of phenol (mg / L) at 20 min and 60 min of reaction respectively.

[0064] Table 2 Phenol degradation rate test

[0065]

[0066] From the test results in the above table, it can be seen that with the increase in the mass concentration of the macroporous resin-supported Fenton catalyst, the degradation rate of phenol is significantly improved. In Example 8, the degradation rate after 20 minutes of reaction is 70.2%, and the degradation rate after 60 minutes reaches 99.1%. This is because the surface structure of the macroporous resin-supported Fenton catalyst is loose and porous, with high adsorption capacity, and it contains chelating groups and macroporous structures, which are very effective for Fe 2+It has good adsorption and chelation effect, which is beneficial to H 2 O 2 Molecular and organic molecular transport and surface reaction can be 2 O 2 The contact is complete, thereby producing more ·OH, catalyzing the degradation of phenol; in addition, it overcomes the problem of narrow pH range of traditional Fenton catalysts and has a wide pH adaptability.

[0067] Catalyst repeated stability test: 50 mL of 100 mg / L phenol solution was added to the reactor, and the pH was adjusted to 3.1-10.7, followed by 2 mL of 100 mg / L H 2 O 2 and 0.1 g of macroporous resin-supported Fenton-like catalyst, stirred at 25°C for a while, and the 4-aminoantipyrine method was used. The visible spectrophotometer was used at λ max =510nm before and after photodegradation absorbance was measured to calculate the phenol degradation rate; after each experiment, centrifuge to collect the catalyst, dry it and repeat 10 times to calculate the phenol degradation rate.

[0068] Table 3 Catalyst repeated stability test

[0069]

[0070] From the test results in the table above, it can be seen that after 10 repeated catalytic degradation experiments of phenol, the catalytic performance of the macroporous resin-supported Fenton catalyst remained stable, and the degradation of phenol was not much different from the first use, indicating that after repeated use of the prepared macroporous resin-supported Fenton catalyst, Fe 2+ The dissolution rate is low, the reaction activity is good, and the service life is long.

[0071] Although the embodiments of the present invention have been described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a macroporous resin-supported Fenton-type catalyst, characterized in that: The preparation method comprises the following steps: (1) Adding a macroporous phenolic resin and acetone to a reaction flask equipped with a dropping funnel, stirring evenly, adding zinc chloride, dropping 1,4-dichloromethoxybutane, reacting at 50-65° C. for 5-10 hours, dispersing in deionized water, standing overnight, filtering, washing with ethanol and deionized water, and drying to obtain a chloromethylated macroporous phenolic resin; (2) Add chloromethylated macroporous phenolic resin and N,N-dimethylformamide to a reaction flask equipped with a reflux condenser, stir evenly, and add the structural formula The amino Schiff base salicylic acid is stirred for reaction, after the reaction is completed, filtered, washed with ethanol and acetone, and dried to obtain a macroporous chelating phenolic resin; (3) Adding a macroporous chelating phenolic resin and deionized water into a reaction flask, adding a ferrous sulfate aqueous solution with a mass fraction of 15-25%, reacting at a temperature of 20-35° C. and a rotation speed of 100-150 r / min for 12-24 hours, filtering, washing with deionized water and ethanol alternately, and drying to obtain a macroporous resin-supported Fenton-type catalyst.

2. The method for preparing a macroporous resin-supported Fenton-type catalyst according to claim 1, characterized in that: In the step (1), the ratio of the macroporous phenolic resin, acetone, zinc chloride and 1,4-dichloromethoxybutane is 1 g: (10-30) mL: (0.3-0.8) g: (2.5-6) ​​g.

3. The method for preparing a macroporous resin-supported Fenton-type catalyst according to claim 1, characterized in that: In the step (2), the ratio of chloromethylated phenolic resin, N,N-dimethylformamide, and amino Schiff base salicylic acid is 1 g: (15-30) mL: (0.8-2) g.

4. The method for preparing a macroporous resin-supported Fenton-type catalyst according to claim 1, characterized in that: In the step (2), the reaction temperature is 80-110° C. and the reaction time is 24-48 h.

5. The method for preparing a macroporous resin-supported Fenton-type catalyst according to claim 1, characterized in that: The mass concentration of the macroporous chelating phenolic resin in step (3) is 0.5-2.5 g / L.

6. The method for preparing a macroporous resin-supported Fenton-type catalyst according to claim 1, characterized in that: The preparation method of amino Schiff base salicylic acid in step (2) comprises the following steps: Step S1, adding 5-aminosalicylic acid and methanol to a reaction flask equipped with a reflux condenser, stirring evenly, adding p-nitrobenzaldehyde, reacting at 60-80° C. for 2-5 hours, cooling to room temperature, filtering and drying to obtain nitroschiff base salicylic acid; Step S2, adding nitroschiff base salicylic acid and ethanol into a reaction flask, stirring evenly, adding sodium dithionite, reacting at 45-60° C. for 2-4 hours, filtering, washing with deionized water, and recrystallizing with ethanol to obtain amino Schiff base salicylic acid.

7. The method for preparing a macroporous resin-supported Fenton-type catalyst according to claim 6, characterized in that: In the step S1, the ratio of 5-aminosalicylic acid, methanol and p-nitrobenzaldehyde is 1 g: (10-20) mL: (1.05-1.2) g.

8. The method for preparing a macroporous resin-supported Fenton-type catalyst according to claim 6, characterized in that: In the step S2, the ratio of nitro Schiff base salicylic acid, ethanol, and sodium dithionite is 1 g: (25-40) mL: (3-4.2) g.

9. Use of a macroporous resin-supported Fenton-type catalyst obtained by the preparation method according to any one of claims 1 to 8 in degrading organic pollutants.

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