Preparation method and application of macroporous resin loaded fenton-like catalyst

Abstract

The application relates to the technical field of chemical catalytic materials, and discloses a preparation method and application of a macroporous resin loaded Fenton-like catalyst, which is prepared by using 5-amino salicylic acid, p-nitrobenzaldehyde and the like as reaction raw materials, obtaining an amino Schiff base salicylic acid, reacting the amino Schiff base salicylic acid with chloromethylated macroporous phenolic resin, and chelating and adsorbing Fe 2+ to obtain the macroporous resin loaded Fenton-like catalyst, which is beneficial to H2O2 and organic molecule transmission and surface reaction, and can further generate more OH, so as to catalyze the degradation of phenol; the macroporous resin loaded Fenton-like catalyst overcomes the problem of a narrow pH range of a traditional Fenton catalyst, and has wide pH adaptability; after the macroporous resin loaded Fenton-like catalyst is used for many times, Fe 2+ The macroporous resin loaded Fenton-like catalyst has low dissolution rate and good reaction activity; the generated OH can oxidize and degrade H2S and NH3 molecules, eliminate hydrogen sulfide and ammonia gas generated in industrial production and a breeding farm, and purify air.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical catalytic materials, in particular to a preparation method and application of a macroporous resin loaded Fenton-like catalyst. BACKGROUND

[0002] With the rapid development of social economy and technology, the pollution of pollutants to the water environment is becoming more and more serious. Organic matter is one of the main pollutants causing water environmental pollution. Phenolic compounds in pollutants exist widely in petrochemical industry, textile industry, dye industry, pharmaceutical industry and other industries, resulting in a large amount of phenol and its derivatives in industrial wastewater. In addition, industrial production almost produces industrial tail gas. The untreated industrial tail gas contains harmful and odor gases such as hydrogen sulfide and ammonia. Direct discharge will cause serious air pollution problems. Fenton catalytic method as a kind of advanced oxidation technology has attracted much attention in the field of organic wastewater treatment due to its simple reaction device, mild reaction conditions and low operation cost. Homogeneous catalyst has high catalytic activity for Fenton reaction, but there are many problems in homogeneous Fenton system, such as certain danger in transportation of H2O2, slow reduction rate of Fe 3+ to Fe 2+ , narrow optimal pH value range, large amount of iron-containing sludge, etc. These shortcomings limit the application of homogeneous Fenton method.

[0003] Heterogeneous Fenton catalysis mainly utilizes Fe 2+ catalyze the decomposition of H2O2 to generate hydroxyl radicals (·OH), and ·OH can oxidize and decompose target pollutants, so that the separation and reuse of solid catalysts can be realized. In particular, porous support loaded heterogeneous Fenton catalysis can effectively combine the adsorption performance of porous support and the high reaction activity of nano catalyst particles, and is becoming an important research direction in advanced oxidation technology. Although significant progress has been made in supported Fenton catalysis, there are still some deficiencies in this technology at present, such as large catalyst dosage, large H2O2 dosage, poor catalyst stability, short service life, etc., which still limit its application in industry.

[0004] The commonly used Fenton catalyst carrier in 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 out, which is not conducive to the reuse of the material. Chelating resin is widely used for the capture and separation of metal ions due to its large adsorption capacity and the advantage of releasing chelated metal ions under appropriate conditions. However, the specific surface energy of traditional iron oxide heterogeneous Fenton catalyst is large, which is easy to agglomerate and cannot fully utilize the active sites on the surface of the catalyst, which is not conducive to the degradation of phenol. The present application aims to introduce chelating groups into macroporous phenolic resin, which can significantly improve the dispersion of Fe 2+The load efficiency of Fe and the degradation rate of organic pollutants are improved. SUMMARY

[0005] The present application aims to overcome the deficiencies in the prior art, and provides a preparation method and application of a macroporous resin loaded Fenton-like catalyst, which improves the load efficiency of Fe 2+ and the degradation rate of organic matter.

[0006] To achieve the above object, the technical scheme adopted by the present application is as follows.

[0007] A preparation method of a macroporous resin loaded Fenton-like catalyst comprises the following steps:

[0008] (1) A reaction flask equipped with a dropping funnel is added with macroporous phenolic resin and acetone, and after being stirred uniformly, zinc chloride is added, 1,4-dichloromethoxy butane is added dropwise, and the reaction is carried out at 50-65 DEG C for 5-10 h, and then the product is dispersed in deionized water, left overnight, filtered, washed with ethanol and deionized water, and dried to obtain chloromethylated macroporous phenolic resin.

[0009] (2) A reaction flask equipped with a reflux condenser is added with chloromethylated macroporous phenolic resin and N,N-dimethylformamide, and after being stirred uniformly, an amino Schiff base salicylic acid with a structural formula of is added, and the reaction is stirred, and after the reaction is completed, the product is filtered, washed with ethanol and acetone, and dried to obtain macroporous chelating phenolic resin.

[0010] (3) The reaction flask is added with macroporous chelating phenolic resin and deionized water, and a ferrous sulfate aqueous solution with a mass fraction of 15-25% is added, and the reaction is carried out at a temperature of 20-35 DEG C and a rotation speed of 100-150 r / min for 12-24 h, and then the product is filtered, washed alternately with deionized water and ethanol, and dried to obtain a macroporous resin loaded Fenton-like catalyst.

[0011] Preferably, in step (1), the ratio of macroporous phenolic resin, acetone, zinc chloride and 1,4-dichloromethoxy butane 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 DEG C, and the reaction time is 24-48 h.

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

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

[0016] Step S1, 5-amino salicylic acid and methanol are added to a reaction flask equipped with a reflux condenser, after stirring uniformly, p-nitrobenzaldehyde is added, and the reaction is carried out at 60-80 DEG C for 2-5 h, and then the reaction mixture is cooled to room temperature, filtered and dried to obtain the nitro Schiff base salicylic acid.

[0017]

[0018] Step S2, the nitro Schiff base salicylic acid and ethanol are added to a reaction flask, after stirring uniformly, sodium dithionite is added, and the reaction is carried out at 45-60 DEG C for 2-4 h, and then filtered, washed with deionized water, and recrystallized with ethanol to obtain the amino Schiff base salicylic acid.

[0019]

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

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

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

[0023] By adopting the technical scheme, the application has the following beneficial effects:

[0024] The application uses 5-amino salicylic acid, p-nitrobenzaldehyde and sodium dithionite as reaction raw materials to prepare the amino Schiff base salicylic acid with a double functional chelating group, grafts the chloromethylated macroporous phenolic resin with the amino Schiff base salicylic acid to obtain the macroporous chelating phenolic resin, and then loads Fe 2+ The chelating adsorption is generated to obtain the macroporous resin loaded Fenton-like catalyst, and the method is simple and has strong implementability.

[0025] (1) The macroporous phenolic resin has rich pore structure, large pore size and specific surface area, and can adsorb Fe 2+ ; the amino Schiff base salicylic acid has Schiff base and salicylic acid chelating groups, the Schiff base can be electrostatically coordinated with Fe 2+ to increase the adsorption of Fe 2+ ; the salicylic acid has carboxyl and hydroxyl bidentate coordination groups, and can be coordinated with Fe 2+Strong coordination chelation effect is generated to form a stable six-membered chelate ring, and chelation and coordination work together to make the prepared macroporous chelating phenolic resin have strong adsorption and chelation effects on Fe 2+ Strong adsorption behavior is exhibited, which provides favorable conditions for subsequent improvement of the degradation rate of organic pollutants.

[0026] (2) The macroporous resin loaded Fenton-like catalyst has loose surface structure and high adsorption capacity, and contains chelating groups and macroporous structures, so that the macroporous resin loaded Fenton-like catalyst has strong adsorption and chelation effects on Fe 2+ , and is beneficial to the transmission and surface reaction of H2O2 molecules and organic molecules, can be in full contact with H2O2, and then more hydroxyl radicals (·OH) are generated to catalyze the degradation of phenol; in addition, the problem of narrow pH range of traditional Fenton catalysts is overcome, and the macroporous resin loaded Fenton-like catalyst has wide pH adaptability; after the macroporous resin loaded Fenton-like catalyst is used for many times, Fe 2+ has low dissolution rate, good reaction activity, and long service life.

[0027] (3) Fe 2+ in the macroporous resin loaded Fenton-like catalyst can catalyze H2O2 to generate Fe 3+ and ·OH, and the mechanism is as follows: Fe 2+ + H2O2→ Fe 3+ + ·OH + HO - The generated ·OH can oxidize and degrade H2S and NH3 molecules, and the mechanism is as follows: H2S + ·OH→ H2O + S→ SO2 + H2O; NH3 + ·OH→ H2O + N2; and then hydrogen sulfide and ammonia generated in industrial production and breeding farms can be eliminated, which can be effectively used for the treatment of gaseous pollutants, air purification, and reduction of harmful and odor gases generated in industrial production. DETAILED DESCRIPTION

[0028] The technical solutions of the present application will be described below. Obviously, the described embodiments are only some of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0029] The preparation method of the macroporous phenolic resin is as follows: 240 mL of distilled water, 60 mL of tetraethyl orthosilicate, and 60 mL of 25% polyacrylic acid are added into a three-necked flask, and stirred uniformly, and then the pH is adjusted to 1 by hydrochloric acid to form a stable O / W type emulsion system; 40 mL of the synthesized phenolic resin prepolymer is slowly added, heated to 80℃, and kept for 0.5 h; then 6 g of hexamethylenetetramine and 0.9 g of resorcinol are added, and the pH of the reaction system is adjusted to 1 by 6 mol / L hydrochloric acid; the temperature is increased to 90℃, and reacted for 4.5 h; after filtration, washing with deionized water and ethanol, the macroporous phenolic resin is obtained.

[0030] Example 1

[0031] (1) Into a reaction flask equipped with a reflux condenser, 35 g of 5- aminosalicylic acid and 560 mL of methanol were added, stirred uniformly, and then 39.2 g of p-nitrobenzaldehyde was added, and reacted at 70°C for 4 h, cooled to room temperature, filtered and dried to obtain nitro Schiff base salicylic acid.

[0032] (2) Into a reaction flask, 30 g of nitro Schiff base salicylic acid and 950 mL of ethanol were added, stirred uniformly, and then 105 g of sodium hydrosulfite was added, and reacted at 55°C for 3 h, filtered, washed with deionized water, recrystallized with ethanol to obtain amino Schiff base salicylic acid.

[0033] (3) Into a reaction flask equipped with a dropping funnel, 25 g of macroporous phenolic resin and 450 mL of acetone were added, stirred uniformly, and then 15 g of zinc chloride was added, and 80 g of 1,4-dichloromethoxybutane was added dropwise, and reacted at 60°C for 8 h, dispersed in deionized water, left overnight, filtered, washed with ethanol and deionized water, and dried to obtain chloromethylated macroporous phenolic resin.

[0034] (4) Into a reaction flask equipped with a reflux condenser, 18 g of chloromethylated macroporous phenolic resin and 450 mL of N,N-dimethylformamide were added, stirred uniformly, and then 27 g of amino Schiff base salicylic acid was added, and reacted at 100°C for 32 h, filtered, washed with ethanol and acetone, and dried to obtain macroporous chelating phenolic resin.

[0035] Example 2

[0036] (1) Into a reaction flask equipped with a reflux condenser, 60 g of 5- aminosalicylic acid and 600 mL of methanol were added, stirred uniformly, and then 63 g of p-nitrobenzaldehyde was added, and reacted at 80°C for 2 h, cooled to room temperature, filtered and dried to obtain nitro Schiff base salicylic acid.

[0037] (2) Into a reaction flask, 50 g of nitro Schiff base salicylic acid and 1250 mL of ethanol were added, stirred uniformly, and then 150 g of sodium hydrosulfite was added, and reacted at 60°C for 2 h, filtered, washed with deionized water, recrystallized with ethanol to obtain amino Schiff base salicylic acid.

[0038] (3) Into a reaction flask equipped with a dropping funnel, 45 g of macroporous phenolic resin and 450 mL of acetone were added, stirred uniformly, and then 13.5 g of zinc chloride was added, and 112.5 g of 1,4-dichloromethoxybutane was added dropwise, and reacted at 65°C for 5 h, dispersed in deionized water, left overnight, filtered, washed with ethanol and deionized water, and dried to obtain chloromethylated macroporous phenolic resin.

[0039] (4) Into a reaction flask equipped with a reflux condenser, 32 g of chloromethylated macroporous phenol-formaldehyde resin and 480 mL of N,N-dimethylformamide were added, and after stirring, 25.6 g of amino Schiff base salicylic acid was added, and the mixture was reacted at 110°C for 24 hours. After filtration, ethanol and acetone were added for washing, and after drying, macroporous chelating phenol-formaldehyde resin was obtained.

[0040] Example 3

[0041] (1) Into a reaction flask equipped with a reflux condenser, 25 g of 5-amino salicylic acid and 500 mL of methanol were added, and after stirring, 30 g of p-nitrobenzaldehyde was added, and the mixture was reacted at 60°C for 5 hours. After cooling to room temperature, filtration and drying, nitro Schiff base salicylic acid was obtained.

[0042] (2) Into a reaction flask, 20 g of nitro Schiff base salicylic acid and 800 mL of ethanol were added, and after stirring, 84 g of sodium hydrosulfite was added, and the mixture was reacted at 45°C for 4 hours. After filtration, deionized water was added for washing, and after recrystallization with ethanol, amino Schiff base salicylic acid was obtained.

[0043] (3) Into a reaction flask equipped with a dropping funnel, 15 g of macroporous phenol-formaldehyde resin and 450 mL of acetone were added, and after stirring, 12 g of zinc chloride was added. Then, 90 g of 1,4-dichloromethoxybutane was added dropwise, and the mixture was reacted at 50°C for 10 hours. After dispersion in deionized water and standing overnight, filtration, ethanol and deionized water were added for washing, and after drying, chloromethylated macroporous phenol-formaldehyde resin was obtained.

[0044] (4) Into a reaction flask equipped with a reflux condenser, 12 g of chloromethylated macroporous phenol-formaldehyde resin and 360 mL of N,N-dimethylformamide were added, and after stirring, 24 g of amino Schiff base salicylic acid was added, and the mixture was reacted at 105°C for 36 hours. After filtration, ethanol and acetone were added for washing, and after drying, macroporous chelating phenol-formaldehyde resin was obtained.

[0045] Comparative Example 1

[0046] Into a reaction flask equipped with a dropping funnel, 25 g of macroporous phenol-formaldehyde resin and 450 mL of acetone were added, and after stirring, 15 g of zinc chloride was added. Then, 80 g of 1,4-dichloromethoxybutane was added dropwise, and the mixture was reacted at 60°C for 8 hours. After dispersion in deionized water and standing overnight, filtration, ethanol and deionized water were added for washing, and after drying, chloromethylated macroporous phenol-formaldehyde resin was obtained.

[0047] Adsorption capacity test: A 0.01 mol / L ferrous sulfate solution was prepared, and 30 mL of chromium was taken and placed in four conical flasks with stoppers. 0.1 g of the phenol-formaldehyde resin prepared in the examples and comparative examples was added, respectively, and constant temperature oscillation was performed under nitrogen. After reaching adsorption equilibrium, separation was performed, and the equilibrium concentration of Fe2+ ions in the supernatant was measured. Then, the adsorption capacity = V(C0-C 2+ e ​) x 56 / m, wherein V is the volume of the solution (mL), Co is the initial concentration of Fe 2+ ions (mol / L), C e is the equilibrium concentration of Fe 2+ ions (mol / L), m is the mass of the phenolic resin (g), and the molar mass of Fe atom is 56 g / mol.

[0048] Table 1 adsorption capacity test

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

[0050] From the test results in the above table, after chloromethylation of the macroporous phenolic resin and surface grafting of the amino Schiff base salicylic acid, the adsorption capacity of the macroporous chelating phenolic resin for Fe 2+ is obviously improved, and the adsorption capacity in Example 3 is 205.6 mg / g. This is because, on the one hand, the macroporous phenolic resin has a rich pore structure, a large pore size and a large specific surface area, and can adsorb Fe 2+ ; on the other hand, the grafted amino Schiff base salicylic acid has Schiff base and salicylic acid chelating groups, wherein the Schiff base can have electrostatic coordination with Fe 2+ to increase the adsorption of Fe 2+ , and the salicylic acid has bidentate coordination groups of carboxyl and hydroxyl groups, which can produce strong coordination chelation with Fe 2+ to form a stable six-membered chelate ring, and chelation and coordination work together to make the prepared macroporous chelating phenolic resin exhibit strong adsorption behavior for Fe 2+ , which provides favorable conditions for subsequent improvement of the degradation rate of organic pollutants.

[0051] Example 4

[0052] The macroporous chelating phenolic resin (prepared in Example 3) and deionized water were added to a reaction flask, and the macroporous chelating phenolic resin was configured to have a mass concentration of 0.5 g / L. Then, a 20% ferrous sulfate aqueous solution was added, and the reaction was carried out at a temperature of 25°C and a rotation speed of 120 r / min for 16 h. After filtration, the product was washed with deionized water and ethanol alternately, and dried to obtain a macroporous resin loaded Fenton-like catalyst.

[0053] Example 5

[0054] The macroporous chelating phenolic resin (prepared in Example 3) and deionized water were added to a reaction flask, and the macroporous chelating phenolic resin was configured to have a mass concentration of 1 g / L. Then, a 15% ferrous sulfate aqueous solution was added, and the reaction was carried out at a temperature of 35°C and a rotation speed of 150 r / min for 12 h. After filtration, the product was washed with deionized water and ethanol alternately, and dried to obtain a macroporous resin loaded Fenton-like catalyst.

[0055] Example 6

[0056] A macroporous chelating phenolic resin (prepared in Example 3) and deionized water were added to a reaction flask, the macroporous chelating phenolic resin was configured to have a mass concentration of 1.5 g / L, then a 25% mass fraction ferrous sulfate aqueous solution was added, the reaction was carried out at a temperature of 20°C and a rotation speed of 100 r / min for 24 h, filtration was performed, and deionized water and ethanol were alternately washed, and after drying, a macroporous resin loaded Fenton-like catalyst was obtained.

[0057] Example 7

[0058] A macroporous chelating phenolic resin (prepared in Example 3) and deionized water were added to a reaction flask, the macroporous chelating phenolic resin was configured to have a mass concentration of 2 g / L, then a 20% mass fraction ferrous sulfate aqueous solution was added, the reaction was carried out at a temperature of 30°C and a rotation speed of 140 r / min for 16 h, filtration was performed, and deionized water and ethanol were alternately washed, and after drying, a macroporous resin loaded Fenton-like catalyst was obtained.

[0059] Example 8

[0060] A macroporous chelating phenolic resin (prepared in Example 3) and deionized water were added to a reaction flask, the macroporous chelating phenolic resin was configured to have a mass concentration of 2.5 g / L, then a 25% mass fraction ferrous sulfate aqueous solution was added, the reaction was carried out at a temperature of 35°C and a rotation speed of 140 r / min for 24 h, filtration was performed, and deionized water and ethanol were alternately washed, and after drying, a macroporous resin loaded Fenton-like catalyst was obtained.

[0061] Comparative Example 2

[0062] A macroporous chelating phenolic resin (prepared in Comparative Example 1) and deionized water were added to a reaction flask, the macroporous chelating phenolic resin was configured to have a mass concentration of 0.5 g / L, then a 20% mass fraction ferrous sulfate aqueous solution was added, the reaction was carried out at a temperature of 25°C and a rotation speed of 120 r / min for 16 h, filtration was performed, and deionized water and ethanol were alternately washed, and after drying, a macroporous resin loaded Fenton-like catalyst was obtained.

[0063] Phenol degradation rate test: 50 mL of a phenol solution with a concentration of 100 mg / L was added to a reactor, the pH was adjusted to 3.1-10.7, then 2 mL of a H2O2 solution with a mass concentration of 100 mg / L and 0.1 g of a macroporous resin loaded Fenton-like catalyst were added, and the mixture was stirred at a constant temperature of 25°C for a certain period of time, the absorbance before and after photodegradation was measured at λ max = 510 nm using a 4-aminoantipyrine method and a visible spectrophotometer, and the phenol degradation rate was calculated, the phenol degradation rate η = (C0-C t) / C0 x 100%, wherein C0 is the initial mass concentration of phenol (mg / L), C t phenol mass concentration (mg / L) at 20 min and 60 min of reaction, respectively.

[0064] Table 2 Phenol degradation rate test

[0065]

[0066] From the above test results, it can be seen that as the mass concentration of the macroporous resin loaded Fenton-like catalyst increases, the degradation rate of phenol is significantly improved. In Example 8, the degradation rate after 20 min of reaction is 70.2%, and the degradation rate after 60 min of reaction reaches 99.1%. This is because the macroporous resin loaded Fenton-like catalyst has a loose porous surface structure, a high adsorption capacity, and contains chelating groups and macroporous structures. It has a good adsorption and chelation effect, is beneficial to the transmission and surface reaction of H2O2 molecules and organic molecules, can be in full contact with H2O2, and can generate more ·OH, thereby 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. 2+

[0067] Catalyst repeated stability test: 50 mL of phenol solution with a concentration of 100 mg / L was added to the reactor, the pH was adjusted to 3.1-10.7, then 2 mL of H2O2 with a mass concentration of 100 mg / L and 0.1 g of macroporous resin loaded Fenton-like catalyst were added, and the mixture was stirred at 25°C for a certain period of time. The 4-aminoantipyrine method was used, and the absorbance before and after photodegradation was measured at λ max = 510 nm using a visible spectrophotometer. The phenol degradation rate was calculated. After each experiment, the catalyst was collected by centrifugation and dried for reuse 10 times. The phenol degradation rate was calculated.

[0068] Table 3 Catalyst repeated stability test

[0069]

[0070] From the above test results, it can be seen that after 10 times of repeated catalytic degradation of phenol experiments, the catalytic performance of the macroporous resin loaded Fenton-like catalyst remains stable, and the degradation of phenol is not much different from the first use. This indicates that the prepared macroporous resin loaded Fenton-like catalyst has a low Fe 2+ dissolution rate, good reaction activity, and a long service life.

[0071] ​While embodiments of the application have been described, it will be apparent to those skilled in the art that many more modifications, substitutions, replacements and alterations can be made hereto without departing from the spirit and scope of the present application, which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a macroporous resin supported Fenton-like catalyst, characterized in that, The preparation method comprises the following steps: (1) adding macroporous phenolic resin and acetone into a reaction flask provided with a dropping funnel, stirring uniformly, then adding zinc chloride, and dropping 1,4-dichloromethoxy butane, and reacting at 50-65 DEG C for 5-10 h, dispersing in deionized water, standing overnight, filtering, washing with ethanol and deionized water, and drying to obtain chloromethylated macroporous phenolic resin; (2) adding chloromethylated macroporous phenolic resin and N,N-dimethylformamide into a reaction flask equipped with a reflux condenser, stirring uniformly, then adding an amino Schiff base salicylic acid with the structural formula , stirring and reacting, filtering after the reaction is completed, washing with ethanol and acetone, and drying to obtain macroporous chelating phenolic resin; (3) adding macroporous chelating phenolic resin and deionized water into a reaction flask, adding 15-25% ferrous sulfate aqueous solution, and reacting at a temperature of 20-35 DEG C and a rotating speed of 100-150 r / min for 12-24 h, filtering, washing with deionized water and ethanol alternately, and drying to obtain macroporous resin loaded Fenton-like catalyst.

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

3. The method for preparing macroporous resin supported Fenton-like 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 1g:(15-30)mL:(0.8-2)g. 4.The method for preparing macroporous resin supported Fenton-like catalyst according to claim 1, characterized in that, In the step (2), the reaction temperature is 80-110 DEG C, and the reaction time is 24-48 h. 5.The method for preparing macroporous resin supported Fenton-like catalyst according to claim 1, characterized in that, In the step (3), the mass concentration of macroporous chelating phenolic resin is 0.5-2.5 g / L. 6.The method for preparing macroporous resin supported Fenton-like catalyst according to claim 1, characterized in that, The preparation method of the amino Schiff base salicylic acid in the step (2) comprises the following steps: Step S1, adding 5-amino salicylic acid and methanol into a reaction flask provided with a reflux condenser, stirring uniformly, then adding p-nitrobenzaldehyde, and reacting at 60-80 DEG C for 2-5 h, cooling to room temperature, filtering and drying to obtain nitro Schiff base salicylic acid; Step S2, adding nitro Schiff base salicylic acid and ethanol into a reaction flask, stirring uniformly, then adding sodium dithionite, and reacting at 45-60 DEG C for 2-4 h, filtering, washing with deionized water, recrystallizing with ethanol to obtain amino Schiff base salicylic acid.

7. The method for preparing macroporous resin supported Fenton-like catalyst according to claim 6, characterized in that, In the step S1, the ratio of 5-amino salicylic acid, methanol and p-nitrobenzaldehyde is 1g:(10-20)mL:(1.05-1.2)g. 8.The method for preparing a macroporous resin supported Fenton-like 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 1g:(25-40)mL:(3-4.2)g.

9. Application of the macroporous resin loaded Fenton-like catalyst obtained by the preparation method of any one of claims 1-8 in degradation of organic pollutants.

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