Method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low-molecular-weight humic acid

Abstract

The invention provides a method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low-molecular-weight humic acid, which comprises the following steps: carboxyl, phenolic hydroxyl, Kunyl and the like in the low-molecular-weight humic acid can dissolve part of Fe in the iron-manganese intercalated montmorillonite and form a Fe (II) / Fe (III)-organic matter complex; the complexes can shuttle electrons to O2 from Fe (II) in the interlayer structure of the ferro-manganese intercalated montmorillonite so as to promote the generation of active oxygen species; in addition, a Kunyl in the low-molecular-weight humic substance can also serve as a bridge-mediated electron to shuttle Fe (II) in an interlayer structure of the iron-manganese intercalated montmorillonite to O2, so that more active oxygen species are generated; therefore, the purpose of degrading pollutants in the water body is achieved. The removal rate of antibiotics in water reaches 90-98%, the removal rate of estrogens reaches 92-99%, and the removal rate of endocrine disruptors reaches 95-99%.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage treatment, and in particular relates to a method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low-molecular-weight humic acid. Background Art

[0002] In recent years, due to frequent human activities and rapid development of industry and agriculture, a large number of emerging pollutants have appeared in surface water, such as endocrine disruptors, antibiotics and estrogens. Reactive oxygen species are highly active substances generated by oxygen in water during electron transfer, including hydroxyl radicals (•OH), singlet oxygen ( 1 O2), and triplet free radicals ( 3 CDOM * ) etc. Active species have the characteristics of high redox potential and strong activity. They can directly attack pollutants in water bodies, oxidize and degrade pollutants into low-toxic or non-toxic small molecules, and finally completely degrade them into carbon dioxide and water. It is generally believed that when the widely existing reduced iron or organic matter in water bodies encounters oxygen, electron transfer and energy transition will occur, thereby generating reactive oxygen species. Therefore, finding iron minerals and organic matter with high reactive oxygen production potential, supplemented by appropriate reduction-oxidation processes, is the key to efficiently generating reactive oxygen species and degrading water pollutants.

[0003] Montmorillonite is a layered mineral composed of extremely fine-grained hydrous aluminum silicate. It is widely found in nature and can be used in fields such as pollutant adsorption and catalytic degradation. However, the interlayer spacing of traditional montmorillonite is limited (about 1.0~1.5 nm), which is not enough to achieve rapid electron transitions and energy transfer. Humic acid is an organic substance widely present in lake waters. It contains active groups such as carboxyl, phenolic hydroxyl and kunyl. The oxidation process of reduced humic acid is an important source of reactive oxygen species in water bodies. Compared with high molecular weight (1 kDa~0.45μm) humic acid, low molecular weight (<1 kDa) humic acid contains higher aromaticity or more active groups, and has a higher potential to produce reactive oxygen species. However, whether it is iron-manganese intercalated montmorillonite or low molecular weight humic acid, the potential for the generation of reactive oxygen species in the reduction-oxidation process is limited in a single system. Therefore, developing a method for efficiently generating reactive oxygen species and applying it to the degradation of emerging pollutants in water bodies can maximize the ecological, environmental, economic and social benefits. It is of great strategic significance for the purification and treatment of polluted lake water bodies, polluted river water bodies, urban sewage plant effluent, and aquaculture wastewater. Summary of the invention

[0004] In order to solve the above defects and shortcomings in the prior art, the present invention provides a method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid.

[0005] In order to solve the above technical problems, the present invention provides a method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid, comprising the following steps: The iron-manganese intercalated montmorillonite and the low molecular weight humic acid solution are mixed to form a mixed treatment liquid, which is slowly added into a sealed degradation tank, and the air in the degradation tank is discharged to form a first reaction environment, and the reaction is carried out for 36-60 hours under stirring conditions; air is filled into the degradation tank to form a second reaction environment, and the reaction is carried out for 3-6 hours under stirring conditions; then the polluted water is added to degrade the pollutants in the water; wherein the solid-liquid ratio of the iron-manganese intercalated montmorillonite and the low molecular weight humic acid solution in the mixed treatment liquid is 1g:500~1000mL; the first reaction environment is that the oxygen content in the air is less than 4%, and the dissolved oxygen in the water is less than 0.2 mg / L; the second reaction environment is that the oxygen content in the air is greater than 15%, and the dissolved oxygen in the water is greater than 15 mg / L.

[0006] Among them, the preparation process of iron-manganese intercalated montmorillonite is as follows: S1: Add montmorillonite to deionized water and stir in a water bath at 25-40℃ for 2h to allow it to fully swell and form a montmorillonite suspension; S2 Take 0.40~0.60M FeCl3·6H2O solution and 0.35~0.60M MnCl2 solution and slowly add them to the montmorillonite suspension, stir at 300-500rpm for 1.5~2.5h, and then heat for 50~70 o C for 12-24 hours; centrifuge, dry and grind to obtain Fe-Mn intercalated montmorillonite.

[0007] Furthermore, the volume ratio of the FeCl3·6H2O solution to the montmorillonite suspension is 0.50-0.60:1; the volume ratio of the MnCl2 solution to the montmorillonite suspension is 0.20-0.30:1.

[0008] Furthermore, the mass ratio of deionized water / montmorillonite is 45~65:1.

[0009] Among them, the preparation process of low molecular weight humic acid is as follows: Weigh humic acid powder, dissolve it in deionized water, the solid-liquid ratio of humic acid powder to deionized water is 1g:5~20mL, stir for 1-2h at room temperature pH value of 7~10, and obtain humic acid solution after 0.45μm micropore filtration; The humic acid solution is filtered tangentially, the cutoff pore size of the tangential ultrafiltration membrane is 1.0~2.0 kDa, the pressure is 0.05~0.2Mpa, and the solution that passes through the ultrafiltration membrane is collected, which is the low molecular weight humic acid.

[0010] Furthermore, sources of humic acid powder include soil, water, and coal.

[0011] Furthermore, an exhaust valve is provided on the top of the degradation pool, a filter membrane is laid on the inner surface of the bottom, and a water outlet is provided in the middle of the bottom; the degradation pool adjusts the environment inside the degradation pool through the exhaust valve.

[0012] Furthermore, the degradation tank is made of stainless steel or polytetrafluoroethylene, and the filter membrane is made of acetate fiber or glass fiber.

[0013] Furthermore, the volume ratio of the mixed treatment liquid to the water to be treated is 1:300~600.

[0014] The beneficial technical effects achieved by the present invention are as follows: the present invention provides a method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid, wherein the carboxyl group, phenolic hydroxyl group and kunyl group in the low molecular weight humic acid can dissolve part of the Fe in the iron-manganese intercalated montmorillonite and form Fe(Ⅱ) / Fe(Ⅲ)-organic matter complexes, which can shuttle electrons from Fe(Ⅱ) in the interlayer structure of the iron-manganese intercalated montmorillonite to O2 to promote the generation of active oxygen species; in addition, the kunyl group in the low molecular weight humic substance can also act as a bridge to mediate electrons to shuttle Fe(Ⅱ) in the interlayer structure of the iron-manganese intercalated montmorillonite to O2 to generate more active oxygen species; thereby achieving the purpose of degrading pollutants in water bodies. Montmorillonite and humic acid are both taken from the natural environment and are non-toxic and harmless; the preparation methods of iron-manganese montmorillonite and low-molecular-weight humic acid are simple and low-cost; compared with traditional water pollutant degradation methods, the operating conditions of this application are mild, the equipment requirements are low, the safety factor is high, and the removal rate of antibiotics in water bodies reaches 90-98%, the removal rate of estrogen reaches 92-99%, and the removal rate of endocrine disruptors reaches 95-99%. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 SEM image of the iron-manganese intercalated montmorillonite of the present invention; Figure 2 A schematic diagram of the degradation pool structure of the present invention; Figure 3 Effects of different sewage treatment materials on reactive oxygen species production and estrogen degradation efficiency in one embodiment of the present invention; Figure 4 Another embodiment of the present invention is the effect of different sewage treatment materials on the production of reactive oxygen species and the degradation efficiency of estrogen; Figure 5 Effects of different sewage treatment materials on the production of reactive oxygen species and the degradation efficiency of endocrine disruptors in one embodiment of the present invention; Figure 6 Another embodiment of the present invention is the effect of different sewage treatment materials on the production of reactive oxygen species and the degradation efficiency of estrogen; Figure 7In one embodiment of the present invention, different sewage treatment materials affect the production of active oxygen species and the degradation efficiency of antibiotics. DETAILED DESCRIPTION

[0016] The present invention will be further described below in conjunction with specific examples. The following examples are only used to more clearly illustrate the technical solutions of the present invention, and are not intended to limit the scope of protection of the present invention.

[0017] The present invention is further described below in conjunction with the accompanying drawings and embodiments. Example 1

[0018] Preparation of iron-manganese intercalated montmorillonite: 10 g of montmorillonite was added to 450 mL of deionized water, stirred in a water bath at 35 °C for 2 h, then 250 mL of 0.50 M FeCl3·6H2O solution and 135 mL of 0.45 M MnCl2 solution were added, stirred vigorously for 2.0 h and aged at 60 °C for 24 h to obtain iron-manganese intercalated montmorillonite. Example 2

[0019] Preparation of iron-manganese intercalated montmorillonite: 10 g of montmorillonite was added to 500 mL of deionized water, stirred in a water bath at 45 °C for 2 h, then 250 mL of 0.60 M FeCl3·6H2O solution and 100 mL of 0.35 M MnCl2 solution were added, stirred vigorously for 2.5 h and aged at 70 °C for 12 h to obtain iron-manganese intercalated montmorillonite. Example 3

[0020] Preparation of iron-manganese intercalated montmorillonite: 10 g of montmorillonite was added to 650 mL of deionized water, stirred in a water bath at 25 °C for 2 h, then 390 mL of 0.40 M FeCl3·6H2O solution and 160 mL of 0.6 M MnCl2 solution were added, stirred vigorously for 1.5 h and aged at 50 °C for 20 h to obtain iron-manganese intercalated montmorillonite.

[0021] The iron-manganese intercalated montmorillonite prepared in Example 1 was subjected to scanning electron microscopy, and the results were as follows: Figure 1 As shown, A is the SEM picture of montmorillonite, and B is the iron-manganese intercalated montmorillonite. It can be clearly seen from the figure that after the montmorillonite is treated, the iron and manganese metal ions are inserted into the interlayer of the montmorillonite, thereby increasing the interlayer spacing, thereby improving the electronic transition and energy transfer efficiency of the montmorillonite. Example 4

[0022] Humic acid from soil was selected and dissolved in deionized water at a solid-liquid ratio of 1:10 to obtain a humic acid solution with a pH value of 8. Tangential ultrafiltration was used with a tangential ultrafiltration membrane cutoff of 1.0 kDa and an ultrafiltration pressure of 0.05 MPa to obtain low molecular weight humic acid; the ultrafiltration membrane material was modified polyethersulfone (purchased from Millipore). Example 5

[0023] Humic acid from water source was selected and dissolved in deionized water at a solid-liquid ratio of 1:5 to obtain a humic acid solution with a pH value of 7. A tangential ultrafiltration method was used with a tangential ultrafiltration membrane cutoff diameter of 2.0 kDa and an ultrafiltration pressure of 0.2 Mpa to obtain low molecular weight humic acid. Example 6

[0024] Humic acid from coal was selected and dissolved in deionized water at a solid-liquid ratio of 1:20 to obtain a humic acid solution with a pH value of 10. A tangential ultrafiltration method was used with a tangential ultrafiltration membrane cutoff diameter of 1 kDa and an ultrafiltration pressure of 0.05 MPa to obtain low molecular weight humic acid.

[0025] Test Example 1 As one of the test examples, the iron-manganese intercalated montmorillonite prepared in Example 1 and the low molecular weight humic acid obtained in Example 4 were mixed to form a mixed treatment liquid to treat the estrogen-contaminated water in the Longchi Lake pollution area in Nanjing City for illustration.

[0026] The mixed treatment solution was slowly added into the sealed degradation tank, and at the same time, the quencher 2,4,6-trimethylphenol (TMP, 3 DOM * probe), furfuryl alcohol (FFA, 1 O2 probe), and terephthalic acid (TPA, ·OH probe), the final concentration of TMP was 0.75~1.25 mM, the final concentration of furfuryl alcohol was 0.75~1.25 mM, and the final concentration of TPA was 1.75~2.25 mM; samples were collected regularly during the first reaction environment and the second reaction environment, and the production of active oxygen species was determined by high performance liquid chromatography. The results are shown in Figure 3 The degradation tank can be made of stainless steel or polytetrafluoroethylene. As the best solution, polytetrafluoroethylene can be selected. An exhaust valve is provided at the top of the degradation tank, a water outlet is provided at the bottom, and a filter membrane is laid on the inner surface of the bottom. The filter membrane is made of acetate fiber or glass fiber. As the preferred solution, acetate fiber is used. The schematic diagram of the degradation tank structure is shown in Figure 2 shown.

[0027] The exhaust valve set at the top is used to adjust the environment in the degradation tank. The first reaction environment keeps the oxygen content in the air in the degradation tank less than 4%, and the dissolved oxygen in the water less than 0.2 mg / L; the second reaction environment keeps the oxygen content in the air in the degradation tank greater than 15%, and the dissolved oxygen in the water greater than 15 mg / L.

[0028] The solid-liquid ratio of iron-manganese intercalated montmorillonite and low molecular weight humic acid in the mixed treatment liquid is 1:500; the iron-manganese intercalated montmorillonite and low molecular weight humic acid react for 48 hours under the stirring conditions of the first reaction environment, and react for 4.5 hours under the stirring conditions of the second reaction environment; then add polluted water to degrade the pollutants in the water, and the volume ratio of the mixed treatment liquid to the polluted water is 1:300. Single iron-manganese intercalated montmorillonite and single low molecular weight humic acid are used as the control group. Calculate the degradation efficiency of water pollutants: Degradation efficiency of water pollutants = (C0-C 降 ) / C0 Test results such as Figure 3 As shown in Figures 3A, 3B and 3C, it can be seen that as the reaction time increases, the production of active oxygen species produced by the mixed treatment liquid increases. In the single low molecular weight humic acid system, 3 DOM * , 1 The O2 and ·OH production were 302.35, 292.55 and 54.34 μmol / L, respectively. In the single Fe-Mn intercalated montmorillonite system, 3 DOM * , 1 The production of O2 and ·OH were 583.40, 574.65 and 117.32 μmol / L, respectively. 3 DOM * , 1 The production of O2 and ·OH were 1193.54, 1156.45 and 240.67 μmol / L, respectively. It can be seen that the production of active oxygen species in the mixed system was significantly increased. Figure 3 As can be seen from the 3D, the degradation efficiencies of the single low molecular weight humic acid system and the single iron-manganese intercalated montmorillonite on estrogen in the inner lake water are 25.64% and 33.21% respectively, while the degradation efficiency of the mixed system of the two on estrogen in the inner lake water is as high as 97.23%, achieving enhanced degradation of pollutants in the inner lake water.

[0029] Test Example 2 As one of the test examples, the iron-manganese intercalated montmorillonite prepared in Example 1 and the low molecular weight humic acid obtained in Example 4 were mixed to form a mixed treatment liquid to treat the estrogen-contaminated water in the Pearl River in Nanjing for illustration.

[0030] The difference from Experimental Example 1 is that the solid-liquid ratio of the iron-manganese intercalated montmorillonite and the low molecular weight humic acid in the mixed treatment liquid is 1:700; the iron-manganese intercalated montmorillonite and the low molecular weight humic acid are reacted for 40 hours under the stirring conditions of the first reaction environment, and for 4 hours under the stirring conditions of the second reaction environment; then the polluted water is added to degrade the pollutants in the water, and the volume ratio of the mixed treatment liquid to the polluted water is 1:400. The results are as follows Figure 4 shown.

[0031] from Figure 4 It can be seen from Figures 4A, 4B and 4C that as the reaction time increases, the production of active oxygen species produced by the mixed treatment liquid increases. In the single low molecular weight humic acid system, 3 DOM * , 1 The production of O2 and ·OH were 285.51, 276.34 and 50.15 μmol / L, respectively. 3 DOM * , 1 The production of O2 and ·OH were 556.50, 560.15 and 104.28 μmol / L respectively, while in the mixed liquid system, 3 DOM * , 1 The production of O2 and ·OH were 1121.42, 1089.02 and 220.00 μmol / L respectively, and the production of active oxygen species in the mixed system was significantly increased. Figure 4 It can be seen from Figure 4D that the degradation efficiency of estrogen in river water by a single low molecular weight humic acid system and a single iron-manganese intercalated montmorillonite is 24.17% and 31.22% respectively, while the degradation efficiency of the mixed system of the two for estrogen in inner lake water is as high as 98.08%, achieving enhanced degradation of pollutants in river water.

[0032] Test Example 3 As one of the test examples, the iron-manganese intercalated montmorillonite prepared in Example 1 and the low molecular weight humic acid obtained in Example 4 were mixed to form a mixed treatment liquid to treat the endocrine disrupting substances polluted water at the estuary of Nanfei River.

[0033] The difference from Experimental Example 1 is that the solid-liquid ratio of the iron-manganese intercalated montmorillonite and the low molecular weight humic acid in the mixed treatment liquid is 1:600; the iron-manganese intercalated montmorillonite and the low molecular weight humic acid react for 60 hours under the stirring conditions of the first reaction environment, and react for 5.5 hours under the stirring conditions of the second reaction environment; then the polluted water is added to degrade the pollutants in the water, and the volume ratio of the mixed treatment liquid to the polluted water is 1:450. The results are as follows Figure 5 shown.

[0034] from Figure 5It can be seen from Figures 5A, 5B and 5C that as the reaction time increases, the production of active oxygen species produced by the mixed treatment liquid increases. : In the single low molecular weight humic acid system, 3 DOM * , 1 The O2 and ·OH production were 325.33, 315.09 and 62.93 μmol / L, respectively. In the single Fe-Mn intercalated montmorillonite system, 3 DOM * , 1 The production of O2 and ·OH were 623.33, 614.78 and 134.27 μmol / L respectively, while in the mixed liquid system, 3 DOM * , 1 The production of O2 and ·OH were 1254.22, 1216.09 and 262.38 μmol / L, respectively. The production of active oxygen species in the mixed system was significantly increased. Figure 5 As can be seen from Figure 5D, the degradation efficiencies of single low molecular weight humic acid system and single iron-manganese intercalated montmorillonite on secretion disruptors in estuarine water are 27.11% and 35.18%, respectively, while the degradation efficiency of the mixed system of the two on estuarine water estrogens is as high as 99.16%, achieving enhanced degradation of pollutants in estuarine water.

[0035] Test Example 4 As one of the test examples, the iron-manganese intercalated montmorillonite prepared in Example 1 and the low molecular weight humic acid obtained in Example 4 were mixed to form a mixed treatment liquid to treat the estrogen-contaminated water effluent from Suzhou Chengyang Wastewater Treatment Plant for illustration.

[0036] The difference from Experimental Example 1 is that the solid-liquid ratio of the iron-manganese intercalated montmorillonite and the low molecular weight humic acid in the mixed treatment liquid is 1:800; the iron-manganese intercalated montmorillonite and the low molecular weight humic acid are reacted for 40 hours under the stirring conditions of the first reaction environment, and for 3 hours under the stirring conditions of the second reaction environment; then the polluted water is added to degrade the pollutants in the water, and the volume ratio of the mixed treatment liquid to the polluted water is 1:600. The results are as follows Figure 6 shown.

[0037] from Figure 6 It can be seen from Figures 6A, 6B and 6C that as the reaction time increases, the production of active oxygen species produced by the mixed treatment liquid increases. : In the single low molecular weight humic acid system, 3 DOM * , 1 The O2 and ·OH production were 316.14, 304.15 and 57.28 μmol / L, respectively. In the single Fe-Mn intercalated montmorillonite system, 3 DOM * , 1The production of O2 and ·OH were 601.25, 593.18 and 126.30 μmol / L respectively, while in the mixed liquid system, 3 DOM * , 1 The production of O2 and ·OH were 1221.19, 1202.31 and 260.22 μmol / L, respectively. The production of active oxygen species in the mixed system was significantly increased. Figure 6 It can be seen from Figure 6D that the degradation efficiency of estrogen in sewage treatment plant effluent by single low molecular weight humic acid system and single iron-manganese intercalated montmorillonite are 22.94% and 30.12% respectively, while the degradation efficiency of the mixed system of the two is as high as 98.05%, achieving enhanced degradation of pollutants in sewage treatment plant effluent.

[0038] Test Example 5 As one of the test examples, the iron-manganese intercalated montmorillonite prepared in Example 1 and the low molecular weight humic acid obtained in Example 4 were mixed to form a mixed treatment liquid to treat the antibiotic-contaminated water body of Nanjing Fumin poultry farm wastewater for illustration.

[0039] The difference from Experimental Example 1 is that the solid-liquid ratio of the iron-manganese intercalated montmorillonite and the low molecular weight humic acid in the mixed treatment liquid is 1:1000; the iron-manganese intercalated montmorillonite and the low molecular weight humic acid react for 30 hours under the stirring conditions of the first reaction environment, and react for 6 hours under the stirring conditions of the second reaction environment; then the polluted water is added to degrade the pollutants in the water, and the volume ratio of the mixed treatment liquid to the polluted water is 1:500. The results are as follows Figure 7 shown.

[0040] from Figure 7 It can be seen from Figures 7A, 7B and 7C that as the reaction time increases, the production of active oxygen species produced by the mixed treatment liquid increases. : In the single low molecular weight humic acid system, 3 DOM * , 1 The production of O2 and ·OH were 283.54, 274.89 and 46.33 μmol / L, respectively. In the single Fe-Mn intercalated montmorillonite system, 3 DOM * , 1 The production of O2 and ·OH were 540.21, 522.16 and 91.07 μmol / L respectively, while in the mixed liquid system, 3 DOM * , 1 The production of O2 and ·OH were 1104.59, 1036.45 and 193.32 μmol / L, respectively. The production of active oxygen species in the mixed system was significantly increased. Figure 7It can be seen from Figure 7D that the degradation efficiency of aquaculture wastewater antibiotics by a single low molecular weight humic acid system and a single iron-manganese intercalated montmorillonite are 23.15% and 32.26% respectively, while the degradation efficiency of the mixed system of the two is as high as 99.22%, achieving enhanced degradation of aquaculture wastewater pollutants.

[0041] The present invention has been disclosed above with preferred embodiments, but they are not intended to limit the present invention. Any technical solutions obtained by adopting equivalent replacement or equivalent transformation solutions fall within the protection scope of the present invention.

Claims

1. A method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid, characterized in that The following steps are involved: The iron-manganese intercalated montmorillonite and the low molecular weight humic acid solution are mixed to form a mixed treatment liquid, which is slowly added into a sealed degradation tank, and the air in the degradation tank is discharged to form a first reaction environment, and the reaction is carried out for 36-60 hours under stirring conditions; air is filled into the degradation tank to form a second reaction environment, and the reaction is carried out for 3-6 hours under stirring conditions; then the polluted water is added to degrade the pollutants in the water; wherein the solid-liquid ratio of the iron-manganese intercalated montmorillonite and the low molecular weight humic acid solution in the mixed treatment liquid is 1g:500~1000mL; the first reaction environment is that the oxygen content in the air is less than 4%, and the dissolved oxygen in the water is less than 0.2 mg / L; the second reaction environment is that the oxygen content in the air is greater than 15%, and the dissolved oxygen in the water is greater than 15 mg / L.

2. The method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid according to claim 1, characterized in that: The preparation process of iron-manganese intercalated montmorillonite is as follows: S1: Add montmorillonite to deionized water and stir in a water bath at 25-40℃ for 2h to fully swell and form a montmorillonite suspension; S2 Take 0.40~0.60M FeCl3·6H2O solution and 0.35~0.60M MnCl2 solution and slowly add them to the montmorillonite suspension, stir at 300-500rpm for 1.5~2.5h, and then heat for 50~70 o C for 12-24 hours; centrifuge, dry and grind to obtain Fe-Mn intercalated montmorillonite.

3. The method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid according to claim 2, characterized in that: The volume ratio of FeCl3·6H2O solution to montmorillonite suspension is 0.50~0.60:1; the volume ratio of MnCl2 solution to montmorillonite suspension is 0.20~0.30:

1.

4. The method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid according to claim 2, characterized in that: The mass ratio of deionized water / montmorillonite is 45~65:

1.

5. The method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid according to claim 1, characterized in that: The preparation process of low molecular weight humic acid is as follows: Weigh humic acid powder, dissolve it in deionized water, the solid-liquid ratio of humic acid powder to deionized water is 1g:5~20mL, stir for 1-2h at room temperature pH value of 7~10, and obtain humic acid solution after 0.45μm micropore filtration; The humic acid solution is filtered tangentially, the cutoff pore size of the tangential ultrafiltration membrane is 1.0~2.0 kDa, the pressure is 0.05~0.2Mpa, and the solution that passes through the ultrafiltration membrane is collected, which is the low molecular weight humic acid.

6. The method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid according to claim 5, characterized in that: The sources of humic acid powder include soil, water and coal.

7. The method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid according to claim 1, characterized in that: An exhaust valve is provided on the top of the degradation pool, a filter membrane is laid on the inner surface of the bottom, and a water outlet is provided in the middle position of the bottom; the degradation pool adjusts the environment inside the degradation pool through the exhaust valve.

8. The method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid according to claim 1, characterized in that: The degradation tank is made of stainless steel or polytetrafluoroethylene, and the filter membrane is made of cellulose acetate or glass fiber.

9. The method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid according to claim 1, characterized in that: The volume ratio of the mixed treatment liquid to the water to be treated is 1:300~600.

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