Method for degrading pollutants in water based on iron-manganese intercalated montmorillonite and low molecular weight humic acid
By using a mixed treatment solution of iron-manganese intercalated montmorillonite and low molecular weight humic acid under a specific reaction environment, the problem of insufficient potential for reactive oxygen species generation was solved, and efficient degradation of water pollutants was achieved, especially high removal rates of antibiotics, estrogens and endocrine disruptors.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- NANJING INST OF GEOGRAPHY & LIMNOLOGY
- Filing Date
- 2024-11-04
- Publication Date
- 2026-06-30
AI Technical Summary
In existing technologies, the single system of iron-manganese intercalated montmorillonite and low molecular weight humic acid has limited potential for generating reactive oxygen species during the reduction-oxidation process, making it difficult to effectively degrade emerging pollutants in water bodies.
By mixing iron-manganese intercalated montmorillonite with a low molecular weight humic acid solution to form a mixed treatment solution, the reaction is carried out under a specific reaction environment to promote the generation of reactive oxygen species. This includes a two-step reaction environment that controls the concentration of air and dissolved oxygen, thereby improving the efficiency of electron transition and energy transfer.
It significantly increased the yield of reactive oxygen species and achieved efficient degradation of antibiotics, estrogens and endocrine disruptors in water, with removal rates of 90% to 99%, respectively.
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Figure CN119263457B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of wastewater treatment technology, specifically relating to a method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid. Background Technology
[0002] In recent years, due to frequent human activities and rapid industrial and agricultural development, a large number of emerging pollutants have appeared in surface water bodies, such as endocrine disruptors, antibiotics, and estrogens. Reactive oxygen species (ROS) are highly reactive substances generated during electron transfer from oxygen in water, including hydroxyl radicals (•OH) and singlet oxygen (•OH). 1 O2), and triplet free radicals ( 3 CDOM * Reactive oxygen species (ROS) are characterized by high redox potential and strong activity, allowing them to directly attack pollutants in water, oxidizing and degrading them into low-toxicity or non-toxic small molecules, and ultimately completely degrading them into carbon dioxide and water. It is generally believed that when widely present reducing iron or organic matter in water encounters oxygen, electron transfer and energy transitions occur, leading to the generation of ROS. Therefore, finding iron minerals and organic matter with high ROS generation potential, coupled with a suitable reduction-oxidation process, is key to efficiently generating ROS and degrading water pollutants.
[0003] Montmorillonite is a layered mineral composed of extremely fine-grained hydrated aluminosilicates, widely found in nature, and can be used for pollutant adsorption and catalytic degradation. However, the interlayer spacing of traditional montmorillonite is limited (approximately 1.0–1.5 nm), insufficient for rapid electron transitions and energy transfer. Humic acid is a widely distributed organic substance in lake waters, containing active groups such as carboxyl, phenolic hydroxyl, and quinone groups. The oxidation process of reduced humic acid is an important source of reactive oxygen species in water. Compared to high molecular weight (1 kDa–0.45 μm) humic acid, low molecular weight (<1 kDa) humic acid contains higher aromaticity or more active groups, and has a higher potential for generating reactive oxygen species. However, whether it is iron-manganese intercalated montmorillonite or low molecular weight humic acid, the potential for generating reactive oxygen species in a single system during the reduction-oxidation process is limited. Therefore, developing a highly efficient method for generating reactive oxygen species and applying it to the degradation of emerging pollutants in water bodies can maximize ecological, environmental, economic, and social benefits. This is of great strategic significance for the purification and treatment of polluted lakes, rivers, urban wastewater treatment plant effluent, and aquaculture wastewater. Summary of the Invention
[0004] In order to overcome the above-mentioned defects and deficiencies 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] To address the aforementioned technical problems, this invention provides a method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid, comprising the following steps:
[0006] A mixed treatment solution is formed by mixing iron-manganese intercalated montmorillonite and a low molecular weight humic acid solution. This solution is then slowly added to a sealed degradation tank, and the air inside the tank is expelled to create the first reaction environment. The reaction is carried out for 36-60 hours under stirring. Air is then introduced into the degradation tank to create the second reaction environment, and the reaction is carried out for 3-6 hours under stirring. Finally, the solution is added to polluted water to degrade the pollutants in the water. The solid-liquid ratio of the iron-manganese intercalated montmorillonite to the low molecular weight humic acid solution in the mixed treatment solution is 1 g: 500-1000 mL. The first reaction environment has an oxygen content of less than 4% in the air and a dissolved oxygen content of less than 0.2 mg / L in the water. The second reaction environment has an oxygen content of more than 15% in the air and a dissolved oxygen content of more than 15 mg / L in the water.
[0007] The preparation process of iron-manganese intercalated montmorillonite is as follows:
[0008] S1. Add montmorillonite to deionized water and stir in a water bath at 25~40℃ for 2 hours to allow it to fully swell and form a montmorillonite suspension.
[0009] S2. Slowly add 0.40~0.60M FeCl3·6H2O solution and 0.35~0.60M MnCl2 solution dropwise to the montmorillonite suspension, stir at 300-500 rpm for 1.5~2.5 h, and let stand for 50~70 h. o Aged at C for 12-24 hours; centrifuged, dried and ground to obtain iron-manganese intercalated montmorillonite.
[0010] Furthermore, 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.
[0011] Furthermore, the mass ratio of deionized water to montmorillonite is 45~65:1.
[0012] The preparation process of low molecular weight humic acid is as follows:
[0013] Weigh out humic acid powder and 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 and pH 7~10. After filtration through 0.45μm micropores, obtain humic acid solution.
[0014] The humic acid solution is tangentially filtered. The pore size of the tangential ultrafiltration membrane is 1.0~2.0 kDa, the pressure is 0.05~0.2 MPa, and the solution that permeates through the ultrafiltration membrane is collected as low molecular weight humic acid.
[0015] Furthermore, the sources of humic acid powder include soil, water bodies, and coal.
[0016] Furthermore, the degradation tank is equipped with an exhaust valve at the top, a filter membrane on the inner surface of the bottom, and an outlet in the middle of the bottom; the degradation tank regulates the environment inside the degradation tank through the exhaust valve.
[0017] Furthermore, the degradation tank is made of stainless steel or polytetrafluoroethylene, and the filter membrane is made of cellulose acetate or glass fiber.
[0018] Furthermore, the volume ratio of the mixed treatment solution to the water to be treated is 1:300~600.
[0019] The beneficial technical effects achieved by this invention are as follows: This invention provides a method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid. In this method, the carboxyl groups, phenolic hydroxyl groups, and kun groups in the low molecular weight humic acid can dissolve some of the Fe in the iron-manganese intercalated montmorillonite and form Fe(II) / Fe(III)-organic complexes. These complexes can shuttle electrons from Fe(II) in the interlayer structure of iron-manganese intercalated montmorillonite to O2 to promote the generation of reactive oxygen species. In addition, the kun groups in the low molecular weight humic acid can also act as a bridge to mediate the shuttle of electrons from Fe(II) in the interlayer structure of iron-manganese intercalated montmorillonite to O2, thereby generating more reactive oxygen species. Thus, the purpose of degrading pollutants in water is achieved. Montmorillonite and humic acid are both derived from the natural environment and are non-toxic and harmless. Furthermore, the preparation methods for iron-manganese montmorillonite and low molecular weight humic acid are simple and low-cost. Compared with traditional methods for degrading water pollutants, 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 reaches 90-98%, the removal rate of estrogen reaches 92-99%, and the removal rate of endocrine disruptors reaches 95-99%. Attached Figure Description
[0020] Figure 1 SEM image of iron-manganese intercalated montmorillonite of the present invention;
[0021] Figure 2 Schematic diagram of the degradation tank structure of this invention;
[0022] Figure 3 In one embodiment of the present invention, the effects of different wastewater treatment materials on reactive oxygen species yield and estrogen degradation efficiency are described.
[0023] Figure 4 Another embodiment of the present invention shows the effect of different wastewater treatment materials on the yield of reactive oxygen species and the degradation efficiency of estrogen;
[0024] Figure 5One embodiment of the present invention describes the effect of different wastewater treatment materials on the yield of reactive oxygen species and the degradation efficiency of endocrine disruptors.
[0025] Figure 6 Another embodiment of the present invention shows the effect of different wastewater treatment materials on the yield of reactive oxygen species and the degradation efficiency of estrogen;
[0026] Figure 7 One embodiment of the present invention describes the effect of different wastewater treatment materials on the yield of reactive oxygen species and the degradation efficiency of antibiotics. Detailed Implementation
[0027] The present invention will be further described below with reference to specific embodiments. These embodiments are only used to more clearly illustrate the technical solutions of the present invention and should not be construed as limiting the scope of protection of the present invention.
[0028] The present invention will be further described below with reference to the accompanying drawings and embodiments. Example 1
[0029] Preparation of iron-manganese intercalated montmorillonite: 10 g of montmorillonite was added to 450 mL of deionized water and 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 M MnCl2 solution were added, and the mixture was stirred vigorously for 2.0 h and aged at 60 °C for 24 h to obtain iron-manganese intercalated montmorillonite. Example 2
[0030] Preparation of iron-manganese intercalated montmorillonite: 10g of montmorillonite was added to 500mL of deionized water and stirred in a water bath at 45℃ for 2h. Then, 250mL of 0.60M FeCl3·6H2O solution and 100mL of 0.35M M MnCl2 solution were added, and the mixture was stirred vigorously for 2.5h and aged at 70℃ for 12h to obtain iron-manganese intercalated montmorillonite. Example 3
[0031] Preparation of iron-manganese intercalated montmorillonite: 10 g of montmorillonite was added to 650 mL of deionized water and 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 M MnCl2 solution were added, and the mixture was stirred vigorously for 1.5 h and aged at 50 °C for 20 h to obtain iron-manganese intercalated montmorillonite.
[0032] Scanning electron microscopy was performed on the iron-manganese intercalated montmorillonite prepared in Example 1, and the results are as follows: Figure 1As shown in the figure, A is a SEM image of montmorillonite, and B is an iron-manganese intercalated montmorillonite. It can be clearly seen from the figure that after the montmorillonite is processed, iron-manganese metal ions are inserted into the interlayer of montmorillonite, thereby increasing the interlayer spacing and improving the electron transition and energy transfer efficiency of montmorillonite. Example 4
[0033] Soil-derived humic acid was selected and dissolved in deionized water at a solid-liquid ratio of 1:10 to obtain a humic acid solution with a pH of 8. Tangential ultrafiltration was used, with a pore size 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
[0034] Aquatic humic acid was selected and dissolved in deionized water at a solid-liquid ratio of 1:5 to obtain a humic acid solution with a pH of 7. Low molecular weight humic acid was obtained by tangential ultrafiltration with a membrane pore size of 2.0 kDa and an ultrafiltration pressure of 0.2 MPa. Example 6
[0035] 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 of 10. Low molecular weight humic acid was obtained by tangential ultrafiltration with a membrane pore size of 1 kDa and an ultrafiltration pressure of 0.05 MPa.
[0036] Experimental Example 1
[0037] As one of the experimental 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 solution to treat the estrogen-polluted water body in the Longchi Lake pollution area of Nanjing City for illustration.
[0038] The mixed treatment solution was slowly added to a sealed degradation tank, and at the same time, the quenching agent 2,4,6-trimethylphenol (TMP) was added. 3 DOM * probe), furfuryl alcohol (FFA, 1 The final concentrations of TMP, furfuryl alcohol, and TPA were 0.75–1.25 mM, respectively. Samples were collected periodically during the first and second reaction environments, and the yield of reactive oxygen species was determined by high-performance liquid chromatography (HPLC). The results are as follows: Figure 3As shown in the diagram. The degradation tank can be made of stainless steel or polytetrafluoroethylene (PTFE). PTFE is the optimal choice. An exhaust valve is located at the top of the tank, and an outlet is located at the bottom. A filter membrane is laid on the inner surface of the bottom, made of cellulose acetate or glass fiber, with cellulose acetate being the preferred option. A schematic diagram of the degradation tank structure is shown below. Figure 2 As shown.
[0039] The environment inside the degradation tank is regulated by an exhaust valve installed at the top. The first reaction environment maintains an oxygen content of less than 4% in the air and a dissolved oxygen content of less than 0.2 mg / L in the water. The second reaction environment maintains an oxygen content of more than 15% in the air and a dissolved oxygen content of more than 15 mg / L in the water.
[0040] The solid-liquid ratio of iron-manganese intercalated montmorillonite and low molecular weight humic acid in the mixed treatment solution was 1:500. The first reaction was carried out under stirring conditions for 48 hours, and the second reaction was carried out under stirring conditions for 4.5 hours. Then, polluted water was added to degrade the pollutants in the water. The volume ratio of the mixed treatment solution to the polluted water was 1:300. Single iron-manganese intercalated montmorillonite and single low molecular weight humic acid were used as control groups. The degradation efficiency of the water pollutants was calculated.
[0041] Degradation efficiency of water pollutants = (C0 - C) 降 ) / C0
[0042] Test results as follows Figure 3 As shown in Figures 3A, 3B, and 3C, it can be seen that the yield of reactive oxygen species in the mixed treatment solution increases with increasing reaction time. In a single low-molecular-weight humic acid system, 3 DOM * , 1 The yields of O2 and ·OH were 302.35, 292.55, and 54.34 μmol / L, respectively, in a single iron-manganese intercalated montmorillonite system. 3 DOM * , 1 The yields of O2 and ·OH were 583.40, 574.65, and 117.32 μmol / L, respectively, while in the mixed treatment system, 3 DOM * , 1 The yields of O2 and ·OH were 1193.54, 1156.45, and 240.67 μmol / L, respectively, indicating a significant increase in the yield of reactive oxygen species in the mixed system. Furthermore, from... Figure 3The 3D model shows that the degradation efficiencies of a single low molecular weight humic acid system and a single iron-manganese intercalated montmorillonite system for estrogen in inland lake water are 25.64% and 33.21%, respectively, while the degradation efficiency of the mixed system for estrogen in inland lake water is as high as 97.23%, achieving enhanced degradation of pollutants in inland lake water.
[0043] Experimental Example 2
[0044] As one of the experimental 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 solution to treat the estrogen-polluted water body in the Pearl River channel of Nanjing City for illustration.
[0045] The difference from Experimental Example 1 is as follows: the solid-liquid ratio of iron-manganese intercalated montmorillonite and low molecular weight humic acid in the mixed treatment solution is 1:700; the iron-manganese intercalated montmorillonite and low molecular weight humic acid react for 40 hours under stirring conditions in the first reaction environment, and for 4 hours under stirring conditions in the second reaction environment; then polluted water is added to degrade the pollutants in the water, and the volume ratio of the mixed treatment solution to the polluted water is 1:400. The results are as follows. Figure 4 As shown.
[0046] from Figure 4 As can be seen from 4A, 4B, and 4C, the yield of reactive oxygen species in the mixed treatment solution increases with increasing reaction time. In a single low-molecular-weight humic acid system, 3 DOM * , 1 The yields of O2 and ·OH were 285.51, 276.34, and 50.15 μmol / L, respectively, in a single iron-manganese intercalated montmorillonite system. 3 DOM * , 1 The yields of O2 and ·OH were 556.50, 560.15, and 104.28 μmol / L, respectively, while in the mixed solution system, 3 DOM * , 1 The yields of O2 and ·OH were 1121.42, 1089.02, and 220.00 μmol / L, respectively, indicating a significant increase in the yield of reactive oxygen species in the mixed system. Furthermore, Figure 4 The 4D model shows that the degradation efficiencies of a single low molecular weight humic acid system and a single iron-manganese intercalated montmorillonite system for estrogen in river water are 24.17% and 31.22%, respectively, while the degradation efficiency of the mixed system for estrogen in inland lake water is as high as 98.08%, achieving enhanced degradation of pollutants in river water.
[0047] Experimental Example 3
[0048] As one of the experimental 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 solution to treat the endocrine disturbance polluted water body at the mouth of the Nanfei River flowing into the lake for illustration.
[0049] The difference from Experimental Example 1 is as follows: the solid-liquid ratio of iron-manganese intercalated montmorillonite and low molecular weight humic acid in the mixed treatment solution is 1:600; the iron-manganese intercalated montmorillonite and low molecular weight humic acid react for 60 hours under stirring conditions in the first reaction environment, and for 5.5 hours under stirring conditions in the second reaction environment; then polluted water is added to degrade the pollutants in the water, and the volume ratio of the mixed treatment solution to the polluted water is 1:450. The results are as follows. Figure 5 As shown.
[0050] from Figure 5 As can be seen from 5A, 5B, and 5C, the yield of reactive oxygen species produced by the mixed treatment solution increases with increasing reaction time. In a single low-molecular-weight humic acid system... 3 DOM * , 1 The yields of O2 and ·OH were 325.33, 315.09, and 62.93 μmol / L, respectively, in a single iron-manganese intercalated montmorillonite system. 3 DOM * , 1 The yields of O2 and ·OH were 623.33, 614.78, and 134.27 μmol / L, respectively, while in the mixed solution system, 3 DOM * , 1 The yields of O2 and ·OH were 1254.22, 1216.09, and 262.38 μmol / L, respectively, indicating a significant increase in the yield of reactive oxygen species in the mixed system. From... Figure 5 The 5D model shows that the degradation efficiencies of a single low molecular weight humic acid system and a single iron-manganese intercalated montmorillonite system for endocrine disruptors in estuarine water were 27.11% and 35.18%, respectively, while the degradation efficiency of the mixed system for estrogen in estuarine water was as high as 99.16%, achieving enhanced degradation of pollutants in estuarine water.
[0051] Test Example 4
[0052] As one of the experimental 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 solution to treat the estrogen-polluted water body in the effluent of Suzhou Chengyang Wastewater Treatment Plant for illustration.
[0053] The difference from Experimental Example 1 is as follows: the solid-liquid ratio of iron-manganese intercalated montmorillonite and low molecular weight humic acid in the mixed treatment solution is 1:800; the iron-manganese intercalated montmorillonite and low molecular weight humic acid react for 40 hours under stirring conditions in the first reaction environment, and for 3 hours under stirring conditions in the second reaction environment; then polluted water is added to degrade the pollutants in the water, and the volume ratio of the mixed treatment solution to the polluted water is 1:600. The results are as follows. Figure 6 As shown.
[0054] from Figure 6 As can be seen from 6A, 6B, and 6C, the yield of reactive oxygen species produced by the mixed treatment solution increases with increasing reaction time. In a single low-molecular-weight humic acid system... 3 DOM * , 1 The yields of O2 and ·OH were 316.14, 304.15, and 57.28 μmol / L, respectively, in a single iron-manganese intercalated montmorillonite system. 3 DOM * , 1 The yields of O2 and ·OH were 601.25, 593.18, and 126.30 μmol / L, respectively, while in the mixed solution system, 3 DOM * , 1 The yields of O2 and ·OH were 1221.19, 1202.31, and 260.22 μmol / L, respectively, indicating a significant increase in the yield of reactive oxygen species in the mixed system. From... Figure 6 As can be seen from 6D, the degradation efficiencies of a single low molecular weight humic acid system and a single iron-manganese intercalated montmorillonite system for estrogen in wastewater effluent are 22.94% and 30.12%, respectively, while the degradation efficiency of the mixed system for estrogen in wastewater effluent is as high as 98.05%, achieving enhanced degradation of pollutants in wastewater effluent.
[0055] Experimental Example 5
[0056] As one of the experimental 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 solution to treat the antibiotic-polluted water body of Nanjing Fumin Poultry Farm wastewater for illustration.
[0057] The difference from Experimental Example 1 is as follows: the solid-liquid ratio of iron-manganese intercalated montmorillonite and low molecular weight humic acid in the mixed treatment solution is 1:1000; the iron-manganese intercalated montmorillonite and low molecular weight humic acid react for 30 hours under stirring conditions in the first reaction environment, and for 6 hours under stirring conditions in the second reaction environment; then polluted water is added to degrade the pollutants in the water, and the volume ratio of the mixed treatment solution to the polluted water is 1:500. The results are as follows. Figure 7 As shown.
[0058] from Figure 7 As can be seen from 7A, 7B, and 7C, the yield of reactive oxygen species produced by the mixed treatment solution increases with increasing reaction time. In a single low-molecular-weight humic acid system... 3 DOM * , 1 The yields of O2 and ·OH were 283.54, 274.89, and 46.33 μmol / L, respectively, in a single iron-manganese intercalated montmorillonite system. 3 DOM * , 1 The yields of O2 and ·OH were 540.21, 522.16, and 91.07 μmol / L, respectively, while in the mixed solution system, 3 DOM * , 1 The yields of O2 and ·OH were 1104.59, 1036.45, and 193.32 μmol / L, respectively, indicating a significant increase in the yield of reactive oxygen species in the mixed system. From... Figure 7 As can be seen from 7D, the degradation efficiencies of a single low molecular weight humic acid system and a single iron-manganese intercalated montmorillonite system for antibiotics in aquaculture wastewater are 23.15% and 32.26%, respectively, while the degradation efficiency of the mixed system for antibiotics in aquaculture wastewater is as high as 99.22%, achieving enhanced degradation of pollutants in aquaculture wastewater.
[0059] The present invention has been disclosed above with reference to preferred embodiments, but it is not intended to limit the present invention. All technical solutions obtained by adopting equivalent substitutions or equivalent transformations 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... Includes the following steps: A mixed treatment solution is prepared by mixing iron-manganese intercalated montmorillonite and a low molecular weight humic acid solution. This solution is then slowly added to a sealed degradation tank, and the air inside the tank is expelled to create the first reaction environment. The reaction is carried out under stirring for 36-60 hours. Air is then introduced into the degradation tank to create the second reaction environment, and the reaction is carried out under stirring for 3-6 hours. Finally, polluted water is added to the solution to degrade the pollutants. The solid-liquid ratio of the iron-manganese intercalated montmorillonite to the low molecular weight humic acid solution in the mixed treatment solution is 1 g: 500-1000 mL. The first reaction environment has an oxygen content of less than 4% in the air and a dissolved oxygen content of less than 0.2 mg / L in the water. The second reaction environment has an oxygen content of more than 15% in the air and a dissolved oxygen content of more than 15 mg / L in the water. 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 2 hours to allow it to fully swell and form a montmorillonite suspension. S2. Slowly add 0.40~0.60M FeCl3·6H2O solution and 0.35~0.60M MnCl2 solution dropwise to the montmorillonite suspension, stir at 300-500 rpm for 1.5~2.5 h, and let stand for 50~70 h. o Aged at C for 12-24 hours; centrifuged, dried and ground to obtain iron-manganese intercalated montmorillonite; The volume ratio of the mixed treatment solution to the water to be treated is 1:300~600.
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 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.
3. 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 mass ratio of deionized water to montmorillonite is 45~65:
1.
4. 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 out humic acid powder and 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 and pH 7~10. After filtration through 0.45μm micropores, obtain humic acid solution. The humic acid solution is tangentially filtered. The pore size of the tangential ultrafiltration membrane is 1.0~2.0 kDa, the pressure is 0.05~0.2 MPa, and the solution that permeates through the ultrafiltration membrane is collected as low molecular weight humic acid.
5. The method for degrading water pollutants based on iron-manganese intercalated montmorillonite and low molecular weight humic acid according to claim 4, characterized in that: Humic acid powder can be obtained from soil, water, and coal.
6. 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 equipped with an exhaust valve at the top, a filter membrane on the inner surface of the bottom, and an outlet in the middle of the bottom. The environment inside the degradation tank is regulated by the exhaust valve.
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: The degradation tank is made of stainless steel or polytetrafluoroethylene, and the filter membrane is made of cellulose acetate or glass fiber.