Advanced treatment device for wastewater containing antibiotic organic pollutants

Abstract

The present invention relates to a deep treatment device for wastewater containing antibiotic organic pollutants, belonging to the technical field of water treatment, and comprising an advanced oxidation column, a multi-media filter, an ultrafiltration membrane column and a disinfection module connected in sequence; the water inlet of the advanced oxidation column is connected to a biological pond and an H2O2 automatic dosing device, and the wastewater in the biological pond is premixed with a quantitative H2O2 dosed by the H2O2 automatic dosing device and then enters the advanced oxidation column together; a heterogeneous Fenton Co-Cu catalyst is filled in the advanced oxidation column for water quality oxidation treatment; the multi-media filter adopts pressure filtration, the ultrafiltration membrane column adopts ultrafiltration membrane filtration, and the disinfection module adopts the combination of ultraviolet lamps and disinfection powder to realize the disinfection treatment of water quality. By using the device of the present invention, the deep purification and treatment of wastewater can be realized, and the treatment effect is good and the treatment efficiency is high.

Description

Technical Field

[0001] The present invention belongs to the technical field of water treatment, and particularly relates to a deep treatment device for wastewater containing antibiotic organic pollutants. Background Art

[0002] Metronidazole (MNZ) is a major synthetic antibiotic, with broad-spectrum antibacterial and highly effective antigenic protozoal effects, and is a commonly used clinical drug. Antibiotics have been widely used in the treatment of various human diseases and animal husbandry. However, due to severe abuse, they have a large amount of residues in various water environments, thus indirectly or directly causing adverse effects on human health and the living environment. Therefore, it is particularly important to achieve efficient treatment of antibiotic wastewater.

[0003] There are various wastewater treatment technologies in the prior art, such as biological methods, ozonation, Fenton method, and photocatalysis. Among them, the biological method has the disadvantages of low removal efficiency and long operation cycle; adsorption method, ozonation, etc. have problems such as high operation cost, possible secondary pollution that still needs to be treated, etc.; photocatalytic oxidation technology has large infrastructure investment, low light utilization rate, and is difficult to be industrially applied. As one of the advanced oxidation processes (AOPs), the Fenton process has received extensive attention in solving the pollution of toxic, refractory, and non-biodegradable organic pollutants in global water bodies due to its advantages of high efficiency, simplicity, and low cost. The Fenton reaction is a highly promising advanced oxidation process, which can cause the in-situ generated hydrogen peroxide (H2O2) to react with active metal ions to produce strongly oxidizing hydroxyl radicals (·OH, Eθ = 2.8V). Hydroxyl radicals can react non-selectively with organic pollutants until they are completely mineralized into carbon dioxide, water, and inorganic ions. However, due to problems such as poor catalytic activity, poor stability, and environmental unfriendliness of the existing Fenton system catalysts, their performance in the removal of organic pollutants is poor, which limits the development and application of wastewater treatment processes. Summary of the Invention

[0004] In order to solve the deficiencies in the prior art, the purpose of the present invention is to provide a deep treatment device for wastewater containing antibiotic organic pollutants. By using the above device, deep purification and treatment of wastewater can be achieved, with good treatment effect and high treatment efficiency.

[0005] In order to achieve the above purpose, the specific solution adopted by the present invention is as follows:

[0006] A deep treatment device for wastewater containing antibiotic organic pollutants, comprising an advanced oxidation column, a multi-media filter, an ultrafiltration membrane column, and a disinfection module connected in sequence;

[0007] The inlet of the advanced oxidation column is connected to the biological pool and the H2O2 automatic dosing device. The wastewater in the biological pool is premixed with a quantified amount of H2O2 dosed by the H2O2 automatic dosing device and then enters the advanced oxidation column together.

[0008] The advanced oxidation column is filled with a heterogeneous Fenton Co-Cu catalyst. The heterogeneous Fenton Co-Cu catalyst is prepared by the following method: At room temperature of 25 °C, 0.01 mol of Cu(NO3)2•3H2O and Co(NO3)2•6H2O in total are mixed at a Co / Cu molar ratio of 4:1 and dissolved in 30 mL of ethylene glycol. The resulting solution is precipitated at 20 °C for 1 h with 100 mL of 0.2 mol / L Na2CO3 under vigorous stirring, then aged at room temperature for 2 h. The precipitate is centrifuged and thoroughly washed with deionized water, then dried overnight at 60 °C, and prepared into granular form through roasting and molding, and filled into the advanced oxidation column.

[0009] As a further optimization of the above advanced treatment device, online monitors for on-line monitoring of COD, pH or temperature are installed at the outlets of the advanced oxidation column, the multi-media filter and the ultrafiltration membrane column.

[0010] As a further optimization of the above advanced treatment device, the molding method of the heterogeneous Fenton Co-Cu catalyst is: mixing the heterogeneous Fenton Co-Cu catalyst with activated carbon to prepare a mixture; adding ultrapure water to the binder bentonite to prepare a binder solution; mixing the mixture with the binder solution evenly, pressing and molding with a spherical mold, and drying to make it granular.

[0011] As a further optimization of the above advanced treatment device, ultraviolet lamps are installed in the disinfection module, and at the same time, a first automatic dosing device for dosing disinfection powder is provided at the inlet.

[0012] As a further optimization of the above advanced treatment device, a flocculation tank is installed between the advanced oxidation column and the multi-media filter, and a second automatic dosing device for dosing flocculation drugs is provided at the inlet of the flocculation tank.

[0013] As a further optimization of the above advanced treatment device, the advanced treatment device includes a housing. A handle is provided outside the housing of the housing, and universal wheels for movement are provided at the bottom; the advanced oxidation column, the multi-media filter, the ultrafiltration membrane column and the disinfection module are arranged in the housing and are connected in sequence through pipelines; interfaces are provided at the input and output ends of the advanced oxidation column, the multi-media filter, the ultrafiltration membrane column and the disinfection module, and plugs matching the interfaces are provided at both ends of the pipeline, and the pipeline is disassembled and installed through the cooperation of the interface and the plug.

[0014] Furthermore, the interface includes a connecting pipe. A first baffle is fixedly connected to the inner wall of the top end of the connecting pipe. A second baffle is fixedly connected to the inner wall of the end of the connecting pipe away from the first baffle. A first spring is fixedly connected to the end of the second baffle close to the first baffle. The end of the first spring away from the second baffle is fixedly connected to a sealing plate. A first through hole is provided on the first baffle, and a second through hole is provided on the second baffle. The sealing plate is made of rubber, and the diameter of the sealing plate is larger than that of the first through hole. Through the above settings, the reaction column can remain in a sealed state after being disassembled, avoiding the leakage of wastewater.

[0015] Furthermore, the plug includes an insertion pipe. A fixed cluster is fixedly connected inside the insertion pipe. A thimble is fixedly connected to one side of the fixed cluster. A plurality of pressing plates are fixedly connected to the outside of the insertion pipe near the thimble. Protrusions are fixedly connected to the outer surfaces of the plurality of pressing plates. Through the above settings, the thimble can push open the sealing plate to connect the passage and allow the wastewater to flow. A fixing plate is fixedly connected to the outside of the end of the insertion pipe away from the thimble. A second spring is fixedly connected to the fixing plate. The end of the second spring away from the fixing plate is fixedly connected to a sleeve. The inner wall of the end of the sleeve close to the pressing plate is inclined. The sleeve and the insertion pipe are slidably matched with each other. Through the above settings, the pressing plates and the insertion pipe can be pressed and matched to press and fix the connecting pipe.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] 1. The advanced oxidation column of the present invention is filled with a special heterogeneous Fenton Co-Cu catalyst. This catalyst has high catalytic activity, good stability, a simple preparation method and no pollution. Under certain optimized conditions, the degradation rate of this catalyst for metronidazole (MNZ) can reach more than 90%, which can better achieve the deep treatment of wastewater containing antibiotic organic pollutants and has good treatment effects.

[0018] 2. The device of the present invention reasonably arranges multiple modules. Interfaces are provided on the column bodies of each module, and plugs are provided at both ends of the pipeline, making the connection between the reaction column and the pipeline more convenient. At the same time, the sealing performance of the reaction column is improved to avoid the leakage of wastewater. Through the series connection of several reaction columns, the medical wastewater can be deeply purified to avoid environmental pollution by the wastewater. And through the universal wheels, the whole can be conveniently moved to improve the treatment efficiency. Description of the Drawings

[0019] Figure 1 is the SEM image of the heterogeneous Fenton Co-Cu catalyst prepared in Example 1;

[0020] Figure 2 is the structural schematic diagram of the device described in Example 2;

[0021] Figure 3 is the overall structure diagram of the device described in Example 4;

[0022] Figure 4 is the internal structure diagram of the device described in Example 4;

[0023] Figure 5 is the interface cross-sectional view of the device described in Example 4;

[0024] Figure 6 is the plug structure diagram of the device described in Example 4;

[0025] In the figure: 1, outer shell; 2, universal wheel; 3, handle; 4, water inlet pipe; 5, water outlet pipe; 6, fixing seat; 7, fixing frame; 8, advanced oxidation column; 9, multi-media filter; 10, ultrafiltration membrane column; 11, disinfection module; 12, first drug dispenser; 13, H2O2 automatic drug dispenser; 14, interface; 141, connecting pipe; 142, first baffle; 143, first through hole; 144, second baffle; 145, second through hole; 146, first spring; 147, sealing plate; 15, plug; 151, inserting pipe; 152, extrusion plate; 153, fixing seat; 154, thimble; 155, fixing plate; 156, sleeve; 157, second spring; 16, biological pond or water tank Detailed implementation manners

[0026] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention.

[0027] In the description of the present invention, it should be understood that the orientation or positional relationship indicated by the terms "inner", "outer", "top", "bottom", etc. is based on the drawings shown, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, specific orientation structure and operation, and therefore should not be construed as a limitation to the present invention.

[0028] Example 1 Preparation of heterogeneous Fenton Co-Cu catalyst.

[0029] At room temperature of 25°C, a total of 0.01 mol of Cu(NO3)2•3H2O and Co(NO3)2•6H2O were mixed at a Co / Cu molar ratio of 4:1 and dissolved in 30 mL of ethylene glycol (EG). The resulting solution was precipitated with 100 mL of Na2CO3 (0.2 M) at 20°C under vigorous stirring for 1 h, then aged at room temperature for 2 h. The precipitate was centrifuged and thoroughly washed with deionized water, and then dried overnight at 60°C. The SEM diagram of the resulting catalyst is as Figure 1 shown.

[0030] According to the BET results and surface content analysis, the specific surface area of the catalyst is 199 m2 / g, the surface Co content is 4.8%, and the surface Cu content is 23%. Among them, the + / Cu 2+ ratio is 0.4, and the 3+ / Co 2+ ratio is 1.5.

[0031] The crystal phase of the heterogeneous Fenton-like Co-Cu catalyst as described above is Co(CO3) 0.5 (OH) 0.11 H2O and CuO.

[0032] It can be known from experiments that under the conditions of an initial reaction pH value of 7.15 and a reaction temperature of 50 °C, when the H2O2 dosage is 1600 ppm, the degradation rate of metronidazole (MNZ) can reach more than 90%. The excellent performance and stability of this catalyst make it have good industrial application prospects in the field of treating antibiotic organic pollutants.

[0033] Example 2 A deep treatment device for wastewater containing antibiotic organic pollutants.

[0034] A deep treatment device for wastewater containing antibiotic organic pollutants, including a sequentially connected advanced oxidation column 8, a multi-media filter 9, an ultrafiltration membrane column 10, and a disinfection module 11; the water inlet of the advanced oxidation column 8 is connected to a tee, one end of the tee is connected to the water outlet of the biological pond or water tank 16, and the other end is connected to the H2O2 automatic dosing device 13. The wastewater in the biological pond or water tank 16 is premixed with the quantitative H2O2 dosed by the H2O2 automatic dosing device 13 and then enters the advanced oxidation column 8 together.

[0035] The advanced oxidation column 8 is filled with the heterogeneous Fenton-like Co-Cu catalyst prepared in Example 1 above. Since the catalyst prepared in Example 1 is in powder form, it needs to be formed into granular form and then filled into the advanced oxidation column. The forming method is as follows: mixing the heterogeneous Fenton-like Co-Cu catalyst with activated carbon to prepare a mixture; adding ultrapure water to the binder bentonite to prepare a binder solution; mixing the mixture with the binder solution evenly, pressing and forming with a spherical mold, and drying to make it granular.

[0036] An ultra-UV lamp can also be installed in the advanced oxidation column 8 to further improve the treatment efficiency.

[0037] The multi-media filter 9 uses pressure filtration, and the filler is MnO2 mixed with other filter materials to remove H2O2 and other impurities and protect the subsequent membrane equipment.

[0038] Online monitors for on-line monitoring of COD, pH or temperature are provided at the water outlets of the advanced oxidation column 8, the multi-media filter 9, and the ultrafiltration membrane column 10.

[0039] An ultraviolet lamp is arranged in the disinfection module 11, and at the same time, a first automatic drug dispenser 12 for adding disinfection powder is arranged at the water inlet to realize the disinfection treatment of wastewater.

[0040] The above-mentioned entire device is arranged in an integrated iron box, and all equipment is made of stainless steel. The bottom of the integrated iron box is provided with rollers and is movable. Each module in the entire device can be repeatedly set according to the water volume or treatment situation, and the modules are adjusted in series and parallel to be incorporated into the original process.

[0041] Example 3 A deep treatment device for wastewater containing antibiotic organic pollutants.

[0042] The structure of this example is basically the same as that of Example 2, except that: a flocculation tank is installed between the advanced oxidation column 8 and the multi-media filter 9, and a second automatic drug dispenser for adding flocculation drugs is arranged at the water inlet of the flocculation tank.

[0043] Example 4

[0044] Please refer to Figure 3 and Figure 4 , a deep treatment device for medical wastewater, including a housing 1. A plurality of universal wheels 2 are rotatably connected to the lower end of the housing 1. A handle 3 is fixedly connected to one side of the housing 1. A plurality of fixing seats 6 are fixedly connected to the inner side wall of the housing 1. A granular heterogeneous Fenton Co-Cu catalyst is filled in the advanced oxidation column 8 according to the method described in Example 1, and an ultraviolet irradiation tube is arranged in the disinfection module.

[0045] A pair of fixing frames 7 are fixedly connected to the bottom inner wall of the housing 1. A first drug dispenser 12 for adding disinfection powder into the disinfection module and an H2O2 automatic drug adder 13 are respectively fixedly connected to the pair of fixing frames 7. A water inlet pipe 4 is fixedly connected to the bottom of the housing 1, and the water inlet pipe 4 is connected to a biological pond or a water tank 16. A water outlet pipe 5 is also fixedly connected to the bottom of the housing 1.

[0046] The advanced oxidation column 8, the multi-media filter 9, the ultrafiltration membrane column 10 and the disinfection module 11 are all connected by pipelines. Interfaces 14 are fixedly connected to the top and bottom of the advanced oxidation column 8, the multi-media filter 9, the ultrafiltration membrane column 10 and the disinfection module 11, and plugs 15 are fixedly connected to both ends of the pipeline.

[0047] One end of the advanced oxidation column 8 is connected to the water inlet pipe 4, one end of the disinfection module 11 is connected to the water outlet pipe 5, the water inlet pipe 4 is connected to the H2O2 automatic drug adder 13 through a pipeline, the water outlet pipe 5 is connected to the first drug dispenser 12 through a pipeline, and the first drug dispenser 12 is filled with disinfection powder.

[0048] As shown Figure 5 in FIG. 1, the interface 14 includes a connecting pipe 141. The inner wall of the top end of the connecting pipe 141 is fixedly connected with a first baffle 142. The inner wall of one end of the connecting pipe 141 away from the first baffle 142 is fixedly connected with a second baffle 144. One end of the second baffle 144 close to the first baffle 142 is fixedly connected with a first spring 146. One end of the first spring 146 away from the second baffle 144 is fixedly connected with a sealing plate 147. A first through hole 143 is formed in the first baffle 142. A second through hole 145 is formed in the second baffle 144. The sealing plate 147 is made of rubber, and the diameter of the sealing plate 147 is larger than that of the first through hole 143.

[0049] As shown Figure 6 in FIG. 2, the plug 15 includes an insertion pipe 151. A fixed cluster 153 is fixedly connected inside the insertion pipe 151. One side of the fixed cluster 153 is fixedly connected with a thimble 154. A plurality of pressing plates 152 are fixedly connected to the outside of one end of the insertion pipe 151 close to the thimble 154. Protrusions are fixedly connected to the outer surfaces of the plurality of pressing plates 152. A fixing plate 155 is fixedly connected to the outside of one end of the insertion pipe 151 away from the thimble 154. A second spring 157 is fixedly connected to the fixing plate 155. One end of the second spring 157 away from the fixing plate 155 is fixedly connected with a sleeve 156. The inner wall of one end of the sleeve 156 close to the pressing plates 152 is inclined, and the sleeve 156 is slidably matched with the insertion pipe 151.

[0050] During use, wastewater enters through the water inlet pipe 4. After hydrogen peroxide is automatically added by the H2O2 chemical feeder 13, it enters the advanced oxidation column 8 for water quality oxidation treatment, and then is filtered by the multi-media filter in the multi-media filter 9 to filter out impurities. Then it is filtered by the ultrafiltration membrane in the ultrafiltration membrane column 10. Finally, it is irradiated and disinfected by the ultraviolet lamp in the disinfection module 11. Disinfection powder is added by the first chemical feeder 12. Then the purified water is discharged through the water outlet pipe 5. When the reaction column is removed, the first spring 146 pushes the sealing plate 147 to block the first through hole 143 to seal the reaction column and avoid contamination. When connection is required, first move the sleeve 156 backward to expose the pressing plates 152. Insert the insertion pipe 151 into the connecting pipe 141 to make the thimble 154 push open the sealing plate 147. At the same time, lower the pipe 156. Under the push of the second spring 157, the sleeve 156 moves towards the pressing plates 152. Through the cooperation between the inclined inner wall of the pipe 156 and the protrusions outside the pressing plates 152, the pressing plates 152 are closed inward, and the connecting pipe 141 is clamped and fixed by the pressing plates 152 and the insertion pipe 151.

[0051] It should be noted that the above-described embodiments should be understood as illustrative and not limiting the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims. For those skilled in the art, without departing from the essence and scope of the present invention, some non-essential improvements and adjustments made to the present invention still fall within the scope of protection of the present invention.

Claims

1. An advanced treatment device for wastewater containing antibiotic organic pollutants, characterized in that: It includes a sequentially connected advanced oxidation column (8), multi-media filter (9), ultrafiltration membrane column (10) and disinfection module (11). The water inlet of the advanced oxidation column (8) is connected to the biological pond (16) and the H2O2 automatic dosing device (13). The wastewater in the biological pond (16) and the quantified H2O2 dosed by the H2O2 automatic dosing device (13) are premixed and then enter the advanced oxidation column (8) together. The advanced oxidation column (8) is filled with a heterogeneous Fenton Co-Cu catalyst. The heterogeneous Fenton Co-Cu catalyst is prepared by the following method: At room temperature of 25 °C, 0.01 mol of Cu(NO3)2•3H2O and Co(NO3)2•6H2O in total are mixed at a Co / Cu molar ratio of 4:1 and dissolved in 30 mL of ethylene glycol. The obtained solution is precipitated at 20 °C for 1 h with 100 mL of Na2CO3 with a concentration of 0.2 mol / L under vigorous stirring, then aged at room temperature for 2 h. The precipitate is centrifuged and thoroughly washed with deionized water, then dried overnight at 60 °C, and prepared into granular form by molding after calcination, and filled into the advanced oxidation column (8). The molding method of the heterogeneous Fenton Co-Cu catalyst is: mixing the heterogeneous Fenton Co-Cu catalyst with activated carbon to prepare a mixture; adding ultrapure water to the binder bentonite to prepare a binder solution; mixing the mixture with the binder solution evenly, pressing and molding with a spherical mold, and drying to make it granular.

2. The depth treatment device according to claim 1, wherein: Online monitors for on-line monitoring of COD, pH or temperature are installed at the water outlets of the advanced oxidation column (8), multi-media filter (9) and ultrafiltration membrane column (10).

3. The depth treatment device according to claim 1, characterized in that: An ultraviolet lamp is installed in the disinfection module (11), and a first automatic dosing device (12) for dosing disinfection powder is provided at the water inlet.

4. The depth treatment device according to claim 1, characterized in that: A flocculation pond is installed between the advanced oxidation column (8) and the multi-media filter (9), and a second automatic dosing device for dosing flocculation drugs is provided at the water inlet of the flocculation pond.

5. The depth treatment device according to claim 1, wherein: The advanced treatment device includes a housing (1). A handle (3) is provided outside the housing of the housing (1), and universal wheels (2) for moving are provided at the bottom; the advanced oxidation column (8), multi-media filter (9), ultrafiltration membrane column (10) and disinfection module (11) are arranged inside the housing and are sequentially connected by pipelines; interfaces (14) are provided at the input and output ends of the advanced oxidation column (8), multi-media filter (9), ultrafiltration membrane column (10) and disinfection module (11), and plugs (15) matching the interfaces (14) are provided at both ends of the pipeline. The pipeline is disassembled and installed by the cooperation of the interface (14) and the plug (15).

6. The depth treatment device according to claim 5, wherein: The interface (14) includes a connecting pipe (141). The inner wall of the top end of the connecting pipe (141) is fixedly connected with a first baffle (142). The inner wall of the end of the connecting pipe (141) far from the first baffle (142) is fixedly connected with a second baffle (144). One end of the second baffle (144) close to the first baffle (142) is fixedly connected with a first spring (146). One end of the first spring (146) far from the second baffle (144) is fixedly connected with a sealing plate (147). A first through hole (143) is formed in the first baffle (142). A second through hole (145) is formed in the second baffle (144). The sealing plate (147) is made of rubber, and the diameter of the sealing plate (147) is larger than that of the first through hole (143).

7. The depth treatment device according to claim 6, wherein: The plug (15) includes an insertion pipe (151). A fixed bundle (153) is fixedly connected inside the insertion pipe (151). One side of the fixed bundle (153) is fixedly connected with a thimble (154). A plurality of pressing plates (152) are fixedly connected to the outside of the insertion pipe (151) near the thimble (154). Protrusions are fixedly connected to the outer surfaces of the plurality of pressing plates (152). A fixing plate (155) is fixedly connected to the outside of the end of the insertion pipe (151) far from the thimble (154). A second spring (157) is fixedly connected to the fixing plate (155). One end of the second spring (157) far from the fixing plate (155) is fixedly connected with a sleeve (156). The inner wall of the end of the sleeve (156) close to the pressing plates (152) is inclined, and the sleeve (156) is slidably matched with the insertion pipe (151).

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