Synergistic removal equipment for antibiotic total nitrogen in water body based on magnetic filler

Abstract

The invention discloses equipment for synergistically removing antibiotic total nitrogen in a water body based on magnetic filler, and belongs to the technical field of wastewater treatment.The equipment comprises a water inlet tank, a reaction tank, an aeration fan and a PLC, a water wheel is arranged in the middle in the reaction tank, and the water wheel corresponds to the water outlet position of the tail end of a water inlet pipe so that the water wheel can rotate under water power; a plurality of rotating arms are arranged on the water wheel, the rotating arms are sleeved with first magnetic filler blocks in a sliding mode, the two sides of the interior of the reaction tank are filled with second magnetic filler blocks, and the first magnetic filler blocks and the second magnetic filler blocks are the same in structure, are of hollow cylindrical porous structures and are prepared by mixing neodymium iron boron and high-density polyethylene. According to the invention, efficient, rapid and synergistic removal of antibiotic total nitrogen can be realized, functional microorganisms in wastewater grow in the magnetic filler and on the surface of the magnetic filler in a biofilm culturing manner, uniform mass transfer distribution of gas and effective fluidization of the magnetic filler are realized, and efficient removal of antibiotics and nitrogen pollutants is synchronously realized in the same tank body.

Description

Technical Field

[0001] The invention relates to the technical field of wastewater treatment, and in particular to a device for collaboratively removing total nitrogen from antibiotics in water based on magnetic fillers. Background Art

[0002] The existing traditional wastewater treatment process based on activated sludge biochemical technology cannot effectively remove antibiotics, resulting in a large amount of antibiotic parent and biological metabolites discharged into the natural water environment, seriously threatening the safety of the water environment. Antibiotics show "pseudo-persistent" residues in water bodies and inhibit natural processes including nitrification and denitrification.

[0003] Membrane bioreactors have shown excellent performance in removing antibiotics due to their long hydraulic retention time, high economic benefits, low sludge production and high biomass. At the same time, membrane bioreactors can also take into account the removal of conventional pollutants such as nitrogen. Microorganisms have magnetic biological effects, and magnetic field enhanced biological methods are a very promising treatment method for the development of a green and energy-saving society. Studies have shown that magnetic fields are conducive to the coagulation and aggregation of microorganisms, and magnetic fields have been proven to enhance antibiotic removal, nitrification, and denitrification biological denitrification.

[0004] In the application for rapid antibiotic total nitrogen synergistic removal in biofilm reactors related to the prior art disclosure, such as the application with Chinese patent publication number CN202410848819, a functional carrier filler and its preparation method and application are disclosed. The functional carrier filler includes a polyethylene carrier, and a functional layer loaded on the surface of the polyethylene carrier; the components of the functional layer include amino graphene. The present invention fixes amino graphene on the surface of the polyethylene carrier so that the surface of the filler is rich in nitrogen functional groups that can mediate electron transfer, which can promote microbial electron transfer and enhance antibiotic biodegradation. At the same time, it increases the specific surface area of ​​the carrier to facilitate biofilm formation, and uses it as a suspended filler in a moving bed biofilm reactor for post-denitrification MBBR process for wastewater treatment, which not only improves the denitrification rate but also promotes antibiotic degradation, while reducing the use of carbon sources, which is beneficial to energy conservation and emission reduction. However, the relevant processes of magnetic filler carriers are not involved therein. Summary of the invention

[0005] In view of the above-mentioned problems, the present invention provides a device for synergistically removing total nitrogen from antibiotics in water based on magnetic fillers.

[0006] The technical solution of the present invention is:

[0007] A device for the synergistic removal of antibiotic total nitrogen in water based on magnetic fillers, comprising a water inlet tank, a reaction tank, an aeration fan and a PLC controller;

[0008] The water inlet tank is connected to the lower part of one side wall of the reaction tank through a water inlet pipe, and a water inlet pump is provided on the water inlet pipe;

[0009] A water wheel is provided in the middle of the reaction tank, and the water wheel corresponds to the water outlet position at the end of the water inlet pipe so that the water wheel rotates under the water power. The water wheel includes a rotating shaft, a plurality of rotating arms evenly arranged on the rotating shaft, and a water baffle provided at the end of each rotating arm. A first magnetic filler block is provided on the sliding sleeve of the rotating arm, and second magnetic filler blocks are filled on both sides of the reaction tank. A water outlet pipe is provided in the middle of one side wall of the reaction tank relative to the water inlet pipe, and an overflow port is provided on the side wall of the reaction tank above the water outlet pipe;

[0010] The PLC controller is electrically connected to the water inlet pump and the aeration fan.

[0011] Furthermore, the number of the rotating arms and the water baffles is 15 to 20.

[0012] Description: By optimizing the number of baffles to ensure that the spacing between them is appropriate, the wastewater flow can continuously drive the water wheel to rotate in a hydrodynamic manner.

[0013] Furthermore, when the water wheel rotates, the water baffle at the bottom extends to the bottom of the reaction tank, and the top of the water baffle at the top exceeds the wastewater level in the reaction tank, accounting for 1 / 5 to 1 / 4 of the water wheel rotation radius.

[0014] Note: By optimizing and adjusting the proportional relationship between the water wheel radius and the wastewater level, it can be ensured that the second magnetic filler block on the water wheel can absorb oxygen by being exposed to the water surface, thereby alleviating the aeration pressure.

[0015] Furthermore, the first magnetic filler block and the second magnetic filler block each include: a cylindrical porous outer frame located on the outside, and an internally hollow hexagonal porous inner frame located at the center; a cylindrical porous support frame is provided between the porous inner frame and the porous outer frame; porous support walls are provided between the porous inner frame and the porous support frame, and between the porous support frame and the porous outer frame; and the porous outer frame, the porous inner frame, the porous support frame and the porous support wall each have a plurality of holes with a pore size of 0.2 to 0.5 mm.

[0016] Description: The structure of the first magnetic filler block and the second magnetic filler block designed in the present invention has a large specific surface area, providing a good carrier for the growth of biofilm. At the same time, the combination of the water wheel and the stirring rod group can further increase the frequency of the irregular movement of the second magnetic filler block in the water body, promote the disturbance mixing between the second magnetic filler block and the wastewater, and improve the wastewater treatment effect.

[0017] Furthermore, the porous inner frame of the first magnetic filler block is slidably mounted on the rotating arm, each rotating arm is provided with 6 to 10 first magnetic filler blocks, and the total length of the first magnetic filler blocks provided on each rotating arm is 70 to 80% of the length of the rotating arm.

[0018] Note: By optimizing and adjusting the length ratio of the first magnetic filler block on the rotating arm, a balance between the formation efficiency of the biofilm on the first magnetic filler block and the oxygen absorption rate can be maintained.

[0019] Furthermore, both ends of the rotating shaft are rotatably connected to the inner walls of both sides of the reaction pool respectively, and a number of stirring rod groups are symmetrically arranged at both ends of the rotating shaft. The stirring rod groups on the same side are arranged at equal intervals, and the stirring rod groups include a number of stirring rods arranged at equal intervals along the circumference of the rotating shaft. The stirring rod groups are separated by a porous water-permeable partition, and a number of reaction zones are formed inside the reaction pool. The second magnetic filler block is evenly filled inside each of the reaction zones, and the porous water-permeable partition has a number of pores with a size of 2 to 5 mm.

[0020] Description: By setting up the stirring rod group, the irregular movement frequency of the second magnetic filler block can be increased. At the same time, the rotation of the stirring rod group depends on the rotation of the water wheel, and no other power source is required, thereby improving the integration of the device.

[0021] Furthermore, the height of the second magnetic filler block is 5 to 20 mm, the radius of the second magnetic filler block is 3 to 10 mm, and the total volume of the second magnetic filler blocks in each reaction zone is calculated based on the volume enclosed by the second magnetic filler blocks. The total volume of the second magnetic filler blocks in the entire reaction tank is not less than 20% of the total volume of the wastewater in the reaction tank.

[0022] Note: By optimizing and adjusting the total volume ratio of the reaction zone and the second magnetic filler block inside the reaction tank, the wastewater purification efficiency inside the reaction tank can be ensured.

[0023] Furthermore, an aeration main pipe is provided at the output end of the aeration fan, and the aeration main pipe is connected to the bottom of each reaction zone through a plurality of aeration branch pipes one by one, and an aeration plate connected to the aeration branch pipe is provided on both sides of the bottom of each reaction zone.

[0024] Description: Oxygen in the air can be dissolved into the flowing water layer through aeration branches and aeration plates, and transferred to the biofilm on the magnetic filler through the attached water layer for microorganisms to breathe.

[0025] Furthermore, a solenoid valve is provided on the water outlet pipe, and the PLC controller is electrically connected to the solenoid valve.

[0026] Furthermore, the preparation method of the first magnetic filler block and the second magnetic filler block is: NdFeB and high-density polyethylene are mixed in a mass ratio of 1:15-18, and then a hydrophilic auxiliary material is added, wherein the hydrophilic auxiliary material is clinoptilolite, and the amount of clinoptilolite added is 0.4-0.8% of the total weight of NdFeB and high-density polyethylene. After mixing together, the material particles with a length not exceeding 2 mm are obtained by an extrusion granulator under a temperature condition of 280-320°C, and the material particles are placed in a corresponding mold for shaping to obtain the first magnetic filler block or the second magnetic filler block.

[0027] Description: High-density polyethylene is used as the main carrier of the magnetic filler block. It will not be degraded or toxic to organisms if immersed in wastewater for a long time.

[0028] The beneficial effects of the present invention are:

[0029] (1) The equipment of the present invention can achieve efficient and rapid synergistic removal of antibiotics and total nitrogen. Functional microorganisms in wastewater grow biofilms inside and on the surface of magnetic fillers. Air exposure and aeration discs are used to achieve uniform mass transfer distribution of gas and effective fluidization of magnetic fillers. Efficient removal of antibiotics and nitrogen pollutants is achieved simultaneously in the same tank body, solving the problems of existing biofilm multi-reaction tanks. The equipment has a compact structure, simple equipment maintenance, and low basic cost.

[0030] (2) The magnetic filler block designed in the present invention has a high specific surface area. The magnetic filler block itself is a multi-layer, porous columnar structure. The biofilm can attach and grow on the multi-layer structure of the magnetic filler block at the same time. The biomass per unit volume is high, which greatly improves the antibiotic removal rate and denitrification effect of the biofilm, shortens the HRT, and can achieve a larger wastewater treatment capacity in a limited area, making full use of space and enhancing economy. This meets the requirements of my country's increasingly scarce land resources for the construction of wastewater treatment plants.

[0031] (3) The equipment of the present invention innovatively utilizes magnetic fillers to enhance the pollutant removal efficiency of the biofilm, and forms a multi-layer functional biofilm on the magnetic filler block. Under the action of the magnetic field, not only is rapid biofilm formation started, but also the required aeration effect can be achieved without a very high aeration volume when combined with air exposure, causing the magnetic filler block to be disturbed, thereby increasing the movement speed of the second magnetic filler block to accelerate biofilm formation, which is beneficial to the removal of antibiotics and the rapid establishment of a denitrification microbial community. It also significantly improves the pollutant removal efficiency of the biofilm and promotes the activity of the biofilm. The magnetic filler block enhances the pollutant removal efficiency of the biofilm by promoting microbial electron transfer, energy metabolism, and enzyme activity, and optimizing the microbial community and functional composition, thereby providing an effective way to further achieve wastewater treatment and accelerate the synergistic removal of new pollutants such as total nitrogen and synergistic carbon reduction. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is a schematic diagram of the overall structure of the device of the present invention;

[0033] Figure 2 is a top view of the apparatus of the present invention;

[0034] Figure 3 This is a schematic diagram of the water wheel and reaction zone structure inside the reaction tank;

[0035] Figure 4 is a front view of the rotating arm of the water wheel after the first magnetic filler block is installed;

[0036] Figure 5 is a top view of a first magnetic filler block;

[0037] Figure 6 is a front view of the second magnetic filler block.

[0038] Among them, 1-water inlet tank, 11-water inlet pipe, 12-water inlet pump, 2-reaction tank, 21-porous permeable baffle, 22-reaction zone, 23-overflow, 3-aeration fan, 31-aeration branch pipe, 32-aeration plate, 33-aeration main pipe, 4-PLC controller, 5-water wheel, 51-rotating arm, 52-water baffle, 53-rotating shaft, 6-first magnetic filler block, 61-porous outer frame, 62-porous inner frame, 63-porous support frame, 64-porous support wall, 7-second magnetic filler block, 8-water outlet pipe, 81-solenoid valve, 9-stirring rod group, 91-stirring rod. DETAILED DESCRIPTION

[0039] Example 1: Figure 2 As shown, a device for synergistically removing total nitrogen from antibiotics in water based on magnetic fillers comprises a water inlet tank 1, a reaction tank 2, an aeration fan 3 and a PLC controller 4, wherein the aeration fan 3 is a commercially available high-pressure aeration fan, and the PLC controller 4 is a commercially available PLC control cabinet;

[0040] like Figure 1 As shown, the water inlet box 1 is connected to the lower part of one side wall of the reaction tank 2 through the water inlet pipe 11, and the water inlet pipe 11 is provided with a water inlet pump 12, which is a commercially available high-pressure water inlet pump;

[0041] like Figure 2 to Figure 4As shown, a water wheel 5 is provided in the middle of the reaction tank 2, and the water wheel 5 corresponds to the water outlet position at the end of the water inlet pipe 11 so that the water wheel 5 rotates under the water power. The water wheel 5 includes a rotating shaft 53, 16 rotating arms 51 evenly arranged on the rotating shaft 53, and a water retaining plate 52 arranged at the end of each rotating arm 51. A first magnetic filler block 6 is slidably sleeved on the rotating arm 51, and 6 first magnetic filler blocks 6 are arranged on each rotating arm 51. The total length of the first magnetic filler block 6 arranged on each rotating arm 51 is 75% of the length of the rotating arm 51. Second magnetic filler blocks 7 are filled on both sides of the reaction tank 2. A water outlet pipe 8 is provided in the middle of one side wall of the reaction tank 2 relative to the water inlet pipe 11, and an overflow port 23 is provided on the side wall of the reaction tank 2 above the water outlet pipe 8. When the water wheel 5 rotates, the water retaining plate 52 located at the bottom extends to the bottom of the reaction tank 2, and the part of the top of the water retaining plate 52 located at the top that exceeds the wastewater liquid level in the reaction tank 2 accounts for 1 / 5 of the rotation radius of the water wheel 5;

[0042] like Figure 2 and Figure 3 As shown, both ends of the rotating shaft 53 are rotatably connected to the inner walls of both sides of the reaction tank 2, and four stirring rod groups 9 are symmetrically arranged at both ends of the rotating shaft 53. The stirring rod groups 9 on the same side are arranged at equal intervals. The stirring rod group 9 includes three stirring rods 91 arranged at equal intervals along the circumference of the rotating shaft 53. The stirring rod groups 9 are separated by a porous water-permeable partition 21, and four reaction zones 22 are formed inside the reaction tank 2. The second magnetic filler block 7 is evenly filled inside each reaction zone 22. The porous water-permeable partition 21 has a plurality of holes with an aperture size of 3 mm. The height of the second magnetic filler block 7 is 10 mm, and the radius of the second magnetic filler block 7 is 5 mm. Calculated based on the volume enclosed by the outside of the second magnetic filler block 7, the total volume of the second magnetic filler block 7 in each reaction zone 22 accounts for 29% of the volume of the reaction zone 22, and the total volume of the second magnetic filler block 7 in the entire reaction tank 2 accounts for 26% of the total volume of the wastewater in the reaction tank 2.

[0043] like Figure 5 and Figure 6As shown, the first magnetic filler block 6 and the second magnetic filler block 7 have the same structure, both of which are hollow cylindrical porous structures. The first magnetic filler block 6 and the second magnetic filler block 7 are prepared by mixing neodymium iron boron with high-density polyethylene, adding a hydrophilic auxiliary material clinoptilolite, extruding granulation and carrier shaping. The first magnetic filler block 6 and the second magnetic filler block 7 both include: a cylindrical porous outer frame 61 located on the outside, and an internal hollow hexagonal porous inner frame 62 located at the center. The porous inner frame 62 of the first magnetic filler block 6 is slidably sleeved on the rotating arm 51, and a cylindrical porous supporting frame 63 is provided between the porous inner frame 62 and the porous outer frame 61. A porous supporting wall 64 is provided between the porous inner frame 62 and the porous supporting frame 63, and between the porous supporting frame 63 and the porous outer frame 61. The porous outer frame 61, the porous inner frame 62, the porous supporting frame 63 and the porous supporting wall 64 all have a plurality of holes with a pore size of 0.3 mm.

[0044] The preparation method of the first magnetic filler block 6 and the second magnetic filler block 7 is as follows: NdFeB and high-density polyethylene are mixed in a mass ratio of 1:16, and then a hydrophilic auxiliary material is added, wherein the hydrophilic auxiliary material is clinoptilolite, and the amount of clinoptilolite added is 0.6% of the total weight of NdFeB and high-density polyethylene, and after mixing together, the material particles are extruded through an extrusion granulator at a temperature of 300° C. to obtain material particles with a length of 1 mm, and the material particles are placed in a corresponding mold for shaping to obtain the first magnetic filler block 6 or the second magnetic filler block 7;

[0045] like Figure 1 and Figure 2 As shown, the PLC controller 4 is electrically connected to the water inlet pump 12 and the aeration fan 3, a solenoid valve 81 is provided on the water outlet pipe 8, the PLC controller 4 is electrically connected to the solenoid valve 81, an aeration main pipe 33 is provided at the output end of the aeration fan 3, and is connected to the bottom of each reaction zone 22 through 8 aeration branch pipes 31 one by one, an aeration plate 32 connected to the aeration branch pipe 31 is provided on both sides of the bottom of each reaction zone 22, and an aeration branch pipe 31 corresponds to the middle of the reaction tank 2, and the aeration branch pipe 31 is provided with three aeration plates 32 at equal intervals at the bottom of the reaction tank 2.

[0046] Embodiment 2: This embodiment differs from Embodiment 1 in that:

[0047] The water wheel 5 is provided with 15 rotating arms 51, and the porous inner frame 62 of the first magnetic filler block 6 is slidably mounted on the rotating arms 51. Eight first magnetic filler blocks 6 are provided on each rotating arm 51. The total length of the first magnetic filler block 6 provided on each rotating arm 51 is 80% of the length of the rotating arm 51. When the water wheel 5 rotates, the portion of the top that exceeds the wastewater level in the reaction tank 2 accounts for 1 / 5 of the rotation radius of the water wheel 5.

[0048] Embodiment 3: This embodiment differs from Embodiment 1 in that:

[0049] The water wheel 5 is provided with 20 rotating arms 51, and the porous inner frame 62 of the first magnetic filler block 6 is slidably mounted on the rotating arm 51. Each rotating arm 51 is provided with 10 first magnetic filler blocks 6. The total length of the first magnetic filler block 6 provided on each rotating arm 51 is 70% of the length of the rotating arm 51. When the water wheel 5 rotates, the portion of the top that exceeds the wastewater level in the reaction tank 2 accounts for 1 / 4 of the rotation radius of the water wheel 5.

[0050] Note: In Examples 1 to 3, different limitations are imposed on the size and arrangement of the first magnetic filler block 6. When the length of the rotating arm 51 occupied by the first magnetic filler block 6 is shorter, the height of the top of the water wheel 5 above the wastewater level in the reaction tank 2 should be increased as much as possible when the water wheel 5 rotates, so as to ensure the air exposure effect of the first magnetic filler block 6.

[0051] Embodiment 4: This embodiment differs from Embodiment 1 in that:

[0052] The porous water-permeable partition plate 21 has a plurality of holes with a pore size of 2 mm, the height of the second magnetic filler block 7 is 5 mm, the radius of the second magnetic filler block 7 is 3 mm, and the total volume of the second magnetic filler block 7 in each reaction zone 22 accounts for 25% of the volume of the reaction zone 22 based on the volume enclosed by the second magnetic filler block 7, and the total volume of the second magnetic filler block 7 in the entire reaction tank 2 accounts for 22% of the total volume of the wastewater in the reaction tank 2;

[0053] The porous outer frame 61 , the porous inner frame 62 , the porous support frame 63 and the porous support wall 64 all have a plurality of holes with a pore size of 0.2 mm.

[0054] Embodiment 5: This embodiment differs from Embodiment 1 in that:

[0055] The porous water-permeable partition plate 21 has a plurality of holes with a pore size of 5 mm, the height of the second magnetic filler block 7 is 20 mm, the radius of the second magnetic filler block 7 is 10 mm, and the total volume of the second magnetic filler block 7 in each reaction zone 22 accounts for 40% of the volume of the reaction zone 22, and the total volume of the second magnetic filler block 7 in the entire reaction tank 2 accounts for 30% of the total volume of the wastewater in the reaction tank 2, calculated based on the volume enclosed by the second magnetic filler block 7 outside.

[0056] The porous outer frame 61 , the porous inner frame 62 , the porous support frame 63 and the porous support wall 64 all have a plurality of holes with a pore size of 0.5 mm.

[0057] Note: In Example 1, Example 4 and Example 5, different restrictions are imposed on the specifications of the second magnetic filler block 7. When the amount of wastewater to be treated is larger, the size of the second magnetic filler block 7 needs to be increased accordingly, and the pore size on the porous water-permeable partition 21 should be increased to prevent the second magnetic filler block 7 from crossing the reaction zone 22. The ratio of the total volume of the second magnetic filler block 7 inside the entire reaction tank 2 to the total volume of the wastewater in the reaction tank 2 can be reasonably adjusted as needed.

[0058] Embodiment 6: This embodiment differs from Embodiment 1 in that:

[0059] The preparation method of the first magnetic filler block 6 and the second magnetic filler block 7 is as follows: NdFeB and high-density polyethylene are mixed in a mass ratio of 1:15, and then a hydrophilic auxiliary material is added, wherein the hydrophilic auxiliary material is clinoptilolite, and the amount of clinoptilolite added is 0.4% of the total weight of NdFeB and high-density polyethylene. After mixing together, the mixture is extruded through an extrusion granulator at a temperature of 280°C to obtain material particles with a length of 0.5 mm, and the material particles are placed in a corresponding mold for shaping to obtain the first magnetic filler block 6 or the second magnetic filler block 7.

[0060] Embodiment 7: This embodiment is different from Embodiment 1 in that:

[0061] The preparation method of the first magnetic filler block 6 and the second magnetic filler block 7 is as follows: NdFeB and high-density polyethylene are mixed in a mass ratio of 1:18, and then a hydrophilic auxiliary material is added, wherein the hydrophilic auxiliary material is clinoptilolite, and the amount of clinoptilolite added is 0.8% of the total weight of NdFeB and high-density polyethylene. After mixing together, the material particles are extruded through an extrusion granulator at a temperature of 320°C to obtain material particles with a length of 2 mm, and the material particles are placed in a corresponding mold for shaping to obtain the first magnetic filler block 6 or the second magnetic filler block 7.

[0062] Note: In Example 1, Example 6 and Example 7, different limitations are imposed on the preparation parameters of the first magnetic filler block 6 and the second magnetic filler block 7. The parameters given in each example are conventional adjustments within the parameter range of the present invention. Any set of parameters can achieve similar technical effects.

[0063] Embodiment 8: This embodiment differs from Embodiment 1 in that:

[0064] Five stirring rod groups 9 are symmetrically arranged at both ends of the rotating shaft 53 . The stirring rod groups 9 on the same side are arranged at equal intervals. The stirring rod group 9 includes five stirring rods 91 arranged at equal intervals along the circumference of the rotating shaft 53 .

[0065] Embodiment 9: This embodiment differs from Embodiment 1 in that:

[0066] Six stirring rod groups 9 are symmetrically arranged at both ends of the rotating shaft 53 . The stirring rod groups 9 on the same side are arranged at equal intervals. The stirring rod group 9 includes six stirring rods 91 arranged at equal intervals along the circumference of the rotating shaft 53 .

[0067] Working principle: The working principle of the present invention is briefly described below. When treating wastewater, the wastewater to be treated stored in the water inlet tank 1 is introduced into the reaction tank 2 through the water inlet pump 12 and the water inlet pipe 11. The water flow impacts the water baffle 52, driving each rotating arm 51 to rotate, thereby driving the rotating shaft 53 to rotate, and then driving each stirring rod group 9 to rotate, so that each stirring rod 91 rotates and disturbs the second magnetic filler block 7 in each reaction zone 22 to move irregularly and accelerate. The air provided by the aeration fan 3 is used to aerate the wastewater in the reaction zone 22 through the aeration branch pipe 31 and the aeration disk 32, further accelerating the movement of organic pollutants and microorganisms and attaching them to the surfaces of the first magnetic filler block 6 and the second magnetic filler block 7. Then, the organic pollutants are degraded by the microorganisms attached to the first magnetic filler block 6 and the second magnetic filler block 7. At the same time, the microorganisms undergo metabolism, growth, reproduction and other processes, and gradually form a thin biofilm in the local area of ​​the first magnetic filler block 6 and the second magnetic filler block 7.

[0068] As the culture and acclimatization time increases, the biofilm grown on the surface of the first magnetic filler block 6 and the second magnetic filler block 7 also grows rapidly, gradually covering the entire surface of the first magnetic filler block 6 and the second magnetic filler block 7, and begins to thicken, dissolving the oxygen in the air provided by the aeration fan 3 and the air brought in by the contact between the first magnetic filler block 6 and the air into the flowing water layer, and passing it to the biofilm through the water layer for microorganisms to breathe, forming an aerobic layer biofilm on the outer layer of the biofilm, and the microorganisms in the aerobic layer can perform nitrification / denitrification to degrade ammonia nitrogen, and at the same time degrade organic pollutants such as antibiotics and COD;

[0069] During the thickening process of the biofilm, the biofilm near the surface of the first magnetic filler block 6 and the second magnetic filler block 7 has insufficient oxygen utilization, and an anoxic / anaerobic layer biofilm is formed on the inner side of the biofilm. The anoxic / anaerobic layer biofilm can perform anaerobic ammonia oxidation / denitrification to remove total nitrogen and degrade organic matter.

[0070] In order to verify the effect of the device for synergistic removal of total nitrogen from antibiotics in water based on magnetic fillers of the present application, the following experiment was conducted.

[0071] The following field simulation test was carried out according to the equipment in Example 1 and the prepared first magnetic filler 6 and second magnetic filler 7. The influent was the effluent from the primary sedimentation tank of a wastewater plant in Yixing. The specific water quality indicators of the influent were as follows: sulfamethoxazole concentration was 80.5-145.2 ug / L, ammonia nitrogen concentration (NH 4+-N) is 21.0~33.4mg / L, and the nitrite concentration (NO 2- -N) is 0.1~0.6mg / L, and the nitrate concentration (NO 3- -N) is 0.7~2.0mg / L, total phosphorus (TP) concentration is 4.3~6.2mg / L, COD concentration is 86.3~110.0mg / L, pH value is 7.3~7.8, temperature is 26.5~30.1℃, inoculated sludge comes from aerobic pool sludge of a certain urban wastewater treatment plant in Yixing, and the effective volume of reaction pool 2 is 2.4m 3 .

[0072] Biofilm formation stage: add the second magnetic filler block 7 into the reaction tank 2, the filling rate is 26%, the magnetic strength of the magnetic filler block is 0.8-1.3mT, and install the first magnetic filler block 6 to start inoculating the aerobic tank activated sludge. Use the rapid sludge discharge method to form biofilms. Automatically operate in a sequential batch mode, the drainage ratio is 33.4%, and 6 cycles are operated every day, with water intake for 10 minutes, aeration operation for 440 minutes, and sedimentation and standing for 30 minutes. The DO concentration of the reaction tank is maintained at 2-5mg / L by frequency conversion control of the aeration fan air volume. At this stage, the effluent ammonia nitrogen and COD removal rates reach 50.9% and 60.0% respectively; the biofilm formation is completed, and then enters the antibiotic total nitrogen synergistic removal stage:

[0073] Antibiotic total nitrogen synergistic removal stage: 9 cycles per day, aeration operation for 120 minutes, sedimentation and standing for 30 minutes, DO concentration controlled at 4.2-5.8 mg / L;

[0074] The equipment has been in operation for more than 500 days. During this stage, the sulfamethoxazole removal rate of the reactor 2 wastewater was 82.9% to 84.1%, the total nitrogen removal rate was about 80.1%, the total nitrogen in the effluent was stable below 10 mg / L for 15 consecutive days, and the COD removal rate was 62.7% to 65.7%.

[0075] At the same time, we compared with other treatment methods according to the same test method. Comparative Example 1 is: only the second magnetic filler block 7 is added, and the filling rate is 30%;

[0076] Comparative Example 2: only the second magnetic filler block 7 is added, and the filling rate is 35%;

[0077] Comparative Example 3: only the second magnetic filler block 7 is added, and the filling rate is 40%;

[0078] In Comparative Examples 1 to 3, the reaction zone 22 was not distinguished and the water wheel 5 was not provided. The treatment results after the antibiotic total nitrogen synergistic removal stage was operated for 30 days are shown in Table 1.

[0079] Table 1 Treatment effect of wastewater in each case

[0080] Case Sulfamethoxazole removal rate % COD removal rate % Example 1 80.5 61.2 Comparative Example 1 73.6 55.2 Comparative Example 2 81.1 61.5 Comparative Example 3 78.3 59.6

[0081] It can be seen from the data in Table 1 that in Comparative Example 1, the reaction zone 22 was not distinguished, the water wheel 5 was not set, and only the second magnetic filler block 7 was added. The sulfamethoxazole removal rate and COD removal rate after 30 days of operation in the antibiotic total nitrogen synergistic removal stage were not as good as those in Example 1, indicating that the two magnetic fillers and the water wheel in Example 1 can improve the contact aeration efficiency of the magnetic fillers, accelerate the construction of the biofilm, and promote the nitrification / denitrification of aerobic and anaerobic microorganisms.

[0082] The sulfamethoxazole removal rate and COD removal rate of the antibiotic total nitrogen synergistic removal stage in Comparative Example 2 after 30 days of operation were slightly improved compared with Example 1. This is because increasing the amount of the second magnetic filler block 7 can further accelerate the construction of the biofilm of the second magnetic filler block 7, but at the same time the equipment cost is also increased accordingly;

[0083] In Comparative Example 3, the amount of the second magnetic filler block 7 added was further increased, but the sulfamethoxazole removal rate and COD removal rate were not further improved, but decreased. This is because adding too much second magnetic filler block 7 without the assistance of the stirring component 9 will cause serious accumulation, affecting the nitrification / denitrification of microorganisms in the aerobic layer and the anaerobic layer.

Claims

1. A device for the synergistic removal of total nitrogen from antibiotics in water based on magnetic fillers, characterized in that: It comprises a water inlet tank (1), a reaction tank (2), an aeration fan (3) and a PLC controller (4); The water inlet box (1) is connected to the lower part of a side wall of the reaction tank (2) through a water inlet pipe (11), and a water inlet pump (12) is provided on the water inlet pipe (11); A water wheel (5) is provided in the middle of the reaction pool (2), the water wheel (5) corresponds to the water outlet position of the end of the water inlet pipe (11) so that the water wheel (5) rotates under water power, the water wheel (5) comprises a rotating shaft (53), a plurality of rotating arms (51) evenly arranged on the rotating shaft (53), and a water retaining plate (52) provided at the end of each rotating arm (51), a first magnetic filler block (6) is slidably sleeved on the rotating arm (51), and second magnetic filler blocks (7) are filled on both sides of the reaction pool (2), a water outlet pipe (8) is provided in the middle of one side wall of the reaction pool (2) relative to the water inlet pipe (11), and an overflow port (23) is provided on the side wall of the reaction pool (2) above the water outlet pipe (8); The PLC controller (4) is electrically connected to the water inlet pump (12) and the aeration fan (3).

2. The device for synergistically removing total nitrogen from water using antibiotics based on magnetic fillers according to claim 1 is characterized in that: The number of the rotating arms (51) and the water baffles (52) is 15 to 20.

3. The device for synergistically removing total nitrogen from water using antibiotics based on magnetic fillers according to claim 1, characterized in that: When the water wheel (5) rotates, the water baffle (52) located at the bottom extends to the bottom of the reaction pool (2), and the portion of the top of the water baffle (52) located at the top that exceeds the wastewater level in the reaction pool (2) accounts for 1 / 5 to 1 / 4 of the rotation radius of the water wheel (5).

4. The device for synergistically removing total nitrogen from water using antibiotics based on magnetic fillers according to claim 1, characterized in that: The first magnetic filler block (6) and the second magnetic filler block (7) both comprise: a cylindrical porous outer frame (61) located on the outside, and a hollow hexagonal porous inner frame (62) located at the center; a cylindrical porous support frame (63) is provided between the porous inner frame (62) and the porous outer frame (61); porous support walls (64) are provided between the porous inner frame (62) and the porous support frame (63), and between the porous support frame (63) and the porous outer frame (61); and the porous outer frame (61), the porous inner frame (62), the porous support frame (63) and the porous support wall (64) all have a plurality of holes with a pore size of 0.2 to 0.5 mm.

5. The device for synergistically removing total nitrogen from water using antibiotics based on magnetic fillers according to claim 4 is characterized in that: The porous inner frame (62) of the first magnetic filler block (6) is slidably mounted on the rotating arm (51), and each rotating arm (51) is provided with 6 to 10 first magnetic filler blocks (6), and the total length of the first magnetic filler blocks (6) provided on each rotating arm (51) is 70 to 80% of the length of the rotating arm (51).

6. The device for synergistically removing total nitrogen from water using antibiotics based on magnetic fillers according to claim 1, characterized in that: The two ends of the rotating shaft (53) are rotatably connected to the inner walls of the reaction pool (2) on both sides respectively. A plurality of stirring rod groups (9) are symmetrically arranged at the two ends of the rotating shaft (53). The stirring rod groups (9) located on the same side are arranged at equal intervals. The stirring rod groups (9) include a plurality of stirring rods (91) arranged at equal intervals along the circumference of the rotating shaft (53). The stirring rod groups (9) are separated by porous water-permeable partitions (21). A plurality of reaction zones (22) are formed inside the reaction pool (2). The second magnetic filler block (7) is evenly filled inside each of the reaction zones (22). The porous water-permeable partition (21) has a plurality of holes with a pore size of 2 to 5 mm.

7. The device for synergistically removing total nitrogen from water using antibiotics based on magnetic fillers according to claim 6, characterized in that: The height of the second magnetic filler block (7) is 5 to 20 mm, the radius of the second magnetic filler block (7) is 3 to 10 mm, and the total volume of the second magnetic filler block (7) in each reaction zone (22) accounts for 25 to 40% of the volume of the reaction zone (22) based on the volume enclosed by the second magnetic filler block (7). The total volume of the second magnetic filler block (7) in the entire reaction tank (2) is not less than 20% of the total volume of the wastewater in the reaction tank (2).

8. The device for synergistically removing total nitrogen from water using antibiotics based on magnetic fillers according to claim 6, characterized in that: An aeration main pipe (33) is provided at the output end of the aeration fan (3), and the aeration main pipe (33) is connected to the bottom of each of the reaction zones (22) through a plurality of aeration branch pipes (31) in a one-to-one correspondence, and an aeration plate (32) connected to the aeration branch pipe (31) is provided on both sides of the bottom of each reaction zone (22).

9. The device for synergistically removing total nitrogen from water using antibiotics based on magnetic fillers according to claim 1, characterized in that: The water outlet pipe (8) is provided with a solenoid valve (81), and the PLC controller (4) is electrically connected to the solenoid valve (81).

10. The device for synergistically removing total nitrogen from water using antibiotics based on magnetic fillers according to claim 1, characterized in that: The preparation method of the first magnetic filler block (6) and the second magnetic filler block (7) is as follows: NdFeB and high-density polyethylene are mixed at a mass ratio of 1:15-18, and then a hydrophilic auxiliary material is added, wherein the hydrophilic auxiliary material is clinoptilolite, and the amount of clinoptilolite added is 0.4-0.8% of the total weight of the NdFeB and high-density polyethylene. After mixing together, the mixture is extruded through an extrusion granulator at a temperature of 280-320°C to obtain material particles with a length not exceeding 2 mm, and the material particles are placed in a corresponding mold for shaping to obtain the first magnetic filler block (6) or the second magnetic filler block (7).

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