Culture tail water treatment method for synchronously removing pollutants and antibiotics

Abstract

The invention discloses a culture tail water treatment method for synchronously removing pollutants and antibiotics, and belongs to the technical field of culture tail water treatment. According to the invention, the regulating tank is used for carrying out precipitation pretreatment on the culture tail water, then the integrated anoxic-aerobic bio-membrane reactor is used for carrying out biological removal on organic matters, ammonia nitrogen and total nitrogen in the culture tail water, and then the adsorption and ozone coupling device is used for removing total phosphorus and antibiotics in the culture tail water. The effluent quality can meet the primary standard of a fresh water receiving area in Discharge Standard of Pond Culture Tail Water in Jiangsu Province (DB32 / 4043-2021), the up-to-standard discharge of the culture tail water is realized, and meanwhile, the antibiotic removal rate is greater than 90%. According to the treatment method, pollutants and antibiotics in the aquaculture tail water are synchronously removed, and the treatment method has a relatively good application prospect.

Description

Technical Field

[0001] The invention relates to a method for treating aquaculture tail water for simultaneously removing pollutants and antibiotics, and belongs to the technical field of aquaculture tail water treatment. Background Art

[0002] With the rapid development of aquaculture, a large amount of aquaculture tailwater is discharged into natural water bodies. These tailwaters usually contain a large amount of nutrients (such as nitrogen and phosphorus) and antibiotic residues, which will not only lead to eutrophication of water bodies, but also pose potential hazards to the ecological environment and human health. At present, the treatment technologies for aquaculture tailwater mainly include three-pond and two-dam technology, artificial wetland technology, etc. However, these technologies have problems such as low treatment efficiency, large footprint, unstable treatment effect, and poor removal of antibiotics.

[0003] An existing patent (CN 218232139 U) provides a tailwater purification device based on a moving bed biofilm reactor (MBBR), which includes a filter tank, a disinfection tank, and several biofilm reaction tanks connected in sequence, and achieves good C and N treatment effects. However, this technology has problems such as large footprint, complex process, and poor phosphorus and antibiotic removal effects.

[0004] At present, common deep phosphorus removal technologies include biotechnology, adsorption technology, chemical technology and membrane separation technology. Biological phosphorus removal requires the discharge of phosphorus-rich sludge to achieve TP removal; chemical phosphorus removal has problems such as secondary water pollution, high reagent costs, and impact on the water ecological environment; membrane separation technology has problems such as high operating costs and difficulty in membrane regeneration. Adsorption phosphorus removal technology is widely used in the field of water treatment due to its high efficiency and flexible operating conditions. It is especially suitable for occasions where low concentrations of phosphorus need to be removed. Existing phosphorus removal adsorbents are mainly made of natural bentonite and zeolite as raw materials, and metal elements such as Fe, Mg, and Al as modifiers. Their adsorption effect is relatively limited, and there are problems such as low adsorption rate and insufficient adsorption capacity.

[0005] In summary, the existing aquaculture tailwater treatment technologies generally have the problems of large footprint, unstable treatment effect, and poor removal of phosphorus and antibiotics; the existing adsorption phosphorus removal technology has problems such as low adsorption rate and insufficient adsorption capacity, which makes it difficult to meet the requirements of deep phosphorus removal from aquaculture tailwater. Therefore, an efficient, low-cost and environmentally friendly aquaculture tailwater treatment technology is urgently needed to solve the above problems. Summary of the invention

[0006] To achieve the above-mentioned purpose, the present invention provides a method for the simultaneous removal of nutrients and antibiotics in aquaculture tail water, which mainly utilizes a regulating tank to perform sedimentation pretreatment on the aquaculture tail water, and then uses an integrated anoxic aerobic biofilm reactor to biologically remove C and N in the aquaculture tail water, and then uses an adsorption and ozone coupling device to remove P and antibiotics in the aquaculture tail water, thereby realizing the simultaneous removal of pollutants and antibiotics.

[0007] The first object of the present invention is to provide a device for simultaneously removing pollutants and antibiotics, which consists of a regulating tank, an integrated anoxic aerobic biofilm reactor, a lanthanum-modified glass pumice adsorption device and an ozone generator.

[0008] Furthermore, the regulating tank is connected to the aerobic zone of the integrated anoxic aerobic biofilm reactor through a water pipe, and a water inlet pump is installed in the middle of the water pipe to pump water from the regulating tank into the integrated anoxic aerobic biofilm reactor.

[0009] Furthermore, the integrated anoxic aerobic biofilm reactor is a columnar structure with a partition inside. The aerobic zone is located above the partition and the anoxic zone is located below. Both the aerobic zone and the anoxic zone have polyurethane sponge carriers. An aeration pipe is installed in the aerobic zone, and an aeration pump introduces air into the aerobic zone through the aeration pipe. The integrated anoxic aerobic biofilm reactor also has a water pipe connecting the anoxic zone and the aerobic zone. A water pump is installed in the middle of the water pipe to return water from the aerobic zone to the anoxic zone.

[0010] Furthermore, the partition is provided with a plurality of circular holes with a diameter of 3-5 cm to facilitate the flow of substances.

[0011] Furthermore, the volume ratio of the aerobic zone to the anoxic zone is 2.5-3.5:1.

[0012] Preferably, the volume ratio of the aerobic zone to the anoxic zone is 3:1.

[0013] Furthermore, the mixing ratio of the polyurethane sponge carrier in the aerobic zone and the anoxic zone is 10-30%.

[0014] Furthermore, the mixing ratio is a volume ratio, that is, the volume of the polyurethane sponge carrier accounts for 10-30% of the volume of the aerobic zone and the anoxic zone respectively.

[0015] Furthermore, the lanthanum-modified glass pumice adsorption device is cylindrical, with a water distribution tray installed at the bottom, and a water outlet pipe is provided near the top of the integrated anoxic aerobic biofilm reactor, which is connected to the water inlet at the bottom of the lanthanum-modified glass pumice adsorption device; the lanthanum-modified glass pumice adsorption device is filled with lanthanum-modified glass pumice; the lanthanum-modified glass pumice adsorption device is provided with a hollow tube, which vertically connects the bottom and the outside of the adsorption device; the bottom of the lanthanum-modified glass pumice adsorption device is also provided with an aeration device, and the adsorption device is aerated through the aeration device.

[0016] Furthermore, the lanthanum-modified glass pumice is prepared by the following preparation method:

[0017] A lanthanum chloride aqueous solution with a concentration of 0.05-0.2 mol / L is prepared, and then the pH of the lanthanum chloride solution is adjusted to 9-11, and then glass pumice is added to the lanthanum chloride aqueous solution at a solid-liquid ratio of 1g:10-30mL, and the glass pumice is taken out after heating and stirring, washed with water and dried to obtain lanthanum-modified glass pumice.

[0018] Furthermore, the heating and stirring is stirring at 50-70° C. for 1-5 hours.

[0019] Furthermore, the filling rate of the lanthanum modified glass pumice is 20%-30%.

[0020] Furthermore, the filling rate is a volume ratio, that is, the volume of the lanthanum-modified glass pumice accounts for 10-20% of the volume of the lanthanum-modified glass pumice adsorption device.

[0021] Furthermore, the ozone generator is connected to the aeration device through an air pipe, an air pump is installed in the middle of the air pipe, and the ozone generated by the ozone generator is output to the aeration device through the air pump.

[0022] The second object of the present invention is to use the device for simultaneously removing pollutants and antibiotics in sewage treatment.

[0023] Furthermore, the sewage includes one or more of aquaculture tail water, industrial sewage, and domestic sewage.

[0024] Furthermore, the application is to remove antibiotics, COD, ammonia nitrogen, TN and TP in sewage.

[0025] The third object of the present invention is to provide a method for simultaneously removing pollutants and antibiotics in aquaculture tail water, the method being carried out using the above-mentioned device and specifically comprising the following steps:

[0026] (1) placing the aquaculture tail water in a regulating tank, allowing it to stand, and then pumping the standing aquaculture tail water into an integrated anoxic aerobic biofilm reactor through a water pump;

[0027] (2) Control the hydraulic retention time in the integrated anoxic aerobic biofilm reactor to be 1 to 5 h, the temperature to be 20 to 30 °C, the reflux ratio of water from the aerobic zone to the anoxic zone to be 100% to 150%, the dissolved oxygen concentration in the aerobic zone to be 3 to 10 mg / L, and aeration to complete NH4 + - Removal of N, COD and TN;

[0028] (3) The effluent from the integrated anoxic aerobic biofilm reactor is passed through a water pipe into a lanthanum-modified glass pumice adsorption device, and the residence time of the effluent in the adsorption device is controlled to be 30 to 50 minutes. The ozone concentration in the adsorption device is 1 to 5 mg / L, and the filling rate of the lanthanum-modified glass pumice is 20 to 30%. Aeration is performed at the same time to achieve the simultaneous removal of TP and antibiotics, thereby achieving standard discharge of aquaculture effluent.

[0029] In one embodiment of the present invention, the COD of the aquaculture tail water is 50-100 mg / L, NH3-N is 1-10 mg / L, TN is 5-15 mg / L, TP is 1-5 mg / L, pH is 7-7.5, and the antibiotic concentration is 100-1000 ug / L.

[0030] In one embodiment of the present invention, the COD of the aquaculture tail water is 65-75 mg / L, NH3-N is 4-5 mg / L, TN is 8.5-9.5 mg / L, TP is 1.3-1.5 mg / L, pH is 7-7.5, and the antibiotic concentration is 100-500 ug / L.

[0031] In one embodiment of the present invention, the standing time in step (1) is 1 to 24 hours.

[0032] In one embodiment of the present invention, the aeration in step (2) can be intermittent aeration or continuous aeration; the intermittent aeration is aeration for 2 to 10 minutes every 10 to 40 minutes; and the gas used for aeration is air.

[0033] In one embodiment of the present invention, the aeration method in the lanthanum-modified glass pumice adsorption device in step (3) is intermittent aeration or continuous aeration; the intermittent aeration is aeration for 2 to 10 minutes every 10 to 40 minutes; the gas used for aeration includes ozone or a mixture of ozone and air, as long as the ozone concentration requirement in the adsorption device is met.

[0034] Specifically, the lanthanum-modified glass pumice adsorption device is intermittently aerated, specifically aerated for 3 to 6 minutes every 20 to 40 minutes; the gas used for aeration is ozone.

[0035] Beneficial effects of the present invention:

[0036] (1) The present invention replaces the traditional biofilm reactor with aerobic and anoxic tanks separated horizontally with an integrated anoxic and aerobic biofilm reactor separated vertically, thereby realizing the integrated operation of nitrification and denitrification reactions, improving the TN removal rate, and reducing the occupied area.

[0037] (2) The present invention provides a lanthanum-modified glass pumice, which has the advantages of simple preparation, cheap and easy-to-obtain materials, high adsorption rate of the obtained materials, and strong adsorption capacity. In addition, the lanthanum-modified glass pumice can be used in combination with ozone aeration to achieve a synergistic effect, thereby realizing the simultaneous and efficient removal of pollutants and antibiotics in sewage, and the removal rate of antibiotics is above 99%.

[0038] (3) The present invention treats aquaculture tail water by combining an integrated anoxic aerobic biofilm reactor with lanthanum-modified glass pumice adsorption technology, thereby removing both residual nutrients and antibiotics contained in the aquaculture tail water, thereby achieving standard discharge of aquaculture tail water. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 A schematic diagram of the structure of a method for simultaneously removing pollutants and antibiotics from aquaculture tail water according to the present invention;

[0040] In the figure: 1. regulating tank; 2. integrated anoxic aerobic biofilm reactor; 3. lanthanum modified glass pumice adsorption device; 4. water inlet pump; 5. reflux pump; 6. first aeration pump; 7. second aeration pump; 8. aeration plate; 9. aerobic zone; 10. anoxic zone; 11. valve; 12. aeration device; 13. lanthanum modified glass pumice; 14. polyurethane sponge carrier; 15. partition; 16. hollow pipe; 17. water distribution tray; 18. ozone generator; 19. outlet; 20. top cover. DETAILED DESCRIPTION

[0041] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0042] In the present invention, unless otherwise clearly specified and limited, the terms "connected", "connected", and "fixed" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0043] In the present invention, unless otherwise clearly specified and limited, a first feature being "above" or "below" a second feature may include that the first and second features are in direct contact, or may include that the first and second features are not in direct contact but are in contact through another feature between them. Moreover, a first feature being "above", "above" and "above" a second feature includes that the first feature is directly above and obliquely above the second feature, or simply indicates that the first feature is higher in level than the second feature. A first feature being "below", "below" and "below" a second feature includes that the first feature is directly below and obliquely below the second feature, or simply indicates that the first feature is lower in level than the second feature.

[0044] Source of raw materials

[0045] The polyurethane sponge carrier was purchased from Wuxi Mier Environmental Protection Technology Co., Ltd., with a specification of 1.5*1.5*1.5cm, which expanded to 2.5*2.5*2.5cm after absorbing water, and a porosity of ≥98%. The glass pumice was purchased from Jiangsu Jingruite Environmental Protection New Materials Co., Ltd., with a specification of J2 and a dry density of 0.3-0.5g / cm 3 , compressive strength is 2.5~3.0Mpa, and particle size is 1~2cm.

[0046] Example 1

[0047] A lanthanum chloride aqueous solution with a concentration of 0.1 mol / L was prepared, and then the pH of the lanthanum chloride solution was adjusted to 10 using a NaOH aqueous solution. Then, glass pumice with a particle size of about 1 cm was added to the lanthanum chloride aqueous solution at a solid-liquid ratio of 1:15 (g:mL). Then, the beaker was placed on a magnetic stirrer, stirred at 60°C for 4 hours, and then the glass pumice was taken out and washed with deionized water until the pH of the supernatant was consistent with that of the deionized water. Then, the glass pumice was dried at 60°C for 24 hours to obtain lanthanum-modified glass pumice.

[0048] Example 2

[0049] like Figure 1 As shown, this embodiment provides a device for simultaneously removing pollutants and antibiotics in aquaculture tail water, and the device includes a regulating tank 1, an integrated anoxic aerobic biofilm reactor 2, a lanthanum-modified glass pumice adsorption device 3, and an ozone generator 18.

[0050] The regulating tank 1 is open and used for standing aquaculture tail water; the regulating tank 1 is connected to the aerobic zone of the integrated anoxic aerobic biofilm reactor 2 through a water pipe, and a water inlet pump 4 is installed in the middle of the water pipe to pump water from the regulating tank 1 into the integrated anoxic aerobic biofilm reactor 2.

[0051] The integrated anoxic aerobic biofilm reactor 2 is a columnar filter cartridge structure, which is open at the top and connected to a conical funnel at the bottom. A discharge port 19 is provided at the bottom of the funnel for discharging sediments. A partition 15 is provided in the integrated anoxic aerobic biofilm reactor 2, and a plurality of circular holes with a diameter of 3-5 cm are opened on the partition for material circulation. The upper part of the partition is an aerobic zone 9, and the lower part is an anoxic zone 10. The volume ratio of the aerobic zone to the anoxic zone is 3:1. Both the aerobic zone and the anoxic zone have polyurethane sponge carriers 14, and the carrier dosing ratio is 10%. An aeration pipe 8 is installed at a position 10 cm above the partition in the aerobic zone, and a first aeration pump 6 introduces air into the aerobic zone through the aeration pipe 8. The integrated anoxic aerobic biofilm reactor 2 also has a water pipe connecting the bottom of the anoxic zone and the upper part of the aerobic zone. A reflux pump 5 is installed in the middle of the water pipe for refluxing water from the aerobic zone to the anoxic zone, and the reflux ratio is 100%-150%.

[0052] The lanthanum-modified glass pumice adsorption device 3 is cylindrical, with a top cover 20 on the top and a water distribution tray 17 on the bottom. A water outlet pipe is provided near the top of the integrated anoxic aerobic biofilm reactor 2 and is connected to the water inlet at the bottom of the lanthanum-modified glass pumice adsorption device 3. The hydraulic pressure difference between the two drives the water flow from the membrane reactor into the water distribution tray 17 of the adsorption device. A valve 11 is provided on the water outlet pipe to control the flow rate; the lanthanum-modified glass pumice adsorption device 3 is filled with lanthanum-modified glass pumice 13, and the filling rate is 20%-30%; a hollow tube 16 is provided in the lanthanum-modified glass pumice adsorption device 3, one end of the hollow tube 16 is located at the bottom of the adsorption device, and the other end is connected to the outside through the opening of the top cover; the adsorption device is aerated by the aeration device 12, the lanthanum-modified glass pumice is flushed, and the fluidity of the glass pumice is improved.

[0053] The ozone generator 18 is connected to the aeration device 12 through an air pipe in the hollow tube 16. A second aeration pump 7 is installed in the middle of the air pipe. The ozone generated by the ozone generator can be output to the aeration device through the air pump, and the ozone is used to aerate the adsorption device.

[0054] The working principle of the device provided in this embodiment is as follows: the aquaculture tail water is precipitated in the regulating tank 1 to reduce the concentration of suspended solids, and then pumped into the aerobic zone 9 in the integrated anoxic aerobic biofilm reactor 2 through the water inlet pump 4; the aerobic zone 9 is continuously flushed by the aeration disk 8 to ensure that the polyurethane sponge biofilm carrier 14 is fully in contact with the water flow, and the NH4 +After the removal of -N and part of COD, the aquaculture tail water is returned to the anoxic zone 10 through the reflux pump 5, and the TN removal is completed in the anoxic zone to achieve the standard discharge of TN; then the aquaculture tail water overflows into the lanthanum-modified glass light stone adsorption device 3 through the outlet of the integrated anoxic aerobic biofilm reactor 2, and the aeration device 12 is used to ensure that the water body and the lanthanum-modified glass light stone 13 are in full contact to achieve the adsorption and removal of TP and achieve the standard discharge of TP; the aeration device 12 is connected to the ozone generator 18, and ozone oxidation can be carried out in the adsorption device to achieve the oxidative removal of antibiotics; the aquaculture tail water is discharged from the adsorption device 3, which can meet the first-level standard of freshwater receiving waters in the "Jiangsu Province Pond Aquaculture Tail Water Discharge Standard" (DB32 / 4043-2021), and the antibiotics can be effectively removed at the same time.

[0055] Example 3

[0056] In order to verify the treatment effect of the device described in Example 2, an experiment was conducted with simulated aquaculture tail water, where COD 65-75 mg / L, NH4 + -N 4~5mg / L, TN 8.5~9.5mg / L, TP 1.3~1.5mg / L, the specific values ​​are shown in Table 1. The target antibiotics in the simulated aquaculture tail water are sulfamethoxazole (SMX), ciprofloxacin (CIP), enrofloxacin (ENR), tetracycline (TC) and erythromycin (ERY), and the concentrations of the above antibiotics are all 100ug / L.

[0057] The device described in Example 2 was used to conduct an experiment, controlling the hydraulic retention time (HRT) in the integrated anoxic aerobic biofilm reactor 2 to 3 h, the temperature to 25° C., the reflux ratio to 150%, the polyurethane sponge carrier dosage ratio to 10%, and the dissolved oxygen in the aerobic zone 9 to 5 mg / L; the hydraulic retention time in the adsorption device was 39 min, the ozone concentration was 1.25 mg / L, the aeration method was intermittent aeration, aeration for 5 min every 35 minutes, and the gas used for aeration was ozone produced by an ozone generator; the filling rate of the lanthanum-modified glass pumice 13 in the lanthanum-modified glass pumice adsorption device 3 was 30%.

[0058] Table 1 Removal effect of pollutants

[0059] index COD Ammonia nitrogen TN TP Influent (mg / L) 70.21 4.96 9.07 1.41 Integrated anoxic aerobic biofilm reactor effluent (mg / L) 9.71 0.10 2.55 1.15 Water output from adsorption device (mg / L) 9.71 0.10 2.55 0.02 Removal rate 86％ 98％ 72％ 98％

[0060] Table 2 Removal effect of antibiotics

[0061] index SMX CIP ENR TC ERY Influent (ug / L) 100 100 100 100 100 Integrated anoxic aerobic biofilm reactor effluent (ug / L) 90.78 82.08 83.78 89.55 93.70 Water output from adsorption device (ug / L) 0.20 1.00 6.20 0.20 7.10 Removal rate 99.80％ 99.00％ 93.80％ 99.80％ 92.90％

[0062] The experimental results are shown in Tables 1 and 2 above. It can be seen that after the aquaculture tail water is treated by the device, the effluent TN is less than 3mg / L, the effluent TP is less than 0.4mg / L, and the effluent water quality can meet the first-level standard of freshwater receiving waters in the "Jiangsu Province Pond Aquaculture Tail Water Discharge Standard" (DB32 / 4043-2021), achieving the standard discharge of aquaculture tail water. After the antibiotics are treated by the device, the effluent antibiotic concentration is less than 10ug / L, and the antibiotic removal rate is greater than 90%, indicating that the device can achieve the simultaneous removal of pollutants and antibiotics.

[0063] Comparative Example 1

[0064] This comparative example explores the effect of different anoxic tank volume ratios on the nutrient removal rate. The device described in Example 2 was used for the experiment, in which the volume of the fixed integrated anoxic aerobic biofilm reactor was 3L, and different anoxic tank volume ratios were achieved only by adjusting the positions of the aeration disk and the baffle, and the effect of different anoxic tank volume ratios on the nutrient removal rate was investigated. The same simulated aquaculture tail water as in Example 3 was used, with a hydraulic retention time (HRT) of 3h, a temperature of 25°C, a reflux ratio of 150%, a polyurethane sponge carrier dosage ratio of 10%, and the dissolved oxygen in the aerobic zone 9 was controlled at 5mg / L. The parameter settings of the lanthanum-modified glass pumice adsorption device 3 were the same as in Example 3.

[0065] Table 3 Removal effect of different anoxic tank volume ratios

[0066] Index / Different volume ratio <![CDATA[V A :V O =1:2]]> <![CDATA[V A :V O =1:3]]> <![CDATA[V A :V O =1:4]]> TN 52％ 72％ 59％ Ammonia nitrogen 90％ 98％ 98％ COD 86％ 86％ 86％ TP 18％ 19％ 16％

[0067] Note: VA is the volume of the anoxic pool; VO is the volume of the aerobic pool.

[0068] The experimental results are shown in Table 3 above. It can be seen that the volume ratio of the anoxic tank has an impact on the removal effect of aquaculture tail water, among which the impact on TN is greater. Therefore, in order to achieve the best removal effect, the volume ratio of the anoxic tank needs to be controlled at about 1:3.

[0069] Comparative Example 2

[0070] This comparative example explores the effects of different treatment processes on the removal rate of antibiotics. The device described in Example 2 was used, wherein the filling rate of the lanthanum-modified glass pumice adsorption process was 30%, and the hydraulic contact time was 39 minutes; the single ozone oxidation process was ozone intermittent aeration, and the adsorption device was not filled with lanthanum-modified glass pumice, and aeration was performed for 5 minutes every 35 minutes, and the gas used for aeration was ozone; the coupling process filled the adsorption device with 30% lanthanum-modified glass pumice, and ozone intermittent aeration was provided at the same time, and aeration was performed for 5 minutes every 35 minutes, and the gas used for aeration was ozone. The same simulated aquaculture tail water as in Example 3 was used, and the parameter settings of the integrated anoxic aerobic biofilm reactor 2 were the same as in Example 3.

[0071] Table 4 Removal effect of different treatment processes

[0072] Antibiotics / Process Lanthanum modified glass pumice Ozone oxidation Coupling process SMX 3.6％ 71.2％ 99.8％ CIP 15.8％ 52.1％ 99.0％ ENR 13.4％ 59.3％ 93.8％ TC 7.9％ 78.2％ 99.8％ ERY 6.5％ 77.3％ 92.9％ TP 76.1％ 5.2％ 98.3％

[0073] The experimental results are shown in Table 4 above. It can be seen that the use of lanthanum-modified glass pumice or ozone oxidation alone cannot achieve satisfactory removal effects. When lanthanum-modified glass pumice and ozone oxidation are used in combination, the removal rates of antibiotics and TP reach more than 90%, achieving a synergistic effect.

[0074] Comparative Example 3

[0075] This comparative example explores the effects of different treatment processes on TP removal rates. Using the device described in Example 2, an equal amount of glass pumice (unmodified) was weighed and filled into the adsorption column, with a filling rate of 30% and a hydraulic contact time of 39 minutes. The adsorption process alone is to fill only 30% glass pumice without aeration; the glass pumice + aeration process is to fill 30% lanthanum-modified glass pumice in the adsorption device, and provide intermittent ozone aeration at the same time, aerating for 5 minutes every 35 minutes. The inlet TP concentration is 1 mg / L.

[0076] Table 5 TP effluent concentrations of different treatment processes (mg / L)

[0077] Process / Time(d) 1 2 3 4 5 6 Adsorption process 0.24 0.46 0.66 0.89 0.99 1.00 Adsorption + aeration process 0.02 0.08 0.20 0.30 0.38 0.46

[0078] The experimental results are shown in Table 5 above. It can be seen that when lanthanum-modified glass pumice is used alone for adsorption, there are problems such as low removal efficiency and short use time. However, when the adsorption process is coupled with the aeration process to intermittently flush the glass pumice, the removal efficiency and use time of TP are greatly improved, and high-efficiency removal of TP is achieved.

[0079] Although the present invention has been disclosed as above in the form of a preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A device for simultaneously removing pollutants and antibiotics, characterized in that: The device is composed of a regulating tank, an integrated anoxic aerobic biofilm reactor, a lanthanum-modified glass pumice adsorption device and an ozone generating device; The regulating tank is connected to the aerobic zone of the integrated anoxic aerobic biofilm reactor through a water pipe, and a water inlet pump is installed in the middle of the water pipe to pump water from the regulating tank into the integrated anoxic aerobic biofilm reactor; the integrated anoxic aerobic biofilm reactor is a columnar structure, and a partition is provided inside, and a circular hole is opened on the partition, the upper part of the partition is the aerobic zone, and the lower part is the anoxic zone, the volume ratio of the aerobic zone to the anoxic zone is 2.5-3.5:1, and both the aerobic zone and the anoxic zone have polyurethane sponge carriers; an aeration pipe is installed in the aerobic zone, and the aeration pump introduces air into the aerobic zone through the aeration pipe; there is also a water pipe in the integrated anoxic aerobic biofilm reactor to connect the anoxic zone and the aerobic zone, and a water pump is installed in the middle of the water pipe to return water from the aerobic zone to the anoxic zone; An outlet pipe is provided near the top of the integrated anoxic aerobic biofilm reactor and is connected to the water inlet at the bottom of the lanthanum-modified glass pumice adsorption device; the lanthanum-modified glass pumice adsorption device is filled with lanthanum-modified glass pumice and is provided with a hollow tube, and the hollow tube is vertically connected to the bottom and the outside of the adsorption device; an aeration device is installed at the bottom of the lanthanum-modified glass pumice adsorption device, and the adsorption device is aerated through the aeration device; the ozone generator is connected to the aeration device through an air pipe, and an air pump is installed in the middle of the air pipe, and the ozone generated by the ozone generator is output to the aeration device through the air pump; The lanthanum modified glass pumice is prepared by the following preparation method: A lanthanum chloride aqueous solution with a concentration of 0.05-0.2 mol / L is prepared, and then the pH of the lanthanum chloride solution is adjusted to 9-11, and then glass pumice is added to the lanthanum chloride aqueous solution at a solid-liquid ratio of 1g:10-30mL, and the glass pumice is taken out after heating and stirring, washed with water and dried to obtain lanthanum-modified glass pumice.

2. The device according to claim 1, characterized in that The volume ratio of the aerobic zone to the anoxic zone is 3:

1.

3. The device according to claim 1, characterized in that The polyurethane sponge carrier is mixed in the aerobic zone and the anoxic zone at a ratio of 10-30%.

4. The device according to claim 1, characterized in that The filling rate of the lanthanum modified glass pumice is 20%-30%.

5. Use of the device for simultaneously removing pollutants and antibiotics according to any one of claims 1 to 4 in sewage treatment.

6. The use according to claim 5, characterized in that The sewage includes one or more of aquaculture tail water, industrial sewage, and domestic sewage.

7. A method for simultaneously removing pollutants and antibiotics from aquaculture tail water, characterized in that: The method is carried out using the device according to any one of claims 1 to 4, and the method specifically comprises the following steps: (1) placing the aquaculture tail water in a regulating tank, allowing it to stand, and then pumping the standing aquaculture tail water into an integrated anoxic aerobic biofilm reactor through a water pump; (2) Control the hydraulic retention time in the integrated anoxic aerobic biofilm reactor to be 1 to 5 h, the temperature to be 20 to 30 °C, the reflux ratio of water from the aerobic zone to the anoxic zone to be 100% to 150%, the dissolved oxygen concentration in the aerobic zone to be 3 to 10 mg / L, and aeration to complete NH4 + - Removal of N, COD and TN; (3) The effluent from the integrated anoxic aerobic biofilm reactor is passed through a water pipe into a lanthanum-modified glass pumice adsorption device, and the residence time of the effluent in the adsorption device is controlled to be 30 to 50 minutes. The ozone concentration in the adsorption device is 1 to 5 mg / L, and the filling rate of the lanthanum-modified glass pumice is 20 to 30%. Aeration is performed at the same time to achieve the simultaneous removal of TP and antibiotics, thereby achieving standard discharge of aquaculture effluent.

8. The method according to claim 1, characterized in that The aquaculture tail water has a COD of 50-100 mg / L, an NH3-N of 1-10 mg / L, a TN of 5-15 mg / L, a TP of 1-5 mg / L, a pH of 7-7.5, and an antibiotic concentration of 100-1000 ug / L.

9. The method according to claim 1, characterized in that The standing time in step (1) is 1 to 24 hours.

10. The method according to claim 1, characterized in that In step (3), the aeration method in the lanthanum-modified glass pumice adsorption device is intermittent aeration or continuous aeration; the gas used for aeration includes ozone or a mixture of ozone and air.

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