Device for removing antibiotic resistance genes in water

Abstract

The utility model discloses a device for removing antibiotic resistance genes in water. The device comprises a dosing tank and a reaction box, the dosing tank comprises a first water inlet, a first water suction pump, a liquid medicine box, a second water inlet and a second water suction pump; the reaction box comprises a clamping groove, a reaction groove, a water outlet groove, a catalytic membrane, a first water outlet, a third water inlet, a second water outlet and a fourth water suction pump; and the upper end of the reaction box is connected with a bypass circulating device. The device disclosed by the utility model has the characteristics that the purpose of recycling the fixed catalyst is achieved, the advanced oxidation efficiency is improved and pollutants are efficiently degraded by regulating and controlling the proportion of the added activating agent and the hydraulic retention time, and the blockage of the membrane component is inhibited and the performance of the device is improved by utilizing transverse water flow and a bypass circulating device.

Description

Technical Field

[0001] The utility model belongs to the technical field of water treatment, and in particular relates to a device for removing antibiotic resistance genes in water. Background Art

[0002] Due to the abuse of antibiotics, antibiotic resistance has become one of the major threats to human health, causing more than 700,000 deaths worldwide each year. It is estimated that by 2050, more than 10 million people will die each year from antibiotic resistance, causing related losses of up to $100 trillion. Wastewater treatment plants receive wastewater from industries such as life, aquaculture and medical care, and are hot spots for the presence of antibiotic resistance genes (ARGs). The accumulation of high concentrations of antibiotics will further promote the horizontal transfer of ARGs.

[0003] Simple membrane separation technology is based on size screening and can only filter bacteria in water, but cannot remove difficult-to-degrade organic pollutants in water. Advanced oxidation technology that uses transition metal elements to activate permonosulfate (PMS) to generate reactive oxygen species in situ has developed rapidly and can efficiently remove a variety of organic pollutants in wastewater. Among them, single-atom catalysts have the advantages of both homogeneous and heterogeneous catalysts. Compared with traditional transition metal catalysts, they have uniform active sites and high atomic utilization efficiency. They are easy to activate PMS, but there are problems such as difficulty in collecting catalysts. Combining membrane separation technology with advanced oxidation technology can efficiently degrade ARGs in water, fix the catalyst, and improve the efficiency of advanced oxidation by controlling the hydraulic retention time.

[0004] Under long-term circulation, background impurities in the actual water body will block the catalyst and membrane pores. The lateral water flow can deposit impurities by gravity during the flow; the bypass circulation device can increase the liquid disturbance on the membrane surface and play a cleaning effect, thus avoiding the blockage of membrane components by impurities due to gravity. Utility Model Content

[0005] The utility model aims to provide a device for removing antibiotic resistance genes in water in view of the deficiencies of the prior art.

[0006] The purpose of the utility model is achieved through the following technical solutions: a device for removing antibiotic resistance genes in water, comprising a dosing tank and a reaction box;

[0007] The dosing tank is connected to the reaction box; a first water inlet is opened above the side wall of the dosing tank, and a first water pump is arranged in the first water inlet, and the first water pump is used to pump sewage into the dosing tank through the first water inlet; a liquid medicine tank is arranged above the other side wall of the dosing tank, and a water pipe is arranged at the lower end of the liquid medicine tank; the liquid medicine tank is used to store PMS mother liquid, and the PMS mother liquid is added to the dosing tank through the water pipe; a second water inlet is opened below the side where the dosing tank is connected to the reaction box, and a second water pump is arranged in the second water inlet, and the second water pump is used to pump sewage in the dosing tank into the reaction box through the second water inlet;

[0008] A slot is provided in the middle of the reaction box, with one side close to the dosing tank as the reaction tank and the other side as the water outlet tank; the slot is used to place a catalytic membrane, on which an iron single-atom catalyst is loaded; a first water outlet and a third water inlet are provided at the upper end of the reaction box, the first water outlet is close to the water tank, and the third water inlet is close to the dosing tank; the upper end of the reaction box is connected to a bypass circulation device;

[0009] The bypass circulation device comprises a first water pumping pipe, a third water pumping pump and a second water pumping pipe; one end of the first water pumping pipe is connected to the first water outlet, and the other end is connected to the third water pumping pump; one end of the second water pumping pipe is connected to the third water inlet, and the other end is connected to the third water pumping pump;

[0010] A second water outlet is provided above the side wall of the water outlet trough, and a fourth water pump is arranged in the second water outlet.

[0011] Furthermore, a filter screen is provided on the first water inlet, and the filter screen is used to filter impurities in sewage.

[0012] Furthermore, a water pipe clamp is provided at the lower end of the water pipe, and the amount of PMS mother solution added to the dosing tank is controlled by opening and closing the water pipe clamp and adjusting the aperture of the water pipe.

[0013] Furthermore, a stirring blade is fixed at the upper end of the dosing tank, and the stirring blade is used to mix the sewage and the PMS solution in the dosing tank.

[0014] Furthermore, the thickness of the catalyst film is 200-500 μm.

[0015] Furthermore, a reaction tank cleaning water outlet is provided at the lower end of the reaction tank close to the card slot.

[0016] The beneficial effects of the utility model are:

[0017] 1) Combine membrane separation technology with advanced oxidation technology, fix powdered catalysts to make filter membranes, and facilitate catalyst recycling; automatically add reagents and control the ratio to reduce the waste of activators; improve the efficiency of advanced oxidation by controlling the hydraulic retention time, and efficiently degrade antibiotics and resistance genes in water;

[0018] 2) The horizontal water flow reduces the impurities deposited by gravity, and through the bypass circulation device, increases the liquid disturbance on the membrane surface, which has a cleaning effect, reduces the occurrence of membrane module blockage and the frequency of cleaning and replacement of membrane modules. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic diagram of the structure of a device for removing antibiotic resistance genes in water in Example 1;

[0020] Figure 2 This is a schematic diagram of the water flow direction in a device for removing antibiotic resistance genes in water in Example 1;

[0021] Figure 3 This is a schematic diagram of the structure of a device for removing antibiotic resistance genes in water in Example 3;

[0022] Figure 4 This is a schematic diagram of the structure of a device for removing antibiotic resistance genes in water in Example 4;

[0023] Figure 5 This is a schematic diagram of the structure of a device for removing antibiotic resistance genes in water in Example 6;

[0024] Figure 6 is the removal rate of different antibiotic resistance genes by activating PMS with the iron single atom catalyst prepared in Example 7;

[0025] Figure 7 The iron dissolution rate of the iron single-atom catalyst prepared in Example 7 is a graph showing the iron ion concentration in the solution during the reaction process;

[0026] Figure 8 This is a graph showing the degradation rate of tetracycline by PMS activated by the iron single atom catalyst prepared in Example 7 and Example 8;

[0027] Fig. 9 This is a graph showing the dissolution rate of iron ions during the process of activating PMS to degrade tetracycline using the iron single-atom catalyst prepared in Example 7 and Example 8;

[0028] In the figure, 1: dosing tank; 1-1: first water inlet; 1-2: first water pump; 1-3: liquid medicine tank; 1-4: second water inlet; 1-5: second water pump; 1-6: stirring blade; 2: reaction tank; 2-1: card slot; 2-2: reaction tank; 2-3: water outlet tank; 2-4: catalytic membrane; 2-5: first water outlet; 2-6: third water inlet; 2-7: second water outlet; 2-8: fourth water pump; 2-9: reaction tank cleaning outlet; 3: bypass circulation device; 3-1: first water pump; 3-2: third water pump; 3-3: second water pump. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solution and advantages of the utility model more clear, the utility model is further described in detail in combination with the drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the utility model, rather than all embodiments. Based on the embodiments in the utility model, all other embodiments obtained by ordinary technicians in this field without making creative work are within the protection scope of the utility model.

[0030] Example 1

[0031] like Figure 1 As shown, the utility model provides a device for removing antibiotic resistance genes in water, comprising a dosing tank 1 and a reaction box 2.

[0032] The dosing tank 1 is connected to the reaction box 2; a first water inlet 1-1 is opened above the side wall of the dosing tank 1, and a first water pump 1-2 is arranged in the first water inlet 1-1, and the first water pump 1-2 is used to pump sewage into the dosing tank 1 through the first water inlet 1-1; a liquid medicine tank 1-3 is arranged above the other side wall of the dosing tank 1, and a water pipe 1-3-1 is arranged at the lower end of the liquid medicine tank 1-3; the liquid medicine tank 1-3 is used to store PMS mother liquor, and the PMS mother liquor is added to the dosing tank 1 through the water pipe 1-3-1; a second water inlet 1-4 is opened below the side where the dosing tank 1 is connected to the reaction box 2, and a second water pump 1-5 is arranged in the second water inlet 1-4, and the second water pump 1-5 is used to pump sewage in the dosing tank into the reaction box 2 through the second water inlet 1-4.

[0033] A slot 2-1 is provided in the middle of the reaction box 2, and the side close to the dosing tank 1 is used as the reaction tank 2-2, and the other side is used as the water outlet tank 2-3; the slot 2-1 is used to place the catalytic membrane 2-4, and the catalytic membrane 2-4 is loaded with an iron single-atom catalyst; the upper end of the reaction box 2 is provided with a first water outlet 2-5 and a third water inlet 2-6, the first water outlet 2-5 is close to the water tank 2-3, and the third water inlet 2-6 is close to the dosing tank 1; the upper end of the reaction box 2 is connected to a bypass circulation device 3.

[0034] The bypass circulation device 3 includes a first pumping pipe 3-1, a third pumping pump 3-2 and a second pumping pipe 3-3; one end of the first pumping pipe 3-1 is connected to the first water outlet 2-5, and the other end is connected to the third pumping pump 3-2; one end of the second pumping pipe 3-3 is connected to the third water inlet 2-6, and the other end is connected to the third pumping pump 3-2.

[0035] A second water outlet 2-7 is provided on the upper side wall of the water outlet trough 2-3, and a fourth water pump 2-8 is provided in the second water outlet 2-7.

[0036] Working process: When removing antibiotic resistance genes in sewage, a new catalytic membrane 2-4 is placed in the card slot 2-1, and then the first pump 1-2 is started to pump sewage from the first water inlet 1-1 to the dosing tank 1; then the PMS mother liquid is placed in the liquid tank 1-3, and then the PMS solution is mixed with the sewage in the dosing tank 1 to obtain a mixed liquid; then the second pump 1-5 is started to pump the mixed liquid from the second water inlet 1-4 to the reaction tank 2; as the mixed liquid in the reaction tank 2 increases, the catalytic membrane 2-4 and the mixed liquid The reaction occurs continuously; at the same time, the bypass circulation device 3 works continuously to extract the mixed liquid in the reaction box 2 from the first water outlet 2-5 to the third water inlet 2-6, and extract the mixed liquid in front of the catalytic membrane 2-4 upward. The extraction process can clean the sediment on the membrane and improve the utilization rate of the catalytic membrane 2-4; after the mixed liquid reacts with the catalytic membrane 2-4, it enters the water outlet 2-3, and finally the fourth pumping pump 2-8 is started to pump the liquid treated by the catalytic membrane 2-4 out of the water outlet 2-3 from the second water outlet 2-7, thereby completing the removal of antibiotic resistance genes in the sewage.

[0037] like Figure 2 As shown, the process of removing antibiotic resistance genes in sewage, the arrows indicate the direction of water flow.

[0038] Example 2

[0039] On the basis of Example 1, a filter screen is further provided on the first water inlet 1 - 1 , and the filter screen is used to filter impurities in sewage.

[0040] Example 3

[0041] On the basis of Example 1, Figure 3 As shown, a water pipe clamp 1-3-2 is provided at the lower end of the water pipe 1-3-1, and the amount of PMS mother solution added to the dosing tank 1 is controlled by opening and closing the water pipe clamp 1-3-2 and adjusting the aperture of the water pipe 1-3-1.

[0042] Example 4

[0043] On the basis of Example 1, Figure 4As shown, stirring blades 1-6 are fixed at the upper end of the dosing tank 1, and the stirring blades 1-6 are used to mix the sewage and PMS solution in the dosing tank 1.

[0044] Example 5

[0045] Based on Example 1, the thickness of the catalytic film 2-4 is 200-500 μm.

[0046] Example 6

[0047] On the basis of Example 1, Figure 5 As shown, the reaction tank 2-2 is provided with a reaction tank cleaning outlet 2-9 at the lower end near the card slot 2-1. The reaction tank cleaning outlet 2-9 is used to clean the impurities deposited in front of the submerged catalytic membrane assembly and is only used when cleaning the reaction tank.

[0048] Example 7

[0049] The catalytic membrane is prepared by the first method:

[0050] (1) After dissolving 0.8-0.9 g of oxalic acid in 80-100 mL of ultrapure water, 0.9-1.0 g of ferric nitrate nonahydrate is poured into the oxalic acid solution at 20-30° C. to dissolve, thereby obtaining a solution a; 1.8-2.0 g of cyanuric acid is dissolved in 340-380 mL of ultrapure water by heating in a water bath at 80-85° C., and the solution a is poured into the cyanuric acid solution and stirred to obtain a solution b; 2.9-3.1 g of melamine is dissolved in 280-320 mL of ultrapure water by heating in a water bath at 80-85° C., and the solution a is poured into the melamine solution and stirred to obtain a solution c, which is stirred for 3-5 hours and then filtered to obtain a supramolecular solid.

[0051] (2) The supramolecular solid was placed in an oven and dried for 8 h; in a high-purity argon atmosphere, the solid was heated to 550-650°C at a heating rate of 4-6°C / min and kept at that temperature for 3-6 h, and then cooled to room temperature to obtain Fe1 / CN (iron single atom catalyst).

[0052] (3) Add 2-3 g of iron single atom catalyst to 35-40 mL of NMP solvent, ultrasonicate for 4-5 h to evenly disperse the catalyst, add 6-8 g of PSF (membrane matrix material) and 1-2 g of PVP (porogen), oscillate at 60°C for 24 h, and then ultrasonicate for 1 h to degas to obtain a casting solution. Spread the casting solution evenly on a glass plate, dry it for 30 seconds, and then immerse it in a coagulation bath. After the membrane automatically falls off the glass plate, immerse the membrane in deionized water, and change the water every 48 hours to obtain a catalytic membrane.

[0053] When removing antibiotic resistance genes, the catalytic membrane prepared in this example is placed in the card slot, and then the first pump is started to add the resistance gene solution to be treated into the dosing tank by the first pump. The resistance gene concentration is 10 7 copies / μL; prepare the PMS solution and put it in the drug tank with a concentration of 1mM; then mix the PMS solution with the resistance gene solution to be treated in the drug adding tank to obtain a mixed liquid; then start the second pump to pump the mixed liquid from the second water inlet to the reaction tank; as the mixed liquid in the reaction tank increases, the catalytic membrane and the mixed liquid continue to react; at the same time, the bypass circulation device continues to work, pumping the mixed liquid in the reactor from the first water outlet to the third water inlet, and the mixed liquid in front of the catalytic membrane The liquid is extracted upwards, and the extraction process can clean the sediment on the membrane and improve the utilization rate of the catalytic membrane; the mixed liquid reacts with the catalytic membrane and enters the water outlet tank, and finally the fourth pump is started to pump the liquid treated by the catalytic membrane out of the water outlet tank from the second water outlet. A syringe is used to take samples at the outlet of the water outlet tank at 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 and 10h, and the samples are filtered through a 0.22μm filter. The resistance gene concentration in the solution is determined by real-time fluorescence quantitative PCR (qPCR); according to Figure 6 The degradation curve of this reaction device shows that it is effective in removing different antibiotic resistance genes (tetM, tetA, cat, addA and other resistance genes) in water, and can stably and effectively remove resistance genes in water within 10 hours.

[0054] Figure 7 This is a graph showing the iron dissolution rate of the iron single-atom catalyst (Fe1 / CN) prepared in Example 7 and the iron ion concentration in the solution during the reaction.

[0055] Example 8

[0056] The catalytic film is prepared by the second method:

[0057] (1) After dissolving 0.45-0.55 g of ferrous sulfate heptahydrate in 80-100 mL of ultrapure water, 0.5-0.6 g of thioacetamide is poured into the ferrous sulfate heptahydrate solution at 20-30° C. to dissolve, thereby obtaining a solution a; 2.3-2.5 g of cyanuric acid is dissolved in 340-380 mL of ultrapure water by heating in a water bath at 80-85° C., and the solution a is poured into the cyanuric acid solution and stirred to obtain a solution b; 2.9-3.1 g of melamine is dissolved in 280-320 mL of ultrapure water by heating in a water bath at 80-85° C., and the solution a is poured into the melamine solution and stirred to obtain a solution c, which is stirred for 3-5 hours and then filtered to obtain a supramolecular solid.

[0058] (2) Drying the supramolecular solid in an oven for 8 h; heating to 550-650° C. at a heating rate of 4-6° C. / min in a high-purity argon atmosphere and keeping the temperature for 3-6 h, and then cooling to room temperature to obtain Fe1-S-Fe1 / CN (iron single atom catalyst).

[0059] (3) Add 2-3 g of iron single atom catalyst to 35-40 mL of NMP solvent, ultrasonicate for 4-5 h to evenly disperse the catalyst, add 6-8 g of PSF (membrane matrix material) and 1-2 g of PVP (porogen), oscillate at 60°C for 24 h, and then ultrasonicate for 1 h to degas to obtain a casting solution. Spread the casting solution evenly on a glass plate, dry it for 30 seconds, and then immerse it in a coagulation bath. After the membrane automatically falls off the glass plate, immerse the membrane in deionized water, and change the water every 48 hours to obtain a catalytic membrane.

[0060] When removing antibiotic resistance genes, the catalytic membrane prepared in this example is placed in the card slot, and then the first pump is started to add the resistance gene solution to be treated into the dosing tank by the first pump. The resistance gene concentration is 10 7 The PMS solution is prepared and placed in the drug solution tank with a concentration of 1mM. The PMS solution is then mixed with the resistance gene solution to be treated in the drug adding tank to obtain a mixed liquid. The second pump is then started to extract the mixed liquid from the second water inlet to the reaction tank. As the mixed liquid in the reaction tank increases, the catalytic membrane and the mixed liquid react continuously. At the same time, the bypass circulation device continuously operates to transfer the mixed liquid in the reaction tank 2 from the first water outlet to the third water inlet, and the mixed liquid in front of the catalytic membrane is pumped into the reaction tank. The extraction process can clean the sediment on the membrane and improve the utilization rate of the catalytic membrane; the mixed liquid reacts with the catalytic membrane and enters the water outlet tank, and finally the fourth pump is started to pump the liquid treated by the catalytic membrane out of the water outlet tank from the second water outlet. The syringe is used to take samples at 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 and 10h at the water outlet of the water outlet tank, and pass through a 0.22μm filter. The antibiotic concentration in the solution is determined by high performance liquid chromatography.

[0061] Figure 8 This is a graph showing the degradation rate of tetracycline by PMS activated by the iron single atom catalyst (Fe1 / CN) prepared in Example 7 and the iron single atom catalyst (Fe1-S-Fe1 / CN) prepared in Example 8.

[0062] Fig. 9 This is a graph showing the dissolution rate of iron ions during the degradation of tetracycline by activating PMS using the iron single-atom catalyst (Fe1 / CN) prepared in Example 7 and the iron single-atom catalyst (Fe1-S-Fe1 / CN) prepared in Example 8.

[0063] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A device for removing antibiotic resistance genes in water, characterized in that: It includes a dosing tank and a reaction box; The dosing tank is connected to the reaction box; a first water inlet is opened above the side wall of the dosing tank, and a first water pump is arranged in the first water inlet, and the first water pump is used to pump sewage into the dosing tank through the first water inlet; a liquid medicine tank is arranged above the other side wall of the dosing tank, and a water pipe is arranged at the lower end of the liquid medicine tank; the liquid medicine tank is used to store PMS mother liquid, and the PMS mother liquid is added to the dosing tank through the water pipe; a second water inlet is opened below the side where the dosing tank is connected to the reaction box, and a second water pump is arranged in the second water inlet, and the second water pump is used to pump sewage in the dosing tank into the reaction box through the second water inlet; A slot is provided in the middle of the reaction box, with one side close to the dosing tank as the reaction tank and the other side as the water outlet tank; the slot is used to place a catalytic membrane, on which an iron single-atom catalyst is loaded; a first water outlet and a third water inlet are provided at the upper end of the reaction box, the first water outlet is close to the water tank, and the third water inlet is close to the dosing tank; the upper end of the reaction box is connected to a bypass circulation device; The bypass circulation device comprises a first water pumping pipe, a third water pumping pump and a second water pumping pipe; one end of the first water pumping pipe is connected to the first water outlet, and the other end is connected to the third water pumping pump; one end of the second water pumping pipe is connected to the third water inlet, and the other end is connected to the third water pumping pump; A second water outlet is provided above the side wall of the water outlet trough, and a fourth water pump is arranged in the second water outlet.

2. The device for removing antibiotic resistance genes in water according to claim 1, characterized in that: The first water inlet is also provided with a filter screen, and the filter screen is used to filter impurities in sewage.

3. The device for removing antibiotic resistance genes in water according to claim 1, characterized in that: A water pipe clamp is provided at the lower end of the water pipe, and the amount of PMS mother solution added to the dosing tank is controlled by opening and closing the water pipe clamp and adjusting the aperture of the water pipe.

4. The device for removing antibiotic resistance genes in water according to claim 1, characterized in that: A stirring blade is fixed at the upper end of the dosing tank, and the stirring blade is used to mix the sewage and the PMS solution in the dosing tank.

5. The device for removing antibiotic resistance genes in water according to claim 1, characterized in that: The thickness of the catalytic film is 200-500 μm.

6. The device for removing antibiotic resistance genes in water according to claim 1, characterized in that: The lower end of the reaction tank close to the card slot is provided with a reaction tank cleaning water outlet.

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