A method for efficiently removing antibiotics and resistance genes based on Co3O4-ZIF@CNT catalytic membrane-UV irradiation

Abstract

The present application relates to a kind of based on Co3O4-ZIF@CNT catalytic membrane-UV irradiation efficient removal antibiotic and resistance gene method, the treatment method of the present application is based on catalytic oxidation filter membrane-UV irradiation integration device carries out, catalytic oxidation filter membrane-UV irradiation integration device in the filter membrane-UV reaction component realizes the organic combination of Co3O4-ZIF@CNT catalytic membrane and ultraviolet irradiation, after wastewater is filtered, it is followed by ultraviolet irradiation, enough hydroxyl radical, singlet oxygen, superoxide radical, sulfate radical and other active oxygen components are generated, the efficient removal of antibiotic and resistance gene and other new pollutants is realized.The production and species of active oxygen species such as sulfate radical, singlet oxygen in the system are significantly improved, and high-efficiency water treatment effect is achieved under the condition of low oxidant dosage, low UV irradiation dose.

Description

Technical Field

[0001] This invention relates to a method for efficiently removing antibiotics and resistance genes based on a Co3O4-ZIF@CNT catalytic membrane and UV irradiation, belonging to the field of water treatment technology. Background Technology

[0002] Antibiotic pollution can induce the selective proliferation of antibiotic-resistant microorganisms (ARBs), leading to an increase in the abundance of antibiotic resistance genes (ARGs) in the environment. This poses potential risks to human health and ecological safety. Therefore, the removal of antibiotics and ARGs from water bodies has attracted considerable attention.

[0003] Currently, research on antibiotic removal largely focuses on advanced oxidation technologies. These technologies generate various free radicals to oxidize and degrade antibiotics in water, transforming them into harmless small molecules, or even completely neutralizing them. Advanced oxidation technologies mainly include ozone oxidation, Fenton oxidation, and persulfate oxidation. The water treatment efficiency of advanced oxidation technologies primarily relies on catalytic materials. Due to its advantages such as long cycle time, no sludge production, and easy solid-liquid separation, solid-phase catalysis has become the mainstream catalytic process for advanced oxidation. As a novel solid-phase catalytic material, catalytic membranes combine membrane filtration and catalytic oxidation processes, offering advantages such as high mass transfer efficiency, large reaction surface area, good water treatment effect, and easy equipment integration. The development and application of novel catalytic membranes have become a research hotspot in the field of advanced oxidation. After persulfate and H2O2 are catalyzed by catalytic membranes, they can generate reactive oxygen species (ROS) such as hydroxyl radicals, singlet oxygen, superoxide radicals, and sulfate radicals. These ROS can not only oxidize and degrade antibiotics but also attack cell membranes, oxidize extracellular polysaccharides, causing cell damage, and then enter the cell to oxidize and degrade ARGs. However, compared with antibiotic degradation, advanced oxidation is much less efficient at removing ARGs. Therefore, it is necessary to significantly increase the dosage and prolong the catalytic oxidation reaction time, resulting in increased dosage, higher costs, and impractical application.

[0004] UV irradiation has been widely used in water treatment because it requires no chemicals and does not produce carcinogenic, mutagenic, or teratogenic byproducts. UV irradiation can penetrate cell membranes and act directly on DNA, forming thymine dimers within the double-helix DNA molecule and disrupting its structure. Simultaneously, UV irradiation also has the ability to activate oxidants such as persulfate and H₂O₂, achieving advanced oxidation. However, both disrupting ARGs (autoreactive proteins) and activating oxidants like persulfate and H₂O₂ require UV irradiation intensities of several hundred mJ / cm². 2 The irradiation intensity is high, far exceeding the UV irradiation intensity in actual processes (20-40 mJ / cm). 2This limitation hinders practical applications. Furthermore, the effectiveness of UV irradiation is easily affected by particulate matter and color in the water. These factors restrict the practical application of UV irradiation in advanced water treatment.

[0005] Based on the above situation, it is necessary to develop a method that can generate sufficient reactive oxygen components such as hydroxyl radicals, singlet oxygen, superoxide radicals, and sulfate radicals under low reagent dosage and low UV irradiation intensity conditions, so as to achieve a "one-stop" efficient removal of antibiotics and ARGs from water. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a method for the efficient removal of antibiotics and resistance genes based on a Co3O4-ZIF@CNT catalytic membrane and UV irradiation. The method utilizes a highly dispersed cobalt oxide-modified carbon nanotube catalytic oxidation membrane (Co3O4-ZIF@CNT). After wastewater passes through the Co3O4-ZIF@CNT catalytic membrane, it is simultaneously irradiated with UV light. Under conditions of low reagent dosage and low UV irradiation intensity, sufficient reactive oxygen species such as hydroxyl radicals, singlet oxygen, superoxide radicals, and sulfate radicals are generated, achieving efficient removal of antibiotics and resistance genes. This improves pollutant removal efficiency and overcomes the deficiencies of existing advanced oxidation technologies and UV irradiation.

[0007] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0008] A method for efficiently removing antibiotics and resistance genes based on a Co3O4-ZIF@CNT catalytic membrane and UV irradiation is employed using an integrated catalytic oxidation membrane and UV irradiation device, comprising the following steps:

[0009] (1) The wastewater to be treated is introduced into the integrated catalytic oxidation filter membrane-UV irradiation device through the inlet pipe. The power switch of the UV disinfection lamp is turned on, and the UV irradiation intensity is 10-300 μW / cm. 2 ;

[0010] (2) Turn on the dosing pump and pump the oxidant into the device through the dosing pipe to make the concentration of the oxidant in the water sample to be treated 0.1-3.0 mmol / L. Turn on the power of the outlet pump and make the flow rate at the outlet 0.5-5.0 mL / min. In the integrated device of catalytic oxidation filter membrane-UV irradiation, the wastewater passes through the Co3O4-ZIF@CNT catalytic membrane and is treated by UV irradiation at the same time.

[0011] (3) Collect the water from the outlet. After the sewage sample has been treated, turn off the power, test the water, and discharge it once the treatment requirements are met.

[0012] The catalytic oxidation membrane-UV irradiation integrated device includes an inlet pipe, a dosing pipe, a main water distribution pipe, a membrane-UV reaction assembly, and an outlet pipe. The inlet pipe and the dosing pipe are connected to the main water distribution pipe. A dosing pump is installed on the dosing pipe. Branch water distribution pipes are connected to the main water distribution pipe. Each branch water distribution pipe is connected to a membrane-UV reaction assembly. The outlet pipe of each membrane-UV reaction assembly is connected to an outlet branch water distribution pipe. The outlet branch water distribution pipes are all connected to the main outlet pipe. An outlet pump is installed on the main outlet pipe.

[0013] The filter membrane-UV reaction assembly includes a top plate and a bottom tank that are sealed together. The bottom tank has a hollow area in the middle, and a vacuum UV lamp is installed at the bottom of the hollow area. A ring of protrusions is provided on the side wall of the hollow area. From bottom to top, a sealing rubber gasket, a quartz glass plate, a Co3O4-ZIF@CNT catalyst membrane, and a mounting sealing ring are placed on the protrusions. The mounting sealing ring is higher than the top end of the bottom tank and is located between the top plate and the bottom tank to seal the top plate and the bottom tank. The top plate has a flow equalization channel and an assembly water inlet pipe. The assembly water inlet pipe is connected to the flow equalization channel through a branch pipe. The flow equalization channel is connected to the hollow area of ​​the bottom tank.

[0014] According to a preferred embodiment of the present invention, a uniform flow channel is provided on the quartz glass plate, the uniform flow channel on the quartz glass plate is opposite to the uniform flow channel on the top plate, the uniform flow channel on the quartz glass plate is connected to a converging pipe, and a water outlet pipe is provided on the side wall of the bottom tank, the converging pipe is connected to the water outlet pipe.

[0015] According to a preferred embodiment of the present invention, the water distribution channel is U-shaped, with a channel size of 1-5 mm wide and 1-5 mm deep. The channel density can be adjusted according to the size of the top plate and the quartz glass plate, and is more preferably a groove with a width of 1-3 mm and a depth of 1-2 mm.

[0016] According to a preferred embodiment of the present invention, a slot is provided at the bottom of the hollow region, a vacuum ultraviolet lamp is installed in the slot, and the vacuum ultraviolet lamp is electrically connected to a switch outside the bottom slot.

[0017] According to a preferred embodiment of the present invention, in step (1), the ultraviolet irradiation intensity is 20-100 μW / cm². 2 .

[0018] According to a preferred embodiment of the present invention, in step (1), the irradiation dose is 10-40 mJ / cm². 2 .

[0019] According to a preferred embodiment of the present invention, in step (2), the oxidant is potassium peroxymonosulfate complex salt (PMS, KHSO5·0.5KHSO4·0.5K2SO4).

[0020] According to a preferred embodiment of the present invention, in step (2), the concentration of the oxidant in the water sample to be treated is 0.2-1.0 mmol / L.

[0021] According to a preferred embodiment of the present invention, in step (2), the outlet flow rate is 0.5-2.0 mL / min.

[0022] According to a preferred embodiment of the present invention, the Co3O4-ZIF@CNT catalytic membrane is prepared by the following method:

[0023] 1) 2-Methylimidazole and carbon nanotubes were added to deionized water to form a mixture a. Cobalt nitrate hexahydrate was dissolved in a mixture of deionized water and ethanol to obtain a mixture b. Mixture a and mixture b were mixed and treated with an ultrasonic mixer and a magnetic stirrer to ensure that they were fully mixed and reacted. The product was washed, dried, calcined and sieved to obtain highly dispersed cobalt oxide modified carbon nanotubes (Co3O4-ZIF@CNT).

[0024] 2) Mix Co3O4-ZIF@CNT powder with N-methylpyrrolidone (NMP) evenly, process it with a cell disruptor and an ultrasonic mixer in sequence, filter it onto a PTFE base membrane, and wash it to obtain a highly dispersed cobalt oxide modified carbon nanotube catalytic oxidation filter membrane (Co3O4-ZIF@CNT).

[0025] According to a preferred embodiment of the present invention, in the preparation of the Co3O4-ZIF@CNT catalytic membrane:

[0026] The mass concentration of carbon nanotubes in mixture a is 0.1%-5%, and the mass ratio of 2-methylimidazole to carbon nanotubes is 300:1-10:1.

[0027] In mixture b, the volume ratio of deionized water to ethanol is 5:1 to 1:5, and the concentration of cobalt nitrate hexahydrate is 2% to 20%.

[0028] The volume ratio of mixture a to mixture b is 10:1 to 1:10, and more preferably 1:1.

[0029] The magnetic stirrer has a rotation speed of 100-800 rpm, more preferably 500-600 rpm.

[0030] The stirring time is 0.5-4 hours, and more preferably 1-2 hours.

[0031] The calcination temperature is 700-1200℃, and more preferably 800-1000℃.

[0032] The cell disruptor has a power of 400-600W and processes cells in cycles of 2.0-10 seconds with 3.0-second intervals for 2-20 minutes.

[0033] The ultrasonic mixer has a power of 100-300W and an ultrasonic time of 10-30 minutes.

[0034] The mass-to-volume ratio of Co3O4-ZIF@CNT powder to N-methylpyrrolidone is 1-50 g: 1 L.

[0035] unit area (m 2 The loading of Co3O4-ZIF@CNT on the catalytic membrane is 2-20g.

[0036] The catalytic oxidation membrane-UV irradiation integrated device of the present invention pumps the wastewater to be treated to each membrane-UV reaction unit through an inlet pump. Oxidant is added through a dosing pipe and thoroughly mixed with the inlet water sample using hydraulic action. The membrane-UV reaction units are connected in parallel, and the effluent from each unit is collected in a main outlet pipe. Each membrane-UV reaction unit is independent and can be used simultaneously without affecting the treatment effect.

[0037] Technical features and advantages of the present invention:

[0038] 1. This invention utilizes a Co3O4-ZIF@CNT catalytic membrane to activate potassium persulfate composite salt. Immediately after membrane filtration, ultraviolet (UV) irradiation occurs. During membrane filtration, the molecules are stretched. Low-intensity UV irradiation further stretches the molecules, generating sufficient reactive oxygen species (ROS) such as hydroxyl radicals, singlet oxygen, superoxide radicals, and sulfate radicals. This achieves highly efficient removal of new pollutants such as antibiotics and resistance genes. Compared to independent catalytic membrane activation, independent UV irradiation, combined catalytic membrane and UV irradiation, or UV irradiation followed by catalytic membrane filtration, this invention significantly increases the yield and variety of reactive oxygen species such as sulfate radicals and singlet oxygen in the system, achieving highly efficient water treatment under conditions of low oxidant dosage and low UV irradiation dose.

[0039] 2. The treatment method of the present invention is based on an integrated catalytic oxidation membrane-UV irradiation device. The membrane-UV reaction component in the integrated catalytic oxidation membrane-UV irradiation device realizes the organic combination of Co3O4-ZIF@CNT catalytic membrane and ultraviolet irradiation, so that the wastewater is irradiated with ultraviolet light while passing through the membrane, which significantly improves the treatment effect of antibiotics and resistance genes.

[0040] 3. The processing method of the present invention is based on an integrated device for catalytic oxidation filter membrane-UV irradiation. Multiple filter membrane-UV reaction components can be assembled in parallel. Applicable degradation reaction devices can be flexibly constructed according to actual processing needs, ensuring the feasibility and economy of the process.

[0041] 4. The UV irradiation intensity and dose used in this invention are within the range of conventional UV disinfection doses. It can be improved based on the existing UV disinfection process in sewage treatment plants, simplifying the technical upgrade and construction steps. The low dosage of oxidant and the low UV irradiation dose also greatly reduce treatment costs while ensuring high treatment efficiency, thus ensuring the safety and efficiency of sewage treatment. Attached Figure Description

[0042] Figure 1 This is a schematic diagram showing the disassembled structure of the filter membrane-UV reaction assembly of the present invention.

[0043] In the diagram, 1 is the top plate, 2 is the sealing ring, 3 is the Co3O4-ZIF@CNT catalytic membrane, 4 is the quartz glass plate, 5 is the sealing rubber gasket, 6 is the vacuum ultraviolet lamp, and 7 is the bottom tank.

[0044] Figure 2 This is a schematic diagram of the combined structure of the filter membrane-UV reaction assembly of the present invention.

[0045] Figure 3 The images shown are (a), (b), and (c) of the Co3O4-ZIF@CNT catalytic membrane of this invention. Image (b) shows, from left to right, the SEM image of the membrane surface, the C element, the O element, and the Co element.

[0046] Figure 4 This is a schematic diagram of the integrated catalytic oxidation filter membrane-UV irradiation device of the present invention.

[0047] In the diagram, 8 is the inlet pipe, 9 is the dosing pipe, 10 is the dosing pump, 11 is the filter membrane-UV reaction assembly, 12 is the outlet pump, 13 is the main outlet pipe, and 14 is the branch water main pipe.

[0048] Figure 5 The EPR diagram of the reactive oxygen species generated in Experiment Example 2 is shown.

[0049] Figure 6 The image shows the effect of removing antibiotics from the water sample in Experiment Example 1.

[0050] Figure 7 The effect of removing resistant microorganisms (a) and ARGs from the water sample in Experiment Example 1 is shown in Figure (b). Detailed Implementation

[0051] The present invention will be further described below with reference to the accompanying drawings and embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0052] First, the wastewater to be treated enters the reaction device through the inlet, while potassium persulfate compound salt is injected into the inlet pipe via a dosing pump. The wastewater and potassium persulfate compound salt will mix thoroughly by hydraulic action in the inlet tank of the reactor. After mixing, the water sample enters the integrated catalytic oxidation membrane-UV irradiation device, where sulfate activation generates sulfate free radicals, hydroxyl free radicals, superoxide free radicals, and singlet oxygen, among other reactive oxygen species. Under the synergistic effect of UV irradiation and reactive oxygen species, antibiotics in the water sample are efficiently degraded, and resistance genes are efficiently removed. The treated water sample flows out through the outlet.

[0053] Example 1

[0054] Preparation of Co3O4-ZIF@CNT membranes:

[0055] 1) 10.80 g of 2-methylimidazole and 0.30 g of carbon nanotubes were added to 150 mL of deionized water and ultrasonicated at 200 W for 1 h to form mixture a. 7.68 g of cobalt nitrate hexahydrate was dissolved in 75 mL of a mixed solution of deionized water and ethanol (deionized water: ethanol = 2:1) to obtain mixture b. Mixture a and mixture b were mixed and treated with an ultrasonic mixer and magnetic stirrer for 12 h to ensure thorough mixing and uniform reaction. The precipitate was collected by centrifugation at 10000 rpm for 15 min and washed three times with ethanol to remove residual impurities. The obtained product was dried, ground, and calcined at 900 °C for 2 h under a nitrogen atmosphere at a heating rate of 5 °C / min. The collected black product was labeled as Co3O4-ZIF@CNT.

[0056] 2) Weigh 90 mg of Co3O4-ZIF@CNT powder and add it to 50 mL of N-methylpyrrolidone (NMP). Treat the mixture with a cell disruptor for 10 min (500 W), sonicating for 8.0 s, pausing for 3.0 s, and repeating the process. Then treat the mixture with an ultrasonic mixer for 30 min (200 W) to obtain a homogeneous mixture. Use a vacuum pump to uniformly filter the mixture onto a PTFE membrane with dimensions of 70 × 70 mm and a pore size of 0.45 μm. After filtration, wash the membrane sequentially with 100 ml of anhydrous ethanol, 100 ml of 50% ethanol, and 250 ml of ultrapure water to obtain the Co3O4-ZIF@CNT membrane.

[0057] Photographs, SEM images, and XRD patterns of the prepared Co3O4-ZIF@CNT catalytic membrane are shown below. Figure 3 .

[0058] Example 2

[0059] Preparation of Co3O4-ZIF@CNT membranes:

[0060] 1) Add 8.10 g of 2-methylimidazole and 0.30 g of carbon nanotubes to 150 mL of deionized water and sonicate at 200 W for 1 h using an ultrasonic mixer to form mixture a. Dissolve 6.20 g of cobalt nitrate hexahydrate in a mixed solution of 75 mL of deionized water and ethanol (deionized water: ethanol = 2:1) to obtain mixture b. Mixture a and mixture b are mixed and treated with an ultrasonic mixer and magnetic stirrer for 8 h to ensure thorough mixing and uniform reaction. Collect the precipitate by centrifugation at 10000 rpm for 15 min, wash three times with ethanol to remove residual impurities, dry and grind the obtained product, and calcine at 700 °C for 2 h under a nitrogen atmosphere at a heating rate of 5 °C / min. The collected black product is labeled as Co3O4-ZIF@CNT.

[0061] 2) The method in Example 1 was followed to obtain the Co3O4-ZIF@CNT membrane.

[0062] Example 3

[0063] The integrated catalytic oxidation membrane filter-UV irradiation device has the following structure: Figure 4 As shown, it includes an inlet pipe 8, a dosing pipe 9, a main water distribution pipe 14, a filter membrane-UV reaction assembly 11, and an outlet pipe 13. The inlet pipe 8 and the dosing pipe 9 are connected to the main water distribution pipe 14. A dosing pump 10 is installed on the dosing pipe 9. Branch water distribution pipes are connected to the main water distribution pipe 14. Each branch water distribution pipe is connected to a filter membrane-UV reaction assembly 11. The outlet pipe of each filter membrane-UV reaction assembly is connected to an outlet branch water distribution pipe. The outlet branch water distribution pipes are all connected to the main outlet pipe 13. An outlet pump 12 is installed on the main outlet pipe 13.

[0064] The filter membrane-UV reaction assembly has the following structure: Figure 1 , Figure 2 As shown, the device includes a top plate 1 and a bottom groove 2 that are sealed together (both the top plate 1 and the bottom groove 2 are transparent). The bottom groove 2 has a hollow area in the middle, and a vacuum ultraviolet lamp 6 is installed at the bottom of the hollow area. A slot is provided at the bottom of the hollow area, and the vacuum ultraviolet lamp 6 is installed in the slot. The vacuum ultraviolet lamp is electrically connected to a switch outside the bottom groove.

[0065] A ring of protrusions is provided on the side wall of the hollow area. From bottom to top, a sealing rubber gasket 5, a quartz glass plate 4, a Co3O4-ZIF@CNT catalyst membrane 3 prepared in Example 1, and a sealing ring 2 are placed on the protrusions. The sealing ring is higher than the top end of the bottom tank and located between the top plate and the bottom tank. It is used to seal the top plate 1 and the bottom tank 2. The top plate 1 is provided with a flow equalization channel and a component water inlet pipe. The component water inlet pipe is connected to the flow equalization channel through a branch pipe. The flow equalization channel is connected to the hollow area of ​​the bottom tank. A flow equalization channel is provided on the quartz glass plate. The flow equalization channel is opposite to the flow equalization channel on the top plate. The flow equalization channel on the quartz glass plate is connected to a collection pipe. A water outlet pipe is provided on the side wall of the bottom tank. The collection pipe is connected to the water outlet pipe. The flow equalization channel is U-shaped.

[0066] Example 4

[0067] A method for efficiently removing antibiotics and resistance genes based on a Co3O4-ZIF@CNT catalytic membrane and UV irradiation is carried out using the integrated catalytic oxidation filter membrane and UV irradiation device described in Example 3. The steps are as follows:

[0068] (1) 1000 mL of simulated water sample was introduced into the integrated catalytic oxidation filter membrane-UV irradiation device of Example 3 through the inlet pipe. The UV disinfection lamp was turned on, and the UV irradiation intensity was 50 μW / cm². 2 The simulated water sample contained 10 mg / L sulfamethoxazole and 10 mg / L... 7 Sulfoamine-resistant Escherichia coli at CFU / mL.

[0069] (2) Turn on the dosing pump and pump potassium persulfate compound salt (PMS, KHSO5·0.5KHSO4·0.5K2SO4) into the device through the dosing pipe to make its concentration 0.6 mmol / L. Turn on the power of the outlet pump and make the outlet flow rate 2 mL / min. Use the single membrane treatment mode.

[0070] (3) Collect the water from the outlet. After the sewage sample has been treated, turn off the power and test the water.

[0071] Experimental Example 1

[0072] Water samples were taken from the outlet at different times in Example 4 to test their water quality and to determine the removal efficiency of sulfamethoxazole and ARGs. The results are as follows: Figure 6 , Figure 7 As shown. From Figure 6 As can be seen, the integrated catalytic oxidation filter membrane-UV irradiation device of the present invention can rapidly and efficiently degrade sulfamethoxazole in water samples, maintaining a removal efficiency of over 95%. Figure 7As can be seen, after treatment by the integrated catalytic oxidation membrane-UV irradiation device of the present invention, the resistant microorganisms in the wastewater sample are completely inactivated, and the abundance of the sul1 resistance gene is also significantly reduced. Compared with independent catalytic membrane activation (PMS / CM), independent UV irradiation, catalytic membrane-UV combined use (PMS / CM+UV), and UV-catalytic membrane combined use (UV+PMS / CM) processes, the treatment method of the present invention is based on the integrated catalytic oxidation membrane-UV irradiation device, which allows the wastewater to be irradiated with UV light while passing through the membrane, resulting in a higher removal efficiency of the resistance gene.

[0073] PMS / CM is the method of the present invention for removing ultraviolet radiation. The wastewater is treated only by passing through a Co3O4-ZIF@CNT catalytic membrane and adding PMS.

[0074] UV refers to the treatment of wastewater using only ultraviolet irradiation;

[0075] The PMS / CM+UV process is carried out in two separate devices. The wastewater is treated by passing it through a Co3O4-ZIF@CNT catalytic membrane and adding PMS before being pumped into the ultraviolet irradiation device for further treatment.

[0076] The UV+PMS / CM process is carried out in one device. The active surface (inlet side) of the Co3O4-ZIF@CNT catalytic membrane is irradiated with ultraviolet light, and the wastewater will undergo membrane treatment under ultraviolet irradiation using the Co3O4-ZIF@CNT catalytic membrane.

[0077] Using EPR to detect the integrated catalytic oxidation filter membrane-UV irradiation device, it can be seen that persulfate can activate and generate reactive oxygen species such as sulfate radicals, hydroxyl radicals, superoxide radicals, and singlet oxygen. Moreover, compared with the separate catalytic filter membrane and UV irradiation process, the concentration of reactive oxygen species generated by activated persulfate is higher.

[0078] Experiment Example 2

[0079] To investigate the efficient removal mechanism of the integrated catalytic oxidation membrane-UV irradiation device, the generation of reactive oxygen species in the reaction system of Example 4 was detected by electron paramagnetic resonance (EPR) spectroscopy. 5,5-Dimethyl-1-pyrrolidone N-oxide (DMPO) and 2,2,6,6-tetramethyl-4-piperidinol (TEMP) were used as spin trapping agents in the EPR test. The results are as follows: Figure 5 As shown.

[0080] When the reaction apparatus is equipped with a separate Co3O4@CNT catalytic membrane (PMS / CM), the PMS is activated to generate ·OH and SO4· - O2 - and 1O2. For catalytic oxidation membrane-UV irradiation integrated devices (PMS / CM-UV), DMPO-·OH and DMPO-SO4· - DMPO-·O2 - and TEMP- 1 The strong O2 signal intensity indicates that UV radiation further activated the PMS in the filtrate through photoactivation and photooxidation processes, leading to the generation of various ROS through electron and energy transfer. To verify the role of UV radiation, the formation of ROS in a reactor equipped only with UV radiation (PMS / UV) was detected by EPR testing. The results showed that DMPO-·OH and DMPO-SO4· - and TEMP- 1 The weak signal intensity of O2. Compared with the signal intensity observed in PMS / CM-UV, the signal intensity of ·OH and SO4· in PMS / UV and PMS / CM is weak. - O2 - and 1 The signal intensity of O2 was significantly lower than that observed in PMS / CM-UV, with the difference being particularly pronounced in the PMS / UV process. This observation indicates that the integrated catalytic oxidation membrane-UV irradiation device has a synergistic effect on the activation of PMS, significantly increasing the activation of SO4·2 ... - , 1 The production of reactive oxygen species such as O2 is reduced, thereby achieving ideal water treatment results under conditions of low oxidant dosage and low UV irradiation dose.

Claims

1. A method for efficiently removing antibiotics and resistance genes based on a Co3O4-ZIF@CNT catalytic membrane and UV irradiation, comprising the following steps: (1) The wastewater to be treated is introduced into the integrated catalytic oxidation filter membrane-UV irradiation device through the inlet pipe. The power switch of the UV disinfection lamp is turned on, and the UV irradiation intensity is 10-300 μW / cm. 2 ; (2) Turn on the dosing pump and pump the oxidant into the device through the dosing pipe to make the concentration of the oxidant in the water sample to be treated 0.1-3.0 mmol / L. Turn on the power of the outlet pump and make the flow rate at the outlet 0.5-5.0 mL / min. In the integrated device of catalytic oxidation filter membrane-UV irradiation, the wastewater passes through the Co3O4-ZIF@CNT catalytic membrane and is treated by UV irradiation at the same time. The Co3O4-ZIF@CNT catalytic membrane was prepared by the following method: 2-Methylimidazole and carbon nanotubes were added to deionized water to form mixture a. Cobalt nitrate hexahydrate was dissolved in a mixture of deionized water and ethanol to obtain mixture b. Mixture a and mixture b were mixed and treated with an ultrasonic mixer and a magnetic stirrer to ensure thorough mixing and uniform reaction. The resulting product was washed, dried, calcined, and sieved to obtain highly dispersed cobalt oxide modified carbon nanotubes (Co3O4-ZIF@CNT). Co3O4-ZIF@CNT powder was mixed with N-methylpyrrolidone (NMP) and treated sequentially with a cell disruptor and an ultrasonic mixer. The mixture was then filtered onto a PTFE membrane and washed to obtain a highly dispersed cobalt oxide modified carbon nanotube catalytic oxidation filter membrane (Co3O4-ZIF@CNT). (3) Collect the water from the outlet. After the sewage sample has been treated, turn off the power, test the water, and discharge it once the treatment requirements are met. The catalytic oxidation membrane-UV irradiation integrated device includes an inlet pipe, a dosing pipe, a main water distribution pipe, a membrane-UV reaction assembly, and an outlet pipe. The inlet pipe and the dosing pipe are connected to the main water distribution pipe. A dosing pump is installed on the dosing pipe. Branch water distribution pipes are connected to the main water distribution pipe. Each branch water distribution pipe is connected to a membrane-UV reaction assembly. The outlet pipe of each membrane-UV reaction assembly is connected to an outlet branch water distribution pipe. The outlet branch water distribution pipes are all connected to the main outlet pipe. An outlet pump is installed on the main outlet pipe. The filter membrane-UV reaction assembly includes a top plate and a bottom tank that are sealed together. The bottom tank has a hollow area in the middle, and a vacuum UV lamp is installed at the bottom of the hollow area. A ring of protrusions is provided on the side wall of the hollow area. From bottom to top, a sealing rubber gasket, a quartz glass plate, a Co3O4-ZIF@CNT catalyst membrane, and a mounting sealing ring are placed on the protrusions. The mounting sealing ring is higher than the top end of the bottom tank and is located between the top plate and the bottom tank to seal the top plate and the bottom tank. The top plate has a flow equalization channel and an assembly water inlet pipe. The assembly water inlet pipe is connected to the flow equalization channel through a branch pipe. The flow equalization channel is connected to the hollow area of ​​the bottom tank.

2. The method according to claim 1, characterized in that, The quartz glass plate is provided with a flow equalization channel, which is opposite to the flow equalization channel on the top plate.

3. The method according to claim 1, characterized in that, The equalization channel on the quartz glass plate is connected to the collection pipe. The side wall of the bottom tank is equipped with a water outlet pipe, which is connected to the collection pipe. The equalization channel is U-shaped, with a channel size of 1-5mm wide and 1-5mm deep. The bottom of the hollow area is equipped with a slot, in which a vacuum ultraviolet lamp is installed. The vacuum ultraviolet lamp is electrically connected to a switch outside the bottom tank.

4. The method according to claim 1, characterized in that, In step (1), the ultraviolet irradiation intensity is 20-100 μW / cm. 2 .

5. The method according to claim 1, characterized in that, In step (1), the irradiation dose is 10-40 mJ / cm². 2 .

6. The method according to claim 1, characterized in that, In step (2), the oxidant is potassium hydrogen sulfate complex salt (PMS, KHSO5·0.5KHSO4·0.5K2SO4), and the concentration of the oxidant in the water sample to be treated is 0.2-1.0 mmol / L.

7. The method according to claim 1, characterized in that, In step (1), the flow rate at the outlet is 0.5-2.0 mL / min.

8. The method according to claim 1, characterized in that, In mixture a, the mass concentration of carbon nanotubes is 0.1%-5%, the mass ratio of 2-methylimidazole to carbon nanotubes is 300:1-10:1, the volume ratio of deionized water to ethanol in mixture b is 5:1-1:5, the concentration of cobalt nitrate hexahydrate is 2%-20%, and the volume ratio of mixture a to mixture b is 10:1-1:

10.

9. The method according to claim 1, characterized in that, The magnetic stirrer speed is 100-800 rpm, the stirring time is 0.5-4 hours, the calcination temperature is 700-1200℃, the cell disruptor power is 400-600W, and the ultrasonic treatment is carried out in units of 2.0-10s with 3.0s intervals, with a cycle time of 2-20 minutes. The mass-to-volume ratio of Co3O4-ZIF@CNT powder to N-methylpyrrolidone is 1-50g:1L, and the unit area (m²) is... 2 The loading of Co3O4-ZIF@CNT on the catalytic membrane is 2-20g.

Images