A collaborative treatment method for bromine wastewater and antibiotic wastewater

Abstract

The invention belongs to the technical field of sewage treatment, and is particularly related to a method for the coordinated treatment of bromine sewage and antibiotic sewage, using 2-aminoterephthalic acid and titanium tetraisopropoxide as ligands, preparing a layered metal organic framework material in an organic solvent, and then using the metal organic framework material as a precursor, first removing bromine in a water body containing Br2, preparing a metal organic framework material containing a bromine substituent, and then placing the metal organic framework material containing a bromine substituent in a soluble silver salt, preparing a silver bromide-modified metal organic framework material, and using the silver bromide-modified metal organic framework material to photocatalytically degrade a water body containing antibiotics, and removing antibiotics in the water body. The present invention realizes the coordinated treatment of bromine sewage and antibiotic sewage through the above-mentioned process, and the method is simple and efficient.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage treatment, and in particular relates to a method for co-treating bromine sewage and antibiotic sewage. Background Art

[0002] At present, water pollution not only causes damage to the ecological environment, but also aggravates the problem of water shortage. Wastewater treatment is crucial to improving water ecology, including the treatment of antibiotic wastewater and bromine wastewater.

[0003] The widespread use of antibiotics has posed a huge challenge to public health and the environment. Antibiotics are not only difficult to degrade naturally, but may also cause the spread of drug-resistant bacteria, posing a threat to ecosystems and human health. Existing treatment technologies include biodegradation, physical adsorption and chemical decomposition. Biodegradation is the use of microorganisms to degrade antibiotics, and its ability to degrade antibiotics is limited. Physical adsorption materials perform poorly in complex water bodies, and chemical treatment may cause secondary pollution. For brominated wastewater, the current methods for removing Br2 from water bodies include adsorption and chemical fixation. The chemical fixation method generally requires the use of materials with redox activity, which are not stable in water bodies. The adsorption method uses porous materials for adsorption, and its adsorption capacity is limited.

[0004] It can be seen that due to the differences in the physical and chemical properties of antibiotics and Br2, their traditional treatment methods are also different. When it is necessary to treat antibiotic wastewater and bromine wastewater, if you want to efficiently remove pollutants, it is generally necessary to adopt two wastewater treatment routes based on the respective characteristics of antibiotics and Br2, and use their respective traditional methods for treatment. The treatment steps are cumbersome and the removal effect is not good. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a method for the coordinated treatment of bromine wastewater and antibiotic wastewater. The treatment of antibiotic wastewater and bromine wastewater can be achieved by adopting one sewage treatment route, which simplifies the sewage treatment steps, and has good removal effects on antibiotics and Br2, which is conducive to large-scale application.

[0006] A method for the coordinated treatment of bromine wastewater and antibiotic wastewater comprises the following steps:

[0007] Layered metal-organic framework materials were prepared by solvothermal method in organic solvents using 2-aminoterephthalic acid and titanium tetraisopropoxide as ligands.

[0008] The metal organic framework material is immersed in a water body containing Br2, and the Br2 in the water body is removed through a substitution reaction, thereby obtaining a metal organic framework material containing a bromine substituent.

[0009] The metal organic framework material containing bromine substituents is immersed in a soluble silver salt solution, silver bromide is generated in situ on the metal organic framework material, and the silver bromide modified metal organic framework material is prepared.

[0010] The silver bromide-modified metal organic framework material is placed in water containing antibiotics, first protected from light until adsorption equilibrium is reached, and then catalytic oxidation is carried out under visible light conditions to degrade the antibiotics.

[0011] It should be noted that the present invention treats the layered metal organic framework material in water containing Br2. During this process, Br2 in the water undergoes a substitution reaction with the metal organic framework material to form a metal organic framework material containing a bromine substituent, thereby removing Br2 from the water. After that, the metal organic framework material containing a bromine substituent is added to a soluble silver salt solution, and the free Ag + Due to the strong interaction with bromine groups, they are selectively enriched and anchored on the surface of metal-organic framework materials containing bromine substituents, and then AgBr nanoparticles are grown in situ to prepare silver bromide-modified metal-organic framework materials, which are used as photocatalysts to treat water containing antibiotics.

[0012] The layered metal organic framework material of the present invention can effectively shorten the transmission distance of photogenerated carriers, promote the separation of electrons and holes, and improve the photocatalytic activity of the metal organic framework material. The silver bromide modified metal organic framework material is formed into a heterojunction composite material photocatalyst, and the silver bromide modified metal organic framework material combines the photocatalytic properties of the porous structure material and silver bromide, which can not only effectively adsorb antibiotics, but also decompose antibiotic molecules through photocatalysis. Under visible light, the material exhibits excellent catalytic activity, and the silver ions have antibacterial properties. Through the above steps, the present invention realizes the coordinated treatment of bromine wastewater and antibiotic wastewater, and has a good removal effect on antibiotics and Br2.

[0013] Preferably, during the process of removing Br2 from the water body, after the pH value of the system remains unchanged, the system is subjected to solid-liquid separation. By detecting the change in the pH value of the system, it is determined whether the water body contains Br2. When the pH value remains unchanged, it is proved that the Br2 in the water body is completely removed. More preferably, in the specific operation, the metal organic framework material can be added to the water body containing Br2 according to the mass ratio of the metal organic framework material to Br2 of 1:8 to 32, and the Br2 in the water undergoes a substitution reaction with the metal organic framework material to form a metal organic framework material containing a bromine substituent, thereby removing Br2 from the water body.

[0014] Preferably, the soluble silver salt solution is a silver sulfate aqueous solution, the concentration of the soluble silver salt solution is 0.04 mol / L to 0.06 mol / L, and the amount ratio of the metal organic framework material containing bromine substituents to the soluble silver salt solution is 0.8 mg to 5 mg: 1 mL. It should be noted that when the metal organic framework material containing bromine substituents is immersed in the silver sulfate aqueous solution, the free Ag + Sufficient amount to ensure sufficient generation of AgBr on the surface of the metal organic framework material. In order to generate AgBr, when preparing the silver bromide modified metal organic framework material, the reaction is allowed to stand at room temperature for 10h to 24h.

[0015] Preferably, the silver bromide-modified metal organic framework material is added to the water containing the antibiotic in a mass ratio of 0.4 to 1.2:1.

[0016] Preferably, during catalytic oxidation, the illumination time is 40 min to 45 min. Within this time range, antibiotics can be removed efficiently.

[0017] Preferably, in the process of preparing a layered metal-organic framework material, the molar ratio of 2-aminoterephthalic acid and titanium tetraisopropoxide is 1.5:1, the reaction temperature is 100°C to 150°C, and the organic solvent is a first solvent and a second solvent mixed in a volume ratio of 1:1, the first solvent is N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, 1-methyl-2-pyrrolidone or N,N-dimethylformamide, and the second solvent is methanol, ethanol, ethylene glycol or ethylene glycol monomethyl ether.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The present invention provides a method for the coordinated treatment of bromine wastewater and antibiotic wastewater, wherein 2-aminoterephthalic acid and titanium tetraisopropoxide are used as ligands, a layered metal organic framework material is prepared in an organic solvent, and then the metal organic framework material is used as a precursor, and bromine is first removed by substitution reaction in a water body containing Br2, and a metal organic framework material containing a bromine substituent is obtained at the same time, and then the metal organic framework material containing a bromine substituent is placed in a soluble silver salt to prepare a silver bromide modified metal organic framework material, and the silver bromide modified metal organic framework material is used to photocatalytically degrade the water body containing antibiotics to remove the antibiotics in the water body. The present invention realizes the coordinated treatment of bromine wastewater and antibiotic wastewater through the above process, and the bromine wastewater is used as a raw material for the antibiotic wastewater catalyst, and the bromine wastewater is removed while the photocatalyst is efficiently prepared, and the treatment method is simple, the removal effect is good, and it is conducive to large-scale application. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1This is the pH change curve of the metal organic framework material placed in bromine water.

[0021] Figure 2 In the figure, a is a SEM image of the silver bromide modified metal organic framework material in Example 1, and b is a yellow powder photo of the silver bromide modified metal organic framework material in Example 1.

[0022] Figure 3 It is a comparison chart of the degradation rate of tetracycline in Example 1 and Comparative Examples 1 to 4.

[0023] Figure 4 The figure is a comparison chart of the degradation rates of tetracycline in Example 4, Comparative Example 5 and Comparative Example 6. DETAILED DESCRIPTION

[0024] In order to enable those skilled in the art to better understand the technical solution of the present invention and implement it, the present invention is further described below in conjunction with specific embodiments and drawings, but the embodiments are not intended to limit the present invention. The experimental methods and detection methods described in the following embodiments are conventional methods unless otherwise specified; the reagents and materials described are all commercially available unless otherwise specified.

[0025] In order to explore how to determine whether Br2 in water is completely removed when treating bromine wastewater, the present invention first conducted the following exploratory experiments.

[0026] Test Example 1

[0027] N, N-dimethylacetamide and ethanol were mixed uniformly in a volume ratio of 1:1 to prepare 50 mL of organic solvent. 2-aminoterephthalic acid was added to the organic solvent and stirred uniformly to obtain a first solution, wherein the concentration of 2-aminoterephthalic acid in the first solution was 30 mmol / L. 0.3 mL of titanium tetraisopropoxide was added to the first solution and treated under ultrasonic conditions for 30 min to mix uniformly to obtain a second solution. The second solution was transferred to a 100 mL Teflon-lined stainless steel autoclave, heated at 150 ° C for 28 h under static conditions, and then cooled to room temperature. The centrifugal product was collected by centrifugation, washed several times with DMSO and butanol, and then dried at 100 ° C for 10 h to prepare a layered metal-organic framework material named NMT.

[0028] After adding 2.8µL of bromine to 15mL of deionized water and stirring evenly, add 10mg of NMT and shake evenly. Use a pH meter to test the pH value of the bromine water every hour. Set up three parallel tests. To avoid errors, take the average of the three measurements. The pH value change curve is shown in the figure below: Figure 1 As shown. Figure 1It can be seen that as time goes by, the pH in the system gradually stabilizes. This is because NMT undergoes a substitution reaction with Br2, and the production of HBr will cause a change in pH. - It will not hydrolyze and change the pH. Therefore, in the following examples, the pH of the system is taken as the end point for removing Br2. When the pH remains unchanged, Br2 in the system is removed.

[0029] Example 1

[0030] A method for the coordinated treatment of bromine wastewater and antibiotic wastewater comprises the following steps:

[0031] Step 1, N, N-dimethylacetamide and ethanol are uniformly mixed in a volume ratio of 1:1 to prepare 50mL of organic solvent. 2-aminoterephthalic acid is added to the organic solvent and stirred to obtain a first solution, wherein the concentration of 2-aminoterephthalic acid in the first solution is 30mmol / L. 0.3mL of titanium tetraisopropoxide is added to the first solution and treated under ultrasonic conditions for 30min to mix uniformly to obtain a second solution. The second solution is transferred to a 100mL Teflon-lined stainless steel autoclave, heated at 150°C for 28h under static conditions, and then cooled to room temperature. The centrifugal product is collected by centrifugation, washed several times with DMSO and butanol, and then dried at 100°C for 10h to prepare a layered metal organic framework material named NMT.

[0032] Step 2, add 20 mg of NMT to 30 mL of 0.05 mol / L bromine aqueous solution, and let the reaction stand until the pH value of the solution no longer changes to remove Br2 in the water. Then centrifuge the solution, wash the product obtained by centrifugation with ethylene glycol and deionized water, and then put it in a vacuum oven for drying to obtain a metal organic framework material containing bromine substituents, named NMT@Br.

[0033] Step 3, add 45 mg of NMT@Br to 30 mL of 0.05 mol / L silver sulfate solution, let it react at room temperature for 24 h, centrifuge the solution, wash the centrifuged product with methanol and deionized water, and dry it in a vacuum oven to obtain a silver bromide modified metal organic framework material, named NMT@AgBr.

[0034] Step 4: According to the mass ratio of NMT@AgBr to antibiotics of 1:1, 10 mg of NMT@AgBr was placed in a 20 mg / L tetracycline aqueous solution at room temperature. Before starting the photocatalytic reaction, a 35-min dark reaction phase was set to establish a stable adsorption equilibrium between the catalyst and the pollutant. After the dark reaction phase, a 300W xenon lamp was turned on for 40 minutes to degrade the antibiotics. The wavelength of the xenon lamp was λ>420 nm to block ultraviolet light.

[0035] Figure 2 In the figure, a is a SEM image of the silver bromide modified metal organic framework material prepared in Example 1. It can be seen that the prepared silver bromide modified metal organic framework material has a regular and uniform flaky structure, and b is a yellow powder photo of the silver bromide modified metal organic framework material in Example 1.

[0036] When removing Br2 from water, whether the water still contains Br2 is determined based on the pH value of the system. Therefore, when the pH value remains unchanged, Br2 in the water is removed by the method in Example 1. In order to explore the factors affecting the removal effect of antibiotics, the following comparative examples are also set up.

[0037] Comparative Example 1

[0038] The tetracycline aqueous solution is treated with NMT@Br, and the specific method includes the following steps:

[0039] Step 1, N, N-dimethylacetamide and ethanol are uniformly mixed in a volume ratio of 1:1 to prepare 50 mL of organic solvent. 2-aminoterephthalic acid is added to the organic solvent and stirred to obtain a first solution, wherein the concentration of 2-aminoterephthalic acid in the first solution is 30 mmol / L. 0.3 mL of titanium tetraisopropoxide is added to the first solution and treated under ultrasonic conditions for 30 min to mix uniformly to obtain a second solution. The second solution is transferred to a 100 mL Teflon-lined stainless steel autoclave, heated at 150 ° C for 28 h under static conditions, and then cooled to room temperature. The centrifugal product is collected by centrifugation, washed several times with DMSO and butanol, and then dried at 100 ° C for 10 h to prepare a layered metal organic framework material named NMT.

[0040] Step 2, add 20 mg of NMT to 30 mL of 0.05 mol / L bromine aqueous solution, and let the reaction stand until the pH value of the solution no longer changes to remove Br2 in the water. Then centrifuge the solution, wash the product obtained by centrifugation with ethylene glycol and deionized water, and then put it in a vacuum oven for drying to obtain a metal organic framework material containing bromine substituents, named NMT@Br.

[0041] Step 3: According to the mass ratio of NMT@Br to antibiotics of 1:1, 10 mg of NMT@Br was placed in a 20 mg / L tetracycline aqueous solution at room temperature. Before starting the photocatalytic reaction, a 35-min dark reaction phase was set to establish a stable adsorption equilibrium between the catalyst and the pollutant. After the dark reaction phase, a 300W xenon lamp was turned on for 40 minutes, where the wavelength of the xenon lamp was λ>420 nm to block ultraviolet light.

[0042] Comparative Example 2

[0043] The tetracycline aqueous solution is treated with NMT, and the specific method comprises the following steps:

[0044] Step 1, N, N-dimethylacetamide and ethanol are uniformly mixed in a volume ratio of 1:1 to prepare 50 mL of organic solvent. 2-aminoterephthalic acid is added to the organic solvent and stirred evenly to obtain a first solution, and the concentration of 2-aminoterephthalic acid in the first solution is 30mmol / L. 0.3mL of titanium tetraisopropoxide is added to the first solution, and it is treated under ultrasonic conditions for 30min to mix evenly to obtain a second solution. The second solution is transferred to a 100mL Teflon-lined stainless steel autoclave, heated at 150°C for 28h under static conditions, and then cooled to room temperature. The centrifugal product is collected by centrifugation, washed several times with DMSO and butanol, and then dried at 100°C for 10h to prepare a layered metal organic framework material named NMT.

[0045] Step 2: According to the mass ratio of NMT to antibiotics of 1:1, 10 mg of NMT was placed in a 20 mg / L tetracycline aqueous solution at room temperature. Before starting the photocatalytic reaction, a 35-min dark reaction phase was set to establish a stable adsorption equilibrium between the catalyst and the pollutant. After the dark reaction phase, a 300W xenon lamp was turned on for 40 minutes, where the wavelength of the xenon lamp was λ>420 nm to block ultraviolet light.

[0046] Comparative Example 3

[0047] When treating the tetracycline aqueous solution, there is no light, and the specific method includes the following steps:

[0048] Step 1, N, N-dimethylacetamide and ethanol are uniformly mixed in a volume ratio of 1:1 to prepare 50 mL of organic solvent. 2-aminoterephthalic acid is added to the organic solvent and stirred evenly to obtain a first solution, and the concentration of 2-aminoterephthalic acid in the first solution is 30mmol / L. 0.3mL of titanium tetraisopropoxide is added to the first solution, and it is treated under ultrasonic conditions for 30min to mix evenly to obtain a second solution. The second solution is transferred to a 100mL Teflon-lined stainless steel autoclave, heated at 150°C for 28h under static conditions, and then cooled to room temperature. The centrifugal product is collected by centrifugation, washed several times with DMSO and butanol, and then dried at 100°C for 10h to prepare a layered metal organic framework material named NMT.

[0049] Step 2, add 20 mg of NMT to 30 mL of 0.05 mol / L bromine aqueous solution, and let the reaction stand until the pH value of the solution no longer changes. Centrifuge the solution, wash the product obtained by centrifugation with ethylene glycol and deionized water, and then put it in a vacuum oven for drying to obtain a metal organic framework material containing bromine substituents, named NMT@Br.

[0050] Step 3, add 45 mg of NMT@Br to 30 mL of 0.05 mol / L silver sulfate solution, let it react at room temperature for 24 h, centrifuge the solution, wash the centrifuged product with methanol and deionized water, and dry it in a vacuum oven to obtain a silver bromide modified metal organic framework material, named NMT@AgBr.

[0051] Step 4: According to the mass ratio of NMT@AgBr to antibiotics of 1:1, 10 mg of NMT@AgBr was placed in a 20 mg / L tetracycline aqueous solution at room temperature, followed by a dark reaction for 75 min.

[0052] Comparative Example 4

[0053] Place a 20 mg / L tetracycline aqueous solution at room temperature, avoid light for 35 minutes, and then irradiate with a 300W xenon lamp for 40 minutes, where the wavelength of the xenon lamp is λ>420 nm, isolate ultraviolet light, and irradiate for 40 minutes. This is used as a blank control.

[0054] Example 2

[0055] A method for the coordinated treatment of bromine wastewater and antibiotic wastewater comprises the following steps:

[0056] Step 1, after dimethyl sulfoxide and ethylene glycol are uniformly mixed in a volume ratio of 1:1, 50 mL of organic solvent is prepared. 2-aminoterephthalic acid is added to the organic solvent and stirred evenly to obtain a first solution, and the concentration of 2-aminoterephthalic acid in the first solution is 30mmol / L. 0.3mL of titanium tetraisopropoxide is added to the first solution, and it is treated under ultrasonic conditions for 30 min to mix it evenly to obtain a second solution. The second solution is transferred to a 100mL Teflon-lined stainless steel autoclave, heated at 100°C for 28h under static conditions, and then cooled to room temperature. The centrifugal product is collected by centrifugation, washed several times with DMSO and butanol, and then dried at 100°C for 10h to prepare a layered metal organic framework material named NMT.

[0057] Step 2, add 5 mg of NMT to 20 mL of 0.05 mol / L bromine aqueous solution, and let the reaction stand until the pH value of the solution no longer changes to remove Br2 in the water. Then centrifuge the solution, wash the product obtained by centrifugation with ethylene glycol and deionized water, and then put it in a vacuum oven for drying to obtain a metal organic framework material containing bromine substituents, named NMT@Br.

[0058] Step 3, add 25 mg of NMT@Br to 30 mL of 0.04 mol / L silver sulfate solution, let it react at room temperature for 10 h, centrifuge the solution, wash the centrifuged product with methanol and deionized water, and dry it in a vacuum oven to obtain a silver bromide modified metal organic framework material, named NMT@AgBr.

[0059] Step 4: According to the mass ratio of NMT@AgBr to antibiotics of 0.4:1, 10 mg of NMT@AgBr was placed in a 20 mg / L tetracycline aqueous solution at room temperature. Before starting the photocatalytic reaction, a 35-min dark reaction phase was set to establish a stable adsorption equilibrium between the catalyst and the pollutant. After the dark reaction phase, a 300W xenon lamp was turned on for 40 minutes to degrade the antibiotics. The wavelength of the xenon lamp was λ>420 nm, and the ultraviolet light was blocked. The light was irradiated for 40 minutes.

[0060] Example 3

[0061] A method for the coordinated treatment of bromine wastewater and antibiotic wastewater comprises the following steps:

[0062] Step 1, N, N-dimethylformamide and methanol are uniformly mixed in a volume ratio of 1:1 to prepare 50 mL of organic solvent. 2-aminoterephthalic acid is added to the organic solvent and stirred evenly to obtain a first solution, and the concentration of 2-aminoterephthalic acid in the first solution is 30mmol / L. 0.3mL of titanium tetraisopropoxide is added to the first solution, and it is treated under ultrasonic conditions for 30min to mix evenly to obtain a second solution. The second solution is transferred to a 100mL Teflon-lined stainless steel autoclave, heated at 150°C for 10h under static conditions, and then cooled to room temperature. The centrifugal product is collected by centrifugation, washed several times with DMSO and butanol, and then dried at 100°C for 10h to prepare a layered metal organic framework material named NMT.

[0063] Step 2, add 10 mg of NMT to 10 mL of 0.05 mol / L bromine aqueous solution, and let the reaction stand until the pH value of the solution no longer changes to remove Br2 in the water. Then centrifuge the solution, wash the product obtained by centrifugation with ethylene glycol and deionized water, and then put it in a vacuum oven for drying to obtain a metal organic framework material containing bromine substituents, named NMT@Br.

[0064] Step 3, add 50 mg of NMT@Br to 10 mL of 0.06 mol / L silver sulfate solution, let it react at room temperature for 24 h, centrifuge the solution, wash the centrifuged product with methanol and deionized water, and dry it in a vacuum oven to obtain a silver bromide-modified metal organic framework material, named NMT@AgBr.

[0065] Step 4: According to the mass ratio of NMT@AgBr to antibiotics of 1.2:1, 10 mg of NMT@AgBr was placed in a 20 mg / L tetracycline aqueous solution at room temperature. Before starting the photocatalytic reaction, a 35-min dark reaction phase was set to establish a stable adsorption equilibrium between the catalyst and the pollutant. After the dark reaction phase, a 300W xenon lamp was turned on for 40 minutes to degrade the antibiotics. The wavelength of the xenon lamp was λ>420 nm to block ultraviolet light.

[0066] Example 4

[0067] A method for the coordinated treatment of bromine wastewater and antibiotic wastewater comprises the following steps:

[0068] Step 1, N, N-dimethylacetamide and ethanol are uniformly mixed in a volume ratio of 1:1 to prepare 50 mL of organic solvent. 2-aminoterephthalic acid is added to the organic solvent and stirred evenly to obtain a first solution, and the concentration of 2-aminoterephthalic acid in the first solution is 30mmol / L. 0.3mL of titanium tetraisopropoxide is added to the first solution, and it is treated under ultrasonic conditions for 30min to mix evenly to obtain a second solution. The second solution is transferred to a 100mL Teflon-lined stainless steel autoclave, heated at 150°C for 28h under static conditions, and then cooled to room temperature. The centrifugal product is collected by centrifugation, washed several times with DMSO and butanol, and then dried at 100°C for 10h to prepare a layered metal organic framework material named NMT.

[0069] Step 2, add 20 mg of NMT to 30 mL of 0.05 mol / L bromine aqueous solution, and let the reaction stand until the pH value of the solution no longer changes to remove Br2 in the water. Then centrifuge the solution, wash the product obtained by centrifugation with ethylene glycol and deionized water, and then put it in a vacuum oven for drying to obtain a metal organic framework material containing bromine substituents, named NMT@Br.

[0070] Step 3, add 45 mg of NMT@Br to 30 mL of 0.05 mol / L silver sulfate solution, let it react at room temperature for 24 h, centrifuge the solution, wash the centrifuged product with methanol and deionized water, and dry it in a vacuum oven to obtain a silver bromide modified metal organic framework material, named NMT@AgBr.

[0071] Step 4: According to the mass ratio of NMT@AgBr to antibiotics of 1:1, 10 mg of NMT@AgBr was placed in a 20 mg / L tetracycline aqueous solution at an ambient temperature of 38°C. Before starting the photocatalytic reaction, a 35-min dark reaction phase was set to establish a stable adsorption equilibrium between the catalyst and the pollutant. After the dark reaction phase, the system was placed under natural light for catalytic degradation, and the light was irradiated for 45 minutes.

[0072] Comparative Example 5

[0073] At an ambient temperature of 38 degrees Celsius, the tetracycline aqueous solution is treated with NMT, and the specific method includes the following steps:

[0074] Step 1, N, N-dimethylacetamide and ethanol are uniformly mixed in a volume ratio of 1:1 to prepare 50 mL of organic solvent. 2-aminoterephthalic acid is added to the organic solvent and stirred evenly to obtain a first solution, and the concentration of 2-aminoterephthalic acid in the first solution is 30mmol / L. 0.3mL of titanium tetraisopropoxide is added to the first solution, and it is treated under ultrasonic conditions for 30min to mix evenly to obtain a second solution. The second solution is transferred to a 100mL Teflon-lined stainless steel autoclave, heated at 150°C for 28h under static conditions, and then cooled to room temperature. The centrifugal product is collected by centrifugation, washed several times with DMSO and butanol, and then dried at 100°C for 10h to prepare a layered metal organic framework material named NMT.

[0075] Step 2: According to the mass ratio of NMT to antibiotics of 1:1, 10 mg of NMT was placed in a 20 mg / L tetracycline aqueous solution at an ambient temperature of 38°C. Before starting the photocatalytic reaction, a 35-min dark reaction phase was set to establish a stable adsorption equilibrium between the catalyst and the pollutant. After the dark reaction phase, the system was placed under natural light for catalytic degradation, and the light was irradiated for 45 minutes.

[0076] Comparative Example 6

[0077] A 20 mg / L tetracycline aqueous solution was placed at an ambient temperature of 38°C, protected from light for 35 minutes, and then placed under natural light for catalytic degradation for 45 minutes. This was used as a blank control.

[0078] During the whole treatment process, 2 mL of the above-mentioned examples and comparative examples were collected at regular intervals, and the supernatant was obtained by centrifugation, and then filtered through a filter head. Finally, the absorbance of the supernatant was measured at 357 nm using an ultraviolet-visible spectrophotometer. By measuring the absorbance at this wavelength, the degradation of tetracycline in the aqueous solution was accurately calculated. Figure 3 and Figure 4 In the figure, C represents the concentration of tetracycline in water during sampling and testing, and C0 represents the initial concentration of tetracycline in water. C / C0 represents the ratio of the concentration of tetracycline in water during sampling and testing to the initial concentration. As time goes by, C / C0 decreases. The faster the decrease, the faster the degradation of tetracycline.

[0079] Figure 3 The figure is a comparison of the degradation rates of tetracycline in Example 1 and Comparative Examples 1 to 4, wherein Example 1 is NMT@AgBr in the figure, Comparative Example 1 is NMT@Br in the figure, Comparative Example 2 is NMT in the figure, Comparative Example 3 is no light in the figure, and Comparative Example 4 is a blank control in the figure. Figure 3 It can be seen that at the same concentration, after the NMT@AgBr in Example 1 was exposed to no light and UV-free light, the tetracycline degradation rate reached 99% in only 40 minutes, which was much higher than that of other comparison samples.

[0080] Figure 4 The figure is a comparison of the degradation rates of tetracycline in Example 4, Comparative Example 5 and Comparative Example 6, wherein Example 4 is NMT@AgBr in the figure, Comparative Example 5 is NMT in the figure, and Comparative Example 6 is a blank control in the figure. It can be seen that at 38°C, after the NMT@AgBr in Example 4 undergoes the no-light and natural light illumination stages, the tetracycline removal capacity is much greater than that of Comparative Examples 5 and 6.

[0081] The same detection method was used to obtain a tetracycline degradation rate of 96% in only 40 minutes in Example 2 and 99% in only 40 minutes in Example 3. However, the removal effect of tetracycline in the prior art is generally about 80% in 1 to 2 hours.

[0082] When doxycycline, chlortetracycline, salicylic acid, and isoquinoline are selected as research objects, they can all be degraded by photocatalysis, and this application will not elaborate on them here.

[0083] It can be seen from the above embodiments and comparative examples that the present invention realizes the coordinated treatment of bromine wastewater and antibiotic wastewater, and the bromine wastewater is used as a raw material for the antibiotic wastewater catalyst. While the photocatalyst is efficiently prepared, the bromine wastewater is removed.

[0084] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, they are also intended to be included.

Claims

1. A method for the coordinated treatment of bromine wastewater and antibiotic wastewater, characterized in that: The following steps are involved: Using 2-aminoterephthalic acid and titanium tetraisopropoxide as ligands, a layered metal-organic framework material was prepared by a solvothermal method in an organic solvent. Immersing the metal organic framework material in water containing Br2, removing the Br2 in the water through a substitution reaction, and obtaining a metal organic framework material containing a bromine substituent; The metal organic framework material containing a bromine substituent is immersed in a soluble silver salt solution, and allowed to react at room temperature for 10 hours to 24 hours, so as to generate silver bromide in situ on the metal organic framework material, thereby obtaining a silver bromide modified metal organic framework material; The silver bromide-modified metal organic framework material is placed in water containing antibiotics, first protected from light until adsorption equilibrium is reached, and then catalytic oxidation is carried out under visible light conditions to degrade the antibiotics; According to the mass ratio of silver bromide-modified metal organic framework material to antibiotics being 0.4-1.2:1, the silver bromide-modified metal organic framework material is added into the water body containing antibiotics; During catalytic oxidation, the illumination time is 40 min to 45 min.

2. The method for co-treatment of bromine wastewater and antibiotic wastewater according to claim 1, characterized in that: In the process of removing Br2 from water, after the pH value of the system remains unchanged, the system is subjected to solid-liquid separation.

3. The method for co-treatment of bromine wastewater and antibiotic wastewater according to claim 1, characterized in that: The soluble silver salt solution is a silver sulfate aqueous solution, the concentration of the soluble silver salt solution is 0.04 mol / L to 0.06 mol / L, and the usage ratio of the metal organic framework material containing bromine substituents and the soluble silver salt solution is 0.8 mg to 5 mg: 1 mL.

4. The method for co-treatment of bromine wastewater and antibiotic wastewater according to claim 1, characterized in that: The molar ratio of 2-aminoterephthalic acid to titanium tetraisopropoxide is 1.5:

1.

5. The method for co-treatment of bromine wastewater and antibiotic wastewater according to claim 1, characterized in that: In the process of preparing the layered metal organic framework material by the solvent thermal method, the reaction temperature is 100°C to 150°C.

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