CN115814855A - Method for removing antibiotics in livestock and poultry wastewater by using COFs-based composite photocatalyst - Google Patents
Method for removing antibiotics in livestock and poultry wastewater by using COFs-based composite photocatalyst Download PDFInfo
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Abstract
The invention discloses a method for removing antibiotics in livestock wastewater by using a COFs-based composite photocatalyst, wherein the COFs-based composite photocatalyst comprises a spherical vinyl functionalized covalent organic framework and silver phosphate particles. In the invention, the processing method comprises the following steps: (1) Introducing the livestock and poultry wastewater into a reaction tank of a catalytic reaction device, and then adding a COFs-based composite photocatalyst for catalytic reaction treatment, wherein the reaction time is 12-20 min; (2) Overflowing the wastewater reacted in the step (1) into a sedimentation tank, wherein the sedimentation time is 30-90 min; (3) discharging the supernatant after precipitation out of the catalytic reaction device; (4) Pumping the precipitated catalyst back to the reaction tank, setting a material regeneration tank, and carrying out activation regeneration treatment on the precipitated catalyst by taking 1-3 months as a period. The method has the advantages of high treatment efficiency, simplicity in operation and the like, can completely degrade and remove antibiotics in the livestock wastewater under the stress of high-concentration COD, ammonia nitrogen and total phosphorus, and has excellent adaptability and good industrial application prospects.
Description
Technical Field
The invention belongs to the technical field of photocatalytic application and environmental protection of semiconductor materials, relates to a treatment method of livestock and poultry wastewater, and particularly relates to a method for removing antibiotics in the livestock and poultry wastewater by using a COFs-based composite photocatalyst.
Background
China is a big country for livestock and poultry breeding, and the data of Chinese statistical yearbook in 2021 shows that the number of the slaughtered pork pigs in China only reaches 5.3 hundred million in 2020, and the discharge amount of the pig-raising wastewater generated in 2020 can reach 57.2 million tons according to the second national pollution source general survey, emission source statistical survey product discharge accounting method and coefficient manual and pollutant discharge standard of livestock and poultry breeding (GB 18596-2001). In order to improve the yield of livestock and poultry and prevent and treat diseases, antibiotics are added in the breeding process. As the antibiotics can not be completely absorbed and metabolized in the animal body, 60 to 90 percent of the antibiotics are discharged into the livestock wastewater along with the feces and urine in the form of original medicine. Therefore, the livestock wastewater not only has large water quantity, but also contains antibiotics besides high-concentration carbon, nitrogen and phosphorus.
At present, the treatment of livestock and poultry wastewater has the following problems: (1) Because antibiotics and intermediates thereof contained in the wastewater can generate strong inhibition effect on microorganisms, the anaerobic biological treatment process of the livestock wastewater is unstable and even ineffective; (2) Residual antibiotics in wastewater are extremely easy to induce the enrichment of drug-resistant bacteria and the spread of Antibiotic Resistance Genes (ARGs), thereby generating great potential threats to the receiving environment and human health. In conclusion, due to the biotoxicity of antibiotics, the anaerobic biological treatment process of livestock and poultry wastewater is difficult to carry out efficiently, and needs to be reinforced to improve the biochemical performance and eliminate the environmental risk caused by long-term exposure of antibiotics. Therefore, research and development of an economical and efficient livestock wastewater treatment technology for efficiently removing antibiotics in livestock wastewater are urgently needed.
The photocatalysis technology is a green technology which is concerned in the fields of environment and energy by the advantages that the reaction condition is mild, and solar energy can be directly utilized and converted into chemical energy. In recent years, researchers have conducted a series of studies on photocatalytic technology as a pretreatment unit for biological treatment to enhance the bioavailability of wastewater. Numerous studies have shown that the photocatalytic technology has the following significant advantages in the enhanced treatment of organic wastewater: 1) The composite material has good oxidative decomposition performance on biological toxic substances such as antibiotics and the like, and can obviously improve the bioavailability of organic wastewater; 2) The strong oxidizing active species generated in the photocatalytic reaction process endows the catalyst with a good self-cleaning antibacterial function, so that the catalyst has long-acting stability in the organic wastewater treatment process; 3) The reaction condition is mild, and no other chemical reagent is required to be introduced. Therefore, the application of photocatalysis in the pretreatment unit of the biological treatment process to improve the bioavailability of the livestock wastewater is a feasible and promising treatment technology.
The core of realizing the high-efficiency photocatalytic reaction is the optimization, design and development of the photocatalyst with high-efficiency and stable catalytic activity. Covalent organic framework materials (COFs) are novel crystalline porous polymers formed by connecting organic small molecular monomers through covalent bonds, have the unique properties of large specific surface area, high porosity, low density, good stability, high charge carrier mobility, rich and adjustable structure and the like, and are concerned in the fields of photoelectrocatalysis, adsorption, energy storage, gas trapping and the like. However, at present, most of the synthesis conditions of COFs are generally harsh, and the synthesis needs to be carried out under the conditions of high temperature, high pressure and oxygen isolation; under the condition of complex water quality, the selective affinity and adsorption capacity of the COFs material to specific target pollutants need to be improved; the intrinsic photogenerated carrier separation efficiency of the COFs monomer material is low, and the photocatalytic activity needs to be further enhanced. Therefore, how to overcome the problems of harsh preparation conditions, low separation efficiency of photo-generated electron-hole pairs, poor photocatalytic activity, poor selectivity, poor tolerance to high COD and ammonia nitrogen and the like in the conventional COFs material so as to obtain the COFs-based composite photocatalyst with simple preparation process, good photocatalytic performance and high COD and ammonia nitrogen resistance has very important significance for realizing the high-efficiency treatment of antibiotics in livestock and poultry wastewater.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for removing antibiotics in livestock wastewater by using a COFs-based composite photocatalyst, which has the advantages of simple preparation process, high treatment efficiency, strong selectivity, high COD resistance and good ammonia nitrogen resistance.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for removing antibiotics in livestock and poultry wastewater by using a COFs-based composite photocatalyst is further characterized in that the antibiotics in the livestock and poultry wastewater are removed by using the COFs-based composite photocatalyst; the COFs-based composite photocatalyst comprises a spherical vinyl functionalized covalent organic framework, and silver phosphate particles are loaded on the vinyl functionalized covalent organic framework.
In the method, the quality ratio of the vinyl functionalized covalent organic framework to the silver phosphate particles in the COFs-based composite photocatalyst is 1.0 x 10 -4 ～5.0×10 -3 (ii) a The molar ratio of vinyl functional groups to the covalent organic framework in the vinyl functionalized covalent organic framework is from 10 to 1.
The preparation method of the COFs-based composite photocatalyst comprises the following steps:
s1, preparing a covalent organic framework dispersion liquid from a vinyl functionalized covalent organic framework, and adding Ag + Stirring the solution to prepare covalent organic framework/Ag + A dispersion liquid;
s2, mixing HPO 4 2- The solution is added to the covalent organic framework/Ag prepared in step S1 + And stirring, washing, centrifuging and drying the dispersion under the condition of keeping out of the sun to obtain the vinyl functionalized covalent organic framework composite photocatalyst.
In step S1, the preparation method of the vinyl functionalized covalent organic framework includes the following steps:
(1) Feeding 1,3,5-tri (4-aminophenyl) benzene and 1,4-dialdehyde-2,5-divinylbenzene with the molar ratio of 1:1-1:2 into acetonitrile, and fully dissolving to obtain a mixed solution; the concentration of 1,3,5-tri (4-aminophenyl) benzene in the mixed solution is 5-20 mmol/L;
(2) Adding 10-15 mol/L acetic acid solution into the mixed solution obtained in the step (1), violently stirring for 10-45 s, standing at room temperature for 48-80 h, washing, and vacuum drying to obtain a vinyl functionalized covalent organic framework; the volume ratio of the acetic acid solution to the acetonitrile is 0.04 to 0.2.
More preferably, in step S1 of the above method, the Ag is + The concentration of the solution is 0.2-0.5 mol/L; the Ag is + The solution is AgNO 3 A solution; the covalent organic framework dispersion liquid is obtained by mixing a vinyl functionalized covalent organic framework and water; the concentration of the covalent organic framework dispersion liquid is 0.05-0.5 g/L; the Ag is + The dropping speed of the solution is 0.1-0.4 mL/min; the stirring time is 5-12 h;
in step S2, the HPO 4 2- HPO in solution 4 2- With a common organic frame/Ag + Ag in the dispersion + The molar ratio of (A) to (B) is 1: 3; the HPO 4 2- The solution is Na 2 HPO 4 ·12H 2 O solution; the HPO 4 2- The dropping speed of the solution is 0.03-0.1 mL/min; the stirring time is 2-6 h; the drying process is carried out under vacuum.
Further improved, when the COFs-based composite photocatalyst is used for treating antibiotics in livestock and poultry wastewater, the method comprises the following steps: mixing the COFs-based composite photocatalyst with livestock and poultry wastewater in a catalytic reaction device, and carrying out degradation reaction under the illumination condition to complete the treatment of antibiotics in the livestock and poultry wastewater; the addition amount of the COFs-based composite photocatalyst is 0.05 g-0.5 g of the COFs-based composite photocatalyst added into each liter of livestock and poultry wastewater; the livestock and poultry wastewater is wastewater containing COD, ammonia nitrogen, phosphorus and antibiotics; the initial concentration of antibiotics in the livestock wastewater is 0.1-100 mg/L, and the initial concentration of COD is 100-10000 mg/L; the initial concentration of ammonia nitrogen is 10 mg/L-1000 mg/L; the initial concentration of total phosphorus is 5 mg/L-100 mg/L; the antibiotic of the antibiotic in the livestock and poultry wastewater is at least one of tetracycline, oxytetracycline, chlortetracycline, sulfadiazine, sulfamethazine, sulfamethoxazole, sulfamethazine, gentamicin, erythromycin, clarithromycin and azithromycin.
Further, a catalytic reaction device is adopted to treat the livestock and poultry wastewater; the catalytic reaction device comprises a reaction tank, a sedimentation tank, a material regeneration tank, an aeration ring, a gas flowmeter and a liquid flowmeter, and the treatment of antibiotics in the livestock wastewater comprises the following steps:
(a1) Introducing the livestock and poultry wastewater into a reaction tank of a catalytic reaction device, and then adding a COFs-based composite photocatalyst for treatment, wherein the treatment time is 12-20 min; carrying out degradation reaction under the illumination condition;
(a2) Overflowing and conveying the reaction solution obtained after the degradation reaction in the step (a 1) into a sedimentation tank, wherein the sedimentation time is 30-90 min, and obtaining supernatant and sedimentation material;
(a3) Filtering the supernatant obtained in the step (a 2) and discharging the filtered supernatant out of a catalytic reaction device;
(a4) Pumping the precipitation material obtained in the step (a 2) back to the reaction tank to continuously treat the livestock wastewater, and finishing the continuous treatment of antibiotics in the livestock wastewater;
(a5) Conveying the precipitation material continuously treated for 1-3 months in the step (a 4) to a material regeneration tank, and activating and regenerating the catalytic material, wherein the regeneration treatment method specifically comprises the following steps: adding a hydrogen peroxide solution and a phosphoric acid solution, and reacting for 10-30 min under the stirring condition to obtain a regenerated COFs-based composite photocatalyst;
(a6) And (b) returning the regenerated COFs-based composite photocatalyst obtained in the step (a 5) to a reaction tank to continuously treat the livestock and poultry wastewater.
Further, in the method, light source chambers are arranged around the reaction tank and in the central area, and the reaction tank and the light source chambers are separated by a light-transmitting partition plate; an aeration ring is arranged at the bottom of the reaction tank; and a xenon lamp or an LED energy-saving lamp is arranged in the light source chamber.
Preferably, the material of the light-transmitting partition plate is polymethyl methacrylate; the aeration flow of the aeration ring is 5 to 20m 3 /min。
Compared with the prior art, the invention has the advantages that:
(1) The invention provides a method for removing antibiotics in livestock and poultry wastewater by using a COFs-based composite photocatalyst, which is used for treating the livestock and poultry wastewater and effectively removing the antibiotics in the livestock and poultry wastewater through the degradation of the catalyst. The COFs-based composite photocatalyst adopted in the invention is formed by compounding a vinyl functionalized covalent organic framework and silver phosphate particles, has the advantages of simple preparation process, mild preparation conditions, strong photocatalytic activity, good COD (chemical oxygen demand) and ammonia nitrogen resistance and the like, is a reusable novel high-efficiency visible light photocatalyst, can degrade and remove antibiotics in wastewater in a short time under visible light, and can effectively degrade the antibiotics in the wastewater after being used for many times, so that the method for removing the antibiotics in the livestock and poultry wastewater by using the COFs-based composite photocatalyst has the advantages of good antibiotic degradation performance, short reaction time and the like, more importantly, the COFs-based COD photocatalyst adopted in the method can be suitable for treating the livestock and poultry wastewater containing high concentration, ammonia nitrogen and total phosphorus, can completely degrade and remove the antibiotics in the wastewater under the stress of high COD, ammonia nitrogen and total phosphorus, and has very good adaptability, and has very high use value and very good application prospect.
(2) In the invention, the mass ratio of the vinyl functionalized covalent organic framework to the silver phosphate particles in the adopted COFs-based composite photocatalyst is 1.0 multiplied by 10 -4 ～5.0×10 -3 By optimizing the mass ratio of the vinyl functionalized covalent organic framework to the silver phosphate particles, the catalytic activity of the catalyst can be more effectively improved, so that the antibiotics in the wastewater can be more efficiently degraded; meanwhile, the molar ratio of the vinyl functional group in the vinyl functionalized covalent organic framework to the covalent organic framework is optimized to be 10-15, and the selective adsorption and degradation performance of the covalent organic framework material on antibiotic molecules can be improved more effectively, so that the effective degradation of the antibiotic in the wastewater can be realized more efficiently.
(3) The invention also comprises regeneration treatment of the photocatalyst after continuous and cyclic use for 1-3 months, and the regeneration treatment of the used catalyst by adopting the hydrogen peroxide solution and the phosphoric acid solution can realize the regeneration of the COFs-based composite photocatalyst and restore the photocatalytic activity of the COFs-based composite photocatalyst, thereby realizing the continuous treatment of the livestock and poultry wastewater and further reducing the treatment cost.
(4) The preparation method of the COFs-based composite photocatalyst has the advantages of simple process, easiness in operation, low requirements on preparation conditions and preparation equipment, high yield, greenness, no pollution and the like, is suitable for large-scale preparation, and is beneficial to industrial application, so that the low-cost and high-efficiency treatment of the livestock and poultry wastewater is realized.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a graph showing the degradation effect of the COFs-based composite photocatalyst on tetracycline in example 1 of the present invention under different time conditions.
FIG. 2 is a graph showing the effect of the COFs-based composite photocatalyst on tetracycline degradation under different concentrations of COD in example 2 of the present invention.
FIG. 3 is a graph showing the degradation effect of the COFs-based composite photocatalyst on tetracycline under ammonia nitrogen conditions of different concentrations in example 3 of the present invention.
FIG. 4 is a graph showing the degradation effect of the COFs-based composite photocatalyst on tetracycline under the conditions of different concentrations of total phosphorus in example 4 of the present invention.
FIG. 5 is a graph showing the degradation effect of the COFs-based composite photocatalyst on tetracycline in example 5 of the present invention under different time conditions.
FIG. 6 is a schematic view showing the structure of a catalytic reactor used in example 5 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the processes used were conventional processes, the equipment used were conventional equipment, and the data obtained were average values of three or more experiments.
Example 1
A method for treating antibiotic wastewater by using a COFs-based composite photocatalyst, in particular to a method for treating tetracycline-containing livestock wastewater by using a COFs-based composite photocatalyst, which comprises the following steps:
weighing COFs-based composite photocatalyst (10 mLCOFs/Ag) 3 PO 4 ) 50mg, adding into 100mL tetracycline solution with concentration of 20mg/L, ultrasonic treating for 1min, stirring in dark for 30min to reach adsorption balance, and placing in 300W xenon lamp (lambda)>420 nm) under irradiation.
Blank group: the tetracycline waste water is treated under the condition of not adding a photocatalytic material, and other conditions are the same.
In the degradation reaction process, reaction solutions under different reaction times are taken, the content of tetracycline in the reaction solutions is measured by high performance liquid chromatography, and the degradation effect of the COFs-based composite photocatalyst on the tetracycline solutions in different times is obtained by calculation, and the result is shown in FIG. 1.
FIG. 1 is a graph showing the degradation effect of different COFs-based composite photocatalysts on tetracycline in example 1 of the present invention under different time conditions. As can be seen from FIG. 1, under the condition of no addition of the photocatalytic material, the concentration of tetracycline is almost unchanged and cannot be degraded by itself under the illumination condition; after adding the photocatalytic material (COFs-based composite photocatalyst), stirring for 30min under a dark condition, adsorbing about 3% of tetracycline by the photocatalyst, rapidly degrading and removing the tetracycline by the catalyst under a visible light condition (lambda is more than 420 nm), and after illuminating for 5min, the tetracycline removal rate can reach 100%.
In this example, the COFs-based composite photocatalyst (10 mLCOFs/Ag) was used 3 PO 4 ) Comprises a spherical vinyl functionalized covalent organic framework, silver phosphate particles are loaded on the spherical vinyl functionalized covalent organic framework, wherein the spherical ethyleneThe mass ratio of the radical functionalized covalent organic framework to the silver phosphate particles is 4.97 multiplied by 10 -4 (ii) a The molar ratio of vinyl functional groups in the vinyl functionalized covalent organic framework to the covalent organic framework is 12.
In this example, the adopted COFs-based composite photocatalyst (10 mLCOFs/Ag) 3 PO 4 ) The preparation method comprises the following steps:
(1) Weighing 0.04mmol of 1,3,5-tri (4-aminophenyl) benzene and 0.06mmol of 1,4-dialdehyde-2,5-divinylbenzene, placing the mixture in a centrifuge tube, then transferring 5mL of acetonitrile into the centrifuge tube, and carrying out ultrasonic treatment on the mixture for 20 s;
(2) And (2) adding 0.4mL of 12mol/L acetic acid solution into the mixed solution obtained in the step (1), shaking vigorously for 15s, standing at room temperature for 72h, centrifuging, washing, and drying in vacuum to obtain the vinyl functionalized covalent organic framework.
(3) And (3) weighing 0.1g of the vinyl functionalized covalent organic framework obtained in the step (2), and dispersing in 400mL of ultrapure water to prepare a vinyl functionalized covalent organic framework dispersion liquid.
(4) Transferring 10.0mL of the vinyl-functionalized Covalent Organic Framework (COF) dispersion obtained in the step (3), diluting the dispersion with ultrapure water to 60mL, and adding 15mL of AgNO with a concentration of 0.6mol/L at a dropping rate of 0.3mL/min 3 Stirring the solution for 12h in the dark to prepare the covalent organic framework/Ag + And (3) dispersing the mixture.
(5) Adding the covalent organic framework/Ag obtained in the step (4) at a dropping speed of 0.1mL/min + 15mL of Na with a concentration of 0.2mol/L was added to the dispersion 2 HPO 4 ·12H 2 Stirring O solution for 6h in dark condition, washing with ultrapure water and ethanol for several times, centrifuging, vacuum drying at 60 deg.C for 12h to obtain COFs-based composite photocatalyst, 10mLCOFs/Ag 3 PO 4 。
For comparison, vinyl functionalized covalent organic framework monomers without added silver phosphate were prepared according to the above steps (1), (2) and (3) and are noted as COFs; preparing silver phosphate monomers without addition of a covalent organic framework, noted as Ag, according to steps (4) and (5) above 3 PO 4 。
Example 2
A method for removing antibiotics in livestock wastewater by using a COFs-based composite photocatalyst is basically the same as that in example 1, and the difference is only that: the livestock wastewater solution of example 2 contains COD concentrations of 0, 100mg/L, 2000mg/L, 5000mg/L and 10000mg/L, respectively.
FIG. 2 is a diagram showing the removal efficiency of the COFs-based composite photocatalyst in the treatment of livestock and poultry wastewater under COD conditions of different concentrations in example 2 of the present invention. As can be seen from FIG. 2, under the stress of COD with different concentrations, the COFs-based composite photocatalyst still maintains a good degradation effect on tetracycline, when the COD concentration is 100-2000 mg/L, the degradation efficiency of the catalyst is not changed, when the COD concentration is as high as 100000mg/L, the rate of the catalyst is only slightly reduced, and the removal rate of 93.2% can be achieved within 12 min.
Example 3
A method for removing antibiotics in livestock wastewater by using a COFs-based composite photocatalyst is basically the same as that in example 1, and the difference is only that: the livestock and poultry wastewater solution in the embodiment 3 contains ammonia nitrogen with different concentrations, and the ammonia nitrogen concentrations are respectively 0, 100mg/L, 300mg/L, 500mg/L and 1000mg/L.
FIG. 3 is a diagram showing the removal efficiency of the COFs-based composite photocatalyst in the embodiment 3 of the present invention for tetracycline in livestock and poultry wastewater under ammonia nitrogen conditions of different concentrations. As can be seen from FIG. 3, under the stress of ammonia nitrogen with different concentrations, the COFs-based composite photocatalyst still maintains a good degradation effect on tetracycline, and when the ammonia nitrogen concentration reaches 1000mg/L, the removal rate of 88.3% can be achieved within 12 min.
Example 4
A method for removing antibiotics in livestock wastewater by using a COFs-based composite photocatalyst is basically the same as that in example 1, and the difference is only that: the livestock wastewater solution of example 3 contains total phosphorus with different concentrations, wherein the total phosphorus concentrations are 0, 5mg/L, 30mg/L, 50mg/L and 100mg/L respectively.
FIG. 4 is a diagram showing the removal efficiency of the COFs-based composite photocatalyst in the embodiment 4 of the present invention for tetracycline in livestock and poultry wastewater under the conditions of different concentrations of total phosphorus. As can be seen from FIG. 4, under the stress of total phosphorus with different concentrations, the COFs-based composite photocatalyst still maintains a good degradation effect on tetracycline, and when the concentration of the total phosphorus is as high as 100mg/L, the removal rate of 90.1% can be still achieved within 12 min.
Example 5
A method for removing antibiotics in livestock and poultry wastewater by using a COFs-based composite photocatalyst specifically comprises the following steps of:
(1) 1kg of the COFs-based composite photocatalyst prepared in example 1 (10 mLCOFs/Ag) 3 PO 4 ) Adding into a reaction tank of a catalytic reaction device (with 10m of the reaction tank) 3 Livestock and poultry wastewater containing 10mg/L tetracycline, wherein the COD concentration is 3000mg/L, the ammonia nitrogen concentration is 500mg/L, and the total phosphorus concentration is 30 mg/L);
(2) Starting an aeration ring and an LED lamp, and carrying out photocatalytic degradation reaction for 25min under illumination;
(3) Carrying out photocatalytic degradation reaction to obtain a reaction solution, overflowing and conveying the reaction solution into a sedimentation tank, and settling for 60min to obtain a supernatant and a sedimentation material;
(4) Filtering the supernatant obtained in the step (3) and discharging the filtered supernatant out of the catalytic reaction device;
in this embodiment, in the process of photocatalytic reaction, reaction solutions at different reaction times are taken, the content of tetracycline in the reaction solutions is measured by high performance liquid chromatography, and the degradation effect of the COFs-based composite photocatalyst on the tetracycline solutions at different times is obtained by calculation, with the result shown in fig. 5.
FIG. 5 is a graph showing the degradation effect of the COFs-based composite photocatalyst on tetracycline under different time conditions in example 5 of the present invention. As can be seen from FIG. 5, the concentration of tetracycline hardly changed with the increase of the light irradiation time without adding the photocatalytic material. After the COFs-based composite photocatalyst prepared in example 1 is added, the concentration of tetracycline is rapidly reduced along with the increase of illumination time, and when the illumination time reaches 12min, the tetracycline is degraded and removed by 100%.
In this example, a photocatalytic reaction apparatus was used as shown in FIG. 6, the reaction cell being surrounded by and arranged aroundThe central area is provided with a light source chamber, and the reaction tank is separated from the light source chamber by a light-transmitting partition plate; an aeration ring is arranged at the bottom of the reaction tank; a xenon lamp or an LED energy-saving lamp is arranged in the light source chamber; the light-transmitting partition plate is made of polymethyl methacrylate; the aeration flow of the aeration ring is 5-20 m 3 /min。
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (9)
1. A method for removing antibiotics in livestock and poultry wastewater by using a COFs-based composite photocatalyst is characterized in that the antibiotics in the livestock and poultry wastewater are removed by using the COFs-based composite photocatalyst; the COFs-based composite photocatalyst comprises a spherical vinyl functionalized covalent organic framework, and silver phosphate particles are loaded on the vinyl functionalized covalent organic framework.
2. The method as claimed in claim 1, wherein the mass ratio of the vinyl functionalized covalent organic framework to the silver phosphate particles in the COFs-based composite photocatalyst is 1.0 x 10 -4 ～5.0×10 -3 (ii) a The molar ratio of vinyl functional groups to the covalent organic framework in the vinyl functionalized covalent organic framework is from 10 to 1.
3. The method according to claim 2, wherein the preparation method of the COFs-based composite photocatalyst comprises the following steps:
s1, preparing a covalent organic framework dispersion liquid from a vinyl functionalized covalent organic framework, and adding Ag + Stirring the solution to prepare covalent organic framework/Ag + A dispersion liquid;
s2, mixing HPO 4 2- Solution additionTo the covalent organic framework/Ag prepared in step S1 + And stirring, washing, centrifuging and drying the dispersion under the condition of keeping out of the sun to obtain the vinyl functionalized covalent organic framework composite photocatalyst.
4. The process for preparing a COFs-based composite photocatalyst according to claim 3, wherein in step S1, said process for preparing a vinyl functionalized covalent organic framework comprises the following steps:
(1) Feeding 1,3,5-tri (4-aminophenyl) benzene and 1,4-dialdehyde-2,5-divinylbenzene with the molar ratio of 1:1-1:2 into acetonitrile, and fully dissolving to obtain a mixed solution; the concentration of 1,3,5-tri (4-aminophenyl) benzene in the mixed solution is 5-20 mmol/L;
(2) Adding 10-15 mol/L acetic acid solution into the mixed solution obtained in the step (1), violently stirring for 10-45 s, standing at room temperature for 48-80 h, washing, and vacuum drying to obtain a vinyl functionalized covalent organic framework; the volume ratio of the acetic acid solution to the acetonitrile is 0.04 to 0.2.
5. The method for preparing COFs-based composite photocatalyst according to claim 3, wherein in step S1, said Ag is added + The concentration of the solution is 0.2-0.5 mol/L; the Ag is + The solution is AgNO 3 A solution; the covalent organic framework dispersion liquid is obtained by mixing vinyl functionalized covalent organic framework and water; the concentration of the covalent organic framework dispersion liquid is 0.05-0.5 g/L; the Ag is + The dropping speed of the solution is 0.1-0.4 mL/min; the stirring time is 5-12 h;
in step S2, the HPO 4 2- HPO in solution 4 2- With a common organic frame/Ag + Ag in dispersion + The molar ratio of (A) to (B) is 1: 3; the HPO 4 2- The solution is Na 2 HPO 4 ·12H 2 O solution; the HPO 4 2- The dropping speed of the solution is 0.03-0.1 mL/min; the stirring time is 2-6 h; the drying process is carried out under vacuum.
6. The method as claimed in any one of claims 1 to 5, wherein the treatment of antibiotics in the livestock wastewater by using the COFs-based composite photocatalyst comprises the following steps: mixing the COFs-based composite photocatalyst with the livestock and poultry wastewater in a catalytic reaction device, and carrying out catalytic degradation reaction under the illumination condition to complete the treatment of antibiotics in the livestock and poultry wastewater; the addition amount of the COFs-based composite photocatalyst is that 0.05-0.5 g of the COFs-based composite photocatalyst is added into each liter of livestock and poultry wastewater; the livestock and poultry wastewater is wastewater containing COD, ammonia nitrogen, phosphorus and antibiotics; the initial concentration of antibiotics in the livestock wastewater is 0.1-100 mg/L, and the initial concentration of COD is 100-10000 mg/L; the initial concentration of ammonia nitrogen is 10 mg/L-1000 mg/L; the initial concentration of total phosphorus is 5 mg/L-100 mg/L; the antibiotic in the livestock and poultry wastewater is at least one of tetracycline, oxytetracycline, chlortetracycline, sulfadiazine, sulfamethazine, sulfamethoxazole, sulfadimidine, gentamicin, erythromycin, clarithromycin and azithromycin.
7. The method as claimed in claim 6, wherein the livestock and poultry wastewater is treated by a catalytic reaction device; the catalytic reaction device comprises a reaction tank, a sedimentation tank, a material regeneration tank, an aeration ring, a gas flowmeter and a liquid flowmeter, and the catalytic reaction device comprises the following steps of:
(a1) Introducing the livestock and poultry wastewater into a reaction tank of a catalytic reaction device, and then adding a COFs-based composite photocatalyst for catalytic reaction treatment, wherein the reaction time is 12-20 min; carrying out degradation reaction under the condition of illumination;
(a2) Overflowing and conveying the reaction solution obtained after the catalytic reaction in the step (a 1) into a sedimentation tank, wherein the sedimentation time is 30-90 min, and obtaining supernatant and sedimentation material;
(a3) Filtering the supernatant obtained in the step (a 2) and discharging the filtered supernatant out of a catalytic reaction device;
(a4) Pumping the precipitation material obtained in the step (a 2) back to the reaction tank to continuously treat the livestock wastewater, and finishing the continuous treatment of antibiotics in the livestock wastewater;
(a5) Conveying the precipitation material continuously treated for 1-3 months in the step (a 4) to a material regeneration tank, and activating and regenerating the catalytic material, wherein the regeneration treatment method specifically comprises the following steps: adding a hydrogen peroxide solution and a phosphoric acid solution, and reacting for 10-30 min under the stirring condition to obtain a regenerated COFs-based composite photocatalyst;
(a6) And (b) returning the regenerated COFs-based composite photocatalyst obtained in the step (a 5) to a reaction tank to continuously treat the livestock and poultry wastewater.
8. The method of claim 7, wherein a light source chamber is arranged around and in the central area of the reaction cell, and the reaction cell and the light source chamber are separated by a light-transmitting partition plate; an aeration ring is arranged at the bottom of the reaction tank; and a xenon lamp or an LED energy-saving lamp is arranged in the light source chamber.
9. The method of claim 8, wherein the light-transmissive spacer is made of polymethyl methacrylate; the aeration flow of the aeration ring is 5-20 m 3 /min。
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