CN113087244A - System for purifying antibiotics in drinking water of water plant - Google Patents
System for purifying antibiotics in drinking water of water plant Download PDFInfo
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Abstract
The invention discloses a system for purifying antibiotics in drinking water of a water plant, which comprises a coagulation tank, a sedimentation tank, a sand filter, a degradation device and an active carbon filter which are sequentially connected in series; the treated water after passing through the sand filter enters the degradation device, a degradation pipe is arranged in the degradation device, a degradation gel band and a color-changing light band are arranged in the degradation pipe, and a silver mirror attached layer is arranged on the outer wall of the degradation pipe; water enters a degradation channel, antibiotics are removed under the action of the degradation gel band, the color-changing light band and the silver mirror reflection absorption and degradation of the antibiotics, and then the water enters an active carbon filtering device; the degradable gel belt is formed by compounding a gel carrier, LDHs and metal ions. The invention uses the combined action of the degradation gel, the color-changing light band and the reflection of the silver mirror to adsorb and degrade antibiotics in water, has wide range of degraded antibiotics, high degradation efficiency, high speed, sustainable action and disinfection effect.
Description
Technical Field
The invention relates to the field of water treatment systems, in particular to a system for purifying antibiotics in drinking water of a water plant.
Background
Antibiotics as a typical PPCPs pollutant are a very concerned pollution type, and surface water of many rivers, lakes and seas in ChinaSuch as Zhujiang in south China, Yangtze river in China, and yellow river in North China, etc., were detected. According to statistics, about 21 ten thousand tons of antibiotics are produced in China each year, wherein 42 percent of antibiotics are used for medical treatment and 48 percent of antibiotics are used for animal husbandry. In ecological water environments, a greater variety of antibiotics were detected. Antibiotics in the ecological water environment usually enter a human body through drinking water, so that the drug resistance of the human body is caused, and the long-term harm is large. After the antibiotics enter the water environment, migration and transformation processes mainly comprise adsorption, biodegradation, photodegradation and the like occur in media such as water, suspended particulate matters, sediments, aquatic organisms and the like. Antibiotics are converted into CO via a series of migrations, or completely mineralized2And H2O, or other intermediates and metabolites, but still some antibiotic contaminants continue to accumulate in the environment. Antibiotics can still be detected in the effluent of many waterworks. People drink water polluted by antibiotics for a long time, adverse reactions such as gastrointestinal tract infection, digestive tract flora imbalance and the like are caused, and drug-resistant bacteria in a human body are increased.
At present, the conventional process of water plant includes coagulation-precipitation-sand filtration-activated carbon filtration, and although the process can generally effectively remove organic matters in water, the process can hardly remove antibiotics in drinking water to meet the drinking water demand of people, and patent document (CN201910966483.3) discloses a process using UV/H2O2A method for combined treatment of antibiotics in water, but the method requires continuous injection of H2O2And H2O2The utilization rate is not high, and the good removal effect on various antibiotics can not be achieved.
Disclosure of Invention
In view of the above situation, the present invention aims to provide a system for purifying antibiotics in drinking water of water plants, which can efficiently and rapidly degrade a plurality of antibiotics in drinking water.
The technical proposal for solving the problem is that,
the system for purifying antibiotics in drinking water of water plant comprises a coagulation tank, a sedimentation tank, a sand filter, a degradation device and activated carbon which are connected in series in sequenceThe bottom of the active carbon filtering device is connected with a water outlet pipe; the outlet of the coagulation tank is connected with the inlet of the sedimentation tank, the outlet of the sedimentation tank is connected with the inlet of the sand filter, the outlet of the sand filter is connected with the inlet of the degradation device, the outlet of the degradation device is connected with the inlet of the activated carbon filter, and the outlet of the activated carbon filter is connected with the water outlet pipe; FeZnBi-NO obtained by stripping of the degraded gel3The preparation method comprises the following steps of (1) irradiating a preparation solution obtained by mixing an LDHs colloidal solution and N-methyl maleic acid monoamide and 2- (hydroxymethyl) methyl acrylate by gamma rays to obtain solid hydrogel, and attaching Ti and Cu ions to the solid hydrogel to obtain the LDHs colloidal solution; the drinking raw water enters the degradation device after sequentially passing through the coagulation tank, the sedimentation tank and the sand filter tank, the antibiotics in the water are adsorbed in the degradation pipe through the degradation gel belt, the adsorbed antibiotics are subjected to photodegradation by the color-changing light belt color-changing luminescence irradiation degradation gel, and the drinking water is finally obtained by flowing out of the water outlet pipe through the active carbon filter device.
Further, the degradation device include four flanges, two sections water pipes, degradation pipe, the degradation pipe is located between two sections water pipes, the degradation pipe is located and uses the flange to connect between the water pipe, the port of two water pipes all is connected with the flange, there is the flow valve on the water pipe, there is the light area that discolours in the degradation pipe inside, there is the power cord on the degradation pipe, the power cord is connected with the light area that discolours, it has the degradation gel area to twine on the light area that discolours, there is the support frame water pipe and degradation pipe below, the support frame contacts with water pipe and degradation pipe.
Furthermore, the color-changing light band is a red-orange-yellow-green-blue-purple-seven-color-changing light band, and the irradiation intensity is 600-700mJ/cm2。
Furthermore, the degradation pipe be transparent glass material, degradation pipe's surface adheres to there is a layer silver mirror, and there is the protective layer silver mirror outside.
Furthermore, the flow valve controls the flow of water to be 4-5m3H, and the residence time of the water in the degradation tube is at least 45 seconds.
Further, the degradable gel belt is prepared by the following steps:
(1) adding Bi (NO)3)3·5H2O、Zn(NO3)2·6H2O、FeCl3、NaNO3Boiling the mixed solution prepared by HMT, AcOH and deionized water at the temperature of 105 ℃ and 110 ℃, refluxing for 40-48h, cooling to room temperature, filtering, washing, carrying out vacuum freeze drying for 20-24h at the temperature of-80 ℃ to 60 ℃, grinding and sieving with a 200-mesh sieve to obtain FeZnBi-NO3-LDHs powder;
(2) under the protection of Ar, FeZnBi-NO is added3Adding LDHs powder into formamide, stirring at the speed of 1000-1300rpm for 7-9 days, centrifuging at the speed of 2500-3000rpm, and collecting filtrate to obtain stripped LDHs colloidal solution;
(3)N2under protection, weighing N-methyl maleic acid monoamide monomer, dissolving in deionized water, sequentially adding 2- (hydroxymethyl) methyl acrylate and distilled water, performing ultrasonic treatment for 30-40min to fully mix the solution uniformly, and placing in a brown glass tube to obtain a prepared solution;
(4) under the protection of Ar, dropwise adding the peeled LDHs colloidal solution into the prepared solution, uniformly stirring, irradiating the prepared solution at a temperature of between 80 ℃ below zero and 60 ℃ by using 60 Co-gamma rays as an irradiation source, wherein the irradiation dose is 18 to 20kGy, and washing and drying the solution after 1 to 2 hours of irradiation to obtain solid hydrogel;
(5) adding solid hydrogel to TiCl4And CuSO4·5H2In the mixed solution of O, oscillating for 20-24h at constant temperature under the conditions of 20-30 ℃, 150-300rpm, filtering, washing at room temperature and drying in the air to obtain the adsorption solid hydrogel;
(6) placing the adsorbed solid hydrogel in Na2And in the S solution, fully reacting and oscillating at constant temperature for 10-12h under the conditions of 20-30 ℃ and 300rpm at 150-.
Further, the degradation gel strip is prepared by Bi (NO) in the step (1)3)3·5H2O:Zn(NO3)2·6H2O:FeCl3:NaNO3The mass volume ratio of HMT, AcOH and deionized water is 18-20g, 10-12g, 5-7g, 1-1.2g, 16-18g, 2-3g and 300 mL.
Further, the FeZnBi-NO in the steps (2) and (3) of preparing the degraded gel zone3LDHs powder, formamide, N-methyl maleic acid monoamide monomer, deionized water and 2- (hydroxymethyl) propaneMethyl enoate, distilled water and TiCl4And CuSO4·5H2Mixed solution of O Na2The mass-volume ratio of the S solution is 40-50g:500-600mL:10-12g:40-50mL:50-60g:300-400g:15-20mL:50-60 mL.
Further, the TiCl4And CuSO4·5H2The concentration of the mixed solution of O is 35 to 40mmol/L, and TiCl4And CuSO4·5H2The mass ratio of O is 1: 1.
Further, said Na2The concentration of the S solution is 40-50 mmol/L.
Further, the antibiotics removed by the degradation device include, but are not limited to, roxithromycin, thiamphenicol, florfenicol, chloramphenicol, sulfadimidine, sulfadiazine, trimethoprim, norfloxacin, and ofloxacin.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages;
the system for purifying the antibiotics in the drinking water of the water plant can quickly and efficiently treat various antibiotics in the drinking water of the water plant, and the removal rate of the antibiotics reaches 78-97%. The degradation gel belt in the degradation device is prepared by forming a laminated network structure by an N-methyl maleic acid monoamide monomer, 2- (hydroxymethyl) methyl acrylate and LDHs and doping various photocatalytic metal ions, can adsorb a large amount of antibiotics in water, has a large light absorption band gap and can absorb light with different wavelengths, and can rapidly and strongly respond to the irradiation of a color-changing light belt installed in the degradation device and the reflection action of a silver mirror on a degradation tube to rapidly degrade various antibiotics. In addition, the degradation device is simple and convenient, the degradation gel belt can be repeatedly used, and the sterilization function is also realized.
Drawings
FIG. 1 is a system for purifying antibiotics in drinking water from a water plant according to the present invention;
FIG. 2 is a degradation apparatus;
FIG. 3 is a table showing the detection of the antibiotic content.
Detailed Description
The foregoing and other technical and scientific aspects, features and utilities of the present invention will be apparent from the following detailed description of the embodiments, which is to be read in connection with the accompanying drawings of fig. 1-2. The structural contents mentioned in the following embodiments are all referred to the attached drawings of the specification.
In the following embodiments, the coagulation tank a is connected to a raw water tank, the raw water passes through the coagulation tank a, the sedimentation tank b and the sand filter c to remove other pollutant substances, such as large particulate matters, COD, ammonia nitrogen, total phosphorus, etc., since the processes of the coagulation tank (a), the sedimentation tank (b), the sand filter (c) and the activated carbon filter (e) are all the prior art, which is not described herein, the degradation device (d) is connected between the sand filter (c) and the activated carbon filter (e).
Example 1
1. Preparation of degradable gel tape
(1) Adding Bi (NO)3)3·5H2O 18g、Zn(NO3)2·6H2O 10g、FeCl3 7g、NaNO31g, 16g of HMT, 2g of AcOH and 250mL of deionized water, boiling at 105 ℃, refluxing for 40h, cooling to room temperature, filtering, washing, vacuum freeze-drying for 20h at-80 ℃, grinding and sieving with a 200-mesh sieve to obtain FeZnBi-NO3-LDHs powder;
(2) under the protection of Ar, FeZnBi-NO is added3Adding 40g of LDHs powder into 500mL of formamide, stirring for 7 days at the speed of 1000rpm, performing centrifugal separation at 2500rpm, and collecting filtrate to obtain a stripped LDHs colloidal solution;
(3)N2under protection, weighing 10g of N-methyl maleic acid monoamide monomer, dissolving in 40mL of deionized water, sequentially adding 50g of 2- (hydroxymethyl) methyl acrylate and 300g of distilled water, performing ultrasonic treatment for 30min to fully and uniformly mix the solution, and placing the solution in a brown glass tube to obtain a prepared solution;
(4) under the protection of Ar, dropwise adding the peeled LDHs colloidal solution into the prepared solution, uniformly stirring, irradiating the prepared solution at-80 ℃ by adopting 60 Co-gamma rays as an irradiation source, wherein the irradiation dose is 18kGy, washing and drying after 1h of irradiation to obtain solid hydrogel;
(5) the solid hydrogel was added to 15mL of 40mmol/L TiCl4And CuSO4·5H2Oscillating the mixed solution of O at constant temperature of 20 ℃ and 150rpm for 20h, filtering, washing at room temperature and drying in the air to obtain adsorbed solid hydrogel;
(6) placing the solid hydrogel in 50mL of 40mmol/L Na2And (3) in the S solution, fully reacting at the temperature of 20 ℃ and the speed of 150rpm, oscillating at constant temperature for 10 hours, washing at room temperature and airing to obtain the degraded gel zone.
2. Degradation device
The degradation device (d) comprises four flanges and two water pipes, wherein the four flanges are respectively an inlet flange 1, a first flange 2, a second flange 3 and an outlet flange 4, the two water pipes are respectively a water inlet pipe 5 and a water outlet pipe 6, a flow valve 10 is installed on the water inlet pipe 5, the inlet flange 1 is connected with one end of the water inlet pipe 5, a degradation pipe 7 is arranged at the other end of the water inlet pipe 5, the water inlet pipe 5 is communicated with the degradation pipe 7 through the first flange 2, the other end of the degradation pipe 7 is communicated with the water outlet pipe 6 through the second flange 3, the outlet flange 4 is arranged at the other end of the water outlet pipe 6, a support frame 11 is arranged below the two water pipes and the degradation pipe 7, the support frame 11 is in contact with the two water pipes and the degradation pipe 7, the degradation pipe 7 is made of transparent glass, a layer of silver mirror is attached to the outer side of the degradation pipe 7, a protective, the irradiation intensity was 600mJ/cm2The color-changing light band 9 is positioned on the axis of the degradation tube 7, a power line 13 is arranged on the degradation tube 7, the power line 13 is connected with the color-changing light band 9, and the degradation gel band 8 is wound on the color-changing light band 9.
3. System for purifying antibiotics in drinking water of water plant
A system for purifying antibiotics in drinking water of a water plant comprises a coagulation tank (a), a sedimentation tank (b), a sand filter (c), a degradation device (d) and an active carbon filter (e) which are sequentially connected in series; the outlet a2 of the coagulation tank is connected with the inlet b1 of the sedimentation tank, the outlet b2 of the sedimentation tank is connected with the inlet c1 of the sand filter, the outlet c2 of the sand filter is connected with the inlet flange 1 of the degradation device, the outlet flange 4 of the degradation device is connected with the inlet e1 of the active carbon filter, and the outlet e2 of the active carbon filter is connected with the water outlet pipe (f).
When in use, the drinking raw water passes through the coagulation tank (a), the sedimentation tank (b) and the sand filter in sequenceAfter the pool (c), the water enters the degradation pipe 7 through the water inlet flange 1, the water inlet pipe 5 and the first flange 2, the power line 13 is connected, the color changing light band 9 changes color and emits light, the flow valve 10 is adjusted, and the flow rate of the water is controlled to be 4m3And h, the retention time of water in the degradation pipe 7 is 45 seconds, after the degradation gel zone 8 fully absorbs the antibiotics in the water, the color-changing light zone 9 and the degradation pipe 7 are subjected to mirror reflection to rapidly degrade the antibiotics, and then the antibiotics flow out through the second flange 3, the water outlet pipe 6 and the outlet flange 4 in sequence and flow out through the water outlet pipe (f) through the activated carbon filtering device (e), and finally the drinking water is obtained.
Example 2
1. Preparation of degradable gel tape
(1) Adding Bi (NO)3)3·5H2O 19g、Zn(NO3)2·6H2O 11g、FeCl3 7.5g、NaNO31.1g, HMT 17g, AcOH 2.5g and 300mL of deionized water 250-3-LDHs powder;
(2) under the protection of Ar, FeZnBi-NO is added3Adding 45g of LDHs powder into 550mL of formamide, stirring for 8 days at the speed of 1150rpm, carrying out centrifugal separation at 2750rpm, and collecting filtrate to obtain a stripped LDHs colloidal solution;
(3)N2under protection, 11g of N-methyl maleic acid monoamide monomer is weighed and dissolved in 45mL of deionized water, 55g of 2- (hydroxymethyl) methyl acrylate and 350g of distilled water are sequentially added, the solution is fully and uniformly mixed by ultrasonic treatment for 35min and is placed in a brown glass tube, and a prepared solution is obtained;
(4) under the protection of Ar, dropwise adding the peeled LDHs colloidal solution into the prepared solution, uniformly stirring, irradiating the prepared solution at-70 ℃ by adopting 60 Co-gamma rays as an irradiation source, wherein the irradiation dose is 19kGy, washing and drying after 1.5h of irradiation to obtain solid hydrogel;
(5) the solid hydrogel was added to 18mL of 40mmol/L TiCl4And CuSO4·5H2Oscillating in mixed solution of O at 25 deg.C and 225rpm for 22h, filtering, washing at room temperature, and air drying to obtainAdsorbing the solid hydrogel;
(6) placing the solid hydrogel in 55mL of 40mmol/L Na2And (3) in the S solution, fully reacting at 25 ℃ and 225rpm, oscillating at constant temperature for 11h, washing at room temperature and drying in the air to obtain the degradation gel tape.
2. Degradation device
The degradation device (d) comprises four flanges and two water pipes, wherein the four flanges are respectively an inlet flange 1, a first flange 2, a second flange 3 and an outlet flange 4, the two water pipes are respectively a water inlet pipe 5 and a water outlet pipe 6, a flow valve 10 is installed on the water inlet pipe 5, the inlet flange 1 is connected with one end of the water inlet pipe 5, a degradation pipe 7 is arranged at the other end of the water inlet pipe 5, the water inlet pipe 5 is communicated with the degradation pipe 7 through the first flange 2, the other end of the degradation pipe 7 is communicated with the water outlet pipe 6 through the second flange 3, the outlet flange 4 is arranged at the other end of the water outlet pipe 6, a support frame 11 is arranged below the two water pipes and the degradation pipe 7, the support frame 11 is contacted with the two water pipes and the degradation pipe 7, the degradation pipe 7 is made of transparent glass, a layer of silver mirror is attached to the outer side of the degradation pipe 7, a protective layer 12 is arranged, the degradation tube 7 is provided with a power line 13, the power line 13 is connected with a color-changing light band 9, and the irradiation intensity of the color-changing light band 9 is 650mJ/cm2The color-changing light band 9 is wound with a degradation gel band 8.
3. System for purifying antibiotics in drinking water of water plant
A system for purifying antibiotics in drinking water of a water plant comprises a coagulation tank (a), a sedimentation tank (b), a sand filter (c), a degradation device (d) and an active carbon filter (e) which are sequentially connected in series; the outlet a2 of the coagulation tank is connected with the inlet b1 of the sedimentation tank, the outlet b2 of the sedimentation tank is connected with the inlet c1 of the sand filter, the outlet c2 of the sand filter is connected with the inlet flange 1 of the degradation device, the outlet flange 4 of the degradation device is connected with the inlet e1 of the active carbon filter, and the outlet e2 of the active carbon filter is connected with the water outlet pipe (f).
When in use, drinking raw water sequentially passes through the coagulation tank (a), the sedimentation tank (b) and the sand filter tank (c), then enters the degradation pipe 7 through the water inlet flange 1, the water inlet pipe 5 and the first flange 2, the power line 13 is connected, the color-changing light band 9 changes color and emits light, the flow valve 10 is adjusted, and water is controlledFlow velocity of 4.5m3And h, the retention time of water in the degradation pipe 7 is 50 seconds, after the degradation gel zone 8 fully absorbs the antibiotics in the water, the color-changing light zone 9 and the degradation pipe 7 are subjected to mirror reflection to rapidly degrade the antibiotics, and then the antibiotics sequentially flow out through the second flange 3, the water outlet pipe 6 and the outlet flange 4 and then flow out through the water outlet pipe (f) through the activated carbon filtering device (e), and finally the drinking water is obtained.
Example 3
1. Preparation of degradable gel tape
(1) Adding Bi (NO)3)3·5H2O 20g、Zn(NO3)2·6H2O 12g、FeCl3 8g、NaNO31.2g, 18g of HMT, 3g of AcOH and 300mL of deionized water, boiling at 110 ℃, refluxing for 48h, cooling to room temperature, filtering, washing, vacuum freeze-drying at-60 ℃ for 24h, grinding and sieving with a 200-mesh sieve to obtain FeZnBi-NO3-LDHs powder;
(2) under the protection of Ar, FeZnBi-NO is added3Adding 50g of LDHs powder into 600mL of formamide, stirring at 1300rpm for 9 days, performing centrifugal separation at 3000rpm, and collecting filtrate to obtain a stripped LDHs colloidal solution;
(3)N2under protection, weighing 12g of N-methyl maleic acid monoamide monomer, dissolving the monomer in 50mL of deionized water, then sequentially adding 60g of 2- (hydroxymethyl) methyl acrylate and 400g of distilled water, carrying out ultrasonic treatment for 40min to fully and uniformly mix the solution, and placing the solution in a brown glass tube to obtain a prepared solution;
(4) under the protection of Ar, dropwise adding the peeled LDHs colloidal solution into the prepared solution, uniformly stirring, irradiating the prepared solution at-60 ℃ by adopting 60 Co-gamma rays as an irradiation source, wherein the irradiation dose is 20kGy, washing and drying after irradiating for 2 hours to obtain solid hydrogel;
(5) the solid hydrogel was added to 20mL of 40mmol/L TiCl4And CuSO4·5H2Oscillating the mixed solution of O at constant temperature of 30 ℃ and 300rpm for 24h, filtering, washing at room temperature and drying in the air to obtain adsorbed solid hydrogel;
(6) placing the solid hydrogel in 60mL of 40mmol/L Na2In S solution at 30 ℃ and 300rpAnd m, fully reacting, oscillating at constant temperature for 12h, washing at room temperature, and airing to obtain the degradable gel belt.
2. Degradation device
Referring to fig. 2, the degradation device (d) comprises four flanges and two water pipes, wherein the four flanges are respectively an inlet flange 1, a first flange 2, a second flange 3 and an outlet flange 4, the two water pipes are respectively a water inlet pipe 5 and a water outlet pipe 6, a flow valve 10 is installed on the water inlet pipe 5, the inlet flange 1 is connected with one end of the water inlet pipe 5, the other end of the water inlet pipe 5 is provided with a degradation pipe 7, the water inlet pipe 5 is communicated with the degradation pipe 7 through the first flange 2, the other end of the degradation pipe 7 is communicated with the water outlet pipe 6 through the second flange 3, the other end of the water outlet pipe 6 is provided with the outlet flange 4, a support frame 11 is arranged below the two water pipes and the degradation pipe 7, the support frame 11 is contacted with the two water pipes and the degradation pipe 7, the degradation pipe 7 is made of transparent glass, a layer of silver mirror is attached to the outer side of the degradation pipe 7, a, the irradiation intensity was 700mJ/cm2The color-changing light band 9 is positioned on the axis of the degradation tube 7, a power line 13 is arranged on the degradation tube 7, the power line 13 is connected with the color-changing light band 9, and the degradation gel band 8 is wound on the color-changing light band 9.
3. System for purifying antibiotics in drinking water of water plant
Referring to fig. 1, a system for purifying antibiotics in drinking water of a water plant comprises a coagulation tank (a), a sedimentation tank (b), a sand filter (c), a degradation device (d) and an activated carbon filter (e) which are connected in series in sequence; the outlet a2 of the coagulation tank is connected with the inlet b1 of the sedimentation tank, the outlet b2 of the sedimentation tank is connected with the inlet c1 of the sand filter, the outlet c2 of the sand filter is connected with the inlet flange 1 of the degradation device, the outlet flange 4 of the degradation device is connected with the inlet e1 of the active carbon filter, and the outlet e2 of the active carbon filter is connected with the water outlet pipe (f).
When the device is used, drinking raw water sequentially passes through the coagulation tank (a), the sedimentation tank (b) and the sand filter (c) and then enters the degradation pipe 7 through the water inlet flange 1, the water inlet pipe 5 and the first flange 2, the power line 13 is connected, the color-changing light band 9 changes color and emits light, the flow valve 10 is adjusted, and the flow rate of the water is controlled to be 5m3The retention time of water in the degradation tube 7 is 60 seconds, and the degradation gel belt 8 absorbs antibiotics in water fully and changesThe antibiotics are rapidly degraded through the mirror reflection of the colored light band 9 and the degradation pipe 7, then sequentially flow out through the second flange 3, the water outlet pipe 6 and the outlet flange 4, and then flow out through the water outlet pipe (f) through the activated carbon filtering device (e), and finally the drinking water is obtained.
Test example 1
Adding an antibacterial agent into deionized water to simulate a water source to be treated, adding roxithromycin, thiamphenicol, chloramphenicol, sulfadimidine and norfloxacin into the deionized water, uniformly mixing to obtain a control group 1, adding roxithromycin, florfenicol, chloramphenicol, trimethoprim and ofloxacin into the deionized water, uniformly mixing to obtain a control group 2, adding roxithromycin, florfenicol, chloramphenicol, trimethoprim and norfloxacin into the deionized water, uniformly mixing to obtain a control group 3, and respectively introducing the control group 1, the control group 2 and the control group 3 into the system for purifying antibiotics in drinking water of a water plant in examples 1-3 to obtain an experimental group 1, an experimental group 2 and an experimental group 3. Detecting the content of each antibiotic in the control group 1-3 and the experimental group 1-3 by ultra performance liquid chromatography-mass spectrometry, and making a table (as shown in figure 3);
as can be seen from the table, the system has excellent purification effect on various antibiotics such as roxithromycin, thiamphenicol, florfenicol, chloramphenicol, sulfadimidine, sulfadiazine, trimethoprim, norfloxacin, ofloxacin and the like in water, and the purification rate reaches 78% -97%.
While the invention has been described in further detail with reference to specific embodiments thereof, it is not intended that the invention be limited to the specific embodiments thereof; for those skilled in the art to which the present invention pertains and related technologies, the extension, operation method and data replacement should fall within the protection scope of the present invention based on the technical solution of the present invention.
Claims (9)
1. A system for purifying antibiotics in drinking water of a water plant is characterized by comprising a coagulation tank, a sedimentation tank, a sand filter, a degradation device and an active carbon filter device; the outlet of the coagulation tank is connected with the inlet of the sedimentation tank, the outlet of the sedimentation tank is connected with the inlet of the sand filter tank, and the sand filter tankThe outlet of the degradation device is connected with the inlet of the activated carbon filtering device, and the outlet of the activated carbon filtering device is connected with the water outlet pipe; the degradation device comprises four flanges, two sections of water pipes and a degradation pipe, wherein the degradation pipe is positioned between the two sections of water pipes, the degradation pipe is connected with the water pipes through the flanges, the ports of the two water pipes are connected with the flanges, a flow valve is arranged on the water pipes, a color-changing light band is arranged in the degradation pipe, a power line is arranged on the degradation pipe and connected with the color-changing light band, a degradation gel band is wound on the color-changing light band, a support frame is arranged below the water pipes and the degradation pipe, and the support frame is in contact with the water pipes and the degradation pipe; FeZnBi-NO obtained by stripping of the degraded gel3The preparation method comprises the following steps of (1) irradiating a preparation solution obtained by mixing an LDHs colloidal solution and N-methyl maleic acid monoamide and 2- (hydroxymethyl) methyl acrylate by gamma rays to obtain solid hydrogel, and attaching Ti and Cu ions to the solid hydrogel to obtain the LDHs colloidal solution; the drinking raw water enters the degradation device after sequentially passing through the coagulation tank, the sedimentation tank and the sand filter tank, the antibiotics in the water are adsorbed in the degradation pipe through the degradation gel belt, the adsorbed antibiotics are subjected to photodegradation by the color-changing light belt color-changing luminescence irradiation degradation gel, and the drinking water is finally obtained by flowing out of the water outlet pipe through the active carbon filter device.
2. The system of claim 1, wherein the degradation tube is made of transparent glass, a silver mirror is attached to the outer surface of the degradation tube, and a protective layer is arranged outside the silver mirror.
3. The system for purifying antibiotics in drinking water of water plant as claimed in claim 2, wherein the color-changing light band is a red-orange-yellow-green-blue-purple-seven-color-changing light band with an irradiation intensity of 600-700mJ/cm2。
4. A system for purifying antibiotics in drinking water of water works according to claim 3, characterized in that the flow valve controls the flow rate of water to 4-5m3H, and the residence time of the water in the degradation tube is at least 45 seconds.
5. The system for purifying antibiotics in drinking water of water works according to claim 4, wherein the band of degraded gel is prepared by the following steps:
(1) bi (NO3)3·5H2O、Zn(NO3)2·6H2O、FeCl3、NaNO3Boiling a mixed solution prepared by HMT, AcOH and deionized water at the temperature of 105 ℃ and 110 ℃, refluxing for 40-48h, cooling to room temperature, filtering, washing, carrying out vacuum freeze drying at the temperature of-80 ℃ to-60 ℃ for 20-24h, grinding and sieving with a 200-mesh sieve to obtain FeZnBi-NO3-LDHs powder;
(2) under the protection of Ar, FeZnBi-NO is added3Adding LDHs powder into formamide, stirring at the speed of 1000-1300rpm for 7-9 days, centrifuging at the speed of 2500-3000rpm, and collecting filtrate to obtain stripped LDHs colloidal solution;
(3)N2under protection, weighing N-methyl maleic acid monoamide monomer, dissolving in deionized water, sequentially adding 2- (hydroxymethyl) methyl acrylate and distilled water, performing ultrasonic treatment for 30-40min to fully mix the solution uniformly, and placing in a brown glass tube to obtain a prepared solution;
(4) under the protection of Ar, dropwise adding the peeled LDHs colloidal solution into the prepared solution, uniformly stirring, irradiating the prepared solution at a temperature of between 80 ℃ below zero and 60 ℃ by using 60 Co-gamma rays as an irradiation source, wherein the irradiation dose is 18 to 20kGy, and washing and drying the solution after 1 to 2 hours of irradiation to obtain solid hydrogel;
(5) adding solid hydrogel to TiCl4And CuSO4·5H2In the mixed solution of O, oscillating for 20-24h at constant temperature under the conditions of 20-30 ℃, 150-300rpm, filtering, washing at room temperature and drying in the air to obtain the adsorption solid hydrogel;
(6) placing the adsorbed solid hydrogel in Na2And in the S solution, fully reacting and oscillating at constant temperature for 10-12h under the conditions of 20-30 ℃ and 300rpm at 150-.
6. A system for purifying antibiotics in drinking water of water works according to claim 5, wherein the degradation coagulationPreparation of adhesive tape Bi (NO) in step (1)3)3·5H2O:Zn(NO3)2·6H2O:FeCl3:NaNO3The mass volume ratio of HMT, AcOH and deionized water is 18-20g, 10-12g, 5-7g, 1-1.2g, 16-18g, 2-3g and 300 mL.
7. The system for purifying antibiotics in drinking water of water plant according to claim 6, wherein the gel-degrading zone is prepared by FeZnBi-NO in steps (2) and (3)3LDHs powder, formamide, N-methyl maleic acid monoamide monomer, deionized water, 2- (hydroxymethyl) methyl acrylate, distilled water and TiCl4And CuSO4·5H2Mixed solution of O Na2The mass volume of the S solution is 40-50g, 500-600mL, 10-12g, 40-50mL, 50-60g, 300-400g, 15-20mL and 50-60 mL.
8. The system for purifying antibiotics in drinking water of water works as claimed in claim 7, wherein the TiCl is4And CuSO4·5H2The concentration of the mixed solution of O is 35 to 40mmol/L, and TiCl4And CuSO4·5H2The mass ratio of O is 1: 1.
9. The system for purifying antibiotics in drinking water of water plant according to claim 8, wherein the Na is2The concentration of the S solution is 40-50 mmol/L.
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