A method for removing antibiotics based on the light-responsive activation of peroxymonosulfate system based on food dyes

Abstract

The present invention discloses a method for removing antibiotics by using a persulfate system activated by light response of edible dyes, comprising the following steps: mixing edible dyes and antibiotics to obtain a mixed solution; adding persulfate to the mixed solution to obtain a reaction system; and performing light response activation on the reaction system under simulated sunlight to achieve synergistic removal of edible dyes and antibiotics. The present invention reduces the cost of a traditional PMS light activation system, increases the benefits, improves the pollutant removal efficiency of a persulfate activation system, and achieves the goal of treating waste with waste, while avoiding the risk of secondary pollution caused by the introduction of exogenous catalysts.

Description

Technical Field

[0001] The invention relates to the technical field of organic sewage treatment and resource utilization, and in particular to a method for removing antibiotics based on a light-responsive activated peroxymonosulfate system of edible dyes. Background Art

[0002] With the rapid development of the economy and the continuous adjustment of the industrial structure, the livestock and poultry farming industry is increasingly developing in the direction of intensive and large-scale production. In order to prevent and treat bacterial diseases and promote the growth of livestock and poultry, antibiotics are widely used in agricultural production activities such as livestock and poultry farming and aquaculture, resulting in a large amount of antibiotic pollutants being discharged into water bodies. Due to the large number of these antibiotic pollutants, slow biodegradation rate, and persistence, they are constantly enriched in actual water bodies, posing a serious threat to the water environment and human health. It can be seen that it is urgent to explore an effective antibiotic removal technology for sewage before discharge.

[0003] At present, many processes have been applied to the remediation of antibiotics in water bodies, such as adsorption, traditional photocatalysis and other technologies, which have removed antibiotics in water bodies to a certain extent, but there is a risk of not being able to completely mineralize pollutants or easily inducing the production of byproducts that cause secondary pollution. Traditional technologies such as electrochemical anodization cannot be widely used due to excessive energy consumption. Therefore, we urgently need a suitable, thorough, economical and efficient antibiotic remediation process to reduce the level of antibiotic pollution in actual water bodies, or even achieve complete removal. With the development of environmental technology, advanced oxidation technology (AOPs) has entered people's field of vision. It has many advantages such as relatively low price, high oxidation degree, and good mineralization ability. Among them, the AOPs process based on persulfate (represented by peroxymonosulfate PMS) is the most valuable for research. It has great potential in the treatment of persistent organic pollutants. The strong active free radicals induced by it are expected to oxidize the refractory macromolecular organic matter into small molecular substances, or even completely mineralize them into CO2 and H2O.

[0004] In recent years, researchers have developed a variety of catalysts from various angles to activate PMS to achieve efficient removal of organic pollution in water bodies, such as biochar-based, carbon nitride-based, iron-based and other materials. Although these advanced oxidation processes based on new functional materials have achieved substantial removal and mineralization rates, it is unpredictable that most catalyst-based AOPs, while solving pollution, are also introducing new pollution such as added catalysts. There is widespread leaching and leakage of metals or toxic organic matter, which has been confirmed by the toxicity assessment experiments of the materials and systems of catalyst-based AOPs systems. In order to implement and achieve ecological harmony and ecological safety, efficient catalyst-free AOPs are undoubtedly what everyone expects. Studies have shown that certain special structures (such as phenol ions, quinone structures, and semiquinone free radicals) can activate persulfate through a single-electron reduction mechanism, and a special group of dyes (xanthene dyes, mainly food dyes) have similar chemical structures, represented by erythrosine B, Bengal red, fluorescent pink, and fluorescent pink B, which have high triplet quantum yields and high singlet oxygen yields, showing significant photosensitivity. They have been widely used in the production of weakly acidic foods such as fermented foods, baked foods, ice cream, and pickled foods. Under photosensitization, persulfate can be efficiently activated through a similar electron transfer mechanism, which provides the possibility for the development of effective catalyst-free AOPs. At present, in addition to the discharge of antibiotic wastewater, the discharge of food dye wastewater is also a major source of wastewater. Due to the complexity of the dye structure, it is not always possible to purify it through conventional treatment methods commonly used to remove other pollutants. Moreover, when these dyes are enriched to high concentrations in water bodies, they may also cause allergic reactions in the eyes of people who come into contact with them, irritation to the skin and upper respiratory tract, severe headaches, nausea, dermatitis and other water-borne diseases, and cause serious toxic effects on aquatic organisms. It can be seen that removing food dye pollution from wastewater is also an urgent need to achieve ecological harmony and sustainable development. Imagine if food dyes are used to activate PMS under visible light (sunlight) to repair antibiotic pollution, in addition to reducing the additional cost of adding exogenous catalysts to AOPs, it can also improve the activation efficiency of PMS and the abundance of induced active free radicals, and is expected to reduce the dual burden of dye wastewater and antibiotic wastewater at the same time, achieve waste treatment with waste, and promote the sustainable development process in the national strategy.

[0005] Based on this, we tried to introduce photosensitive edible dyes into the photoactivated persulfate process to significantly enhance the photosensitivity of the system, produce more reactive species, improve the pollutant removal efficiency of the persulfate activation system, reduce the risk of secondary pollution caused by exogenous catalysts, reduce the cost of traditional PMS photoactivation systems, increase profits, and achieve the efficient and synergistic removal of antibiotics and dye pollution in organic wastewater, achieving the goal of treating waste with waste. Summary of the invention

[0006] In response to the above-mentioned technical problems that need to be solved, the present invention provides a novel and efficient method for removing typical antibiotics from water bodies by using a persulfate system activated by light response to edible dyes. Under the premise of avoiding the risk of secondary pollution caused by the introduction of exogenous catalysts, the cost of the traditional PMS light activation system is reduced, the benefits are increased, the pollutant removal efficiency of the persulfate activation system is improved, and the goal of treating waste with waste is achieved.

[0007] In order to achieve the above object, the present invention provides a method for removing antibiotics based on a peroxymonosulfate system activated by a light response of an edible dye, the method comprising the following steps:

[0008] S1, mixing food dye and antibiotic to obtain a mixed solution;

[0009] S2, adding peroxymonosulfate to the mixed solution to obtain a reaction system;

[0010] S3. Activating the reaction system in a light-responsive manner under simulated sunlight to achieve synergistic removal of edible dyes and antibiotics.

[0011] In the above method, further, the edible dye is one or more of erythrosine B, red Bengal, fluorescent pink, and fluorescent pink B. Red Bengal, fluorescent pink, and fluorescent pink B are of the same type as erythrosine, and have similar performances, and based on the same principle, can produce identical or similar technical effects.

[0012] In the above method, further, the antibiotic is one or more of tetracycline, oxytetracycline, sulfamethoxazole, sulfadimethoxine, and sulfadimethoxine. Oxytetracycline, sulfamethoxazole, sulfadimethoxine, and sulfadimethoxine can produce the same or similar technical effects as tetracycline, and tetracycline can be used as a representative to reflect the approximate effect, because the optimal system achieves effective synergistic removal of antibiotic pollution and dye pollution within 10 minutes.

[0013] In the above method, further, the peroxymonosulfate is a potassium hydrogen peroxymonosulfate composite salt, the components of the potassium hydrogen peroxymonosulfate composite salt include KHSO5, KHSO4, and K2SO4, and the molar ratio of KHSO5, KHSO4 and K2SO4 is 1:0.5:0.5.

[0014] In the above method, further, the concentration of the edible dye in the mixed solution in S1 is 0.01-0.04 mM.

[0015] In the above method, further, the concentration of the antibiotic in the mixed solution in S1 is 0.10 to 20.00 mg / L.

[0016] The above method, further, in the reaction system described in S2, the HSO5 of peroxymonosulfate - The concentration is 0.20~0.80mM.

[0017] In the above method, further, the pH of the reaction system in S2 is 3.50-10.00.

[0018] The above method, further, in the light response activation process in S3, the reaction time under simulated sunlight irradiation is 30 to 90 minutes, the temperature of the reaction process is 15 to 35°C, and the average intensity of simulated sunlight irradiation is 300 to 3000 mW / cm 2 .

[0019] In the above method, further, in S3, during the light response activation process of the reaction system, magnetic stirring is performed at a stirring speed of 300 to 600 r / min.

[0020] In the above method, further, in S3, light response activation under simulated sunlight is performed by a simulated sunlight device, wherein the simulated sunlight device uses a xenon lamp, a metal halide lamp, a mercury lamp or an LED lamp as a light source, and filters out light with a wavelength below 420nm through a filter.

[0021] Compared with the prior art, the advantages of the present invention are:

[0022] 1. The present invention provides a method for removing antibiotics based on a permonosulfate system activated by light response of edible dyes. By adding permonosulfate (PMS) to a mixed waste liquid of typical antibiotic wastewater and edible dye wastewater, the photosensitivity of the composite system is enhanced. Under the action of visible light, the electron transfer mechanism between the excited dye molecules and PMS is used to achieve efficient activation of PMS, generate a variety of reactive species (superoxide radicals, singlet oxygen, sulfate radicals, hydroxyl radicals and excited dye cations), improve the pollutant removal efficiency of the permonosulfate activation system, and thus achieve the effect of synergistically removing composite pollutants. At the same time, the risk of secondary pollution caused by the introduction of exogenous catalysts is reduced, the cost of the traditional PMS photoactivation system is reduced, and the goal of treating waste with waste is achieved with high efficiency and low cost.

[0023] 2. The present invention provides a method for removing antibiotics based on the light-responsive activation of peroxymonosulfate system based on edible dyes, which utilizes the photosensitivity of edible dyes to induce efficient activation of PMS in water under visible light, generating a variety of reactive species (excited pigment cations, 1 O2 and O2 -Mainly) to decompose antibiotic organic pollutants in water, among which edible dyes mainly come from food processing wastewater or printing and dyeing wastewater, etc., which can make full use of dye pollution in wastewater, greatly improve the high cost and high energy consumption problems of traditional advanced oxidation technology based on visible light, and the removal effect is remarkable. Within 30 minutes, the antibiotic degradation rate of more than 90% and the dye removal rate of more than 98% can be achieved. After 60 minutes, the total mineralization rate of the system can reach more than 60%. The sewage is basically purified after treatment, without pollution to the environment, meeting the ecological safety needs.

[0024] 3. The present invention provides a method for removing antibiotics based on the light-responsive activation of peroxymonosulfate system of edible dyes, which utilizes visible light to activate PMS to produce reactive species to achieve the effect of synergistically removing dye and antibiotic pollution. The raw material cost is low, the required reagents are small, the energy consumption is low, and the cost is low. The equipment required for the entire reaction is simple, the operability is strong, the management and maintenance are convenient, and it is easy to apply industrially. Two types of typical organic wastewater are directly premixed and stirred evenly, and the photochemical reaction process can be carried out after adjusting the pH. It can be applied on a large scale.

[0025] 4. The present invention provides a method for removing antibiotics by activating a peroxymonosulfate system based on a light-responsive edible dye, using visible light accounting for 45% of the solar spectrum to activate PMS, using a homogeneous photochemical reaction system, and not adding any exogenous adsorbent or photocatalyst in the process of degrading dyes and antibiotics, and not introducing metals, toxic organic matter, etc., with a low risk of secondary pollution. The synergistic removal of composite organic pollution can be achieved only under light conditions, and subsequent solid-liquid separation and photocatalyst recycling problems can be effectively avoided, further reducing the cost of treating organic polluted wastewater. In addition, the reaction system of the present invention is applicable to a wide range of pH (3.50-10.00), is less affected by water quality conditions, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to make the purpose, technical solution and advantages of the embodiments of the present invention more clear, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention.

[0027] Figure 1 The results of the decolorization effect on dyes and the degradation effect on antibiotics in Example 1 of the present invention are shown in FIG. In the figure, a is the decolorization effect on erythrosine B (EB) after PMS is added alone, under light or no light conditions; b is the degradation effect on tetracycline (TC) after PMS is added alone, under light or no light conditions; c and d are the decolorization effect on EB and the degradation effect on TC after PMS is added to the mixed solution of EB and TC, under light or no light conditions, respectively.

[0028] Figure 2This is the total consumption result of PMS in the corresponding system under light or no light conditions in Example 2 of the present invention.

[0029] Figure 3 This is the degradation effect of the EB+TC+PMS reaction system under light conditions after the corresponding active species are inactivated by the quencher in Example 3 of the present invention. In the figure, a is the decolorization effect on EB, and b is the degradation effect on TC.

[0030] Figure 4 It is the treatment effect of the reaction system on the sewage with complex pollution of erythrosin B and tetracycline under different pH conditions in Example 4 of the present invention. In the figure, a and c are the decolorization effects of the reaction system on erythrosin B under different pH conditions (3.00-11.00), and b and d are the removal effects of the reaction system on tetracycline under different pH conditions (3.00-11.00). DETAILED DESCRIPTION

[0031] The present invention is further described below in conjunction with specific preferred embodiments, but the protection scope of the present invention is not limited thereby.

[0032] Unless otherwise defined, all professional terms used hereinafter have the same meaning as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0033] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods. The methods in the following embodiments are conventional methods in the art unless otherwise specified.

[0034] Example

[0035] The materials and instruments used in the following examples are all commercially available.

[0036] Embodiment 1:

[0037] A method for removing typical antibiotics from water bodies by using a peroxymonosulfate system activated by light response of edible dyes, and an application method thereof comprises the following steps:

[0038] (1) Preparation of reaction system: Erythrosin B (EB) and tetracycline (TC) were added to a reaction vessel beaker to prepare a 200 mL mixed solution, wherein the concentration of EB was 0.02 mM and the concentration of TC was 10 mg / L.

[0039] Then, potassium permonosulfate composite salt powder with gradient concentrations is added to the mixed solution to form a reaction system. The effective component of permonosulfate (HSO5 -) were 0, 0.05, 0.10, 0.20, 0.30, 0.40, 0.50 and 1.00 mM, respectively.

[0040] Blank control 1: prepare 0.02mM EB, 0.02mM EB+VL (VL means visible light, which is a system that needs to add simulated visible light irradiation later), 0.02mM EB+0.05mM PMS, 0.02mM EB+0.05mM PMS+VL, 0.02mM EB+0.1mM PMS, 0.02mM EB+0.1mM PMS+VL, 0.02mM EB+0.2mM PMS, 0.02mM EB+0.2mM PMS+VL, 0.02mM EB+0.5mM PMS, 0.02mM EB+0.5mM PMS+VL, 0.02mM EB+1mM PMS, and 0.02mM EB+1mM PMS+VL systems respectively.

[0041] Blank control 2: prepare the systems of 10mg / L TC, 10mg / L TC+VL, 10mg / L TC+0.05mM PMS, 10mg / L TC+0.05mM PMS+VL, 10mg / L TC+0.1mM PMS, 10mg / L TC+0.1mM PMS+VL, 10mg / L TC+0.2mPMS, 10mg / L TC+0.2mM PMS+VL, 10mg / L TC+0.5mM PMS, 10mg / L TC+0.5mM PMS+VL, 10mg / L TC+1mM PMS, and 10mg / L TC+1mM PMS+VL respectively.

[0042] (2) Photoresponse activation: After preheating the device simulating sunlight for 5 min, the beakers containing the reaction system in (1) were placed under the xenon lamp of the device simulating sunlight. Light with a wavelength below 420 nm was filtered out through a filter to simulate sunlight. The average intensity of the simulated sunlight irradiation (VL) was controlled to be 2000 mW / cm 2 The uniform stirring condition of 450r / min was achieved by a magnetic stirrer, and the reaction was maintained for 60 minutes at room temperature (25°C) to achieve effective synergistic removal of edible dyes and antibiotics in water.

[0043] During the reaction, samples were taken at intervals, and the EB concentration and TC concentration at the corresponding time were measured by UV-Vis spectrometer and high performance liquid chromatography, respectively, to draw the EB consumption curve and TC degradation curve.

[0044] Figure 1This is the result of the decolorization effect on the dye and the degradation effect on the antibiotic in Example 1 of the present invention.

[0045] In the figure, a is the decolorization effect of erythrosine B (EB) in the blank control 1 after the addition of PMS alone, under light or no light conditions; b is the degradation effect of tetracycline (TC) in the blank control 2 after the addition of PMS alone, under light or no light conditions;

[0046] Figures c and d show the decolorization effect of EB and the degradation effect of TC in the presence or absence of light after PMS is added to the mixture of EB and TC. It can be seen from the figure that although the direct degradation rate of EB can reach 95.9% within 30 minutes under light, the introduction of PMS significantly accelerates its photoactivated decolorization process, while the addition of PMS alone has no significant promoting effect on the removal of EB. The direct photobleaching of EB benefits from the conjugated carbon-carbon bond network, which provides absorption of light with longer wavelengths. The use of VL, PMS, EB, PMS+VL or EB+VL alone cannot significantly cause the degradation of TC, but when PMS (even a small amount, such as 0.05mM) is added to this EB-based photosensitizer system, it will cause a significant increase in the TC removal efficiency, showing a significantly enhanced PMS activation efficiency.

[0047] At the same time, as the PMS concentration increases from 0.05mM to 0.40mM, the degree of TC removal increases continuously, but when the concentration exceeds 0.40mM, the removal of TC begins to be inhibited. In general, the generation of reactive oxygen species (ROS) is directly related to the concentration of PMS. Therefore, the decrease in the activity of PMS at higher concentrations may be related to the self-cleaning effect of reactive oxygen species produced by excessive PMS. It can be judged that 0.40mM is the optimal oxidant dosage under this embodiment. In addition, the consumption pattern of EB is similar to the removal trend of TC, indicating that TC and EB are effectively synergistically degraded in this system, and the TC removal rate is generally maintained at more than 80%, and the EB removal rate is generally above 95%, which confirms the significant decontamination effect of the invented system and achieves the goal of treating waste with waste.

[0048] Embodiment 2:

[0049] A method for removing typical antibiotics from water based on the light-responsive activation of peroxymonosulfate system by edible dyes was developed. The residual amount of PMS in the reaction system and the activation efficiency of PMS after the introduction of EB were investigated:

[0050] (1) Preparation of reaction system: Prepare the following systems respectively:

[0051] System 1: 0.02mM EB+0.5mM PMS.

[0052] System 2: 0.02mM EB+0.5mM PMS+VL.

[0053] System three: 10mg / L TC+0.5mM PMS.

[0054] System 4: 10mg / L TC+0.5mM PMS+VL.

[0055] System five: 0.02mM EB+10mg / L TC+0.3mM PMS.

[0056] System six, 0.02mM EB+10mg / L TC+0.3mM PMS+VL.

[0057] System seven, 0.02mM EB+10mg / L TC+0.4mM PMS.

[0058] System eight, 0.02mM EB+10mg / L TC+0.4mM PMS+VL.

[0059] System nine: 0.02mM EB+10mg / L TC+0.5mM PMS.

[0060] System 10: 0.02mM EB+10mg / L TC+0.5mM PMS+VL.

[0061] (2) After that, the simulated sunlight device was turned on and preheated for 5 minutes. The beakers containing system 1, 3, 5, 7, and 9 were placed in the dark, and the beakers containing system 2, 4, 6, 8, and 10 were placed under the xenon lamp of the simulated sunlight device. Light with a wavelength below 420 nm was filtered out by a filter to simulate sunlight. The average intensity of the simulated sunlight irradiation (VL) was controlled to be 2000 mW / cm 2 The uniform stirring condition of 450r / min was achieved by a magnetic stirrer, and the reaction was maintained for 60min at room temperature (25°C) to achieve effective synergistic removal of edible dyes and antibiotics in water. Samples were taken at intervals during the reaction, and the PMS residual concentration at the corresponding time was measured using an improved low-concentration iodine titration method and a UV-visible spectrometer to draw a PMS residual curve.

[0062] Results Figure 2 As can be seen from the figure: under light conditions, the consumption of PMS in the EB photoactivation system (0.02mM EB+0.5mMPMS+VL) (TC PMSThe total consumption of PMS is 3.75 times that of the lightless system (0.02mM EB+0.5mM PMS), showing a significant PMS photoactivation efficiency. After the reaction, very little PMS remains in the solution, the system has a high utilization rate of PMS, and the effluent no longer needs to add additional reducing agents to remove the remaining PMS, which has little impact on the ecological environment and lower process costs.

[0063] Embodiment 3:

[0064] A method for removing typical antibiotics from water bodies based on the light-responsive activation of peroxymonosulfate system by edible dyes. The reactive species that play a role in the reaction system are investigated through free radical quenching experiments:

[0065] (1) Erythrosin B (EB) and tetracycline (TC) were added to a reaction vessel beaker to prepare a 200 mL mixed solution with an EB concentration of 0.02 mM and a TC concentration of 10 mg / L. Potassium peroxymonosulfate complex salt powder was then added to increase the peroxymonosulfate active ingredient (HSO5 - ) concentration is 0.40 mM.

[0066] 200 mM methanol (MeOH), 200 mM tert-butyl alcohol (IPA), 2 mM TEMPOL, 2 mM L-tryptophan (L-try) and 2 mM sodium oxalate (Na2C2O4) were added to the reaction system as active species quenchers, and a standard reaction system without adding quenchers was prepared as a blank control group. The pH value of all systems was adjusted to 4.00 using 0.1 M HCl and 0.1 M NaOH.

[0067] (2) After that, the simulated sunlight device was turned on and preheated for 5 min. The beaker containing the mixed solution was placed under a xenon lamp in the simulated sunlight device. Light with a wavelength below 420 nm was filtered out through a filter to simulate sunlight. The average intensity of the simulated sunlight irradiation (VL) was controlled to be 2000 mW / cm 2 The uniform stirring condition of 450r / min was achieved by a magnetic stirrer, and the reaction was maintained for 60min at room temperature (25°C) to achieve effective synergistic removal of edible dyes and antibiotics in water. Samples were taken at intervals during the reaction, and the erythrosin B concentration and tetracycline concentration at the corresponding time were measured by UV-visible spectrometer and high performance liquid chromatography, respectively, to draw the erythrosin B consumption curve and the antibiotic TC degradation curve.

[0068] Results Figure 3In the figure, a is the decolorization effect of the EB+TC+PMS reaction system on EB, and b is the degradation effect of the EB+TC+PMS reaction system on TC. It can be seen from the figure that isopropanol, methanol, sodium oxalate, L-tryptophan and TEMPOL are SO4· - 、Complex free radicals (SO4· - and ·OH), excited dye cations (EB* + ), 1 O2 and O2 - The quencher, after ·O2 - or 1 After O2 quenching, the removal efficiency of TC in the system dropped significantly from 96.8% to 44.0% or 62.2%. When isopropanol, methanol and Na2C2O4 were present in the system, the degradation rates dropped to 86.3%, 79.8% and 74.7%, respectively. Similarly, the consumption efficiency of EB in the quenching system (except EB* + In the system with Na2C2O4 added, the substance directly affected by the quencher is EB*. + , EB showed very obvious decolorization.

[0069] It can be seen that in the reaction system of the invention, the main active species involved in the photocatalytic degradation process of TC is O2 - and 1 O2, followed by EB* + , and SO4· - / ·OH may be mainly involved in the mutual transformation reactions between various active species and play a role in partial oxidation or attack of pollutants. The fading of EB is also directly related to the above-mentioned reactive species. These active species are the key to achieving efficient synergistic degradation of antibiotics and dyes, and are triggered by the electron transfer process toward PMS induced by the excitation of EB under visible light.

[0070] Embodiment 4:

[0071] A method for removing typical antibiotics from water bodies based on the light-responsive activation of peroxymonosulfate system using edible dyes. The effects of different pH conditions on the treatment effect in the reaction system were investigated:

[0072] (1) Erythrosin B (EB) and tetracycline (TC) were added to a reaction vessel beaker to prepare a 200 mL mixed solution, wherein the concentration of EB in the mixed solution was 0.02 mM and the concentration of TC was 10 mg / L, and then potassium permonosulfate composite salt powder was added to the mixed solution to obtain a reaction system, wherein the permonosulfate active ingredient (HSO5 -) was 0.40 mM, and then 0.1 M HCl and 0.1 M NaOH were used to adjust the pH of the reaction system to 3.00, 3.50, 4.00, 5.01, 6.00, 7.02, 8.02, 9.00, 10.03 and 11.00, respectively, and a standard reaction system without adjusting the pH was prepared as a blank control group.

[0073] (2) After that, the simulated sunlight device was turned on and preheated for 5 min. The beaker containing the mixed solution was placed under a xenon lamp in the simulated sunlight device. Light with a wavelength below 420 nm was filtered out through a filter to simulate sunlight. The average intensity of the simulated sunlight irradiation (VL) was controlled to be 2000 mW / cm 2 The uniform stirring condition of 450r / min was achieved by a magnetic stirrer, and the reaction was maintained for 30min at room temperature (25°C) to achieve effective synergistic removal of edible dyes and antibiotics in water. Samples were taken at intervals during the reaction, and the erythrosin B concentration and tetracycline concentration at the corresponding time were measured by UV-visible spectrometer and high performance liquid chromatography, respectively, to draw the erythrosin B consumption curve and the antibiotic TC degradation curve.

[0074] Results Figure 4 , a and c in the figure are the decolorization effects of the reaction system on erythrosine B under different pH conditions (3.00-11.00), and b and d are the removal effects of the reaction system on tetracycline under different pH conditions (3.00-11.00). It can be seen from the figure that the effect of pH on the reaction system is manifested as a significant dual effect on key substances. The enhancement of protonation is not conducive to the photosensitization process of EB, while the increase in deprotonation inhibits the activation of PMS and weakens its intramolecular stability. Acidic conditions have a negative effect on EB and a positive effect on PMS, while alkaline conditions are just the opposite. When the positive and negative effects are coordinated with each other, the optimal pH for the reaction system to work will eventually be displayed. Therefore, under strong base / strong acid conditions, the overall activity of the reaction system will be significantly inhibited, while weak acid / weak base and neutral conditions are conducive to the system to achieve efficient synergistic removal of dye and antibiotic pollution. The optimal pH range after the coordination of positive and negative effects is 5-6, which is in a relatively mild operating condition. In addition, the results also show that the reaction system designed by the present invention can achieve high benefits in a wide pH range (3.50-10.00), showing significant performance advantages overall, and does not require the introduction of exogenous catalysts, is less affected by water quality conditions, and has broad application prospects.

[0075] The above is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as above in the preferred embodiment, it is not used to limit the present invention. Any technician familiar with the art can make many possible changes and modifications to the technical solution of the present invention by using the methods and technical contents disclosed above without departing from the spirit and technical solution of the present invention, or modify it into an equivalent embodiment of equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention, still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for removing antibiotics based on a light-responsive activated peroxymonosulfate system of food dyes, characterized in that: The method comprises the following steps: S1, mixing food dye and antibiotic to obtain a mixed solution; S2, adding peroxymonosulfate to the mixed solution to obtain a reaction system; S3, the reaction system is activated by light response under simulated sunlight to achieve the coordinated removal of edible dyes and antibiotics; the edible dyes are one or more of erythrosine B, Bengal red, fluorescent pink, and fluorescent pink B; The peroxymonosulfate is a potassium peroxymonosulfate composite salt, and the components of the potassium peroxymonosulfate composite salt include KHSO5, KHSO4, and K2SO4. The molar ratio of KHSO5, KHSO4, and K2SO4 is 1:0.5:0.

5.

2. The method according to claim 1, characterized in that The antibiotic is one or more of tetracycline, oxytetracycline, sulfamethoxazole, sulfamethoxazole, and sulfadimethoxine.

3. The method according to claim 1 or 2, characterized in that: The concentration of the edible dye in the mixed solution in S1 is 0.01-0.04 mM; and / or the concentration of the antibiotic is 0.10-20.00 mg / L.

4. The method according to claim 1 or 2, characterized in that: In the reaction system described in S2, HSO5 of peroxymonosulfate - The concentration is 0.20~0.80mM.

5. The method according to claim 1 or 2, characterized in that: The optimum reaction pH of the reaction system in S2 is 3.50-10.

00.

6. The method according to claim 1 or 2, characterized in that: In the light response activation process in S3, the reaction time under simulated sunlight irradiation is 30 to 90 minutes, and the temperature of the reaction process is 15° C. to 35° C.

7. The method according to claim 1 or 2, characterized in that: In S3, during the light response activation process of the reaction system, magnetic stirring is performed at a speed of 300 to 600 r / min.

8. The method according to claim 1 or 2, characterized in that: In S3, light response activation under simulated sunlight is performed by a simulated sunlight device, wherein the simulated sunlight device uses a xenon lamp, a metal halide lamp, a mercury lamp or an LED lamp as a light source, and filters out light with a wavelength below 420nm through a filter.

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