Method for degrading organic pollutants by activating peroxymonosulfate through cooperation of homogeneous copper ions and monoethanolamine

Abstract

The invention provides a method for degrading organic pollutants by activating peroxymonosulfate through homogeneous copper ions in cooperation with monoethanolamine, and belongs to the technical field of organic pollutant wastewater treatment. The method provided by the invention comprises the following steps: uniformly mixing copper salt and monoethanolamine in water to obtain a mixed solution; and adding peroxymonosulfate and the mixed solution into the wastewater containing the organic pollutants for reaction. Homogeneous copper ions cooperate with monoethanolamine to efficiently activate peroxymonosulfate, circulation of Cu (I) / Cu (II) is accelerated, more sulfate free radicals, hydroxyl free radicals, singlet oxygen and Cu (III) are generated, the peroxymonosulfate can be activated by using trace copper ions to generate a large number of free radicals, and the copper ions can be used for purifying the Cu (I) / Cu (II). The problem that existing peroxymonosulfate activation is large in energy consumption is solved, the adding amount of copper ions is greatly reduced, and the influence on environmental pollution and unnecessary loss are reduced.

Description

Technical Field

[0001] The invention relates to the technical field of organic pollutant wastewater treatment, and in particular to a method for degrading organic pollutants by activating peroxymonosulfate with homogeneous copper ions in coordination with monoethanolamine. Background Art

[0002] Compared with traditional wastewater treatment methods, advanced oxidation technology has the advantages of a wide range of applications, fast reaction rate, high treatment efficiency, and relatively less secondary pollution. The advanced oxidation process based on peroxymonosulfate (PMS) as a free radical precursor has attracted widespread attention in the field of wastewater treatment and environmental remediation. Compared with heterogeneous systems, in homogeneous systems, the components are in the same physical state, which is easy for the components to contact each other, the reaction rate is fast, and it is conducive to achieving thermodynamic equilibrium. In addition, transition metal ions such as iron and copper are widely distributed in natural water bodies. Therefore, it is feasible and practical to use transition metals to induce homogeneous activation of PMS. Among transition metals, Co(II) and Fe(II) have been proven to be excellent activators of PMS. However, it cannot be ignored that Co(II) has strong biological toxicity and Fe(II)-based technology has a narrow pH application range. Cu(II) has higher solubility and lower toxicity, and is more active under neutral and alkaline conditions.

[0003] Although Cu(II) is a promising PMS activator, many obstacles have been encountered in the implementation of copper-catalyzed PMS processes. These include: (i) the Cu(II) / PMS system is easily interfered by coexisting inorganic anions; (ii) especially when the Cu(II) dosage is small, the slow redox cycle limits the activation of PMS. Therefore, it is of great practical significance to develop a method to accelerate the cycle of Cu(I) / Cu(II) and reduce the usage restrictions of Cu(II) / PMS. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a method for degrading organic pollutants by using homogeneous copper ions in conjunction with monoethanolamine to activate peroxymonosulfate. The method provided by the present invention overcomes the shortcomings of the prior art of large metal ion dosage and hysteresis in valence state cycle in the removal of organic pollutants by copper ion activation of peroxymonosulfate.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] A method for degrading organic pollutants by using homogeneous copper ions in coordination with monoethanolamine to activate peroxymonosulfate comprises the following steps:

[0007] Mixing copper salt and monoethanolamine in water to obtain a mixed solution;

[0008] Peroxymonosulfate and the mixed solution are added into wastewater containing organic pollutants to react.

[0009] In some embodiments of the present invention, the dosage of the copper salt is: 1-100 μmol of copper salt is added to every 1L of wastewater containing organic pollutants; the copper salt is copper sulfate, copper nitrate or copper chloride, preferably copper sulfate.

[0010] In some embodiments of the present invention, the dosage of the copper salt is: 15-100 μmol of copper salt is added to every 1L of wastewater containing organic pollutants.

[0011] In some embodiments of the present invention, the dosage of the copper salt is: 5-20 μmol of copper salt is added to every 1L of wastewater containing organic pollutants.

[0012] In some embodiments of the present invention, the dosage of the copper salt is: 15-60 μmol of copper salt is added to every 1L of wastewater containing organic pollutants.

[0013] In some embodiments of the present invention, the dosage of the copper salt is: 15-20 μmol of copper salt is added to every 1L of wastewater containing organic pollutants.

[0014] In some embodiments of the present invention, the dosage of monoethanolamine is: 100-2000 μmol of monoethanolamine is added to every 1L of wastewater containing organic pollutants.

[0015] In some embodiments of the present invention, the dosage of monoethanolamine is: 600-2000 μmol of monoethanolamine is added to every 1L of wastewater containing organic pollutants.

[0016] In some embodiments of the present invention, the dosage of monoethanolamine is: 1000-2000 μmol of monoethanolamine is added to every 1L of wastewater containing organic pollutants.

[0017] In some embodiments of the present invention, the dosage of the peroxymonosulfate is: 100-1000 μmol of peroxymonosulfate is added to every 1 L of wastewater containing organic pollutants; the peroxymonosulfate is potassium hydrogen peroxymonosulfate.

[0018] In some embodiments of the present invention, the dosage of the peroxymonosulfate is: 400-1000 μmol of peroxymonosulfate is added to every 1 L of wastewater containing organic pollutants.

[0019] In some embodiments of the present invention, the dosage of the peroxymonosulfate is: 600-1000 μmol of peroxymonosulfate is added to every 1 L of wastewater containing organic pollutants.

[0020] In some embodiments of the present invention, the dosage of the peroxymonosulfate is: 400-600 μmol of peroxymonosulfate is added to every 1 L of wastewater containing organic pollutants.

[0021] In some embodiments of the present invention, the pH value of the wastewater containing organic pollutants is 5-9.

[0022] In some embodiments of the present invention, the reaction temperature is room temperature and the reaction time is 20-30 minutes.

[0023] In some embodiments of the present invention, the organic pollutant in the wastewater containing organic pollutants is at least one of sulfamethoxazole, reactive blue 19 and bisphenol A.

[0024] The present invention discloses the following technical effects:

[0025] The invention uses homogeneous copper ions in coordination with monoethanolamine to efficiently activate peroxymonosulfate, accelerates the circulation of Cu(I) / Cu(II), and generates more sulfate radicals and hydroxyl radicals as well as singlet oxygen and Cu(III). The peroxymonosulfate can be activated to generate a large number of free radicals using trace copper ions, which not only solves the problem of large energy consumption in the existing peroxymonosulfate activation, but also greatly reduces the dosage of copper ions, thereby reducing the impact on environmental pollution and unnecessary losses.

[0026] The method provided by the invention has the advantages of small copper ion dosage, fast degradation efficiency, etc., and is less affected by impurities in the water body and is applicable to a wide pH range of the water body. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0028] Figure 1 The homogeneous copper ion cooperates with monoethanolamine to activate peroxymonosulfate in Example 1 of the present application. (a) is a diagram showing the removal efficiency of sulfamethoxazole in different coupling systems, and (b) is a comparison of the PMS consumption in different systems;

[0029] Figure 2 This is the removal efficiency of sulfamethoxazole under different copper dosage conditions by homogeneous copper ions cooperating with monoethanolamine to activate peroxymonosulfate in Example 2 of the present application;

[0030] Figure 3 The removal efficiency of sulfamethoxazole under different monoethanolamine dosage conditions by homogeneous copper ion-monoethanolamine-activated peroxymonosulfate in Example 3 of the present application;

[0031] Figure 4 The removal efficiency of sulfamethoxazole under different permonosulfate dosage conditions by homogeneous copper ion and monoethanolamine activated permonosulfate in Example 4 of the present application;

[0032] Figure 5 The removal efficiency of sulfamethoxazole under different initial pH conditions by homogeneous copper ion-monoethanolamine-activated peroxymonosulfate in Example 5 of the present application;

[0033] Figure 6 The removal efficiency of sulfamethoxazole under different temperature conditions by homogeneous copper ion and monoethanolamine activated peroxymonosulfate in Example 6 of the present application;

[0034] Figure 7 This is Example 7 of the present application, which shows the removal efficiency of sulfamethoxazole in different actual water bodies by homogeneous copper ions cooperating with monoethanolamine to activate peroxymonosulfate. DETAILED DESCRIPTION

[0035] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0036] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0037] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0038] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are exemplary only.

[0039] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0040] In the present invention, unless otherwise specified, room temperature refers to 15-35°C.

[0041] The present invention provides a method for activating peroxymonosulfate with homogeneous copper ions in coordination with monoethanolamine, which is used to solve the technical defects of high energy consumption and environmental pollution under large copper ion dosage in the existing copper activation method of peroxymonosulfate. The present invention firstly complexes copper salt with specific organic matter to significantly improve the activation performance of the central metal and accelerate the valence cycle of the metal. Monoethanolamine (MEA) is a multidentate ligand that can coordinate with metal ions through amino groups, hydroxyl groups and deprotonated hydroxyl groups. The hydroxyl groups and amino groups carried by it give it excellent chelating ability and can provide lone pairs of electrons, thereby forming a complex with the unoccupied orbits on Cu(Ⅱ), so the ligand effect of monoethanolamine and Cu(Ⅱ) is used to improve the circulation of Cu(Ⅰ) / Co(Ⅱ); then, peroxymonosulfate and the mixed solution are added to wastewater containing organic pollutants for reaction. During the reaction, copper ions activate peroxymonosulfate to generate free radicals to degrade organic pollutants.

[0042] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0043] The technical solutions described in the present invention, unless otherwise specified, are all conventional solutions in the art, and the reagents or raw materials used, unless otherwise specified, are purchased from commercial channels or have been disclosed.

[0044] Example 1

[0045] This example provides a comparative study on the application of homogeneous copper ions in cooperating with monoethanolamine to activate peroxymonosulfate to degrade sulfamethoxazole, comprising the following steps:

[0046] 1. Design four different systems to determine the removal effect of sulfamethoxazole. The four different systems are:

[0047] a. Adding monoethanolamine (MEA) and potassium permonosulfate (PMS) to the organic pollutant wastewater containing sulfamethoxazole to react;

[0048] b. Adding copper sulfate (Cu(II)) and potassium permonosulfate (PMS) to the organic pollutant wastewater containing sulfamethoxazole to react;

[0049] c. Adding copper sulfate (Cu(II)) and monoethanolamine (MEA) to the organic pollutant wastewater containing sulfamethoxazole to react;

[0050] d. Add copper sulfate (Cu(II)), monoethanolamine (MEA) and potassium permonosulfate (PMS) to the organic pollutant wastewater containing sulfamethoxazole to react.

[0051] Experimental conditions: sulfamethoxazole was added to ultrapure water to obtain 100 mL of organic wastewater to be treated with an initial sulfamethoxazole concentration of 5 μmol / L, the dosage of copper sulfate in b, c and d was 15 μmol / L, the dosage of potassium permonosulfate in a, b and d was 600 μmol / L, the dosage of monoethanolamine in a, c and d was 1000 μmol / L, the dosage of potassium permonosulfate in a, b and d was 600 μmol / L, and the initial p The H value was 7.2. The mixture was stirred at constant temperature for 15 min at room temperature. 3.6 mL of the solution was taken out at 0 min, 2.5 min, 5 min, 7.5 min, 10 min, 15 min, 20 min, and 25 min, and filtered through a 0.22 μm filter membrane. 0.4 mL of sodium thiosulfate was added as a free radical quencher to terminate the degradation reaction. The solution was stored in a 5 mL centrifuge tube. After adding the quencher and reacting for 20 min, the solution was filtered through a 0.22 μm filter membrane and stored in a 1.5 mL liquid phase vial.

[0052] Determination of degradation efficiency: The liquid vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, the detection wavelength was 270nm, and the mobile phase was methanol and 1% acetic acid water, the ratio was 40:60. The results are as follows Figure 1 shown.

[0053] pass Figure 1 In (a) (in the figure, MEA / PMS represents system a, Cu(II) / PMS represents system b, Cu(II) / MEA represents system c, and Cu(II) / MEA / PMS represents system d), it can be seen that the removal efficiencies of Cu(II) / PMS, Cu(II) / MEA, MEA / PMS and Cu(II) / MEA / PMS for sulfamethoxazole within 25 minutes are 16.8%, 2.6%, 6.7% and 95.7%, respectively. When monoethanolamine is not added, the removal rate of sulfamethoxazole by the Cu(II) / PMS system at 25 minutes is only 16.8%, because copper has the ability to activate PMS, but the activation ability is limited. When the PMS dosage is 0, the removal rate of the Cu(II) / MEA system at 25 minutes is only 2.6%, because PMS is the source of active substances in the system, and the loss of the source of active substances causes the system to lose its degradation ability. The removal rate of the MEA / PMS system at 25 minutes is 6.7%, indicating that monoethanolamine cannot effectively activate PMS. The removal rate of the Cu(II) / MEA / PMS system at 25 min was 95.7%, far exceeding the sum of the other systems, which shows that MEA has a significant promoting effect on the Cu(II) / PMS system, and there is a positive coupling effect between Cu(II), MEA and PMS. Figure 1In (b), it can be seen that there is a strong consistency between the consumption of PMS and the quality of the degradation effect. At 25 minutes, the Cu(II) / MEA / PMS system consumed 47.8% of PMS, while the MEA / PMS system consumed 14.6% of PMS, and the Cu(Ⅱ) / PMS system consumed only 9.6% of PMS. This shows that the source of the promotion effect of MEA is to promote the utilization rate of PMS in the system. The addition of MEA not only improves the oxidative degradation ability of the system, but also reduces the waste of oxidants.

[0054] Example 2

[0055] A comparative study of the application of different copper sulfate dosages in the degradation of sulfamethoxazole by homogeneous copper ion-cooperated monoethanolamine-activated persulfate, including the following steps:

[0056] Experimental conditions: Sulfamethoxazole was added to eight groups of ultrapure water to obtain 100 mL of organic wastewater to be treated with an initial concentration of 5 μmol / L of sulfamethoxazole. The corresponding amounts of copper sulfate added were 5 μmol / L, 10 μmol / L, 15 μmol / L, 20 μmol / L, 40 μmol / L, 60 μmol / L, 80 μmol / L, and 100 μmol / L, respectively. The amount of potassium permonosulfate added was 600 μmol / L, and the amount of monoethanolamine added was 1000 μmol / L. l / L, the initial pH value was 7.2, and it was stirred at constant temperature for 15 minutes at room temperature. At 0min, 2.5min, 5min, 7.5min, 10min, 15min, 20min, and 25min, 3.6mL of the solution was taken out and filtered through a 0.22μm filter membrane, and 0.4mL of sodium thiosulfate was added as a free radical quencher to terminate the degradation reaction. The solution was stored in a 5mL centrifuge tube, and the quencher was added for 20 minutes before filtering through a 0.22μm filter membrane and stored in a 1.5mL liquid phase vial.

[0057] Determination of degradation efficiency: The liquid vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, the detection wavelength was 270nm, and the mobile phase was methanol and 1% acetic acid water, the ratio was 40:60. The results are as follows Figure 2 shown.

[0058] The removal rates of sulfamethoxazole corresponding to the Cu(II) dosage of 5μmol / L, 10μmol / L, 15μmol / L, 20μmol / L, 40μmol / L, 60μmol / L, 80μmol / L, and 100μmol / L were 67.6%, 80.2%, 95.7%, 97.0%, 94.5%, 92.4%, 98.5%, and 97.9%, respectively. It can be observed that when the Cu(II) dosage increases from 5μmol / L to 20μmol / L, the sulfamethoxazole and reaction rate also increase significantly, especially when the Cu(II) dosage increases from 5μmol / L to 15μmol / L, the removal efficiency of sulfamethoxazole increases significantly. The reason may be that as the Cu(II) concentration increases, the catalytic reaction rate increases, the persulfate activation accelerates, and more active substances will be produced in the same reaction time. However, when the Cu(II) dosage increased from 20μmol / L to 100μmol / L, the removal rate of sulfamethoxazole hardly increased. The reason may be that the PMS activated by Cu(II) reached saturation. But it is more likely that the addition of monoethanolamine increased the catalytic activity of Cu(II), so that the degradation amount can be increased to near the maximum value at a lower Cu(II) dosage, indicating that the addition of monoethanolamine accelerated the reaction. More importantly, the pollutant was efficiently removed at a lower Cu(II) dosage. Considering the comprehensive system treatment effect and cost, the Cu(II) dosage was selected as 15μmol / L.

[0059] Example 3

[0060] A comparative study on the application of different potassium permonosulfate dosages in homogeneous copper ion-cooperated monoethanolamine activated permonosulfate to degrade sulfamethoxazole includes the following steps:

[0061] Experimental conditions: Sulfamethoxazole was added to six groups of ultrapure water to obtain 100 mL of organic wastewater to be treated with an initial sulfamethoxazole concentration of 5 μmol / L. The corresponding amounts of potassium permonosulfate added were 0 μmol / L, 200 μmol / L, 400 μmol / L, 600 μmol / L, 800 μmol / L, and 1000 μmol / L, respectively. The amount of copper sulfate added was 15 μmol / L, the amount of monoethanolamine added was 1000 μmol / L, and the initial p The H value was 7.2. The mixture was stirred at constant temperature for 15 min at room temperature. 3.6 mL of the solution was taken out at 0 min, 2.5 min, 5 min, 7.5 min, 10 min, 15 min, 20 min, and 25 min, and filtered through a 0.22 μm filter membrane. 0.4 mL of sodium thiosulfate was added as a free radical quencher to terminate the degradation reaction. The solution was stored in a 5 mL centrifuge tube. After adding the quencher and reacting for 20 min, the solution was filtered through a 0.22 μm filter membrane and stored in a 1.5 mL liquid phase vial.

[0062] Determination of degradation efficiency: The liquid vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, the detection wavelength was 270nm, and the mobile phase was methanol and 1% acetic acid water, the ratio was 40:60. The results are as follows Figure 3 shown.

[0063] When the dosage of potassium permonosulfate increases from 0μmol / L to 600μmol / L, the reaction rate also increases. This is because as the dosage of permonosulfate increases, the amount of activated persulfate also increases, and the oxidation capacity of the system is enhanced. However, when the dosage of PMS is further increased to 800μmol / L and 1000μmol / L, the degradation rate of sulfamethoxazole in the system also decreases, and the reaction rate also decreases. This may be because excessive PMS will react with sulfate ions, which will lead to a decrease in the oxidation capacity of free radicals. Based on this, considering the comprehensive treatment effect and cost, the dosage of persulfate in the system is 600μmol / L.

[0064] Example 4

[0065] A comparative study of the application of different monoethanolamine dosages in the degradation of sulfamethoxazole by homogeneous copper ion-cooperated monoethanolamine-activated persulfate, including the following steps:

[0066] Experimental conditions: Sulfamethoxazole was added to seven groups of ultrapure water to obtain 100 mL of organic wastewater to be treated with an initial concentration of 5 μmol / L of sulfamethoxazole. The corresponding amounts of monoethanolamine added were 0 μmol / L, 100 μmol / L, 300 μmol / L, 600 μmol / L, 1000 μmol / L, 1500 μmol / L, and 2000 μmol / L, respectively. The amount of copper sulfate added was 15 μmol / L, and the amount of potassium permonosulfate added was 600 μmol / L. / L, the initial pH value was 7.2, and it was stirred at constant temperature for 15 min at room temperature. At 0 min, 2.5 min, 5 min, 7.5 min, 10 min, 15 min, 20 min, and 25 min, 3.6 mL of the solution was taken out and filtered through a 0.22 μm filter membrane, and 0.4 mL of sodium thiosulfate was added as a free radical quencher to terminate the degradation reaction. The solution was stored in a 5 mL centrifuge tube, and after adding the quencher for 20 min, it was filtered through a 0.22 μm filter membrane and stored in a 1.5 mL liquid phase vial.

[0067] Determination of degradation efficiency: The liquid vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, the detection wavelength was 270nm, and the mobile phase was methanol and 1% acetic acid water, the ratio was 40:60. The results are as follows Figure 4 shown.

[0068] When the dosage of monoethanolamine increases from 0μmol / L to 1000μmol / L, the reaction rate also increases. This is because as the dosage of monoethanolamine increases, the chance of coordination with divalent copper ions is greater, and the oxidation capacity of the system is enhanced. When the dosage of monoethanolamine is further increased to 1000μmol / L, the system exhibits the greatest oxidation capacity. However, when the dosage of monoethanolamine increases to 1500μmol / L, the degradation capacity of the system decreases, and when it continues to increase to 2000μmol / L, the degradation capacity continues to decrease. This is because excessive monoethanolamine will change the coordination ratio with divalent copper and form a complex with relatively low catalytic activity. In addition, monoethanolamine has a certain viscosity, and excessive dosage will reduce the mass transfer efficiency of the system. Based on this, considering the comprehensive treatment effect and cost, the dosage of monoethanolamine in the system is 1000μmol / L.

[0069] Example 5

[0070] A comparative study of the application of different initial pH values ​​to the degradation of sulfamethoxazole by homogeneous copper ions in cooperation with monoethanolamine to activate persulfate includes the following steps:

[0071] Experimental conditions: Sulfamethoxazole was added to seven groups of ultrapure water to obtain 100 mL of untreated organic polluted wastewater with an initial sulfamethoxazole concentration of 5 μmol / L, the dosage of potassium permonosulfate was 600 μmol / L, the dosage of monoethanolamine was 1000 μmol / L, the dosage of copper sulfate was 15 μmol / L, the initial pH values ​​were 3, 5, 7, 7.2 (original group pH), 9, and 11, and the mixture was stirred at constant temperature for 15 min at room temperature. 3.6 mL of the solution was taken out and filtered through a 0.22 μm filter membrane at 0 min, 2.5 min, 5 min, 7.5 min, 10 min, 15 min, 20 min, and 25 min, and 0.4 mL of sodium thiosulfate was added as a free radical quencher to terminate the degradation reaction, and the solution was stored in a 5 mL centrifuge tube. After adding the quencher and reacting for 20 min, the solution was filtered through a 0.22 μm filter membrane and stored in a 1.5 mL liquid phase vial.

[0072] Determination of degradation efficiency: The liquid vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, the detection wavelength was 270nm, and the mobile phase was methanol and 1% acetic acid water, the ratio was 40:60. The results are as follows Figure 5 shown.

[0073] When the pH value changes in the range of 5 to 9, the oxidation effect of the system on sulfamethoxazole is similar, and the removal efficiency is high. The system has a higher removal efficiency of sulfamethoxazole under neutral, weakly alkaline and weakly acidic conditions, and strong acidic and strong alkaline conditions have an inhibitory effect on the removal efficiency of sulfamethoxazole in the system.

[0074] Example 6

[0075] The comparative study of the application of homogeneous copper ions in synergistic cooperation with monoethanolamine to activate peroxymonosulfate to degrade sulfamethoxazole at different temperatures includes the following steps:

[0076] Experimental conditions: Sulfamethoxazole was added to six groups of ultrapure water to obtain 100 mL of organic wastewater to be treated with an initial concentration of 5 μmol / L of sulfamethoxazole. The corresponding reaction temperatures were 15°C, 25°C, 35°C, 45°C, 55°C, and 65°C, respectively. The dosage of monoethanolamine was 1000 μmol / L, the dosage of copper sulfate was 15 μmol / L, the dosage of potassium permonosulfate was 600 μmol / L, the initial pH value was 7.2, and the reaction temperature was 15°C, 25°C, 35°C, 45°C, 55°C, and 65°C, respectively. Stir at constant temperature for 15 min under the conditions of , take out 3.6 mL of solution at 0 min, 2.5 min, 5 min, 7.5 min, 10 min, 15 min, 20 min, and 25 min, filter through 0.22 μm filter membrane, add 0.4 mL of sodium thiosulfate as a free radical quencher to terminate the degradation reaction, store in 5 mL centrifuge tube, add quencher and react for 20 min, then filter through 0.22 μm filter membrane and store in 1.5 mL liquid phase vial.

[0077] Determination of degradation efficiency: The liquid vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, the detection wavelength was 270nm, and the mobile phase was methanol and 1% acetic acid water, the ratio was 40:60. The results are as follows Figure 6 shown.

[0078] As the temperature rises, the degradation effect of the system on sulfamethoxazole gradually improves. Because thermal activation is a classic way to activate PMS, it can be considered that high temperature is conducive to the activation of PMS. However, at low temperatures, the molecular motion speed decreases, making it difficult to effectively activate PMS. However, for the Cu(Ⅱ) / PMS system with the addition of monoethanolamine, the effect of temperature on the system is relatively small. In other words, the addition of monoethanolamine reduces the energy barrier of the reaction, indicating that the activation energy required for the system is small, and only a small amount of external energy input is required to complete the reaction process, reflecting the superiority of the system.

[0079] Example 7

[0080] A comparative study of the application of different actual water bodies to the degradation of sulfamethoxazole by homogeneous copper ions in coordination with monoethanolamine to activate peroxymonosulfate includes the following steps:

[0081] Experimental conditions: Sulfamethoxazole was added to five different actual water bodies to obtain 100 mL of organic polluted wastewater to be treated with an initial sulfamethoxazole concentration of 5 μmol / L. The corresponding actual water bodies were ultrapure water, seawater, lake water, actual urban sewage, and landfill leachate. The dosage of monoethanolamine was 1000 μmol / L, the dosage of copper sulfate was 15 μmol / L, the dosage of potassium permonosulfate was 600 μmol / L, the initial pH value was 7.2, and the mixture was stirred at constant temperature for 15 min at room temperature. 3.6 mL of the solution was taken out at 0 min, 2.5 min, 5 min, 7.5 min, 10 min, 15 min, 20 min, and 25 min, and filtered through a 0.22 μm filter membrane, and 0.4 mL of sodium thiosulfate was added as a free radical quencher to terminate the degradation reaction. The solution was stored in a 5 mL centrifuge tube, and the quencher was added for 20 min before filtering through a 0.22 μm filter membrane and stored in a 1.5 mL liquid phase vial.

[0082] Determination of degradation efficiency: The liquid vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, the detection wavelength was 270nm, and the mobile phase was methanol and 1% acetic acid water, the ratio was 40:60. The results are as follows Figure 7 shown.

[0083] In lake water, the degradation efficiency of sulfamethoxazole by the system is no different from that in pure water. When the system was placed in high-salinity seawater for reaction, it maintained good performance. This shows that the system has strong resistance to salinity and inorganic anions. In landfill leachate, the degradation ability of the system decreased, which was due to the excessive turbidity and dissolved organic carbon (TOC) in the landfill leachate, which affected the operation of the system. Finally, the system was placed in a real sewage environment for reaction, and the degradation efficiency was still maintained at about 90%. This proves the versatility of the system and its adaptability to complex environments, and its practical operation value.

[0084] In summary, the trace copper synergistically activated peroxymonosulfate with monoethanolamine of the present invention has high activation performance, low environmental pollution, low cost and the like, and therefore has good application prospects in the treatment of sulfamethoxazole wastewater.

[0085] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for degrading organic pollutants by using homogeneous copper ions in coordination with monoethanolamine to activate peroxymonosulfate, characterized in that: The following steps are involved: Mixing copper salt and monoethanolamine in water to obtain a mixed solution; Peroxymonosulfate and the mixed solution are added into wastewater containing organic pollutants to react.

2. The method for degrading organic pollutants by using homogeneous copper ions in cooperation with monoethanolamine to activate peroxymonosulfate according to claim 1, characterized in that: The dosage of the copper salt is: 1-100 μmol of copper salt is added to every 1L of wastewater containing organic pollutants; the copper salt is copper sulfate, copper nitrate or copper chloride.

3. The method for degrading organic pollutants by using homogeneous copper ions in cooperation with monoethanolamine to activate peroxymonosulfate according to claim 1, characterized in that: The dosage of the monoethanolamine is: 100-2000 μmol of monoethanolamine is added to every 1L of wastewater containing organic pollutants.

4. The method for degrading organic pollutants by homogeneous copper ions in cooperation with monoethanolamine to activate peroxymonosulfate according to claim 1, characterized in that: The dosage of the peroxymonosulfate is: 100-1000 μmol of peroxymonosulfate is added to every 1L of wastewater containing organic pollutants; the peroxymonosulfate is potassium hydrogen peroxymonosulfate.

5. The method for degrading organic pollutants by homogeneous copper ions in cooperation with monoethanolamine to activate peroxymonosulfate according to claim 1, characterized in that: The pH value of the wastewater containing organic pollutants is 5-9.

6. The method for degrading organic pollutants by homogeneous copper ions in cooperation with monoethanolamine to activate peroxymonosulfate according to claim 1, characterized in that: The reaction temperature is room temperature and the reaction time is 20-30 minutes.

7. The method for degrading organic pollutants by homogeneous copper ions in cooperation with monoethanolamine to activate peroxymonosulfate according to claim 1, characterized in that: The organic pollutant in the wastewater containing organic pollutants is at least one of sulfamethoxazole, reactive blue 19 and bisphenol A.

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