A method for degrading organic pollutants by activating peroxymonosulfate with homogeneous copper ions and monoethanolamine

Abstract

The present invention provides a method for degrading organic pollutants by activating permonosulfate with the help of homogeneous copper ions and monoethanolamine, and belongs to the technical field of wastewater treatment with organic pollutants. The method provided by the present invention comprises the following steps: uniformly mixing copper salt and monoethanolamine in water to obtain a mixed solution; adding permonosulfate and the mixed solution to wastewater containing organic pollutants to react. The present invention uses homogeneous copper ions and monoethanolamine to efficiently activate permonosulfate, accelerate the circulation of Cu(I) / Cu(II), and generate more sulfate radicals and hydroxyl radicals as well as singlet oxygen and Cu(III). Trace amounts of copper ions can be used to activate permonosulfate to generate a large number of free radicals, which not only solves the problem of high energy consumption in the existing permonosulfate activation, but also greatly reduces the dosage of copper ions, reducing the impact on environmental pollution and unnecessary losses.

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 to traditional wastewater treatment methods, advanced oxidation technologies offer advantages such as a broad range of applications, rapid reaction rates, high treatment efficiency, and relatively low secondary pollution. Advanced oxidation processes based on peroxymonosulfate (PMS) as a free radical precursor have attracted widespread attention in wastewater treatment and environmental remediation. Compared to heterogeneous systems, homogeneous systems maintain the same physical state, facilitating contact between components, resulting in rapid reaction rates and favorable thermodynamic equilibrium. Furthermore, transition metal ions such as iron and copper are widely distributed in natural waters, making the use of transition metals to induce homogeneous activation of PMS feasible and practical. Among transition metals, Co(II) and Fe(II) have been shown to be excellent activators of PMS. However, the strong biotoxicity of Co(II) and the narrow pH range of Fe(II)-based technologies should not be overlooked. 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, the implementation of copper-catalyzed PMS processes has encountered numerous obstacles. These include: (i) the Cu(II) / PMS system is easily interfered with by coexisting inorganic anions; and (ii) the slow redox cycle, particularly at low Cu(II) dosages, limits PMS activation. Therefore, developing methods to accelerate the Cu(I) / Cu(II) cycle and mitigate the limitations of Cu(II) / PMS is highly desirable. 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 copper ion activation of peroxymonosulfate to remove organic pollutants, such as the large amount of metal ions added and the hysteresis of valence state cycling.

[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 conjunction 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 carry out reaction.

[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 1 L 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 1 L of wastewater containing organic pollutants.

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

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

[0013] In some embodiments of the present invention, the amount of the copper salt is as follows: 15-20 μmol of copper salt is added to every 1 L 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 1 L 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 1 L 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 1 L 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 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 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 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 per 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 present invention uses homogeneous copper ions in conjunction with monoethanolamine to efficiently activate peroxymonosulfate, accelerates the Cu(I) / Cu(II) cycle, and generates more sulfate radicals and hydroxyl radicals as well as singlet oxygen and Cu(III). Peroxymonosulfate can be activated to generate a large number of free radicals using a trace amount of copper ions, which not only solves the problem of high 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 present invention has the advantages of small copper ion dosage, fast degradation efficiency, etc., is less affected by impurities in the water body, and is applicable to a wide pH range of water bodies. 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 following briefly introduces the drawings required for use in the embodiments. 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 any creative work.

[0028] Figure 1 (a) Graph showing the removal efficiency of sulfamethoxazole in different coupling systems using homogeneous copper ions in conjunction with monoethanolamine to activate peroxymonosulfate in Example 1 of the present application; (b) comparison of PMS consumption in different systems;

[0029] Figure 2 This is the removal efficiency of sulfamethoxazole under different copper dosage conditions by homogeneous copper ion-monoethanolamine-activated peroxymonosulfate in Example 2 of the present application;

[0030] Figure 3 This is the removal efficiency of sulfamethoxazole under different potassium monopersulfate dosage conditions using homogeneous copper ions and monoethanolamine activated peroxymonosulfate in Example 3 of the present application;

[0031] Figure 4 This is the removal efficiency of sulfamethoxazole under different monoethanolamine dosage conditions by homogeneous copper ion-assisted monoethanolamine activation of peroxymonosulfate in Example 4 of the present application;

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

[0033] Figure 6 This is the removal efficiency of sulfamethoxazole under different temperature conditions by homogeneous copper ion-assisted monoethanolamine activation of 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 synergistically activated by monoethanolamine with 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 rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

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

[0037] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice 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 any conflict with any incorporated document, the contents 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 described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be 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 address the technical defects of high energy consumption and environmental pollution caused by large copper ion dosage in existing methods for activating peroxymonosulfate with copper. The present invention first 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) acts as a multidentate ligand and can coordinate with metal ions through amino groups, hydroxyl groups, and deprotonated hydroxyl groups. The hydroxyl and amino groups it carries give it excellent chelating ability and can provide lone pairs of electrons, thereby forming a complex with the unoccupied orbitals on Cu(II). Therefore, the ligand effect of monoethanolamine with Cu(II) is utilized to improve the Cu(I) / Co(II) cycle. Subsequently, peroxymonosulfate and the mixed solution are added to wastewater containing organic pollutants to react. During the reaction, copper ions activate peroxymonosulfate to generate free radicals that degrade organic pollutants.

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

[0043] Unless otherwise specified, the technical solutions described in the present invention are all conventional solutions in the field, and the reagents or raw materials used, unless otherwise specified, are purchased from commercial channels or have been disclosed. Example 1

[0044] This example provides a comparative study on the application of homogeneous copper ions in synergistically activating peroxymonosulfate in the degradation of sulfamethoxazole, including the following steps:

[0045] 1. Design four different systems to determine the removal effect of sulfamethoxazole. The four different systems are:

[0046] a. Adding monoethanolamine (MEA) and potassium permonosulfate (PMS) to the organic pollutant wastewater containing sulfamethoxazole to react;

[0047] b. Adding copper sulfate (Cu(II)) and potassium permonosulfate (PMS) to the organic pollutant wastewater containing sulfamethoxazole to react;

[0048] c. Adding copper sulfate (Cu(II)) and monoethanolamine (MEA) to the organic pollutant wastewater containing sulfamethoxazole to react;

[0049] d. Add copper sulfate (Cu(II)), monoethanolamine (MEA) and potassium permonosulfate (PMS) to the organic pollutant wastewater containing sulfamethoxazole to react.

[0050] 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.

[0051] Degradation efficiency determination: The liquid phase vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, with a detection wavelength of 270 nm and a mobile phase of methanol and 1% acetic acid water in a ratio of 40:60. Figure 1 shown.

[0052] pass Figure 1In (a) (where 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 sulfamethoxazole within 25 minutes for Cu(II) / PMS, Cu(II) / MEA, MEA / PMS, and Cu(II) / MEA / PMS were 16.8%, 2.6%, 6.7%, and 95.7%, respectively. Without the addition of monoethanolamine, the removal efficiency of sulfamethoxazole by the Cu(II) / PMS system was only 16.8% at 25 minutes. This is because copper has the ability to activate PMS, but this activation capacity is limited. When the PMS dosage was zero, the removal efficiency of the Cu(II) / MEA system was only 2.6% at 25 minutes. This is because PMS is the source of active species in the system, and the loss of this source of active species results in a loss of degradation capacity. The removal efficiency of the MEA / PMS system was 6.7% at 25 minutes, indicating that monoethanolamine was ineffective in activating PMS. The removal rate of Cu(II) / MEA / PMS system at 25 min was 95.7%, far exceeding the total of other systems, which shows that MEA has a significant promoting effect on Cu(II) / PMS system and there is a positive coupling effect between Cu(II), MEA and PMS. Figure 1 Figure (b) shows a strong correlation between PMS consumption and degradation performance. At 25 minutes, the Cu(II) / MEA / PMS system consumed 47.8% of the PMS, while the MEA / PMS system consumed 14.6% and the Cu(II) / PMS system consumed only 9.6%. This indicates that the MEA-enhancing effect stems from increased PMS utilization. The addition of MEA not only enhances the system's oxidative degradation capacity but also reduces oxidant waste. Example 2

[0053] A comparative study of the application of different copper sulfate dosages in the degradation of sulfamethoxazole by homogeneous copper ion-cooperated monoethanolamine-activated peroxymonosulfate includes the following steps:

[0054] Experimental conditions: Sulfamethoxazole was added to eight 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 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 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, 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.

[0055] Degradation efficiency determination: The liquid phase vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, with a detection wavelength of 270 nm and a mobile phase of methanol and 1% acetic acid water in a ratio of 40:60. Figure 2 shown.

[0056] The corresponding sulfamethoxazole removal efficiencies for Cu(II) dosages of 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 were 67.6%, 80.2%, 95.7%, 97.0%, 94.5%, 92.4%, 98.5%, and 97.9%, respectively. It can be observed that increasing the Cu(II) dosage from 5 to 20 μmol / L significantly increases the sulfamethoxazole content and the reaction rate. In particular, the sulfamethoxazole removal efficiency significantly increases when the Cu(II) dosage is increased from 5 to 15 μmol / L. This may be due to the fact that increasing the Cu(II) concentration increases the catalytic reaction rate, accelerating peroxymonosulfate activation, and producing more active species within the same reaction time. However, when the Cu(II) dosage was increased from 20 μmol / L to 100 μmol / L, the removal rate of sulfamethoxazole barely improved. This may be because the PMS activated by Cu(II) reached saturation. However, it is more likely that the addition of monoethanolamine increased the catalytic activity of Cu(II), allowing the degradation amount to reach near the maximum value at a lower Cu(II) dosage. This indicates that the addition of monoethanolamine accelerated the reaction and, more importantly, achieved efficient removal of pollutants at a lower Cu(II) dosage. Considering the comprehensive system treatment effect and cost, the Cu(II) dosage was selected to be 15 μmol / L. Example 3

[0057] A comparative study of the application of different potassium peroxymonosulfate dosages in the degradation of sulfamethoxazole by homogeneous copper ion-cooperated monoethanolamine-activated peroxymonosulfate includes the following steps:

[0058] 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.

[0059] Degradation efficiency determination: The liquid phase vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, with a detection wavelength of 270 nm and a mobile phase of methanol and 1% acetic acid water in a ratio of 40:60. Figure 3 shown.

[0060] When the potassium permonosulfate dosage increased from 0 μmol / L to 600 μmol / L, the reaction rate also increased. This is because as the permonosulfate dosage increased, the amount of activated persulfate also increased, and the oxidizing ability of the system was enhanced. However, when the PMS dosage was further increased to 800 μmol / L and 1000 μmol / L, the degradation rate of sulfamethoxazole in the system also decreased, and the reaction rate also decreased. This may be due to the side reaction between excessive PMS and sulfate, which led to a decrease in the free radical oxidizing ability. Based on this, considering the comprehensive treatment effect and cost, the persulfate dosage in the system was 600 μmol / L. Example 4

[0061] A comparative study of the application of different monoethanolamine dosages in the degradation of sulfamethoxazole by homogeneous copper ion-cooperated monoethanolamine-activated peroxymonosulfate includes the following steps:

[0062] Experimental conditions: Sulfamethoxazole was added to seven 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 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 monopersulfate added was 600 μmol / L. / 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. 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.

[0063] Degradation efficiency determination: The liquid phase vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, with a detection wavelength of 270 nm and a mobile phase of methanol and 1% acetic acid water in a ratio of 40:60. Figure 4 shown.

[0064] As the monoethanolamine dosage increased from 0 μmol / L to 1000 μmol / L, the reaction rate also increased. This is because as the monoethanolamine dosage increased, the system's oxidative capacity increased. When the monoethanolamine dosage was further increased to 1000 μmol / L, the system exhibited maximum oxidative capacity. However, when the monoethanolamine dosage increased to 1500 μmol / L, the degradation capacity of the system decreased, and further increased to 2000 μmol / L, the degradation capacity continued to decrease. This is because excess monoethanolamine changes the coordination ratio with the divalent copper ion, forming a complex with relatively low catalytic activity. Furthermore, monoethanolamine has a certain viscosity, and excessive addition reduces the system's mass transfer efficiency. Therefore, considering both treatment effectiveness and cost, the monoethanolamine dosage in the system was 1000 μmol / L. Example 5

[0065] A comparative study of the effects of different initial pH values on the degradation of sulfamethoxazole by homogeneous copper ions in combination with monoethanolamine activated peroxymonosulfate includes the following steps:

[0066] 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, and 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. The mixture was stirred at constant temperature for 15 minutes 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 minutes, the solution was filtered through a 0.22 μm filter membrane and stored in a 1.5 mL liquid phase vial.

[0067] Degradation efficiency determination: The liquid phase vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, with a detection wavelength of 270 nm and a mobile phase of methanol and 1% acetic acid water in a ratio of 40:60. Figure 5 shown.

[0068] When the pH value varied between 5 and 9, the system's oxidation efficiency for sulfamethoxazole was similar, resulting in high removal efficiencies. The system exhibited higher sulfamethoxazole removal efficiencies under neutral, weakly alkaline, and weakly acidic conditions, while strong acidic and strong alkaline conditions inhibited sulfamethoxazole removal. Example 6

[0069] A comparative study of the application of homogeneous copper ions in synergistic action with monoethanolamine to activate peroxymonosulfate for degradation of sulfamethoxazole at different temperatures includes the following steps:

[0070] 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 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, and the dosage of potassium permonosulfate was 600 μmol / L. The initial pH value was 7.2. The mixture was stirred at constant temperature for 15 min, and 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, 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 to react for 20 min, then filtered through a 0.22 μm filter membrane and stored in a 1.5 mL liquid phase vial.

[0071] Degradation efficiency determination: The liquid phase vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, with a detection wavelength of 270 nm and a mobile phase of methanol and 1% acetic acid water in a ratio of 40:60. Figure 6 shown.

[0072] As the temperature increases, the system's degradation efficiency for sulfamethoxazole gradually improves. Because thermal activation is a classic method for PMS activation, it can be assumed that high temperatures favor PMS activation. However, at low temperatures, molecular motion slows, making effective PMS activation difficult. However, for the Cu(II) / PMS system with monoethanolamine added, the effect of temperature on the system is relatively small. In other words, the addition of monoethanolamine lowers the reaction energy barrier, indicating that the system requires a low activation energy and only a small amount of external energy input to complete the reaction process, demonstrating the superiority of this system. Example 7

[0073] A comparative study of the application of different actual water bodies to the degradation of sulfamethoxazole by homogeneous copper ions synergistically activated by monoethanolamine with peroxymonosulfate includes the following steps:

[0074] 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 monopersulfate was 600 μmol / L, the initial pH value was 7.2, and constant stirring was carried out at room temperature for 15 minutes. At 0 minutes, 2.5 minutes, 5 minutes, 7.5 minutes, 10 minutes, 15 minutes, 20 minutes, and 25 minutes, 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 minutes, it was filtered through a 0.22 μm filter membrane and stored in a 1.5 mL liquid phase vial.

[0075] Degradation efficiency determination: The liquid phase vial containing the experimental solution was placed in a liquid chromatography-mass spectrometer for detection, with a detection wavelength of 270 nm and a mobile phase of methanol and 1% acetic acid water in a ratio of 40:60. Figure 7 shown.

[0076] In lake water, the system's degradation efficiency of sulfamethoxazole 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 water affecting 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 around 90%. This proves the versatility of the system and its adaptability to complex environments, and its practical operational value.

[0077] In summary, the trace copper-monoethanolamine-activated peroxymonosulfate method of the present invention has high activation performance, low environmental pollution, low cost, and the like. Therefore, it has good application prospects in the treatment of sulfamethoxazole wastewater.

[0078] 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 principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for degrading organic pollutants by activating peroxymonosulfate with homogeneous copper ions in collaboration with monoethanolamine, characterized in that: The following steps are involved: Mixing copper salt and monoethanolamine in water to obtain a mixed solution; adding peroxymonosulfate and the mixed solution to wastewater containing organic pollutants to react; The dosage of the copper salt is: 15-60 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; The dosage of the monoethanolamine is as follows: 1000-2000 μmol of monoethanolamine is added to every 1 L of wastewater containing organic pollutants; The dosage of the peroxymonosulfate is as follows: 400-600 μmol of peroxymonosulfate is added to 1 L of wastewater containing organic pollutants; The pH value of the wastewater containing organic pollutants is 5-9.

2. The method for degrading organic pollutants by using homogeneous copper ions in collaboration with monoethanolamine to activate peroxymonosulfate according to claim 1, characterized in that: The peroxymonosulfate is potassium hydrogen peroxymonosulfate.

3. The method for degrading organic pollutants by using homogeneous copper ions in conjunction 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.

4. The method for degrading organic pollutants by using homogeneous copper ions in conjunction 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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