Method for degrading naproxen in water by using divalent manganese / percarbonate / tetraacetylethylenediamine system

Abstract

The application discloses a method for degrading naproxen in water by using a divalent manganese / percarbonate / tetraacetylethylenediamine system and relates to a method for degrading naproxen in water by using a high-level oxidation technology. The method comprises the following steps: adding percarbonate and tetraacetylethylenediamine into water to be treated containing naproxen, adjusting the pH value of the water to be treated to 5-10, adding divalent manganese for treatment, and stirring and reacting for 10-60 minutes at a water temperature of 5-35 DEG C. The method has the advantages of fast generation speed of active species, high removal efficiency of organic pollutants, high utilization rate of oxidants, no need to increase other treatment equipment, low one-time investment cost, low operation cost, simple operation, wide application range, green environmental protection and the like, and has a wide application prospect in the treatment of organic wastewater, such as medical wastewater and aquaculture wastewater, containing naproxen.

Description

Technical Field

[0001] This invention belongs to the field of water treatment technology, specifically relating to a method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system. Background Technology

[0002] With social development, the rapid growth of the medical and aquaculture industries, and the increasing demand for personal care products, the use of pharmaceuticals and personal care products has also increased. Naproxen, as one of the most common pharmaceutical and personal care product pollutants in the aquatic environment, poses a significant threat to human health and the ecological environment. Currently, traditional wastewater treatment processes are unable to effectively remove it, resulting in its continuous release into the environment. Therefore, advanced oxidation technologies are needed for its effective removal.

[0003] Peracetic acid, a rapidly emerging oxidant in advanced oxidation processes for water treatment in recent years, has been widely used due to its high efficiency in disinfection and bleaching, its non-toxic and harmless properties, and its minimal or no production of disinfection byproducts. The combined use of percarbonate and tetraacetylethylenediamine can generate peracetic acid with higher kinetic activity in situ through a rapid hydrolysis process. Percarbonate is a substitute for liquid hydrogen peroxide, possessing advantages such as good stability, low cost, ease of handling, and favorable storage and transportation, and is widely used in organic synthesis, bleaching agents, and environmental remediation. Tetraacetylethylenediamine is a bleaching activator widely used in the detergent industry. Peracetic acid is often activated through various methods, including UV activation, thermal activation, electrochemical activation, microwave activation, ultrasonic activation, inorganic anion activation, carbon-based material activation, and transition metal activation, to generate a variety of active species, enabling it to efficiently degrade various pollutants in water. Although advanced peracetic acid-based oxidation processes have made progress in water treatment, their widespread practical application is still limited by several drawbacks. For example, activation methods such as heating, ultraviolet light, microwave, and ultrasound incur high initial investment and operating costs; activation using divalent cobalt ions presents secondary metal ion pollution due to the biotoxicity of these ions; furthermore, there are issues such as high peracetic acid residues, narrow pH suitability, unsatisfactory acidification of wastewater, and low decontamination efficiency in real water samples. Therefore, there is an urgent need to develop a peracetic acid activation method that is adaptable, environmentally friendly, economical, and energy-efficient for the degradation of naproxen in water. Summary of the Invention

[0004] The purpose of this invention is to provide a method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system.

[0005] The technical solution of the present invention is as follows:

[0006] A method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system is characterized by the following steps:

[0007] (1) Add percarbonate and tetraacetylethylenediamine to the water to be treated containing naproxen, wherein the concentration of naproxen is 1-50 μM, the concentration of percarbonate is 0.1-10 mM, and the concentration of tetraacetylethylenediamine is 0.1-10 mM;

[0008] (2) Adjust the pH of the water to be treated to 5-10, add divalent manganese to the water containing naproxen after step (1), stir and react at a water temperature of 5-35℃, where the concentration of divalent manganese is 1-50μM and the reaction time is 10-60 minutes.

[0009] Preferably, in step (1), the concentration of naproxen is 5-20 μM.

[0010] In step (1), the percarbonate is one or a mixture of two of potassium percarbonate or sodium percarbonate in any proportion.

[0011] Preferably, in step (1), the concentration of the percarbonate is 0.5-5 mM.

[0012] Preferably, in step (1), the concentration of tetraacetylethylenediamine is 0.5-5 mM.

[0013] Preferably, in step (2), the pH value of the water to be treated is adjusted to 7-9.

[0014] The divalent manganese mentioned in step (2) is one or a mixture of two of manganese sulfate, manganese dichloride and manganese nitrate in any proportion.

[0015] Preferably, in step (2), the concentration of divalent manganese is 5-25 μM.

[0016] Preferably, in step (2), the temperature during the reaction is controlled to be 15-30℃.

[0017] Preferably, in step (2), the reaction time concentration is 15-60 minutes.

[0018] The technical principle of this invention is as follows: a system of divalent manganese and peracetic acid is used to degrade naproxen. Percarbonate introduces carbonic acid buffer to avoid acidification of the aqueous matrix and provides hydrogen peroxide and tetraacetylethylenediamine for rapid hydrolysis to generate peracetic acid with higher kinetic activity in situ. Peracetic acid has a synergistic effect with divalent manganese to produce active manganese species and free radicals, thereby degrading naproxen in water.

[0019] Compared with existing technologies, this technical solution has the following advantages:

[0020] 1. This invention does not require additional aeration, heating, ultraviolet irradiation, microwave irradiation, ultrasonic cavitation, or external electromagnetic fields. It only requires the addition of divalent manganese, percarbonate, and tetraacetylethylenediamine to generate active species to degrade naproxen in water.

[0021] 2. This invention has the advantages of rapid generation of active species, high efficiency in removing organic pollutants, high utilization rate of oxidant, no need to add other treatment equipment, low initial investment cost, low operating cost, simple and easy operation, wide applicability, and green environmental protection. Attached Figure Description

[0022] Figure 1 The effects of each system in Example 1 on the degradation of naproxen are shown in the figures. These systems are: divalent manganese / percarbonate system, percarbonate / tetraacetylethylenediamine system, divalent manganese / tetraacetylethylenediamine system, and divalent manganese / percarbonate / tetraacetylethylenediamine system. The horizontal axis represents the reaction time, and the vertical axis represents the ratio of naproxen concentration to the initial concentration at the corresponding reaction time.

[0023] Figure 2 To illustrate the degradation effect of naproxen under different conditions, Examples 1, 2, 3, 4, 5, and 6 are provided. The horizontal axis represents the reaction time, and the vertical axis represents the ratio of naproxen concentration to the initial concentration at the corresponding reaction time. Detailed Implementation

[0024] The present invention will be further described below with reference to embodiments, which are for illustrative purposes only and are not limited to the following examples.

[0025] Figure 1 The results of different control systems on the degradation of naproxen are shown, among which:

[0026] The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system includes the following steps: adding 1 mM percarbonate and 1 mM tetraacetylethylenediamine to the water to be treated containing 10 μM naproxen, adjusting the pH of the water to be treated to 8.5, and adding 10 μM divalent manganese.

[0027] The method for degrading naproxen in water using a percarbonate / tetraacetylethylenediamine system includes the following steps: adding 1 mM percarbonate and 1 mM tetraacetylethylenediamine to the water to be treated containing 10 μM naproxen, and adjusting the pH of the water to be treated to 8.5;

[0028] The method for degrading naproxen in water using a divalent manganese / percarbonate system includes the following steps: adding 1 mM percarbonate to the water to be treated containing 10 μM naproxen, adjusting the pH of the water to be treated to 8.5, and adding 10 μM divalent manganese.

[0029] The method for degrading naproxen in water using a divalent manganese / tetraacetylethylenediamine system includes the following steps: adding 1 mM tetraacetylethylenediamine to the water to be treated containing 10 μM naproxen, adjusting the pH of the water to be treated to 8.5, and adding 10 μM divalent manganese;

[0030] In all the above examples, the reaction was carried out with stirring at a water temperature of 25°C for 30 minutes.

[0031] Example 1: The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system in this embodiment includes the following steps: 1 mM percarbonate and 1 mM tetraacetylethylenediamine are added to the water to be treated containing 10 μM naproxen, the pH of the water to be treated is adjusted to 8.5, 10 μM divalent manganese is added, and the mixture is stirred and reacted for 30 minutes at a water temperature of 25°C.

[0032] Example 2: The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system in this embodiment includes the following steps: 1 mM percarbonate and 1 mM tetraacetylethylenediamine are added to the water to be treated containing 10 μM naproxen, the pH of the water to be treated is adjusted to 8.5, 20 μM divalent manganese is added, and the mixture is stirred and reacted for 30 minutes at a water temperature of 25°C.

[0033] Example 3: The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system in this embodiment includes the following steps: 1 mM percarbonate and 1 mM tetraacetylethylenediamine are added to the water to be treated containing 10 μM naproxen, the pH of the water to be treated is adjusted to 8.5, 5 μM divalent manganese is added, and the mixture is stirred and reacted for 30 minutes at a water temperature of 25°C.

[0034] Example 4: The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system in this embodiment includes the following steps: 0.5 mM percarbonate and 1 mM tetraacetylethylenediamine are added to the water to be treated containing 10 μM naproxen, the pH of the water to be treated is adjusted to 8.5, 10 μM divalent manganese is added, and the mixture is stirred and reacted for 30 minutes at a water temperature of 25°C.

[0035] Example 5: The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system in this embodiment includes the following steps: 0.5 mM percarbonate and 1 mM tetraacetylethylenediamine are added to the water to be treated containing 10 μM naproxen, the pH of the water to be treated is adjusted to 8.5, 20 μM divalent manganese is added, and the mixture is stirred and reacted for 30 minutes at a water temperature of 25°C.

[0036] Example 6: The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system in this embodiment includes the following steps: 2 mM percarbonate and 2 mM tetraacetylethylenediamine are added to the water to be treated containing 10 μM naproxen, the pH of the water to be treated is adjusted to 8.5, 20 μM divalent manganese is added, and the mixture is stirred and reacted for 30 minutes at a water temperature of 25°C.

[0037] The above description is merely a preferred embodiment of the present invention, and therefore should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made in accordance with the scope of the patent and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A method for degrading naproxen in water by using a divalent manganese / percarbonate / tetraacetylethylenediamine system, comprising the following steps: (1) adding percarbonate and tetraacetylethylenediamine to the water to be treated containing naproxen, wherein The concentration of naproxen is 1-50 μM, the dosing concentration of percarbonate is 0.1-10 mM, and the dosing concentration of tetraacetylethylenediamine is 0.1-10 mM; (2) Adjusting the pH value of the water to be treated to 7-9, adding divalent manganese into the water to be treated containing naproxen after step (1), and stirring and reacting at a water temperature of 5-35 ℃, wherein the concentration of divalent manganese is 1-50 μM, and the reaction time is 10-60 minutes.

2. The method for degrading naproxen in water by using the bivalent manganese / percarbonate / tetraacetylethylenediamine system according to claim 1, characterized in that: In step (1), the concentration of naproxen is 5-20 μM.

3. The method for degrading naproxen in water by using the bivalent manganese / percarbonate / tetraacetylethylenediamine system according to claim 1, characterized in that: In step (1), the percarbonate is one of potassium percarbonate or sodium percarbonate or a mixture of the two in any ratio.

4. The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system according to claim 1, characterized in that: In step (1), the concentration of percarbonate is 0.5-5 mM.

5. The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system according to claim 1, characterized in that: In step (1), the concentration of tetraacetylethylenediamine is 0.5-5 mM.

6. The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system according to claim 1, characterized in that: In step (2), the divalent manganese is one of manganese sulfate, manganese dichloride and manganese nitrate or a mixture of two in any ratio.

7. The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system according to claim 1, characterized in that: In step (2), the concentration of divalent manganese is 5-25 μM.

8. The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system according to claim 1, characterized in that: In step (2), the temperature during the reaction is controlled to be 15-30 ℃.

9. The method for degrading naproxen in water using a divalent manganese / percarbonate / tetraacetylethylenediamine system according to claim 1, characterized in that: In step (2), the reaction time is 15-60 minutes.

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