Method for removing new pollutants by contact electrocatalysis coupled with persulfate advanced oxidation

Abstract

In order to solve the above technical problems, the application provides a method for removing new pollutants by contact electrocatalysis and coupling persulfate advanced oxidation, a persulfate solution is configured, the persulfate solution is added to a reaction container containing pollutants, an organic polymer is added to the reaction container, the organic polymer has a contact electrocatalysis effect with water, then the reaction system of the reaction container is subjected to ultrasonic treatment, the organic polymer and water are subjected to contact electrocatalysis reaction, and electrons are continuously generated. By adding the organic polymer to the reaction system, the organic polymer can continuously generate electrons in the contact electrocatalysis process, the part of the electrons can break the O-O bond in the persulfate molecule and generate active oxygen species, the generated electrons activate the PS by using the contact electrocatalysis, and theoretically, the ROS yield in the system can be increased, and the removal efficiency of the pollutants is strengthened.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of anhydrous treatment, and more particularly relates to a method for removing new pollutants by contact electrocatalysis coupled with persulfate advanced oxidation. BACKGROUND

[0002] Persulfate advanced oxidation has always been a research hotspot for pollutant removal. Persulfate needs to be activated by a suitable method to achieve efficient removal of pollutants. Existing PS activation methods include heat, metal catalysts, and carbon-based catalysts. However, there are generally problems such as low energy conversion rate, easy release of metal ions causing secondary environmental pollution, and poor stability of the catalyst.

[0003] Organic polymers can generate electrons under the action of ultrasound through contact with water, which in turn initiates a catalytic reaction. This process is called contact electrocatalysis. These electrons can react with water molecules or dissolved oxygen molecules to produce strong oxidizing active species, which in turn achieve the removal of pollutants. It has been proven that contact electrocatalysis can achieve the degradation of methyl orange, but the removal efficiency is still at a low level compared with other advanced oxidation methods. Therefore, exploring the application potential of contact electrocatalysis technology in wastewater treatment technology has become a technical problem that needs to be solved by those skilled in the art. SUMMARY

[0004] To solve the above technical problems, the application provides a method for removing new pollutants by contact electrocatalysis coupled with persulfate advanced oxidation. By adding organic polymers to the reaction system, the organic polymers can continuously generate electrons during contact electrocatalysis. These electrons can break the O-O bond in the persulfate molecule and produce active oxygen species. Activating PS with the electrons generated by contact electrocatalysis can increase the production of ROS in the system and enhance the removal efficiency of pollutants. The specific method includes the following steps: configuring a persulfate solution, adding the persulfate solution to a reaction container containing pollutants; adding an organic polymer to the reaction container, the organic polymer having a contact electrocatalysis effect with water; and then ultrasonically treating the reaction system of the reaction container to allow the organic polymer and water to undergo contact electrocatalysis and continuously generate electrons.

[0005] In a further technical solution, the persulfate solution is a potassium monopersulfate solution.

[0006] In a further technical solution, the concentration of the potassium monopersulfate solution is 0.5 mmol / L.

[0007] In a further technical solution, the organic polymer is selected from one or more of polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, and perfluoroethylene propylene copolymer.

[0008] In a further technical solution, the initial concentration of the organic polymer in the reaction vessel is 250 mg / L.

[0009] In a further technical solution, the initial concentration of the SDZ pollutant is 10 mg / L.

[0010] In a further technical solution, in the ultrasonic treatment step, the ultrasonic power is 110 W and the frequency is 40 kHz. According to the method for removing new pollutants by contact electrocatalysis coupled with persulfate advanced oxidation according to claim 7, characterized in that, in the ultrasonic treatment step, the ultrasonic treatment time is set to 3-120 min.

[0011] In a further technical solution, the pollutant is one or more of SDZ, ornidazole, ibuprofen, and bisphenol A.

[0012] In a further technical solution, the pollutant is an SDZ pollutant.

[0013] Beneficial effects: Compared with the prior art, the present application has the following advantages:

[0014] In the pollutant system of SDZ, ornidazole, ibuprofen, and bisphenol A, the present application adds a persulfate solution and an organic polymer such as polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, and perfluoroethylene propylene copolymer, and through the application of ultrasonic waves, contact electrocatalysis occurs between the above-mentioned organic copolymer and water. The organic polymer can continuously generate electrons in the contact electrocatalysis process, and these electrons can break the O-O bond in the persulfate molecule and produce reactive oxygen species. The electrons generated by contact electrocatalysis activate PS, increase the ROS yield in the system, and strengthen the removal efficiency of pollutants. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 is a degradation effect line graph of FEP on SDZ;

[0016] Figure 2 is a degradation effect line graph of FEP on ornidazole;

[0017] Figure 3 is a degradation effect line graph of FEP on ibuprofen;

[0018] Figure 4 is a degradation effect line graph of FEP on bisphenol A;

[0019] Figure 5 is a degradation effect line graph of FEP on SDZ after 6 repeated experiments;

[0020] Figure 6 is a degradation effect line graph of FEP on ornidazole after 6 repeated experiments;

[0021] Figure 7 Figure 6 is a graph showing the degradation effect of FEP on ibuprofen over 6 repeated experiments;

[0022] Figure 8 Figure 7 is a graph showing the degradation effect of FEP on bisphenol A over 6 repeated experiments. DETAILED DESCRIPTION

[0023] The present application is further described in the following Examples, which should not be construed as limiting the application. The techniques used in the Examples, unless otherwise specified, are conventional techniques known to those of skill in the art. Unless otherwise noted, the reagents, methods, and equipment used in the present application are conventional reagents, methods, and equipment used in the art, and are not limited to a specific source, and can be purchased or prepared according to conventional methods known to those of skill in the art.

[0024] Unless otherwise expressly specified, the terms "comprise" or variations such as "comprises" or "comprising," as used throughout this document and claims, specify the inclusion of the stated elements or components but not the exclusion of others.

[0025] The technical solutions of the present application are described below through specific examples. It should be understood that the one or more steps mentioned in the present application do not exclude other methods and steps before and after the combination steps, or other methods and steps can be inserted between the explicitly mentioned steps. It should also be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. Unless otherwise specified, the numbering of each method step is only for the purpose of identifying each method step, and is not intended to limit the arrangement order of each method or to limit the scope of the implementation of the present application. Changes or adjustments of the relative relationship, without substantial technical content changes, can also be considered as the scope of implementation of the present application.

[0026] The foregoing description of specific exemplary embodiments of the application has been presented for the purpose of illustration and description. They are not intended to be exhaustive or to limit the application to the precise forms disclosed, and obviously many modifications, variations and changes can be made without departing from the spirit and scope of the application. The exemplary embodiments were chosen and described in order to explain the principles of the application and its practical application, to enable others skilled in the art to understand the application for various embodiments and with various modifications as are suited to the particular use contemplated, as well as to enable others to implement and use the application in practical ways. The scope of the application is to be defined by the claims and their equivalents.

[0027] Example 1-1

[0028] Reaction vessel: 40 mL glass bottle, the glass bottle contains contaminant SDZ, the initial concentration of SDZ is 10 mg / L, and an initial concentration of 0.5 mmol / L of potassium monopersulfate solution is configured, and the configured potassium monopersulfate solution is added to the glass bottle. In addition, an organic polymer is added to the system according to an initial concentration of 250 mg / L, and the organic polymer is selected from PE [polyethylene]. In this embodiment, the PE [polyethylene] is selected from the MacLyle L875016 reagent. The glass bottle is placed in an ultrasonic cleaner, the ultrasonic power is 110 W, the frequency is 40 kHz, the reaction time is divided into 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min, and the degradation effect of SDZ is determined by sampling.

[0029] Example 1-2

[0030] Reaction vessel: 40 mL glass bottle, the glass bottle contains contaminant SDZ, the initial concentration of SDZ is 10 mg / L, and an initial concentration of 0.5 mmol / L of potassium monopersulfate solution is configured, and the configured potassium monopersulfate solution is added to the glass bottle. In addition, an organic polymer is added to the system according to an initial concentration of 250 mg / L, and the organic polymer is selected from PE [polyethylene]. In this embodiment, the PE [polyethylene] is selected from the MacLyle L875016 reagent. The glass bottle is placed in an ultrasonic cleaner, the ultrasonic power is 110 W, the frequency is 40 kHz, the reaction time is divided into 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min, and the degradation effect of SDZ is determined by sampling.

[0031] Example 1-3

[0032] Reaction vessel: 40 mL glass bottle, the glass bottle contains contaminant SDZ, the initial concentration of SDZ is 10 mg / L, and an initial concentration of 0.5 mmol / L of potassium monopersulfate solution is configured, and the configured potassium monopersulfate solution is added to the glass bottle. In addition, an organic polymer is added to the system according to an initial concentration of 250 mg / L, and the organic polymer is selected from PE [polyethylene]. In this embodiment, the PE [polyethylene] is selected from the MacLyle L875016 reagent. The glass bottle is placed in an ultrasonic cleaner, the ultrasonic power is 110 W, the frequency is 40 kHz, the reaction time is divided into 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min, and the degradation effect of SDZ is determined by sampling.

[0033] Example 1-4

[0034] Reaction container 40ml glass bottle, glass bottle contains pollutants SDZ, the initial concentration of SDZ is 10mg / L, the initial concentration of 0.5mmol / L of potassium monopersulfate solution is configured, and the configured potassium monopersulfate solution is added to the glass bottle. In addition, according to the initial concentration of 250mg / L, the organic polymer is added to the system, and the organic polymer of the embodiment is selected from FEP [perfluoroethylene propylene copolymer]. The glass bottle is placed in an ultrasonic cleaning machine, the ultrasonic power is 110W, the frequency is 40kHz, the reaction time is divided into 5min, 10min, 20min, 30min, 45min, 60min, and the degradation effect of SDZ is determined by sampling.

[0035] The degradation effect of SDZ in the above examples 1-1 to 1-4 is shown in the following table: Figure 1 From the experimental results in Figure 1 , it can be seen that the degradation rate in the 0-10min stage is in a relatively fast stage, and when the ultrasonic time reaches 60min, the degradation rate tends to be relatively flat, at this time the degradation rate of PTFE and FEP two kinds of organic polymers can reach more than 80%, the degradation rate of PE is slightly weak, only can reach 60%, the weakest material is PVDF, also can reach more than 50%. From the above experimental results, it can be seen that the four kinds of organic polymers provided in the scheme can promote the O-O bond cleavage of persulfate and produce reactive oxygen species, thereby realizing the synergistic enhancement of the degradation effect of SDZ pollutants.

[0036] Example 2

[0037] The organic polymer of the embodiment is selected from FEP [perfluoroethylene propylene copolymer], which is purchased from Taobao Mingshuo Chemical Industry, and the initial concentration is 250mg / L. The reaction system is a 40ml glass bottle, and the glass bottle contains an initial concentration of 10mg / L of ornidazole solution. An initial concentration of 0.5mmol / L of potassium monopersulfate solution is configured, and the configured potassium monopersulfate solution is added to the glass bottle. The glass bottle is placed in an ultrasonic cleaning machine, the ultrasonic power is 110W, the frequency is 40kHz, the reaction time is divided into 5min, 10min, 20min, 30min, 45min, 60min, and the degradation effect of ornidazole is determined by sampling. The results are shown in the following table: Figure 2 In the 0-5min stage, the degradation rate of FEP [perfluoroethylene propylene copolymer] on ornidazole is in a relatively fast speed, and the degradation effect is close to 60% near 5min, and then the degradation rate gradually slows down, and the degradation effect is less than 20% in the 60min region. Therefore, it can be seen that FEP [perfluoroethylene propylene copolymer] has good degradation effect on ornidazole.

[0038] Example 3

[0039] The organic polymer of the present embodiment is FEP [fluorinated ethylene propylene copolymer], the initial concentration is 250 mg / L, the reaction system is a 40 mL glass bottle, and the glass bottle contains an initial concentration of 10 mg / L of ibuprofen solution. An initial concentration of 0.5 mmol / L of potassium monopersulfate solution is prepared, and the prepared potassium monopersulfate solution is added to the glass bottle. It is placed in an ultrasonic cleaning machine, the ultrasonic power is 110 W, the frequency is 40 kHz, the reaction time is divided into 5 min, 10 min, 20 min, 30 min, 45 min, 60 min, and the degradation effect of ibuprofen is determined by sampling. The results are as follows Figure 3 In the time range of 1-10 min, the degradation rate of FEP [fluorinated ethylene propylene copolymer] on ibuprofen is in a relatively fast stage, the degradation effect is less than 50% at 10 min, and the degradation effect is close to 20% at 60 min. Therefore, FEP [fluorinated ethylene propylene copolymer] also has good degradation effect on ibuprofen.

[0040] Example 4

[0041] The organic polymer of the present embodiment is FEP [fluorinated ethylene propylene copolymer], the initial concentration is 250 mg / L, the reaction system is a 40 mL glass bottle, and the glass bottle contains an initial concentration of 10 mg / L of bisphenol A solution. An initial concentration of 0.5 mmol / L of potassium monopersulfate solution is prepared, and the prepared potassium monopersulfate solution is added to the glass bottle. It is placed in an ultrasonic cleaning machine, the ultrasonic power is 110 W, the frequency is 40 kHz, the reaction time is divided into 5 min, 10 min, 20 min, 30 min, 45 min, 60 min, and the degradation effect of bisphenol A is determined by sampling. The results are as follows Figure 4 FEP [fluorinated ethylene propylene copolymer] also has good degradation effect on bisphenol A. It is found that the degradation effect of FEP [fluorinated ethylene propylene copolymer] on bisphenol A has reached about 60% when measured at 5 min, the degradation rate gradually slows down between 5 min and 60 min, and gradually flattens at 60 min. The final degradation effect is about 20%, which proves that FEP [fluorinated ethylene propylene copolymer] also has quite good degradation effect on bisphenol A.

[0042] Example 5

[0043] The above experiment is repeated 6 times, and the removal effect of the organic polymer (FEP [fluorinated ethylene propylene copolymer]) on the four pollutants SDZ, ornidazole, ibuprofen and bisphenol A is as shown in Figures 5-8 Figures 5-8 ​It can be known that the degradation effect of the organic polymer (FEP [perfluoroethylene propylene copolymer]) on SDZ, ornidazole, ibuprofen, bisphenol A and other pollutants is close in multiple experiments, proving that the contact electrocatalysis effect between the above-mentioned organic copolymer and water is generated by applying ultrasonic waves, and the organic polymer can continuously generate electrons in the contact electrocatalysis process, and the part of the electrons can break the O-O bond in the persulfate molecule and produce reactive oxygen species, the electrons generated by the contact electrocatalysis activate PS, increase the ROS production in the system, and strengthen the removal efficiency of the pollutants.

[0044] The foregoing description of specific exemplary embodiments of the application is intended to be illustrative only and is not intended to limit the application to the precise forms described. Many modifications and variations are possible in light of the above teachings without departing from the spirit or essential characteristics of the application. The exemplary embodiments are chosen and described in order to explain the principles of the application and its practical application and to allow others skilled in the art to understand the application for various exemplary embodiments with various modifications as are suited to the particular use contemplated. It is intended that the scope of the application be defined by the claims and their equivalents.

Claims

1. A method for removing emerging contaminants by contact electrocatalytic coupled persulfate advanced oxidation, characterized in that, A persulfate solution is configured, the persulfate solution is added to a reaction container containing pollutants, an organic polymer is added to the reaction container, the organic polymer has a contact electrocatalytic effect with water, the reaction system of the reaction container is subjected to ultrasonic treatment, the organic polymer and water are subjected to contact electrocatalytic reaction, and electrons are continuously generated, the persulfate solution is a potassium monopersulfate solution, and the organic polymer is one or a mixture of polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, and perfluoroethylene propylene copolymer.

2. The method for removing emerging contaminants by contact electrocatalysis coupled with persulfate advanced oxidation according to claim 1, characterized in that, The concentration of the potassium monopersulfate solution is 0.5 mmol / L.

3. The method of removing emerging contaminants by contact electrocatalysis coupled with persulfate advanced oxidation according to claim 1, characterized in that, The initial concentration of the organic polymer in the reaction container is 250 mg / L.

4. The method of removing emerging contaminants by contact electrocatalysis coupled with persulfate advanced oxidation according to claim 1, characterized in that, In the ultrasonic treatment step, the ultrasonic power is 110 W, and the frequency is 40 kHz.

5. The method of removing emerging contaminants by contact electrocatalytic coupled persulfate advanced oxidation according to claim 4, characterized in that, In the ultrasonic treatment step, the ultrasonic treatment time is set to 3-120 min.

6. The method of removing emerging contaminants by contact electrocatalysis coupled with persulfate advanced oxidation according to claim 1, characterized in that, The pollutants are one or a mixture of SDZ, ornidazole, ibuprofen, and bisphenol A.

7. The method of removing emerging contaminants by contact electrocatalytic coupled persulfate advanced oxidation according to claim 6, characterized in that, The pollutants are SDZ pollutants.

8. The method of removing emerging contaminants by contact electrocatalytic coupled persulfate advanced oxidation according to claim 7, characterized in that, The initial concentration of the SDZ pollutants is 10 mg / L.

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