Method for degrading PFOS under enhanced subcritical hydrothermal conditions

Abstract

The present application relates to the field of persistent pollutants degradation, and aims to provide a method for enhancing PFOS degradation under subcritical hydrothermal conditions.The method is to add iron-based amorphous alloy and lye into wastewater containing PFOS, and then perform subcritical hydrothermal reaction to realize PFOS degradation; the iron-based amorphous alloy is a powdery metal particle prepared by atomization process, and its composition is iron as matrix and doped with silicon and boron.The present application has the characteristics of simple process, mild conditions, energy saving and high efficiency, easy control, etc., can enhance the effect of subcritical hydrothermal degradation, and can efficiently remove PFOS in PFOS-containing aqueous solution; and the present application is suitable for a wide range of pollutants and has wide application scenarios.

Description

Technical Field

[0001] This invention belongs to the field of persistent pollutant degradation, and more specifically, relates to a method for enhancing the degradation of PFOS under subcritical hydrothermal conditions. Background Technology

[0002] Among numerous compounds, long-chain PFASs, particularly perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), have attracted widespread attention from the scientific community and regulatory authorities worldwide. This is primarily due to the widespread use and persistent nature of PFASs, which have led to their presence in the environment (air, water, soil, and sediment), plants, animals, and even the human body. PFOS and PFOA are the two most typical types of PFASs detectable in environmental media and organisms. Simultaneously, increasing research indicates that existing technologies are insufficient to meet treatment targets, especially in the destruction of PFASs. The destruction of PFASs is particularly challenging, and recent research has described advanced oxidation processes and a range of other innovative technologies for PFAS destruction, including photocatalysis, electrochemistry, sonochemistry, mechanochemistry, plasma, hydrated electrons, and radiolysis. Despite the promising results of some technologies, many methods initially proven effective against PFOA and other perfluoroalkyl carboxylic acids (PFCAs) have been found to be less effective against PFOS and other perfluoroalkyl sulfonic acids (PFSAs).

[0003] In recent years, subcritical water treatment technology (temperature 170-350℃; pressure 2-22MPa) has been considered an innovative and environmentally friendly reaction technology. Subcritical water is defined as hot water with sufficient pressure to remain liquid, whose dielectric constant decreases from ~80 at 25℃ to <20 at 350℃, and whose behavior is more similar to that of a nonpolar solvent. This creates a unique reaction environment that has been shown to catalyze many reactions leading to the decomposition and regeneration of biomass. The effectiveness of subcritical hydrothermal degradation for PFOS has been confirmed. Alkali can be added to subcritical water as an additive to promote this process, a process known as hydrothermal alkali treatment.

[0004] However, existing research also indicates that hydrothermal treatment conditions are relatively harsh (high temperature, high pressure, high concentration of alkaline solution), and lower energy consumption and higher economic efficiency will be the focus of future research. Foreign researchers have introduced metal catalysts into subcritical hydrothermal processes. In their studies, the presence of zero-valent iron can promote the decomposition and mineralization of PFOS, but it still requires a relatively long time (e.g., 6 hours). Related studies have also mentioned that introducing proprietary catalytic surfaces can improve the rate and extent of PFAS degradation. However, due to the poor stability and tendency of iron powder to agglomerate, and the gradual accumulation of an oxide layer on the surface during the reaction, which reduces degradation efficiency, its application is limited. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a method for enhancing the degradation of PFOS under subcritical hydrothermal conditions.

[0006] To solve the technical problem, the solution of the present invention is:

[0007] A method for enhancing the degradation of PFOS under subcritical hydrothermal conditions is provided, which involves adding an iron-based amorphous alloy and an alkaline solution to wastewater containing PFOS, and then carrying out a subcritical hydrothermal reaction to degrade PFOS. In the reaction system, the mass ratio of PFOS:iron-based amorphous alloy:water is 2-3:2000:50000, and the molar ratio of PFOS to alkali is 2-3:25000.

[0008] The iron-based amorphous alloy is a powdered metal microparticle obtained by atomization process. Its composition is iron as the matrix and doped with silicon and boron, wherein the mass ratio of Fe:Si:B is 77:15:8.

[0009] As a preferred embodiment of the present invention, in the subcritical hydrothermal reaction process, the reaction temperature is controlled at 325-350℃, the pressure at 12.04-16.52 MPa, and the reaction time at 60-90 min; the stirring condition at 300 rpm is maintained during the reaction.

[0010] As a preferred embodiment of the present invention, the pH value of the subcritical hydrothermal reaction system is controlled to be 10.0 to 13.0.

[0011] As a preferred embodiment of the present invention, after feeding, the mixture is first purged with flowing nitrogen for 10 to 15 minutes before the reaction is carried out.

[0012] As a preferred embodiment of the present invention, the alkaline solution is any one of an aqueous solution of sodium bicarbonate, sodium carbonate, or sodium hydroxide.

[0013] As a preferred embodiment of the present invention, the concentration of the alkaline solution is 1.0M.

[0014] As a preferred embodiment of the present invention, the particle size range of the iron-based amorphous alloy is 50 to 100 μm.

[0015] As a preferred embodiment of the present invention, the wastewater is wastewater contaminated by fire-fighting water film-forming foam or sewage from fire training grounds, or domestic sewage or industrial wastewater containing PFASs.

[0016] As a preferred embodiment of the present invention, the fire-fighting aqueous film-forming foam is formed by a foam extinguishing agent based on fluorocarbon surfactants on the surface of a hydrocarbon liquid.

[0017] As a preferred embodiment of the present invention, the wastewater further includes perfluorosulfonic acid and perfluorocarboxylic acid with carbon chain lengths of 4 to 10, which are at least one of PFOA, PFBS, PFHpS, PFHxS, PFBA, PFHpA or PFHxA; or, it further includes wastewater organic matter DOC or volatile organic compounds VOCs, specifically at least one of acetic acid, benzoic acid, ethanol, isopropanol, ethylene glycol, ethyl acetate, toluene, chloroform, trichloroethane or ethylene diether.

[0018] Description of the invention principle:

[0019] 1. Iron-based amorphous alloys are a new type of metallic material with short-range ordered and long-range disordered atomic structures. They are commonly used in the protection and decoration of daily necessities, functional films of functional materials, electronics, power, chemical and other fields, and are generally used as the core of distribution transformers.

[0020] 2. The applicant's inventor team discovered in their research that, based on the corrosion resistance, high catalytic activity, environmental friendliness and low cost of iron-based amorphous alloys, their application in the application scenario of enhancing the degradation of PFOS under subcritical hydrothermal conditions can achieve a role that existing metal catalysts cannot.

[0021] This invention first prepares an iron-based amorphous alloy using an atomization process, and then uses it as an additive to enhance the subcritical hydrothermal effect of an alkaline solution system, achieving highly efficient removal of PFOS. The specific technical principle of the reaction process is as follows:

[0022] (1) Under subcritical hydrothermal conditions, high temperature and pressure can cause changes in the physical properties of water, such as an increase in its dielectric constant and solubility. Under these conditions, water molecules form a hydrated layer on the surface of iron-based amorphous alloys, thereby altering the surface's physical and chemical properties. This hydrated layer forms a fine pitted structure on the surface, which is conducive to the formation of active sites. During the reaction process, pitted reaction regions appear on the surface of the iron-based amorphous alloy, increasing the number of active sites. These irregular surface features increase the surface area of ​​the reaction region and improve the density of active sites, which is beneficial to the adsorption and reaction of reactants. In addition, these pitted structures may more easily adsorb water molecules in a hot water environment, forming active sites.

[0023] (2) Under subcritical hydrothermal conditions, metal ions (such as Fe) 2+ and Fe 3+ Fe participates in redox reactions. These redox reactions produce reactive species, such as hydroxides or oxides, which may become active sites for the reactions. Simultaneously, the high temperature and pressure under hydrothermal conditions promote these reactions. During degradation, the active site Fe... 2+ and Fe 3+ The proportions have changed, and the introduction of iron-based amorphous alloys may help generate more active species.

[0024] (3) Doping with silicon and boron improves the electrical conductivity of iron-based amorphous alloys, which is beneficial for electron transport and charge transfer during catalytic reactions. This may increase the electron affinity of active sites, further enhancing catalytic activity. In addition, doping with silicon and boron may also reduce the oxidation and corrosion tendency at the grain boundaries of iron-based amorphous alloys, extending the alloy's lifespan and improving its stability. This helps maintain the activity of the alloy surface and sustain the catalytic reaction.

[0025] (3) Under subcritical hydrothermal conditions, high temperature and high pressure may also promote the interaction between the metal surface and water molecules. Calculations based on multiple sets of reaction data show that the activation energies of the reactions before and after the iron-based alloying are 55.33 kJ / mol. -1 and 37.32 kJmol -1 The addition of iron-based alloys reduced the reaction activation energy by about 32%, which is the main reason why iron-based amorphous alloys have excellent strengthening effects.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1. The method provided by this invention has the characteristics of simple process, mild conditions, energy saving and high efficiency, and easy control. It can enhance the effect of subcritical hydrothermal degradation and efficiently remove PFOS from aqueous solutions containing PFOS.

[0028] 2. The iron-based amorphous alloy raw materials described in this invention are widely available, simple to prepare, have stable morphology, and are easy and simple to process, making them suitable for medium-scale industrial production. The alkaline solution used (especially sodium bicarbonate) is also simple to prepare, cost-effective, and has certain environmental protection characteristics.

[0029] 3. The iron-based amorphous alloy described in this invention increases the number of surface active sites during subcritical hydrothermal degradation, while introducing more active species and reducing the reaction activation energy. The combined effect of these factors results in excellent strengthening effect of the iron-based amorphous alloy, achieving efficient removal of PFOS from water.

[0030] 4. The present invention uses iron-based amorphous alloys, which do not require additional equipment or energy consumption and have high safety; iron-based amorphous alloys can be separated, recycled and have good recyclability.

[0031] 5. The method for enhancing the degradation of PFOS under subcritical hydrothermal conditions provided by this invention has a wide range of targets for pollutants, and can be applied to most PFASs substances, including PFOS. It has a wide range of applications, including fire-fighting water film-forming foam treatment, wastewater treatment containing PFASs, and other applications, providing a solution guide for improving the effectiveness of PFASs treatment technology. Attached Figure Description

[0032] Figure 1 The images are SEM images obtained at multiples of 100 μm before and after the iron-based amorphous alloy in Example 1 participates in the subcritical hydrothermal reaction (left: before reaction; right: after reaction).

[0033] Figure 2 XPS energy dispersive spectroscopy of Fe element in iron-based amorphous alloys before and after participating in subcritical hydrothermal reactions (left: before reaction; right: after reaction).

[0034] Figure 3 XPS analysis of the energy spectrum of F element in iron-based amorphous alloys under three conditions: before participating in subcritical hydrothermal reaction, after pure hydrothermal reaction, and after reaction with added alkali solution (left: before reaction; middle: after pure hydrothermal reaction; right: after reaction with added alkali solution). Detailed Implementation

[0035] The following details the method of enhancing subcritical hydrothermal conditions for PFOS degradation according to the present invention.

[0036] A first aspect of the present invention is to provide a method for enhancing the degradation of PFOS under subcritical hydrothermal conditions, comprising:

[0037] (1) Add iron-based amorphous alloy and alkaline solution to wastewater containing PFOS, so that the mass ratio of PFOS: iron-based amorphous alloy: water in the reaction system is 2-3:2000:50000, and the molar ratio of PFOS to alkali is 2-3:25000.

[0038] The alkaline solution is any one of sodium bicarbonate, sodium carbonate, or sodium hydroxide aqueous solution, preferably with a concentration of 1.0 M; the pH of the reaction system is controlled to be between 10.0 and 13.0.

[0039] The iron-based amorphous alloy is a powdered metal microparticle obtained by atomization process, with a particle size ranging from 50 to 100 μm. Its composition is based on iron and doped with silicon and boron, wherein the mass ratio of Fe:Si:B is 77:15:8.

[0040] The preparation of iron-based amorphous alloys by atomization is an existing technology that can be carried out using conventional processes, and will not be described in detail in this invention.

[0041] (2) After feeding, the mixture is first purged with flowing nitrogen for 10–15 min, and then a subcritical hydrothermal reaction is carried out. During the reaction, the temperature is controlled at 325–350℃, the pressure at 12.04–16.52 MPa, and the time at 60–90 min; the stirring condition is maintained at 300 rpm during the reaction. The degradation and removal of PFOS are achieved through a subcritical hydrothermal reaction.

[0042] A second aspect of the present invention is to provide an application method for the above-described enhanced subcritical hydrothermal conditions for the degradation of PFOS. Specifically, the present invention can be applied to the treatment of fire-fighting water film-forming foam.

[0043] Foam extinguishing agents are based on fluorocarbon surfactants and can form a water film on the surface of certain hydrocarbon liquids, known as fire-fighting water film-forming foam (PFMF). They contain various PFASs pollutants, primarily PFOS. The method for degrading PFOS described in this invention is also applicable to various PFASs, including PFOA, PFBS, PFHpS, PFHxS, PFBA, PFHpA, and PFHxA. For example, wastewater containing PFASs is wastewater contaminated by fire-fighting water film-forming foam or wastewater from fire training grounds. In addition to PFASs, the pollutants include dissolved organic matter (DOC) and volatile organic compounds (VOCs). Due to the special environment of high temperature and high pressure, the application method of this invention can also degrade organic matter (DOC) and volatile organic compounds (VOCs) in wastewater. The DOCs include acetic acid, benzoic acid, ethanol, isopropanol, and ethylene glycol; the VOCs include ethyl acetate, toluene, chloroform, trichloroethane, and ethylene diether.

[0044] Therefore, the above treatment methods can also be used for domestic or industrial wastewater containing similar pollutants.

[0045] The following detailed description of specific embodiments of the present invention, in conjunction with preferred embodiments, further illustrates the relevant details. When numerical ranges are given in the embodiments, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range, as well as any value between the two endpoints, may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by those skilled in the art. In addition to the specific methods, devices, and materials used in the embodiments, the present invention can be implemented using any prior art methods, devices, and materials similar to or equivalent to those described in the embodiments of the present invention, provided that those skilled in the art possess the prior art and the description of the present invention.

[0046] The PFOS-containing aqueous solutions used in Examples 1, 2, and 4 below were prepared by adding deionized water to PFOSK reagent, with a concentration of 4000–6000 ug / L; the PFOSK reagent was from Merck Sigma, and the PFOSK content was ≥99%.

[0047] Example 1

[0048] A method for enhancing the degradation of PFOS under subcritical hydrothermal conditions includes the following steps:

[0049] (1) An iron-based amorphous alloy was prepared by atomization melting, wherein the mass ratio of Fe:Si:B was 77:15:8. Its SEM characterization results are as follows: Figure 1 As shown on the left;

[0050] (1) Weigh 2.0g of iron-based amorphous alloy and place it in 50ml of 1M sodium bicarbonate solution (pH 10.0), then add 400ul of 500mg / L PHOSK solution and transfer it to a 100mL reaction vessel.

[0051] The reaction vessel was sealed and purged with nitrogen for 10 minutes. The stirrer speed was set to 300 rpm, and the temperature was raised to 325°C with a pressure of 12.04 MPa, which was maintained for 60 minutes. Afterward, it was allowed to cool naturally to room temperature in air. The solid and liquid phase products were separated to obtain the reacted iron-based amorphous alloy. The SEM characterization results are as follows: Figure 1 As shown, the residual PFOS content in the liquid phase product was analyzed.

[0052] (3) Investigate the effect of adding iron-based amorphous alloy on the removal of PFOS under subcritical hydrothermal conditions.

[0053] from Figure 1 It can be seen that the surface morphology of the material shows significant differences after the degradation process, with a clearly visible pit-like reaction area indicating an increase in surface active sites. From... Figure 2 It can be seen that Fe is present during the degradation process. 2+ and Fe3+ The proportions have changed; the introduction of iron-based amorphous alloys may help generate more active species. From Figure 3 It can be seen that there are no obvious peaks on the surface of the iron-based amorphous alloy before the reaction. After the reaction under pure hydrothermal conditions, the surface of the iron-based amorphous alloy shows peaks of organic fluorine carbon bonds and inorganic fluorine ions. Under alkaline hydrothermal conditions, only the peak of inorganic fluorine appears on the iron-based amorphous alloy. This also proves that the combination of alkaline hydrothermal and iron-based amorphous alloy enhances the PFOS degradation effect.

[0054] The results of the PFOS removal efficiency evaluation showed that, for a 4000 μg / L PFOS aqueous solution, compared with the pure hydrothermal degradation under the same conditions without the introduction of iron-based amorphous alloy + alkaline solution system, the PFOS removal rate increased from 35.16% to 85.50%, and the proportion of inorganic fluorine in the complete PFOS degradation products increased from 3.72% to 36.55%. Compared with the alkaline solution system hydrothermal degradation under the same conditions without the introduction of iron-based amorphous alloy, the PFOS removal rate increased from 61.14% to 85.50%, and the proportion of inorganic fluorine in the complete PFOS degradation products increased from 21.29% to 36.55%.

[0055] Example 2

[0056] A method for enhancing the degradation of PFOS under subcritical hydrothermal conditions includes the following steps:

[0057] (1) An iron-based amorphous alloy is produced by atomization process, wherein the mass ratio of Fe:Si:B is 77:15:8.

[0058] (2) Weigh 2.0 g of the iron-based amorphous alloy and place it in 50 ml of 1 M sodium carbonate solution (pH 11.8). Then add 600 μL of 500 mg / L PFOSK solution and transfer it to a 100 mL reaction vessel. Seal the reaction vessel and purge it with nitrogen for 12 minutes. Set the stirrer speed to 300 rpm, raise the temperature to 325 °C, and maintain the pressure at 12.04 MPa for 75 minutes. Then allow it to cool naturally to room temperature in air. Separate the solid and liquid phase products to obtain the reacted iron-based amorphous alloy. Analyze the remaining PFOS content in the liquid phase product.

[0059] (3) Investigate the effect of adding iron-based amorphous alloy on the removal of PFOS under subcritical hydrothermal conditions.

[0060] The results of the PFOS removal efficiency evaluation showed that, for a 6000 μg / L PFOS aqueous solution, compared with the pure hydrothermal degradation under the same conditions without the introduction of iron-based amorphous alloy + alkaline solution system, the PFOS removal rate increased from 35.16% to 81.25%, and the proportion of inorganic fluorine in the complete PFOS degradation products increased from 3.72% to 34.14%. Compared with the hydrothermal degradation under the same conditions without the introduction of iron-based amorphous alloy in the alkaline solution system, the PFOS removal rate increased from 69.57% to 81.25%, and the proportion of inorganic fluorine in the complete PFOS degradation products increased from 24.07% to 34.14%.

[0061] Example 3

[0062] A method for enhancing the degradation of PFOS under subcritical hydrothermal conditions includes the following steps:

[0063] (1) An iron-based amorphous alloy is produced by atomization process, wherein the mass ratio of Fe:Si:B is 77:15:8.

[0064] Wastewater samples were collected from a wastewater well at a fire station drill site in Zhejiang Province and diluted to serve as a fire-fighting water film-forming foam solution (PFOS concentration 1.44 g / L).

[0065] (2) Weigh 2.0 g of the iron-based amorphous alloy and place it in 50 ml of 1 M sodium hydroxide solution (pH 13.0). Then add 200 μL of fire-fighting water film-forming foam solution and transfer it to a 100 mL reaction vessel. Seal the reaction vessel and purge it with nitrogen for 15 minutes. Set the stirrer speed to 300 rpm, raise the temperature to 350 °C, and maintain the pressure at 16.52 MPa for 60 minutes. Then allow it to cool naturally to room temperature in air. Separate the solid and liquid phase products to obtain the reacted iron-based amorphous alloy. Analyze the remaining PFOS content in the liquid phase product.

[0066] (3) Investigate the effect of adding iron-based amorphous alloy on the removal of PFOS under subcritical hydrothermal conditions.

[0067] The results of the PFOS removal efficiency study showed that for the diluted fire-fighting water film-forming foam solution, the PFOS removal rate was 81.76% under alkaline hydrothermal conditions without the introduction of iron-based amorphous alloys, and increased to 94.19% under enhanced hydrothermal conditions with the introduction of iron-based amorphous alloys. The degradation of other PFASs in the fire-fighting water film-forming foam solution is shown in Table 1 below.

[0068] Table 1. Degradation of other PFASs in fire-fighting aqueous film-forming foam solution

[0069] Other PFASs Before reaction (μg / L) After alkaline hydrothermal reaction (μg / L) Removal rate (%) Enhanced hydrothermal treatment (μg / L) Removal rate (%) PFHpS 102.30 35.63 65.17 19.31 81.12 PFHxS 56.78 12.18 78.55 5.28 90.70 PFBA 34.25 8.74 74.48 1.38 95.97 PFPeA 18.62 2.52 86.47 1.15 93.82 PFOA 17.47 2.07 88.15 0.23 98.68 PFHpA 5.75 0.23 96.08 0.69 87.93

[0070] Example 4

[0071] A method for enhancing the degradation of PFOS under subcritical hydrothermal conditions includes the following steps:

[0072] (1) An iron-based amorphous alloy is produced by atomization process, wherein the mass ratio of Fe:Si:B is 77:15:8.

[0073] (2) Two operating conditions were set up. In the first condition, 2.0 g of iron-based amorphous alloy was weighed and placed in 50 ml of 1 M sodium bicarbonate solution (pH 10.0), and then 600 μL of 500 mg / L PFOSK solution was added. The solution was transferred to a 100 mL reactor, the reactor was sealed, and the reactor was purged with nitrogen for 10 minutes. The stirrer speed was set to 300 rpm, the temperature was raised to 330 °C, the pressure was 12.85 MPa, and the temperature was maintained for 60 minutes. The residual PFOS content in the liquid phase product was analyzed. In the second condition, 2.0 g of zero-valent iron (particle size 500 nm) was weighed and added, while other conditions remained unchanged.

[0074] (3) Comparison of the hydrothermal degradation effect of alkaline solution system with iron-based amorphous alloy / zero-valent iron under the same conditions.

[0075] The results of the PFOS removal efficiency study showed that for diluted fire-fighting water film-forming foam solution, the PFOS removal rate was 72.05% under hydrothermal conditions with the introduction of zero-valent iron, and 83.42% under hydrothermal conditions with the introduction of iron-based amorphous alloy.

[0076] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A method for enhancing the degradation of PFOS under subcritical hydrothermal conditions, characterized in that, The method involves adding an iron-based amorphous alloy and an alkaline solution to wastewater containing PFOS, followed by a subcritical hydrothermal reaction to degrade PFOS. In the reaction system, the mass ratio of PFOS: iron-based amorphous alloy: water is 2~3:2000:50000, and the molar ratio of PFOS to alkali is 2~3:25000. During the subcritical hydrothermal reaction, the reaction temperature was controlled at 325–350℃, the pressure at 12.04–16.52 MPa, and the reaction time at 60–90 min. During the reaction, the stirring condition was maintained at 300 rpm, and the pH value of the subcritical hydrothermal reaction system was controlled at 10.0–13.

0. The iron-based amorphous alloy is a powdered metal microparticle obtained by atomization process, with a particle size range of 50-100 μm; the composition of the iron-based amorphous alloy is iron as the matrix and doped with silicon and boron, wherein the mass ratio of Fe:Si:B is 77:15:8; the alkaline solution is any one of sodium bicarbonate, sodium carbonate, and sodium hydroxide aqueous solution.

2. The method according to claim 1, characterized in that, After feeding, purge with flowing nitrogen for 10-15 minutes before proceeding with the reaction.

3. The method according to claim 1, characterized in that, The concentration of the alkaline solution is 1.0 M.

4. The method according to claim 1, characterized in that, The wastewater is wastewater contaminated by fire-fighting water film-forming foam or sewage from fire training grounds, or domestic sewage or industrial wastewater containing PFASs.

5. The method according to claim 4, characterized in that, The fire-fighting water-based film-forming foam is formed by a foam extinguishing agent based on fluorocarbon surfactants on the surface of hydrocarbon liquids.

6. The method according to claim 4, characterized in that, The wastewater further includes perfluorosulfonic acid and perfluorocarboxylic acid with carbon chain lengths of 4 to 10, which are at least one of PFOA, PFBS, PFHpS, PFHxS, PFBA, PFHpA or PFHxA; or, it further includes wastewater organic matter DOC or volatile organic compounds VOCs, specifically at least one of acetic acid, benzoic acid, ethanol, isopropanol, ethylene glycol, ethyl acetate, toluene, chloroform, trichloroethane or ethylene diether.

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