An electrocatalytic oxidation device for treating saline industrial organic wastewater and its operating method

Abstract

This invention relates to the field of industrial wastewater treatment technology, and discloses an electrocatalytic oxidation device and its operating method for treating saline industrial organic wastewater. Wastewater enters the reaction chamber through the bottom inlet, is forced through the anode channels, and undergoes an electrochemical oxidation reaction on the anode surface to convert chloride ions into hypochlorous acid. A vacuum ultraviolet light source performs in-situ photolysis of water molecules and hypochlorous acid, exciting various active species, including strongly reducing hydrated electrons, strongly oxidizing hydroxyl radicals, and chloride radicals. This device, through the construction of a reduction-oxidation system, can efficiently degrade various pollutants with both electron-rich and electron-deficient characteristics. This invention utilizes the synergistic coupling of electrochemical generation and photochemical conversion to convert high-concentration chloride ions into active precursors, effectively overcoming the bottlenecks of low degradation efficiency and poor selectivity in traditional technologies for high-salt and complex water quality, and significantly improving the system's mineralization efficiency and energy utilization rate.

Description

Technical Field

[0001] This invention relates to the field of industrial wastewater treatment technology, specifically to an electrocatalytic oxidation device and its operating method for treating saline industrial organic wastewater. Background Technology

[0002] High-salinity industrial organic wastewater from pesticide, pharmaceutical intermediate, and fine chemical industries contains high concentrations of chloride ions and complex organic pollutants, posing a significant challenge to traditional advanced oxidation technologies. Current treatment technologies primarily rely on generating highly oxidizing hydroxyl radicals in the reaction system using precursors such as ozone and hydrogen peroxide to degrade pollutants. However, high concentrations of chloride ions rapidly capture and quench hydroxyl radicals, converting them into weaker secondary chloride radicals, significantly reducing the ability to deeply mineralize organic matter. Secondary chloride radicals generally tend to attack electron-rich organic pollutants, such as phenols and amines, through addition substitution reactions, but their degradation rate against nitrobenzenes or polyhalogenated hydrocarbons is extremely low. Hydroxyl radicals, on the other hand, are non-selective radicals and can effectively mineralize both electron-rich and electron-deficient pollutants. However, the rapid conversion of hydroxyl radicals to chloride radicals in high-salinity wastewater severely inhibits the mineralization efficiency of the oxidation reaction for organic pollutants.

[0003] Electrochemical advanced oxidation technology is considered a promising alternative for high-salinity wastewater. It utilizes the conductivity of the wastewater to directly convert chloride ions into active chlorine, such as hypochlorous acid, through anodic oxidation. However, hypochlorous acid has limited oxidizing power, degrading pollutants only through addition-substitution reactions and failing to achieve complete mineralization of recalcitrant organic matter. Therefore, electrochemical technology often requires a large energy input when treating high-chloride organic wastewater, and electron-deficient organic pollutants (such as nitrobenzene and halogenated hydrocarbons) cannot be effectively removed. Summary of the Invention

[0004] In view of this, the present invention provides an electrocatalytic oxidation device and its operating method for treating saline industrial organic wastewater, so as to solve the problems mentioned in the background art.

[0005] In a first aspect, the present invention provides an electrocatalytic oxidation device for treating saline industrial organic wastewater, comprising:

[0006] The reactor shell has a reaction chamber inside;

[0007] An anode is disposed within the reaction chamber. The anode has a cylindrical structure, and the cylinder wall of the anode has a porous structure to allow wastewater to pass through.

[0008] The cathode is configured as a cylindrical structure, and the cathodes are coaxially arranged at intervals on the outer periphery of the anode. The cathodes are integrally fixed on the inner wall of the reactor shell; the anode and the cathode are electrically connected to a power source.

[0009] A vacuum ultraviolet light source is integrally fixed on the central axis of the anode;

[0010] An inlet and an outlet are provided on the reactor shell, the inlet being connected to the bottom of the reaction chamber and the outlet being connected to the top of the reaction chamber;

[0011] Wastewater enters the reaction chamber through the inlet to undergo an electrochemical oxidation reaction on the anode surface to generate hypochlorous acid. The water molecules and hypochlorous acid in the wastewater are then photolyzed in situ by the vacuum ultraviolet light source to generate hydrated electrons with strong reducing properties, as well as oxidizing free radicals such as hydroxyl radicals, chlorine radicals, and hypochlorous acid radicals. The wastewater is then discharged through the outlet.

[0012] Beneficial Effects: The device integrates the cylindrical anode with the central vacuum ultraviolet light source, and the reactor shell with the coaxial external cylindrical cathode, forming a forced-flow photoelectrocatalytic reaction chamber. Wastewater enters from the bottom and must pass through the microporous channels of the anode before flowing out, ensuring sufficient contact between the wastewater and the active surface of the electrode. This significantly enhances the electrical contact efficiency between high-concentration chloride ions and the anode, thereby efficiently electrochemically oxidizing chloride ions into hypochlorous acid. Placing the vacuum ultraviolet light source on the central axis of the anode enables in-situ photolysis of the newly generated hypochlorous acid. The anode region combines the electrochemical reaction zone and the photolysis reaction zone, resulting in higher mass transfer efficiency and faster photolysis. This avoids ineffective decomposition and loss of hypochlorous acid during diffusion into the bulk solution, allowing it to be rapidly and directionally converted into highly reactive oxides such as hydroxyl radicals, chlorine radicals, and hypochlorous acid radicals. Furthermore, the vacuum ultraviolet light can photolyze water molecules to generate hydrated electrons, effectively reducing water to dehalogenate halogenated organic pollutants and significantly enhancing the degradation efficiency of electron-deficient pollutants by species such as hydroxyl radicals. This synergistic coupling design of electrochemical generation and photochemical conversion overcomes the defect in traditional technology where single hydroxyl radicals are easily quenched by high-salt ions. It transforms high-concentration chloride salts, which originally had an inhibitory effect, into oxidant precursors, and converts the inhibitory state into the driving state, thereby improving the degradation efficiency of organic pollutants in high-salt wastewater and the energy utilization efficiency of the system.

[0013] In some embodiments, the cylinder wall of the anode is configured as a foamed metal substrate, and the surface of the foamed metal substrate is loaded with a metal oxide catalyst layer.

[0014] Beneficial effects: The anode adopts a foamed metal substrate and is loaded with a metal oxide catalyst layer; the foamed metal has a three-dimensional interconnected porous framework structure with a good specific surface area, which can provide a large number of active sites for electrochemical reactions, improving the current efficiency and chloride ion oxidation rate per unit reactor volume; the surface-loaded metal oxide catalyst layer can specifically reduce the overpotential of the chloride evolution reaction, improve the selectivity for chloride ion oxidation, and suppress the oxygen evolution side reaction, thereby resulting in a higher concentration of hypochlorous acid and lower energy consumption, which helps to ensure the stable operation of the reactor in a long-term high-salt and strong oxidation environment.

[0015] In some embodiments, the foamed metal substrate is configured as foamed titanium; the metal oxide catalyst layer comprises at least one oxide selected from ruthenium, iridium, tantalum, and lead oxides; the pore size of the metal oxide catalyst layer is between 50 μm and 1000 μm; and / or;

[0016] The aperture of the anode is between 10mm and 50mm.

[0017] Beneficial effects: Using foamed titanium as the substrate, its excellent corrosion resistance and mechanical strength can withstand the erosion of high-salt industrial wastewater, extending the service life of the electrode. The catalyst layer uses oxides of ruthenium, iridium, tantalum, and lead, all of which have excellent electrocatalytic chlorine evolution activity and electrochemical stability, enabling efficient and continuous conversion of chloride ions into hypochlorous acid. The pore size of the foamed titanium substrate is between 10mm and 50mm, ensuring both smooth wastewater flow and low pressure drop, while providing sufficient electrode surface area. The pore size of the catalyst layer is between 50um and 1000um, ensuring high dispersion and effective utilization of the catalytically active components. This avoids the problems of increased mass transfer resistance due to excessively small pore size or insufficient active sites due to excessively large pore size, achieving an optimized balance between mass transfer efficiency and reaction kinetics.

[0018] In some embodiments, the cathode is a cylinder made of titanium or stainless steel; and / or;

[0019] The distance between the anode and the cathode is between 0.5cm and 2cm.

[0020] Beneficial effects: Using titanium or stainless steel as the cylindrical cathode provides excellent resistance to electrolyte corrosion, making it suitable for high-salt wastewater treatment environments. Limiting the distance between the anode and cathode to 0.5cm-2cm ensures safe operation and a stable flow field while minimizing the ohmic voltage drop of the electrolyte, thus improving current and energy efficiency and further reducing treatment costs.

[0021] In some embodiments, the emission spectrum of the vacuum ultraviolet light source includes ultraviolet light with wavelengths below 180 nm; the irradiation intensity of the vacuum ultraviolet light source is between 5 W and 20 W.

[0022] Beneficial effects: The energy of ultraviolet photons emitted at wavelengths below 180nm is higher than the bond energy of the O-Cl bond in hypochlorous acid molecules, effectively breaking this chemical bond and promoting its efficient photolysis into free radicals such as hydroxyl radicals and chlorine radicals. Furthermore, the vacuum ultraviolet light source can hydrolyze water molecules, simultaneously generating hydrated electrons and hydroxyl radicals. The hydrated electrons can effectively reduce and dechlorinate intermediate chlorinated pollutants. Setting the irradiation intensity of the vacuum ultraviolet light source between 5W and 20W ensures efficient photochemical conversion while matching the rate with the electrochemical process and controlling overall energy consumption.

[0023] In some embodiments, the anode is provided with a particulate catalyst suitable for fluidization, wherein the particulate catalyst is an iron-oxygen complex supported on a carrier.

[0024] Beneficial Effects: A fluidizable granular catalyst, with an iron-oxygen complex as its active component, is added inside the anode. Under the action of circulating water, the granular catalyst is fluidized, ensuring sufficient contact with wastewater and hypochlorous acid, avoiding mass transfer limitations. As a heterogeneous catalyst, the iron-oxygen complex specifically captures hypochlorous acid and undergoes an electron transfer reaction at its coordination center, thereby generating high-valence iron oxides in situ. This oxidation pathway runs parallel to the free radical oxidation pathway, is unaffected by chloride ion interference, and has stronger selectivity, enabling deep degradation of organic pollutants. This scheme generates high-valence iron on the catalyst surface, which, together with other free radicals, forms various active oxide species. Furthermore, this oxidation pathway consumes hypochlorous acid, reducing the formation of residual chlorine and toxic chlorinated byproducts, further improving the safety of the treated wastewater. By placing the catalyst inside the anode, this scheme avoids the traditional method of placing the catalyst between the anode and cathode, mitigating the potential risk of short-circuiting.

[0025] In some embodiments, the iron-oxygen complex is configured as porphyrin, tetraanionic tetraamide macrocyclic ligand (TAML), pyridine carboxylic acid (PICA), or N,N,N'-tris(2-pyridinemethyl)-ethylenediamine-N'-acetic acid (tpena); the support is columnar, granular, or spherical activated carbon.

[0026] Beneficial effects: The iron-oxygen complexes are specifically set as porphyrins, TAML, PICA, or tpena. These ligands have stable macrocyclic structures that can firmly anchor the iron center and regulate its redox potential, making them more inclined to generate highly active, long-lived Fe(IV) / Fe(V) species when reacting with hypochlorous acid. Furthermore, they are not easily oxidized and destroyed, resulting in good catalyst stability. The porous structure and high specific surface area of ​​the activated carbon support not only provide abundant loading sites but also enrich pollutants and hypochlorous acid through adsorption, increasing the local reaction concentration. Its good conductivity also promotes electron transfer between the catalyst particles and the anode.

[0027] In some embodiments, the electrocatalytic oxidation device further includes at least one porous partition, which is horizontally disposed within the anode and adapted to divide the anode, with the particulate catalyst evenly distributed on the upper and lower sides of the porous partition.

[0028] Beneficial effects: The porous baffle can divide the anode in parallel, preventing the fluidized catalyst from agglomerating or stratifying due to density differences or hydraulic impact, ensuring that the catalyst is evenly distributed throughout the anode area, maintaining fluidization stability, avoiding local reaction dead zones, and ensuring the consistency of overall degradation effect.

[0029] In some embodiments, the electrocatalytic oxidation device further includes a circulation pump 10, with two outlets. The inlet of the circulation pump 10 is connected to one of the outlets via a flow pipe, and the outlet of the circulation pump 10 is connected to the reaction chamber and is positioned towards the bottom of the anode region where the anode is located.

[0030] Beneficial effects: The internal circulation design of the device, achieved through the circulation pump 10, involves partially recirculating the treated effluent to the bottom of the reaction chamber and pumping it towards the bottom of the anode. This continuous fluidization of the catalyst enhances solid-liquid mass transfer and mixing, and allows incompletely degraded pollutants to circulate and react within the system, extending their effective residence time and thus improving overall degradation capacity and removal rate. Furthermore, the internal circulation design maintains a high concentration of oxidants, such as hypochlorous acid and free radicals, in the anode zone, promoting the oxidative degradation of pollutants. This design is suitable for treating high-concentration or recalcitrant organic wastewater, increasing the device's maximum treatment load.

[0031] In some embodiments, the electrocatalytic oxidation device further includes a rectifier plate disposed at the bottom of the anode, the rectifier plate having evenly distributed vertical channels.

[0032] Beneficial effects: Adding a rectifier plate with uniformly distributed vertical channels at the bottom of the anode hydraulically distributes the wastewater entering from the bottom, eliminating influent jets and dead zones. This ensures that the water flows vertically upward through the anode at a uniform and stable velocity, preventing catalyst fluidization instability caused by uneven flow velocity. The uniform hydraulic conditions not only guarantee consistent contact time between pollutants and chloride ions with the electrodes and catalyst, improving the controllability and reliability of the reaction, but also reduce the scouring and wear of the electrodes and catalyst by the water flow, thus extending the service life of the device.

[0033] Secondly, the present invention also provides a method for operating an electrocatalytic oxidation device for treating saline industrial organic wastewater, comprising the following steps:

[0034] The saline industrial organic wastewater is introduced into the reaction chamber through the inlet;

[0035] Turn on the power supply connected to the anode and cathode, and turn on the vacuum ultraviolet light source;

[0036] Wastewater is controlled to pass through the micropores of the anode and react on the anode surface, so that chloride ions in the wastewater are converted into hypochlorous acid. Water molecules and hypochlorous acid are photolyzed in situ by a vacuum ultraviolet light source into active species including hydrated electrons, hydroxyl radicals, chloride radicals and hypochlorous acid radicals.

[0037] The treated wastewater is discharged through the outlet.

[0038] Beneficial Effects: This working method achieves the generation and synergistic effect of multiple highly reactive oxide species through the synergistic process of forced flow, electrochemical oxidation, and in-situ photolysis. Specifically, the flow structure of the anode first forces chloride ions in the wastewater to be efficiently converted into hypochlorous acid, which is then immediately photolyzed in-situ into hydroxyl radicals and chloride radicals by built-in ultraviolet light. By constructing a reduction-oxidation system, it can efficiently degrade a variety of pollutants with both electron-rich and electron-deficient characteristics. This invention utilizes the synergistic coupling of electrochemical generation and photochemical conversion to convert high-concentration chloride ions into active precursors, effectively overcoming the bottlenecks of low degradation efficiency and poor selectivity in traditional technologies for high-salinity and complex water quality, and significantly improving the system's mineralization efficiency and energy utilization rate.

[0039] Finally, the residual hypochlorous acid is converted into Fe(IV) / Fe(V) high-valence oxides through a fluidized iron-oxygen complex catalyst. This method utilizes the high concentration of chloride ions, which is unfavorable in traditional technologies, as an oxidant precursor. The high-valence metal oxidation pathway consumes hypochlorous acid, effectively reducing residual chlorine and toxic chlorinated byproducts in the effluent. It fundamentally solves the technical bottleneck of single hydroxyl radicals being quenched and ineffective in high-salt environments, achieving the technical effect of improving pollutant degradation efficiency and significantly reducing toxic chlorinated byproducts under the same energy consumption. This provides a green, efficient, and economical treatment method for high-salt industrial organic wastewater. Attached Figure Description

[0040] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0041] Figure 1 This is a schematic diagram of the electrocatalytic oxidation device according to an embodiment of the present invention;

[0042] Figure 2 This is a schematic diagram of the operation of the electrocatalytic oxidation device according to an embodiment of the present invention;

[0043] Figure 3 This is a top-view structural schematic diagram of the electrocatalytic oxidation device according to an embodiment of the present invention;

[0044] Figure 4 This is a schematic diagram of a conventional flow-through electrode coupled with a UV lamp without a catalyst.

[0045] Figure 5 This is a schematic diagram of a conventional flow-through electrode coupled with a UV lamp loaded with a catalyst.

[0046] Explanation of reference numerals in the attached figures:

[0047] 1. Reaction unit; 2. Anode; 3. Reactor shell; 4. Vacuum ultraviolet light source; 5. Cathode; 6. Power supply; 7. Outlet; 8. Inlet; 9. Power interface; 10. Circulation pump; 11. Rectifier plate; 12. Catalyst; 13. Flow pipe; 14. Porous partition. Detailed Implementation

[0048] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0049] This invention aims to treat wastewater containing various pollutants with electron-rich characteristics (such as phenol) and electron-deficient characteristics (such as nitrobenzene and polyhalogenated hydrocarbons). This type of wastewater is typically industrial wastewater generated by the pesticide, pharmaceutical, and fine chemical industries. Specifically, this invention transforms chloride ions in high-salinity wastewater from an inhibitory factor into a reactive resource. Through the synergistic combination of electrochemistry, photochemistry, and heterogeneous catalysis, a reduction-oxidation parallel degradation system is formed, achieving highly efficient removal of both electron-rich and electron-deficient pollutants.

[0050] The following is combined Figures 1 to 3 The following describes embodiments of the present invention.

[0051] According to embodiments of the present invention, in one aspect, this embodiment provides an electrocatalytic oxidation device for treating saline industrial organic wastewater, such as... Figures 1 to 3 As shown, its core lies in the integrated flow-through photoelectrocatalytic reaction unit 1. Specifically, the reaction unit 1 includes a reactor shell 3, an anode 2, a cathode 5, and a vacuum ultraviolet light source 4. The reactor shell 3 has an internal reaction chamber, where the anode 2 is located. The vacuum ultraviolet light source 4 is integrally fixed on the central axis of the anode 2. The cathode 5 is integrally fixed to the inner wall of the reactor shell 3, and the anode 2 and cathode 5 are electrically connected to a power source 6. The reactor shell 3 has two power interfaces 9, which are connected to the anode 2 and cathode 5 respectively. The anode 2 has a cylindrical structure with a porous wall to allow wastewater to pass through. The cathode 5 has a cylindrical structure and is coaxially spaced around the outer periphery of the anode 2.

[0052] The reactor shell 3 is provided with an inlet 8 and an outlet 7. The inlet 8 is connected to the bottom of the reaction chamber, and the outlet 7 is connected to the top of the reaction chamber. After the wastewater enters from the inlet 8, it flows from bottom to top in the reaction chamber and is finally discharged from the outlet 7.

[0053] In this embodiment, wastewater enters the reaction chamber through inlet 8 to undergo an electrochemical oxidation reaction on the surface of anode 2 to generate hypochlorous acid. Hypochlorous acid is then photolyzed in situ by vacuum ultraviolet light source 4 to generate oxidizing free radicals, including hydroxyl free radicals, chlorine free radicals, and hypochlorous acid free radicals, which are then discharged with the wastewater through outlet 7.

[0054] The device integrates the cylindrical anode 2 with the central vacuum ultraviolet light source 4, and the reactor shell 3 with the coaxial external cylindrical cathode 5, forming a forced-flow photoelectrocatalytic reaction chamber. Wastewater enters from the bottom and must pass through the microporous channels of the anode 2 before flowing out, ensuring sufficient contact between the wastewater and the active surface of the electrode. This greatly enhances the electrical contact efficiency between high-concentration chloride ions and the anode, thereby efficiently electrochemically oxidizing chloride ions into hypochlorous acid. The vacuum ultraviolet light source 4 is positioned on the central axis of the anode 2 to achieve in-situ photolysis of the newly generated hypochlorous acid. The anode region combines the electrochemical reaction zone and the photolysis reaction zone, resulting in higher mass transfer efficiency and faster photolysis. This avoids ineffective decomposition and loss of hypochlorous acid during diffusion into the bulk solution, allowing it to be rapidly and directionally converted into highly reactive oxides such as hydroxyl radicals, chlorine radicals, and hypochlorous acid radicals. This synergistic coupling design of electrochemical generation and photochemical conversion overcomes the defect in traditional technology where single hydroxyl radicals are easily quenched by high-salt ions. It transforms high-concentration chloride salts, which originally had an inhibitory effect, into oxidant precursors, and converts the inhibitory state into the driving state, thereby improving the degradation efficiency of organic pollutants in high-salt wastewater and the energy utilization efficiency of the system.

[0055] The electrocatalytic oxidation device provided in this embodiment achieves a direct combination of the electrochemical and photolysis zones, resulting in high mass transfer efficiency, fast reaction kinetics, improved energy utilization, and a compact structure with a small footprint. It should be noted that the spatial integration design of this invention aims to achieve efficient energy and matter transfer and conversion within a minimized reaction volume. The through-flow structure forces wastewater to pass through the channels of the anode 2, rather than simply flowing over its surface, increasing the mass transfer area and reaction interface. The built-in vacuum ultraviolet light source 4 can directly and efficiently irradiate the hypochlorous acid just generated near the anode surface, achieving rapid photolysis, shortening the diffusion path of the oxidant precursor, and reducing side reactions.

[0056] In a specific embodiment, the cylinder wall of anode 2 is configured as a foamed metal substrate, and the surface of the foamed metal substrate is loaded with a metal oxide catalyst layer. Anode 2 uses a foamed metal substrate and is loaded with a metal oxide catalyst layer; the foamed metal has a three-dimensional interconnected porous framework structure with a good specific surface area, which can provide a large number of active sites for electrochemical reactions, improving the current efficiency and chloride ion oxidation rate per unit reactor volume; the surface-loaded metal oxide catalyst layer can specifically reduce the overpotential of the chloride evolution reaction, improve the selectivity for chloride ion oxidation, and suppress the oxygen evolution side reaction, thereby resulting in a higher concentration of hypochlorous acid and lower energy consumption, which helps to ensure the stable operation of the reactor in a long-term high-salt and strong oxidation environment.

[0057] In a preferred embodiment, the foamed metal substrate is set as foamed titanium; the metal oxide catalyst layer includes at least one oxide selected from ruthenium, iridium, tantalum, and lead oxides; the pore size of the metal oxide catalyst layer is between 50 μm and 1000 μm. Using foamed titanium as the substrate, its excellent corrosion resistance and mechanical strength can withstand the erosion of high-salt industrial wastewater, extending the electrode's service life. The catalyst layer uses oxides of ruthenium, iridium, tantalum, and lead, all of which possess excellent electrocatalytic chlorine evolution activity and electrochemical stability, enabling efficient and continuous conversion of chloride ions into hypochlorous acid, and achieving efficient hypochlorous acid generation with low energy consumption. The pore size of the catalyst layer between 50 μm and 1000 μm ensures high dispersion and effective utilization of the catalytically active components, avoiding the problems of increased mass transfer resistance due to excessively small pore size or insufficient active sites due to excessively large pore size, thus achieving an optimized balance between mass transfer efficiency and reaction kinetics.

[0058] In a specific embodiment, the pore size of anode 2 is between 10mm and 50mm. The pore size of the foamed titanium substrate is between 10mm and 50mm, which ensures both smooth wastewater flow and low pressure drop, while also providing sufficient electrode surface area.

[0059] In a specific embodiment, the cathode 5 is a cylinder made of titanium or stainless steel. Using titanium or stainless steel as the cylindrical cathode 5 provides excellent resistance to electrolyte corrosion, making it suitable for high-salt wastewater treatment environments.

[0060] In a specific embodiment, the distance between the anode and cathode 5 is between 0.5cm and 2cm. This ensures safe operation and a stable flow field while minimizing the ohmic voltage drop of the electrolyte, which helps to improve current efficiency and energy efficiency, thereby further reducing processing costs.

[0061] In a specific embodiment, the emission spectrum of the vacuum ultraviolet light source 4 includes ultraviolet light with wavelengths below 180 nm; the irradiation intensity of the vacuum ultraviolet light source 4 is between 5 W and 20 W. The energy of ultraviolet photons with emission wavelengths below 180 nm is higher than the bond energy of the O-Cl bond in the hypochlorous acid molecule (approximately ~209 kJ / mol), which can effectively break this chemical bond, promoting its efficient photolysis into free radicals such as hydroxyl radicals and chlorine radicals. Setting the irradiation intensity of the vacuum ultraviolet light source 4 between 5 W and 20 W ensures efficient photochemical conversion while matching the rate with the electrochemical process and controlling the overall energy consumption. If the intensity is too low (<5 W), the photolysis rate is slow and the hypochlorous acid conversion rate is low; if the intensity is too high (>20 W), the energy consumption increases significantly and may trigger unnecessary side reactions. The ultraviolet lamps are arranged along the central axis of the anode to ensure uniform light intensity distribution within the anode region, providing sufficient irradiation to the hypochlorous acid-containing wastewater flowing through it.

[0062] In a further embodiment, such as Figure 1 and Figure 2 As shown, a fluidizable particulate catalyst 12 is disposed within the anode 2. The particulate catalyst 12 is an iron-oxygen complex supported on a carrier. The addition of the fluidizable particulate catalyst 12 inside the anode 2, consisting of a carrier and an active component, with the active component being an iron-oxygen complex, allows the particulate catalyst 12 to be fluidized under the action of circulating water, ensuring sufficient contact with wastewater and hypochlorous acid and avoiding mass transfer limitations. As a heterogeneous catalyst 12, the iron-oxygen complex specifically captures hypochlorous acid and undergoes an electron transfer reaction at its coordination center, thereby generating high-valence iron oxides in situ. This oxidation pathway runs parallel to the free radical oxidation pathway, is unaffected by chloride ions, and has stronger selectivity, enabling deep degradation of organic pollutants. This scheme generates high-valence iron on the surface of the catalyst 12, which, together with other free radicals, forms various active oxide species.

[0063] Furthermore, this oxidation pathway consumes hypochlorous acid, reducing the formation of residual chlorine and toxic chlorinated byproducts, thus further improving the safety of the treated wastewater. This scheme avoids the risk of short-circuiting by placing catalyst 12 inside the anode 2, thus avoiding the traditional practice of placing the catalyst between the anode and cathode.

[0064] In this embodiment, through the synergistic effect of electrochemistry, photochemistry and interfacial catalysis, organic pollutants can be deeply degraded, while avoiding the problems of oxidative free radical quenching into chlorine-active species and perchloric acid attacking pollutants to generate chlorinated byproducts.

[0065] In the actual operation, wastewater enters from the bottom and is forced upwards through the channels of anode 2. During this flow, chloride ions are oxidized on the anode surface, and the resulting hypochlorous acid immediately enters the ultraviolet irradiation zone for decomposition. The external design of cathode 5 avoids direct contact with the internal catalyst 12 system, reducing the risk of short circuits.

[0066] The iron-oxygen complex is configured as follows: porphyrin, tetraanionic tetraamide macrocyclic ligand (TAML), pyridinecarboxylic acid (PICA), or N,N,N'-tris(2-pyridinemethyl)-ethylenediamine-N'-acetic acid (tpena). These ligands possess stable macrocyclic structures, which can firmly anchor the iron center and regulate its redox potential, making it more prone to generating highly active, long-lived Fe(IV) / Fe(V) species when reacting with hypochlorous acid. Furthermore, these ligands are not easily oxidized, resulting in good catalyst stability. The porous structure and high specific surface area of ​​the activated carbon support not only provide abundant loading sites but also enrich pollutants and hypochlorous acid through adsorption, increasing the local reaction concentration. Its good conductivity also promotes electron transfer between the catalyst 12 particles and the anode.

[0067] For the preparation of supported iron-oxygen complex catalysts, a direct adsorption method can be used. Taking Fe-TAML as an example, to enhance the hydrophobic interaction between catalyst 12 and the carbon support and prevent its loss in the aqueous phase, catalyst 12 is first modified to be hydrophobic. The original Fe-TAML sodium salt is dissolved in deionized water, and an excess of tetrabutylammonium bromide aqueous solution is added to carry out an ion exchange reaction. Extraction with dichloromethane and rotary evaporation drying are performed to obtain hydrophobic tetrabutylammonium salt Fe-TAML. Next, the modified Fe-TAML is dissolved in 20 mL of methanol to prepare a precursor solution, followed by the addition of 0.5 g of activated carbon. The mixture is continuously shaken at room temperature for 24 hours to ensure that Fe-TAML molecules are fully diffused and saturated adsorbed on the surface sites of the carbon material. After the reaction, the mixture is centrifuged, and the resulting solid is washed twice with 20 mL of deionized water until the supernatant is clear to remove unbound free catalyst. Finally, it is dried in a 60°C oven to obtain the carbon-supported Fe-TAML solid catalyst.

[0068] The optimal loading of Fe-TAML is around 100 μM, while the optimal loading of HClO produced by the reaction is within the range of 1 mM.

[0069] The following is a comparison of how high-priced iron can reduce toxicity:

[0070] Salty raw water containing high concentrations of phenol exhibits extremely high biotoxicity. After contact with luminescent bacteria, the luminescence intensity rapidly decreases, with a relative luminescence inhibition rate as high as 85%-90%, which is classified as highly toxic.

[0071] For the HClO-only treatment group, although the addition of HClO alone partially removed the parent pollutants, the biotoxicity of the effluent was not significantly reduced, and the luminescence inhibition rate remained at 75%-80%. This is attributed to the electrophilic substitution reaction between HClO and organic matter in the absence of a catalyst, generating chlorinated intermediates (such as chlorophenols and chloronitrobenzenes) with toxicity even higher than the parent pollutants.

[0072] For the Fe-TAML / HClO treatment group, the biotoxicity of the effluent decreased significantly after the introduction of the Fe-TAML catalyst to react with HClO. The luminescent bacteria survived well in the treated water samples, and the relative luminescence inhibition rate dropped to 15%-20% (generally considered non-toxic or low-toxic).

[0073] The high-valence metal oxidation pathway in this embodiment consumes hypochlorous acid, effectively reducing the risk of residual chlorine in the effluent and the formation of toxic chlorinated byproducts such as chloroform and haloacetic acid.

[0074] In a specific embodiment, the electrocatalytic oxidation device further includes one or more porous partitions 14, such as... Figure 1 and Figure 2As shown, a porous partition 14 is horizontally arranged inside the anode 2. The porous partition 14 is suitable for dividing the anode 2, and the particulate catalyst 12 is evenly distributed on the upper and lower sides of the porous partition 14. The arrangement of the porous partition 14 can divide the anode in parallel, preventing the fluidized catalyst 12 from agglomerating or stratifying due to density differences or hydraulic impact, ensuring that the catalyst 12 is evenly distributed throughout the anode area, maintaining fluidization stability, avoiding local reaction dead zones, and ensuring the consistency of the overall degradation effect.

[0075] Wastewater flows upward after being evenly distributed by the rectifier plate 11, which promotes the fluidization of the catalyst 12 particles. The pores on the porous baffle plate 14 allow water flow and catalyst 12 to pass through, but also serve to block and redistribute them; it ensures the stability of the flow field within the reaction unit 1 and the uniformity of the catalyst 12 distribution, improves the controllability, reliability and consistency of the overall degradation effect of the reaction, and helps to reduce local scouring and wear.

[0076] In specific embodiments, such as Figure 1 and Figure 2 As shown, the electrocatalytic oxidation device also includes a circulation pump 10, and two outlets 7 are provided. The inlet end of the circulation pump 10 is connected to one of the outlets 7 through a flow pipe 13. The outlet end of the circulation pump 10 is connected to the reaction chamber and is positioned towards the bottom of the anode area where the anode 2 is located.

[0077] The device employs an internal circulation design via a circulating pump 10. Specifically, a portion of the treated effluent is recirculated to the bottom of the reaction chamber and pumped towards the bottom of the anode 2, thereby achieving continuous fluidization of the catalyst 12. This enhances solid-liquid mass transfer and mixing, and allows incompletely degraded pollutants to circulate and react within the system, extending their effective residence time and thus improving overall degradation capacity and removal rate. Furthermore, the internal circulation design maintains a high concentration of oxidants, such as hypochlorous acid and free radicals, in the anode zone, promoting the oxidative degradation of pollutants. This design is suitable for treating high-concentration or recalcitrant organic wastewater, increasing the device's maximum treatment load.

[0078] In a further embodiment, such as Figure 2 As shown, the electrocatalytic oxidation device also includes a rectifier plate 11, which is disposed at the bottom of the anode 2 and has evenly distributed vertical channels.

[0079] A flow rectifier plate 11 with uniformly distributed vertical channels is added to the bottom of anode 2 to hydraulically distribute the wastewater entering from the bottom, eliminating inlet jets and dead zones, and ensuring that the water flows vertically upward through anode 2 at a uniform and stable velocity, avoiding fluidization instability of catalyst 12 due to uneven flow velocity. The uniformly distributed hydraulic conditions not only ensure that the contact time between pollutants and chloride ions and electrodes and catalyst 12 is consistent, improving the controllability and reliability of the reaction, but also reduce the scouring and wear of the electrodes and catalyst 12 by the water flow, which helps to extend the service life of the device.

[0080] The working principle of this device is as follows: Wastewater enters the bottom of the reaction chamber through inlet 8 and is forced through the porous channels of anode 2 under pressure. During this process, chloride ions in the wastewater undergo an electrochemical oxidation reaction on the surface of anode 2 to generate hypochlorous acid. Subsequently, vacuum ultraviolet light source 4 performs in-situ photolysis on water molecules and the newly generated hypochlorous acid to generate hydrated electrons (e.g., electrons). aq - ), hydroxyl radicals ( • OH), chlorine free radicals (Cl) • ) and hypochlorous acid radical (ClO) • The active species, including those mentioned above, work together to efficiently degrade organic pollutants. The treated wastewater is then discharged through outlet 7.

[0081] According to an embodiment of the present invention, in another aspect, a method for operating an electrocatalytic oxidation device for treating saline industrial organic wastewater as described above is also provided, which, in a specific embodiment, includes the following steps:

[0082] The saline industrial organic wastewater is introduced into the reaction chamber through inlet 8. Specifically, the saline industrial organic wastewater, after necessary pretreatment, such as pH adjustment and removal of suspended solids, is introduced into the bottom of the reaction chamber through inlet 8. The wastewater typically contains high concentrations of chloride ions and organic pollutants (such as phenol, heterocyclic compounds, etc.).

[0083] Under pressure or the action of the circulating pump 10, the wastewater is forced upward through the microporous channel of the anode 2; during this process:

[0084] Power supply 6, connected to anode 2 and cathode 5, is started, typically in constant current mode, with the current density controlled between 10-80 mA / cm². 2 Within the range. Simultaneously, the vacuum ultraviolet light source 4 is activated, maintaining its irradiation intensity between 5W and 20W;

[0085] Chloride ions in the wastewater are efficiently electrochemically oxidized on the surface of anode 2 to generate hypochlorous acid (HClO / ClO). -Simultaneously, a small amount of hydroxyl radicals may also be generated on the anode surface through water electrolysis. Water molecules and the generated hypochlorous acid are immediately irradiated by the central vacuum ultraviolet light source 4, and are rapidly photolyzed to produce hydrated electrons (e...). aq - ), hydroxyl radicals ( · OH), chlorine free radicals (Cl) · ) and hypochlorous acid radical (ClO) · Active species such as ≡Fe(IV)=O or ≡Fe(V)=O are present. The fluidized iron-oxygen complex catalyst 12 in the wastewater reacts with hypochlorous acid to form high-valence iron oxides, such as ≡Fe(IV)=O or ≡Fe(V)=O, on the surface of the catalyst 12.

[0086] During the flow process, electron-deficient pollutants are reduced by hydrated electrons to form easily oxidizable intermediates (such as nitrobenzene reduced to aniline), while electron-rich pollutants undergo oxidation reactions with the various oxides (free radicals and high-valence metal oxides) generated above, and are degraded into small-molecule organic matter, CO2, and H2O. The treated wastewater is discharged through effluent outlet 7. Depending on actual needs, a portion of the effluent can be recycled back to the bottom of the reactor via circulation pump 10 for further recirculation treatment.

[0087] This working method achieves the generation and synergistic effect of multiple highly reactive oxide species through a synergistic process of forced flow, electrochemical oxidation, and in-situ photolysis. Specifically, the flow structure of anode 2 first forces chloride ions in wastewater to be efficiently converted into hypochlorous acid. Subsequently, hypochlorous acid is immediately photolyzed in-situ into hydroxyl radicals and chloride radicals by built-in vacuum ultraviolet light, and water molecules are photolyzed into hydroxyl radicals and hydrated electrons. By constructing a reduction-oxidation system, it can efficiently degrade multiple pollutants with both electron-rich and electron-deficient characteristics. This invention utilizes the synergistic coupling of electrochemical generation and photochemical conversion to convert high-concentration chloride ions into active precursors, effectively overcoming the bottlenecks of low degradation efficiency and poor selectivity of traditional technologies in high-salinity and complex water quality, and significantly improving the system's mineralization efficiency and energy utilization rate. Finally, the residual hypochlorous acid was converted into Fe(IV) / Fe(V) high-valence oxides by fluidized iron-oxygen complex catalyst 12, which achieved the technical effect of improving the degradation efficiency of pollutants and significantly reducing toxic chlorinated byproducts under the same energy consumption, providing a green, efficient and economical treatment method for high-salt industrial organic wastewater.

[0088] Regarding experimental data and performance comparison;

[0089] To verify the performance advantages of the device of the present invention, the following series of comparative experiments were conducted:

[0090] 1. Regarding the effect of current density;

[0091] In the fluidized electrocatalytic oxidation device of this invention and the conventional device, the current density was set to 10, 40, and 80 mA / cm², respectively. 2 (All other conditions are the same, phenol 20 mg / L, Cl) - 1 g / L, TAML-supported columnar activated carbon 100 g / L, UV lamp 10 W / 180 nm, 1 hour reaction. Figure 4 This is a schematic diagram of a conventional device with an unloaded catalyst and a flow-through electrode coupled to an ultraviolet lamp.

[0092]

[0093] Experimental results show that at 10 mA / cm 2 At that time, the HClO concentration generated by the device of the present invention was 0.25 mmol / L, which was 15% lower than that of the conventional device, but • OH and Cl • The yields were 40% and 30% higher, respectively; the phenol removal rate was 82%, higher than the 55% of traditional units. (At 40 mA / cm²) 2 At that time, the HClO concentration generated by the device of the present invention was 0.75 mmol / L, which was 10% lower than that of the conventional device. • OH and Cl • The output is 55% and 50% higher; the phenol removal rate is 98%, compared to only 72% for traditional equipment. (At 80 mA / cm²) 2 At that time, the HClO concentration generated by the device of the present invention was 1.4 mmol / L, which was 8% lower than that of the conventional device. • OH and Cl • The output is 70% and 65% higher; the phenol removal rate reaches 99.5%, while the traditional device is 81%. This indicates that the device of the present invention can efficiently promote the conversion of HClO into free radicals, greatly improve the degradation efficiency of pollutants, and increase the removal rate by 20-35% under the same energy consumption.

[0094] 2. The influence of ferrite complex type;

[0095] Compared with the conventional device (without a supported catalyst), the conventional device with Fe-TAML added (catalyst 12 placed between anode 2 and cathode 5), and the device of this invention (using three types of supported columnar activated carbon, Fe-porphyrin, Fe-TAML, and Fe-tpena, respectively, at 100 g / L and a current density of 40 mA / cm²), the device of this invention is a comparison of the conventional device (without a supported catalyst), the conventional device with Fe-TAML added (catalyst 12 placed between anode 2 and cathode 5), and the device of this invention (using three types of supported columnar activated carbon, Fe-porphyrin, Fe-TAML, and Fe-tpena, respectively, at 100 g / L and a current density of 40 mA / cm²). 2 (UV 10W / 180nm, 1 hour reaction). Figure 5 This is a schematic diagram of a conventional device with a catalyst-loaded flow electrode coupled to an ultraviolet lamp.

[0096]

[0097] Experimental results showed that Fe(IV) / Fe(V) was undetectable in the conventional device, and the phenol degradation rate was only 65%. However, after adding Fe-TAML, the phenol degradation rate in the conventional device was approximately 71%. In the device of this invention, with the addition of Fe-TAML, the Fe(IV) / Fe(V) generation was 0.38 mmol / L, the free radical production was 2.5 times that of the conventional device, and the phenol removal rate was 98%, which was 33% higher. In the Fe-tpena system, the Fe(IV) / Fe(V) generation was 0.31 mmol / L, the free radical production was twice that of the conventional device, and the phenol removal rate was 94%, which was 29% higher. In the Fe-porphyrin system, the Fe(IV) / Fe(V) generation was 0.24 mmol / L, the free radical production was 1.6 times that of the conventional device, and the phenol removal rate was 88%, which was 23% higher. This indicates that the degradation efficiency of the device of this invention is significantly improved after synergistic catalysis with ferrite complexes, and Fe-TAML performs best. It also avoids the short circuit between cathode 5 and anode 2 caused by highly conductive activated carbon in the conventional device.

[0098] 3. Regarding the effect of ultraviolet lamp irradiation intensity;

[0099] In the apparatus of the present invention and the conventional apparatus, the intensity of the ultraviolet lamp was set to 5W, 10W, and 20W respectively (all other conditions were the same, and the reaction lasted for 1 hour).

[0100]

[0101] Experimental results show that at 5W, the device of the present invention... • The OH production rate is 1.6 times that of conventional equipment, and the phenol degradation rate is 90%, which is 20% higher than that of conventional equipment; at 10W, the device of this invention... • OH and Cl • The output is 2 times and 1.8 times that of conventional equipment, and the phenol degradation rate is 98%, which is 26% higher; at 20W, the device of this invention... • OH and Cl • The output is 2.3 times and 2.1 times that of the traditional device, and the phenol degradation rate is 99%, which is 22% higher. This shows that under all UV intensities, the device of the present invention can generate more active free radicals, achieve a higher organic pollutant removal rate, and improve the degradation efficiency by 20-26%.

[0102] 4. Regarding the impact of pollutant types;

[0103] Nitrobenzene (20 mg / L), a representative pollutant lacking electrons, was selected for a comparative experiment.

[0104] At a current density of 40 mA / cm 2 Cl -Under the conditions of 1 g / L and a reaction time of 60 minutes, the degradation effect of the fluidized electrocatalytic oxidation device of the present invention under a 185 nm VUV light source and a 254 nm vacuum ultraviolet light source 4, as well as the degradation effect without catalyst under a 185 nm VUV light source, were tested.

[0105]

[0106] Experimental results show that the removal rate of nitrobenzene under a 254nm vacuum ultraviolet light source is only 20%; the removal rate of nitrobenzene in the catalyst-free VUV device is increased to 60%, and aniline at 4.2 mg / L is detected in the product, proving that the strong reducing hydrated electrons generated by the 185nm VUV photolysis of water initiate the nitro reduction reaction; the removal rate of nitrobenzene by the device of this invention is as high as 96%, and the concentration of intermediate products such as aniline in the effluent is undetectable. Experimental results indicate that nitrobenzene is partially reduced to aniline, and then this intermediate is rapidly oxidized by high-valent iron and hydroxyl radicals generated by Fe-TAML catalysis.

[0107] The electrocatalytic oxidation device and its operating method provided by this invention transform high-concentration chloride ions, an inhibitory factor in traditional advanced oxidation processes, into precursors for the production of various active species. This constructs a reduction-oxidation reaction pathway for multiple pollutants, resulting in more thorough and rapid degradation of complex organic pollutants. The cross-flow electrode structure, compact integrated design, optimized electrode spacing, and the combined effect of the internal rectifier plate 11 and baffles enhance the mass transfer process, reduce energy consumption, and improve the processing capacity and current efficiency per unit volume of the reactor. In-situ photolysis and catalytic conversion consume hypochlorous acid, effectively reducing the generation of residual chlorine and toxic chlorinated organic byproducts in the water, thus lowering the ecotoxicity of the effluent and the difficulty of subsequent treatment. Optimized selection of electrode materials, catalyst 12 design, and external cathode 5 layout avoid short-circuit risks, ensuring long-term stable operation of the device in harsh high-salt, highly oxidizing environments.

[0108] Although embodiments of the invention have been described in conjunction with the accompanying drawings, those skilled in the art can make various modifications and variations without departing from the spirit and scope of the invention, and such modifications and variations all fall within the scope defined by the appended claims.

Claims

1. An electrocatalytic oxidation device for treating saline industrial organic wastewater, characterized in that, include: The reactor shell (3) has a reaction chamber inside; An anode (2) is disposed in the reaction chamber. The anode (2) has a cylindrical structure and the cylindrical wall of the anode (2) has a porous structure to allow wastewater to pass through. A cathode (5) is arranged in a cylindrical structure, which is coaxially arranged outside the periphery of the anode (2), and is fixedly arranged on the inner wall of the reactor shell (3); the anode (2) and the cathode (5) are electrically connected with a power supply (6), the anode (2) is provided with a fluidized granular catalyst (12) suitable for fluidization, and the granular catalyst (12) is a carrier loaded iron-oxygen complex; the power supply (6) is configured to provide current to the anode (2) and the cathode (5), so that the working current density of the anode (2) and the cathode (5) is 10-80mA / cm 2 ; A vacuum ultraviolet light source (4) is integrally fixed on the central axis of the anode (2); the emission spectrum of the vacuum ultraviolet light source (4) includes ultraviolet light with wavelengths below 180 nm; An inlet (8) and an outlet (7) are provided on the reactor shell (3). The inlet (8) is connected to the bottom of the reaction chamber, and the outlet (7) is connected to the top of the reaction chamber. Wastewater enters the reaction chamber through the inlet (8) to generate hypochlorous acid through an electrochemical oxidation reaction on the surface of the anode (2). Water molecules and hypochlorous acid are then photolyzed in situ by the vacuum ultraviolet light source (4) to generate active species including hydrated electrons, hydroxyl radicals, chlorine radicals, and hypochlorous acid radicals, which are then discharged from the outlet (7) along with the wastewater. The electrocatalytic oxidation device uses the hydrated electrons generated by the photolysis of water molecules by the vacuum ultraviolet light source (4) to reduce electron-deficient organic pollutants in wastewater. The particulate catalyst (12) reacts with hypochlorous acid to generate high-valence iron oxides to oxidize organic pollutants.

2. The electrocatalytic oxidation device according to claim 1, characterized in that, The cylinder wall of the anode (2) is configured as a foamed metal substrate, and the surface of the foamed metal substrate is loaded with a metal oxide catalyst layer.

3. The electrocatalytic oxidation device according to claim 2, characterized in that, The foamed metal substrate is configured as foamed titanium; the metal oxide catalyst layer comprises at least one oxide selected from ruthenium, iridium, tantalum, and lead; the pore size of the metal oxide catalyst layer is between 50 μm and 1000 μm; and / or The aperture of the anode (2) is between 10 mm and 50 mm.

4. The electrocatalytic oxidation device according to claim 1, characterized in that, The cathode (5) is a cylinder made of titanium or stainless steel; and / or The distance between the anode and the cathode (5) is between 0.5cm and 2cm.

5. The electrocatalytic oxidation device according to claim 1, characterized in that, The iron-oxygen complex is configured as porphyrin, tetraanionic tetraamide macrocyclic ligand, pyridine carboxylic acid, or N,N,N'-tris(2-pyridylmethyl)-ethylenediamine-N'-acetic acid; the support is columnar, granular, or spherical activated carbon; and / or The electrocatalytic oxidation device further includes at least one porous partition (14), which is horizontally disposed within the anode (2). The porous partition (14) is adapted to divide the anode (2), and the particulate catalyst (12) is evenly distributed on the upper and lower sides of the porous partition (14).

6. The electrocatalytic oxidation apparatus according to any one of claims 1-5, characterized in that, The electrocatalytic oxidation device also includes a circulation pump (10), and there are two outlets (7). The inlet end of the circulation pump (10) is connected to one of the outlets (7) through a flow pipe (13). The outlet end of the circulation pump (10) is connected to the reaction chamber and is positioned towards the bottom of the anode area where the anode (2) is located.

7. The electrocatalytic oxidation apparatus according to claim 6, characterized in that, The electrocatalytic oxidation device also includes a rectifier plate (11), which is disposed at the bottom of the anode (2) and has evenly distributed vertical channels.

8. A method of operating an electrocatalytic oxidation device for treating saline industrial organic wastewater as described in any one of claims 1 to 7, characterized in that, Includes the following steps: Salt-containing industrial organic wastewater is introduced into the reaction chamber through the inlet (8); Turn on the power supply (6) connected to the anode (2) and cathode (5) and turn on the vacuum ultraviolet light source (4); Wastewater is controlled to pass through the micropores of the anode (2) and react on the surface of the anode (2), so that chloride ions in the wastewater are converted into hypochlorous acid. Water molecules and hypochlorous acid are photolyzed in situ by a vacuum ultraviolet light source (4) into active species including hydrated electrons, hydroxyl radicals, chloride radicals and hypochlorous acid radicals. The treated wastewater is discharged through the outlet (7).

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