Degradation device and method based on synergistic effect of plasma and ultrasonic waves

Abstract

The invention discloses a degradation device and method based on the synergistic effect of plasma and ultrasonic waves. The device comprises a main reaction cavity and a synergistic discharge module located in the main reaction cavity. The cooperative discharge module comprises a plurality of groups of dielectric barrier discharge device arrays which are arranged at intervals and a plurality of groups of ultrasonic generator arrays which are arranged at intervals; and a photocatalyst is also arranged in the dielectric barrier discharge device. The technical problems of incomplete degradation, high energy consumption, non-uniform reaction and inflexible process control in the existing micropollutant treatment are solved, and the device can be widely applied to broad-spectrum treatment of various refractory pollutants such as various drugs, pesticides and organic dyes, and has the advantages of compact structure, high synergistic efficiency, intelligent control and stable operation.

Description

Technical Field

[0001] This invention belongs to the field of green environmental protection technology and intelligent water treatment equipment integration, and more specifically, relates to a degradation device and method based on the synergistic effect of plasma and ultrasound. Background Technology

[0002] With the acceleration of urbanization and industrialization, the detection concentration of emerging pollutants (ECs) in water bodies has been increasing year by year. Typical pollutants include sulfonamide antibiotics (such as sulfamethoxazole SMX), tetracyclines (such as tetracycline TC), fluoroquinolones (such as ciprofloxacin CIP), organophosphorus pesticides (such as chlorpyrifos CPF), azo dyes (such as methyl orange MO), and bisphenol A (BPA). These pollutants are characterized by environmental persistence, bioaccumulation, and ecotoxicity. Conventional physicochemical treatments (such as flocculation and sedimentation, activated carbon adsorption) can only achieve phase transfer but cannot completely decompose them; biological methods (such as activated sludge) are inefficient because the biotoxicity of pollutants leads to the inactivation of microorganisms.

[0003] In recent years, advanced oxidation processes (AOPs) dominated by hydroxyl radicals (•OH) have become a research hotspot. However, traditional technologies such as the Fenton process and photocatalysis suffer from problems such as catalyst deactivation, strong pH dependence, and secondary pollution. Low-temperature plasma technology generates high-density reactive oxygen and nitrogen species (RONS), including •OH, O3, and hydroxyl radicals (•OH, O3, O3), at the gas phase or gas-liquid interface through dielectric barrier discharge and corona discharge. 1 O2、•O、•O2 - It possesses broad-spectrum oxidation capabilities, including H2O2 and NOx. However, single-plasma treatment has the following drawbacks: 1. Limited liquid-phase mass transfer: Approximately 70% of active species are generated in the gas phase, which is difficult to efficiently dissolve into the liquid phase due to Henry's Law constraints; 2. Low energy utilization: Part of the discharge energy is converted into heat energy, leading to increased system temperature and energy consumption; 3. Byproduct residues: Some intermediate products (such as chlorinated organic compounds) may have higher toxicity.

[0004] Ultrasonic technology creates a micro-reaction zone in a liquid with instantaneous high temperature (>5000 K) and high pressure (>100 MPa) through cavitation, promoting the cleavage of water molecules to generate •OH and enhancing gas-liquid mass transfer and reactant mixing. However, single ultrasonic treatment has problems such as high cavitation bubble collapse energy threshold and low free radical yield.

[0005] Therefore, there is an urgent need for a degradation device that has a fast oxidation process and high mineralization efficiency for tiny organic pollutants in water. Summary of the Invention

[0006] In view of the above-mentioned defects or improvement needs of existing technologies, the present invention provides a degradation device and method based on the synergistic effect of plasma and ultrasound. The purpose is to achieve low-energy consumption, broad-spectrum adaptability, high efficiency and stability of deep degradation of water pollutants by constructing a multi-level synergistic discharge system, a turbulence-enhanced reaction chamber and an AI closed-loop control system, so as to solve the technical problems of incomplete degradation, high energy consumption, uneven reaction and inflexible process control in the existing micro-pollutant treatment.

[0007] To achieve the above objectives, according to one aspect of the present invention, a degradation device based on the synergistic effect of plasma and ultrasound is provided, comprising a main reaction chamber and a synergistic discharge module located within the main reaction chamber; the synergistic discharge module includes a plurality of dielectric barrier discharge devices spaced apart from each other, and a plurality of ultrasonic generators spaced apart from each other; a photocatalyst is also disposed within the dielectric barrier discharge device. Preferably, each dielectric barrier discharge device and each ultrasonic generator are arranged alternately at intervals; the array of dielectric barrier discharge devices is connected to a first power supply, and the array of ultrasonic generators is connected to a second power supply.

[0008] Preferably, it further includes a pretreatment module; the pretreatment module includes a primary filter and a fine filter connected in sequence; the pretreatment module is disposed at the front end of the collaborative discharge module and connected to the collaborative discharge module.

[0009] Preferably, it further includes an end-of-pipe deep treatment unit and an exhaust gas treatment unit; the end-of-pipe deep treatment unit is connected to the bottom of the main reaction chamber; the exhaust gas treatment unit is connected to the top of the main reaction chamber; the end-of-pipe deep treatment unit includes an activated carbon adsorption column and a nanofiltration membrane assembly connected in sequence; the exhaust gas treatment unit includes an activated carbon adsorption module and an α-MnO2 catalytic degradation module connected in sequence. Preferably, it further includes several secondary reaction chambers connected in series; the secondary reaction chambers are connected to the main reaction chamber; the end-stage deep processing unit is connected to the bottom of the secondary reaction chamber; the exhaust gas treatment unit is connected to the top of the secondary reaction chamber; each secondary reaction chamber is equipped with an ultrasonic generator; the ultrasonic generator inside the secondary reaction chamber is connected to the second power supply.

[0010] Preferably, it further includes an intelligent control module; the intelligent control module is electrically connected to the first power supply, the second power supply, the pretreatment module, the collaborative discharge module, several series-connected secondary reaction chambers, and the exhaust gas treatment unit; the intelligent control module includes a data acquisition unit, an integrated machine learning control and analysis unit, and an execution feedback controller.

[0011] Preferably, the dielectric barrier discharge device includes a quartz tube, a metal rod electrode, and a black TiO2 discharge catalyst; the metal rod electrode is located inside the quartz tube and is attached to the inner wall of the quartz tube, and the discharge catalyst is located between the inner wall and the outer wall of the quartz tube; the metal rod electrode is connected to the high-voltage electrode of the first power supply; and an air inlet and an air outlet are provided on the outer wall of the quartz tube. Preferably, the outer wall of the quartz tube is also wrapped with a stainless steel mesh loaded with TiO2 photocatalyst.

[0012] Preferably, the ultrasonic generator operates in the frequency range of 20-40 kHz, and the excitation method is continuous excitation or pulse intermittent excitation; the discharge voltage of the metal rod electrode is 12-16 kV, and the frequency is 5-10 kHz.

[0013] Preferably, the activated carbon adsorption module (9) uses coal-based spherical activated carbon with an iodine value of 1100-1200 mg / g, a filling height of 0.8-1.2m, and a contact time of 15-20 min; the nanofiltration membrane module (8) is a polyamide membrane with a molecular weight cutoff of 150-300 Da. According to another aspect of the present invention, a degradation method based on the synergistic effect of plasma and ultrasound is provided, comprising the following steps: (1) The raw water to be treated is introduced into the main reaction chamber. The main reaction chamber is equipped with a number of dielectric barrier discharge devices and a number of ultrasonic generators spaced apart from each other. The dielectric barrier discharge devices are equipped with photocatalysts. (2) Air is introduced into the dielectric barrier discharge device. The dielectric barrier discharge device with photocatalyst in the main reaction chamber works together with the ultrasonic generator to generate active oxygen and nitrogen components, thereby accelerating the oxidation and decomposition of pollutants in the raw water.

[0014] Preferably, before step (1), the process further includes: passing the raw water through a pretreatment module to sequentially undergo coarse filtration and fine filtration in order to reduce the load on subsequent treatment; Preferably, step (2) is followed by the following steps: S1: The water body treated in step (2) is passed into several stages of series of secondary reaction chambers to recycle the active oxygen and nitrogen components, and to complete the oxidation, chain breaking, bond cleavage, ring opening and final mineralization of the pollutant molecular structure. S2: The water treated in step S1 flows into the end-of-pipe deep purification module, where activated carbon adsorption and nanofiltration membrane interception further remove trace intermediate products, odor substances and residual by-products to ensure water quality stability. S3: The exhaust gas after step S2 enters the exhaust gas treatment unit, which includes an activated carbon adsorption module and an α-MnO2 catalytic degradation module connected in sequence; the residual active oxygen and nitrogen components in the exhaust gas are treated by activated carbon adsorption and α-MnO2 catalytic degradation, and then discharged after meeting the standards. S4: Electrically connect the intelligent control module to the pretreatment module, the collaborative discharge module, several stages of series-connected secondary reaction chambers, and the exhaust gas treatment unit; the intelligent control module automatically completes feedback adjustment based on sensor data to achieve dynamic operation optimization and energy consumption control throughout the entire process.

[0015] In summary, compared with the prior art, the above-described technical solutions conceived by this invention can achieve the following beneficial effects: (1) The present invention uses catalytic discharge and cavitation to enhance degradation efficiency: through the temporal and spatial coupling excitation of dielectric barrier discharge (DBD) structure and high-energy ultrasonic field, supplemented by the activation effect of catalyst on plasma discharge process and the synergistic promotion effect of photocatalyst on pollutant photodegradation, the concentration of RONS is significantly increased, and the gas-liquid mass transfer barrier is broken, so that the pollutant degradation rate is increased by more than 40% compared with the single discharge system, with efficient and broad-spectrum degradation capability and lower unit energy consumption; the synergistic effect of this photocatalytic process with plasma and ultrasound expands the reaction path of pollutant degradation and greatly improves the mineralization efficiency of recalcitrant organic pollutants.

[0016] (2) The present invention can form abundant electron-hole pairs and generate active substance O2 by filling the DBD quartz tube with TiO2 catalyst. - This can effectively increase ozone concentration. Simultaneously, the photocatalyst fixed around the discharge tube, under the excitation of ultraviolet-visible light generated by plasma discharge, produces photogenerated electron-hole pairs, which react with dissolved oxygen and water to further generate •OH and •O2. - Equally strong oxidizing free radicals. The outer wall of the quartz tube is coated with a TiO2 photocatalyst, which mainly utilizes ultraviolet light generated by discharge to excite electron-hole pairs, further generating ·OH free radicals for the deep oxidative degradation of pollutants in the aqueous phase. Both act on the gas-phase and liquid-phase reaction processes respectively, forming a heterogeneous enhanced oxidation system with synergistic effects of discharge catalysis and photocatalysis.

[0017] This invention employs an ultrasonic generator to enable ultrasonic cavitation microjets to break the mass transfer barrier at the gas-liquid interface, thereby improving the migration efficiency of gas-phase RONS to the liquid phase. Simultaneously, the local high-energy environment generated by ultrasonic cavitation can reduce the plasma initiation discharge voltage, thereby improving discharge stability and energy utilization efficiency. The high-density electrons in the plasma discharge region excite and dissociate the water vapor within the ultrasonic cavitation bubble, multiplying the yield of hydroxyl radicals and further enhancing the oxidative degradation process.

[0018] (3) The present invention uses multi-stage series reaction chambers to enhance mass transfer mixing: the multi-stage series reaction chambers improve the utilization rate of RONS and the contact efficiency between pollutants and oxidizing substances, significantly prolonging the reaction path and contact time, ensuring thorough oxidation reaction and mineralization rate of over 90%.

[0019] (4) The present invention specifies that each dielectric barrier discharge device and each ultrasonic generator are arranged alternately in sequence. The purpose is to achieve spatial periodic overlap of electric field and sound field, enhance gas-liquid mass transfer efficiency through acoustic cavitation effect, and at the same time, the high-density electrons in the discharge region and the local high-energy environment in the cavitation region form synergistic excitation, thereby improving free radical yield and overall system degradation efficiency.

[0020] (5) The present invention uses black TiO2 discharge catalyst. Compared with ordinary TiO2, black TiO2 can utilize high-energy electrons to improve ozone generation efficiency. Moreover, it has a lower band gap and abundant oxygen vacancy structure, which can promote electron-hole separation under plasma high-energy electron and ultraviolet excitation to generate active oxygen species such as O2. - This significantly improves ozone generation efficiency and discharge energy utilization.

[0021] (6) The present invention uses a terminal deep treatment unit to treat wastewater. It uses an activated carbon adsorber and a 200Da nanofiltration membrane to achieve multi-stage purification. The TOC of the effluent is controlled below 2 mg / L, and the UV254 is reduced to the background value. The effluent quality can meet the standards for reuse, reclaimed water and drinking water pretreatment, and is suitable for industrial reuse and ecological water replenishment needs.

[0022] (7) The invention operates under normal temperature and pressure conditions throughout the process. The required oxidant is generated in situ through the synergistic effect of plasma and ultrasound. It does not rely on external chemical agents, leaves no chemical reagent residues, avoids secondary pollution, and the process is green and sustainable. It is particularly suitable for the safe purification of drinking water sources and ecologically sensitive areas.

[0023] (8) This system adopts a standardized modular assembly design, with a compact unit structure, small footprint, low noise, and flexible combination to expand the processing capacity. It is particularly suitable for distributed deployment needs such as high-density urban water plants, industrial park edge sites, and emergency mobile treatment vehicles. The present invention has a wide range of pollutant adaptability and good adaptability and synergistic removal capabilities for typical recalcitrant pollutants such as drug residues, hormones, pesticides, and organic dyes. It has the potential for promotion in complex water quality environments and can be widely used in municipal deep treatment, industrial wastewater upgrading and transformation, drinking water source protection and reclaimed water reuse. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the overall structure of the water micro-pollutant degradation device based on the synergistic effect of plasma and ultrasound according to the present invention.

[0025] Figure 2 This is a process flow diagram of the apparatus of the present invention.

[0026] Figure 3 This is a schematic diagram of the combined discharge device of the present invention.

[0027] Figure 4 This is a logical structure diagram of the intelligent control module of the present invention.

[0028] Figure 5 This is a comparison chart of the TOC removal rates of the embodiments of the present invention and traditional advanced oxidation technologies.

[0029] In all the accompanying drawings, the same reference numerals denote the same parts or structures, wherein: 1—raw water inlet; 2—primary filter; 3—fine filter; 4—medium barrier discharge device; 5—ultrasonic generator; 6—main reaction chamber; 7—activated carbon adsorption column; 8—nanofiltration membrane assembly; 9—activated carbon adsorption module; 10—α-MnO2 catalytic degradation module; 11—intelligent control module; 12—purified water outlet; 13—secondary power supply; 14—black TiO2 catalyst; 15—TiO2 photocatalyst; 16—secondary reaction chamber; 17—primary power supply; 18—air inlet; 19—air outlet. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0031] I. Overall System Structure Figure 1 As shown, this system includes the following functional modules: Pretreatment module: Raw water is introduced from raw water inlet 1 and passes through primary filter 2 and fine filter 3 in sequence to remove suspended solids, particles and stabilize water quality.

[0032] The collaborative discharge module includes a dielectric barrier discharge device 4 and an ultrasonic generator 5, which are embedded in parallel within the main reaction chamber 6. The coaxial dual-electrode structure consists of a high-voltage stainless steel electrode (outer diameter 4 mm) and an outer quartz tube (inner diameter 8 mm). The discharge frequency is 10 kHz, and the voltage is 15 kV. The ultrasonic frequency is 28~40 kHz, and the cavitation intensity is ≥0.35 MPa. The dielectric barrier discharge device 4 includes a quartz tube, a metal rod electrode, and a black TiO2 discharge catalyst. The metal rod electrode is located inside the quartz tube and is attached to the inner wall of the quartz tube. The discharge catalyst is located between the inner and outer walls of the quartz tube. The metal rod electrode is connected to the high-voltage electrode of the first power supply 17. The outer wall of the quartz tube has an air inlet 18 and an air outlet 19 to allow air to enter for plasma discharge. The outer wall of the quartz tube is also wrapped with a stainless steel mesh loaded with the TiO2 photocatalyst.

[0033] The quartz tube is filled with a black TiO2 discharge catalyst. The high-energy electrons generated by the plasma can effectively activate the black TiO2 catalyst, forming abundant electron-hole pairs. These electron-hole pairs interact with O2 to produce the active substance O2. - This enhances ozone formation. Simultaneously, the discharge tube is wrapped with a stainless steel mesh loaded with TiO2 photocatalyst. The ultraviolet light generated by DBD discharge (dielectric barrier discharge) causes the catalyst to produce high levels of reduction electrons and high levels of oxidation holes, which act on H2O and O2 respectively, forming highly oxidizing free radicals •OH and •O2. - This accelerates the oxidation and decomposition of pollutants in water. The ultrasonic module effectively disrupts the gas-liquid interface boundary by exciting the liquid-phase cavitation effect. The synergistic effect with DBD plasma, using a resonant matching structure, achieves the coincidence of the electric field and sound field in spatial position and synchronous excitation on the time scale, thereby improving the gas-liquid mass transfer efficiency of RONS and thus improving the degradation efficiency of pollutants. Multi-stage reaction chamber module: Includes 3 to 5 series reaction stages to improve the contact efficiency between RONS and pollutants. Each chamber has a volume of 10-50 L, and the flow rate and energy density are adjustable segment by segment. Energy consumption of the device is reduced by recycling RONS, achieving oxidation, bond breaking, degradation, transformation, and final mineralization of pollutants, thereby improving overall removal efficiency and reactor space utilization. AI Intelligent Control Module: Centered on Intelligent Control Module 11, it integrates a sensor group to collect parameters such as pH, TOC, temperature, conductivity, voltage, and current. It incorporates a hybrid prediction model combining Deep Neural Network (DNN) and Gradient Boosting Decision Tree (GBDT) to adjust the discharge mode (pulse / continuous), frequency, and voltage in real time, regulate ultrasonic power and hydraulic residence time (HRT), and output the optimal discharge parameters, ultrasonic mode, airflow speed, and hydraulic residence time to achieve dynamic closed-loop control of degradation efficiency and energy consumption. End-of-pipe deep treatment unit: The effluent passes sequentially through activated carbon adsorption column 7 and nanofiltration membrane module 8. The former is used to efficiently adsorb residual small molecule organic matter, nitrite and free RONS, while the latter is used to remove micro-pollutant byproducts and impurity ions with a molecular weight of less than 200 Da, ensuring that the effluent TOC < 2 mg / L and UV254 is reduced to the background level.

[0034] Exhaust gas treatment unit: The activated carbon adsorption module 9 and the α-MnO2 catalytic degradation module 10 are used together to treat undissolved RONS. The two modules are configured in series and have efficient and continuous exhaust gas purification capabilities, which can make the concentration of RONS in the exhaust gas meet the exhaust gas emission standards.

[0035] II. Workflow Description The system operates as follows: Raw water is introduced through raw water inlet 1 and passes sequentially through primary filter 2 and fine filter 3; after pretreatment, the water flows into the main reaction chamber 6, where air is introduced into the dielectric barrier discharge device 4. The dielectric barrier discharge device 4 and ultrasonic generator 5 work together to generate a complex oxidation zone containing high-density •OH, O3, and cavitation micro-explosions, initially destroying the molecular structure of micro-pollutants; the treated liquid flows sequentially into the multi-stage reaction unit along the reaction chamber, where the RONS effect is enhanced under turbulent conditions, promoting the stepwise oxidation and mineralization of pollutants; the degradation product liquid flows into the final deep treatment module, first passing through activated carbon adsorption... The column 7 removes recalcitrant intermediate products, and the nanofiltration membrane module 8 then retains residual low molecular weight organic pollutants and some inorganic impurities. Unabsorbed or escaped RONS is purified by the activated carbon adsorption module 9 and the α-MnO2 catalytic degradation module 10 to ensure that the emitted gas meets the standards. During the reaction, the intelligent control module 11 continuously optimizes the discharge strategy and ultrasonic excitation method in real time by combining the operating parameters such as TOC, conductivity, voltage, and power fed back by the sensor group, and dynamically adjusts the hydraulic residence time and power output of each module, thereby ensuring the stable operation of the system and achieving the optimal balance between degradation efficiency and energy consumption ratio.

[0036] Example 1 This invention provides a degradation device based on the synergistic effect of plasma and ultrasound, including a pretreatment module, a main reaction chamber 6, and a synergistic discharge module located in the main reaction chamber 6, as well as two secondary reaction chambers 16 connected in series, an end-stage deep treatment unit, an exhaust gas treatment unit, and an intelligent control module 11; the synergistic discharge module includes an array of several parallel and spaced dielectric barrier discharge devices 4 and an array of several parallel and spaced ultrasonic generators 5. Each dielectric barrier discharge device 4 and each ultrasonic generator 5 are arranged alternately at intervals; the array of dielectric barrier discharge devices 4 is connected to a first power supply 17, and the array of ultrasonic generators 5 is connected to a second power supply 13. The pretreatment module includes a primary filter 2 and a fine filter 3 connected in sequence; the pretreatment module is located at the front end of the collaborative discharge module and connected to the collaborative discharge module.

[0037] The end-stage deep processing unit is connected to the bottom of the main reaction chamber 6; the exhaust gas treatment unit is connected to the top of the main reaction chamber 6; the end-stage deep processing unit includes an activated carbon adsorption column 7 and a nanofiltration membrane assembly 8 connected in sequence; the exhaust gas treatment unit includes an activated carbon adsorption module 9 and an α-MnO2 catalytic degradation module 10 connected in sequence; it also includes several secondary reaction chambers 16 connected in series; the secondary reaction chambers are connected to the main reaction chamber 6; the end-stage deep processing unit is connected to the bottom of the secondary reaction chamber 16; the exhaust gas treatment unit is connected to the top of the secondary reaction chamber 16; each secondary reaction chamber 16 is equipped with an ultrasonic generator; the ultrasonic generator inside the secondary reaction chamber 16 is connected to the second power supply 13. The intelligent control module 11 is electrically connected to the first power supply 17, the second power supply 13, the pretreatment module, the cooperative discharge module, the two secondary reaction chambers 16 connected in series, and the exhaust gas treatment unit; the intelligent control module 11 includes a data acquisition unit, an integrated machine learning control and analysis unit, and an execution feedback controller.

[0038] The dielectric barrier discharge device 4 includes a quartz tube, a metal rod electrode, and a black TiO2 discharge catalyst; the metal rod electrode is located inside the quartz tube and is attached to the inner wall of the quartz tube, and the discharge catalyst is located between the inner wall and the outer wall of the quartz tube; the metal rod electrode is connected to the high voltage electrode of the first power supply 17; the outer wall of the quartz tube is provided with an air inlet 18 and an air outlet 19. The outer wall of the quartz tube is also wrapped with a stainless steel mesh loaded with TiO2 photocatalyst.

[0039] The ultrasonic generator 5 operates at a frequency range of 20 kHz and is continuously excited. The metal rod electrode has a discharge voltage of 15 kV and a frequency of 10 kHz. The activated carbon adsorption module 9 uses coal-based spherical activated carbon with an iodine value of 1200 mg / g, a filling height of 0.9 m, and a contact time of 15 min. The nanofiltration membrane assembly 8 is a polyamide membrane with a molecular weight cutoff of 200 Da.

[0040] Example 2 A degradation method based on the synergistic effect of plasma and ultrasound specifically includes the following steps: Step S01: Multi-stage pretreatment of raw water: The raw water first passes through coarse filtration (500 μm) and fine filtration (10 μm) in sequence to remove large particulate suspended solids and fibers, thereby reducing the load on subsequent treatment.

[0041] Step S02: Synergistic Discharge Reaction Activation: Pretreated water flows into the first discharge reaction chamber, which contains a dielectric barrier discharge array filled with a discharge catalyst and an ultrasonic generator array, forming an electro-acoustic synergistic reaction unit. Simultaneously, a photodegradation catalyst is fixed in the water. The DBD array continuously and stably discharges at an AC voltage of 15kV and a frequency of 10kHz, efficiently and stably generating low-temperature plasma under the action of the discharge catalyst. This induces the generation of highly reactive substances such as hydroxyl radicals (•OH), monatomic oxygen (•O), and ozone (O3). Simultaneously, the ultraviolet-visible light generated by the plasma discharge excites the photocatalyst in the water, producing photogenerated charge carriers, further activating water molecules and dissolved oxygen, generating additional active species such as •OH and •O2⁻, significantly enhancing the redox capacity of the water. The ultrasonic generator array operates at a frequency of 20 kHz and a cavitation intensity of 0.35 MPa, exciting the acoustic cavitation effect in the liquid, effectively disrupting the mass transfer boundary layer and promoting the diffusion and reaction of active substances in the liquid phase. Meanwhile, the structure achieves a high degree of spatial overlap between the electric field and the acoustic field, and synchronous excitation on a time scale, forming a synergistic enhancement effect, which greatly enhances free radical generation, improves energy utilization efficiency, and significantly broadens the reaction pathway for pollutant degradation.

[0042] Step S03: Multi-stage cascade reaction enhancement: The effective volume of each chamber in the multi-stage reaction chamber is 10L, which can be expanded through a modular cascade structure according to the actual load to ensure sufficient contact and reaction between pollutants and active substances, completing the oxidation, chain breaking, bond cleavage, ring opening, and final mineralization of the pollutant molecular structure. Each chamber has a gas channel at the top connecting to the next stage, realizing the recycling of RONS and improving the utilization efficiency of oxidizing substances.

[0043] Step S04: Deep Purification and Tail Gas Treatment: After the effluent flows through a high-iodine-value activated carbon column (iodine value 1100 mg / g) to remove residual small organic molecules, it is further purified by a nanofiltration membrane with a molecular weight cutoff of 200 Da to ensure TOC < 2 mg / L and UV254 reduced to the detection limit. The tail gas is treated by a synergistic process of high-iodine-value activated carbon adsorption and α-MnO2 catalytic degradation, which efficiently adsorbs and decomposes residual RONS in the tail gas. This tandem synergistic degradation ensures that the emitted gas meets national environmental emission standards before being discharged.

[0044] Step S05: AI Closed-Loop Control and Energy Consumption Optimization: The system integrates intelligent control algorithms based on machine learning, and collects data such as pH, ORP, temperature, TOC, UV254, RONS concentration, flow rate, voltage, and current in real time. It automatically adjusts discharge parameters, ultrasonic mode, hydraulic residence time, and cleaning cycle according to the system's operating status to achieve intelligent closed-loop control of "on-demand energy supply, dynamic coordination, and low-carbon operation".

[0045] The discharge and ultrasonic modules support plug-and-play electrode replacement and online acid washing maintenance, which can extend operating time and reduce labor costs. Employing timed gas-liquid pulse cleaning (cycle 200-300 hours), alkaline or citric acid chemical rinsing (concentration 2-5%), and a pre-rinsing mode linked to the cooling system, the entire operation and maintenance process is automated, requiring no manual intervention.

[0046] This invention is applicable to various types of recalcitrant pollutants such as drug residues, pesticides, and organic dyes, and is suitable for applications such as advanced treatment sections of municipal sewage treatment plants, emergency treatment modules for drinking water sources, distributed treatment stations for industrial wastewater, and high-end reclaimed water systems.

[0047] Performance verification This system was tested in the laboratory and pilot-scale platform to treat various pollutants. Typical pollutants—sulfonamide antibiotics, bisphenol A, methyl orange, and norfloxacin—were selected as target degradation agents. Standard solutions with a concentration of 100 mg / L were prepared as test water samples. During the test, the treated water samples were pumped into the reaction chamber at a constant flow rate. The system operating parameters were set as follows: discharge voltage 12-16 kV, frequency 5-10 kHz, and ultrasonic frequency 20-40 kHz. The initial and effluent total organic carbon (TOC) of the test water samples were determined using a TOC analyzer, and the concentrations of various pollutants were determined using HPLC. The results were the average of three parallel experiments.

[0048] The results showed that the removal rates of sulfonamide antibiotics, bisphenol A, methyl orange, and norfloxacin micropollutants all exceeded 95%, and the TOC removal rate reached 94%. The system demonstrated high stability during continuous operation, with an automatic maintenance cycle of ≥200 hours, verifying the technical feasibility and practicality of the invention. For details on the treatment results of norfloxacin degradation, please refer to [link to relevant documentation]. Figure 5 It can be seen that the synergistic plasma system constructed in this invention significantly outperforms the traditional DBD treatment process in terms of pollutant degradation. Throughout the entire treatment cycle, the synergistic system exhibits a faster degradation rate and a higher final removal rate, demonstrating excellent reactivity and mass transfer enhancement. The results show that by introducing synergistic mechanisms such as ultrasound and photocatalysis, the treatment efficiency and mineralization capacity of the plasma system can be effectively improved.

[0049] In summary, this system can achieve efficient and broad-spectrum degradation of various micro-pollutants under environmentally friendly and energy-efficient conditions. It is particularly suitable for emergency treatment of micro-pollutants in drinking water sources, advanced treatment of highly difficult industrial wastewater, and purification of pharmaceutical effluent, demonstrating broad industrial application prospects and distributed deployment value. Those skilled in the art can make various optimizations and adjustments to the system structure, control logic, and module configuration without departing from the core concept of this invention, and all such modifications and adjustments should be considered within the reasonable scope of protection of this invention.

Claims

1. A degradation device based on the synergistic effect of plasma and ultrasound, characterized in that, It includes a main reaction chamber (6) and a co-discharge module located in the main reaction chamber (6); the co-discharge module includes a plurality of dielectric barrier discharge devices (4) arranged at intervals from each other, and a plurality of ultrasonic generators (5) arranged at intervals from each other; a photocatalyst is provided in the dielectric barrier discharge device (4).

2. The degradation device based on the synergistic effect of plasma and ultrasound according to claim 1, characterized in that, Each of the dielectric barrier discharge devices (4) and each of the ultrasonic generators (5) are arranged alternately at intervals; the dielectric barrier discharge devices (4) are connected to the first power supply (17), and the ultrasonic generators (5) are connected to the second power supply (13).

3. The degradation device based on the synergistic effect of plasma and ultrasound according to claim 2, characterized in that, It also includes a pre-processing module; the pre-processing module includes a primary filter (2) and a fine filter (3) connected in sequence; the pre-processing module is located at the front end of the collaborative discharge module and connected to the collaborative discharge module.

4. The degradation device based on the synergistic effect of plasma and ultrasound according to claim 3, characterized in that, It also includes an end-of-life deep treatment unit and an exhaust gas treatment unit; the end-of-life deep treatment unit is connected to the bottom of the main reaction chamber (6); the exhaust gas treatment unit is connected to the top of the main reaction chamber (6); the end-of-life deep treatment unit includes an activated carbon adsorption column (7) and a nanofiltration membrane assembly (8) connected in sequence; the exhaust gas treatment unit includes an activated carbon adsorption module (9) and an α-MnO2 catalytic degradation module (10) connected in sequence.

5. The degradation device based on the synergistic effect of plasma and ultrasound according to claim 4, characterized in that, It also includes several secondary reaction chambers (16) connected in series; the secondary reaction chambers are connected to the main reaction chamber (6); the end depth processing unit is connected to the bottom of the secondary reaction chamber (16); the exhaust gas processing unit is connected to the top of the secondary reaction chamber (16); each secondary reaction chamber (16) is equipped with an ultrasonic generator; the ultrasonic generator is connected to the second power supply (13).

6. The degradation device based on the synergistic effect of plasma and ultrasound according to claim 5, characterized in that, It also includes an intelligent control module (11); the intelligent control module (11) is electrically connected to the first power supply (17), the second power supply (13), the pretreatment module, the cooperative discharge module, several series-connected secondary reaction chambers (16) and the exhaust gas treatment unit; the intelligent control module (11) includes a data acquisition unit, an integrated machine learning control and analysis unit, and an execution feedback controller.

7. The degradation device based on the synergistic effect of plasma and ultrasound according to claim 6, characterized in that, The dielectric barrier discharge device (4) includes a quartz tube, a metal rod electrode, and a black TiO2 discharge catalyst; the metal rod electrode is located inside the quartz tube and is attached to the inner wall of the quartz tube, and the discharge catalyst is located between the inner wall and the outer wall of the quartz tube; the metal rod electrode is connected to the high voltage electrode of the first power supply (17); the outer wall of the quartz tube is provided with an air inlet (18) and an air outlet (19). The outer wall of the quartz tube is also wrapped with a stainless steel mesh loaded with TiO2 photocatalyst.

8. The apparatus according to claim 7, characterized in that, The ultrasonic generator (5) operates in a frequency range of 20-40 kHz and is excited by continuous excitation or pulse intermittent excitation; the discharge voltage of the metal rod electrode is 12-16 kV and the frequency is 5-10 kHz. The activated carbon adsorption module (9) uses coal-based spherical activated carbon with an iodine value of 1100-1200 mg / g, a filling height of 0.8-1.2 m, and a contact time of 15-20 min; the nanofiltration membrane module (8) is a polyamide membrane with a molecular weight cutoff of 150-300 Da.

9. A degradation method based on the synergistic effect of plasma and ultrasound, characterized in that, Includes the following steps: (1) The raw water to be treated is introduced into the main reaction chamber. The main reaction chamber is provided with a number of medium-discharge blocking devices and a number of ultrasonic generators that are spaced apart from each other. The medium-discharge blocking devices are provided with photocatalysts. (2) Air is introduced into the dielectric barrier discharge device. The dielectric barrier discharge device with photocatalyst in the main reaction chamber works together with the ultrasonic generator to generate active oxygen and nitrogen components, thereby accelerating the oxidation and decomposition of pollutants in the raw water.

10. The degradation method based on the synergistic effect of plasma and ultrasound as described in claim 9, characterized in that, Before step (1), the process also includes passing the raw water through a pretreatment module to undergo coarse filtration and fine filtration in sequence to reduce the load on subsequent treatment. Preferably, step (2) is followed by the following steps: S1: The water body treated in step (2) is passed into several stages of series of secondary reaction chambers to recycle the active oxygen and nitrogen components, and to complete the oxidation, chain breaking, bond cleavage, ring opening and final mineralization of the pollutant molecular structure. S2: The water treated in step S1 flows into the end-of-pipe deep purification module, where activated carbon adsorption and nanofiltration membrane interception further remove trace intermediate products, odor substances and residual by-products to ensure water quality stability. S3: The exhaust gas after step S2 enters the exhaust gas treatment unit, which includes an activated carbon adsorption module and an α-MnO2 catalytic degradation module connected in sequence; the residual active oxygen and nitrogen components in the exhaust gas are treated by activated carbon adsorption and α-MnO2 catalytic degradation, and then discharged after meeting the standards. S4: Electrically connect the intelligent control module to the pretreatment module, the collaborative discharge module, several stages of series-connected secondary reaction chambers, and the exhaust gas treatment unit; the intelligent control module automatically completes feedback adjustment based on sensor data to achieve dynamic operation optimization and energy consumption control throughout the entire process.

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