Experimental device and method for enhancing activity of pulse discharge by using acousto-optic combined catalysis

Abstract

The application discloses an experimental device and method for enhancing pulse discharge activity by adopting sound-light combined catalysis, relates to the field of water treatment of new energy and environmental protection, and takes the gas-liquid-solid three-phase pulse discharge reactor filled with CQDs composite catalyst loaded porous medium, provided with quartz glass and an ultrasonic transducer, as the core, is matched with a positive high-voltage direct-current power supply, a negative high-voltage direct-current power supply, a double-channel signal generator, a high-voltage voltage probe, a high-frequency current probe, a four-channel oscilloscope, a gas-liquid supply metering assembly, a high-voltage semiconductor high-speed switch, an ultrasonic power supply and detection equipment, and each component is connected in a specific pipeline circuit to realize sound-light cooperation and parameter monitoring; the method is realized through four steps: first, fixing the gas phase component, selecting the best electrical parameters for the gas phase and the liquid phase flow, then determining the best activation parameters based on the same, then determining the best diffusion parameters in combination with the first two steps, and finally circulating the wastewater to be treated according to the best parameters, and adjusting in real time until reaching the standard; the application realizes multi-parameter dynamic feedback regulation, improves the yield of active ingredients and the treatment efficiency, reduces energy consumption, is strong in adaptability and easy to scale up.

Description

Technical Field

[0001] This invention relates to the fields of new energy and environmental water treatment, specifically an experimental device and method for enhancing pulsed discharge activity using a combination of acoustic and photocatalytic catalysis. Background Technology

[0002] In the field of new energy, breakthroughs in the energy efficiency and mass production of nitrogen fixation in the liquid phase are urgently needed. In the field of environmental protection, water pollution control has always been a key issue awaiting breakthroughs. Discharge plasma technology can generate active components such as ultraviolet light, high-energy electrons, hydroxyl radicals, hydrogen radicals, nitrogen oxides, ozone, and hydrogen peroxide through contact with the liquid phase. Effective control of these active components and their dosages is the key and research hotspot for the application of discharge plasma in nitrogen fixation in the liquid phase and water pollution control.

[0003] However, these technologies still have significant limitations in practical applications. On the one hand, they generally lack dynamic feedback control mechanisms for the reaction process, and parameter optimization relies heavily on trial and error based on experience. This makes it difficult to cope with complex and ever-changing parameter requirements and to adjust operating parameters in a timely manner, resulting in a significant decrease in processing efficiency. On the other hand, the systems have high energy consumption and low energy conversion efficiency. In particular, during the generation, mass transfer, and utilization of active ingredients, a large amount of energy is wasted on ineffective ionization or inefficient diffusion, increasing the cost of industrial applications.

[0004] Meanwhile, traditional photocatalytic systems often use fixed-wavelength light sources, which cannot be adapted to catalysts with broad-spectrum absorption characteristics, resulting in low quantum utilization. Furthermore, the frequency and power control of ultrasonic stimulation are often mismatched with the reaction system, making it difficult to fully leverage the mass transfer-promoting effect of cavitation. These problems collectively restrict the large-scale and efficient application of discharge plasma technology in liquid-phase nitrogen fixation and water pollution control. Therefore, developing a water treatment experimental device and method with dynamic feedback control capabilities, low energy consumption, and high adaptability has become an urgent need for the industry's development. Summary of the Invention

[0005] The purpose of this invention is to provide an experimental apparatus and method for enhancing pulsed discharge activity using a combination of acoustic and optical catalysis, in order to solve the problems of small discharge area, low processing capacity, and low processing efficiency in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: an experimental apparatus and method for enhancing pulsed discharge activity using a combination of acoustic and optical catalysis. The apparatus includes a gas-liquid-solid three-phase pulse discharge reactor, a positive high-voltage DC power supply, a negative high-voltage DC power supply, a first high-voltage semiconductor high-speed switch, a second high-voltage semiconductor high-speed switch, a dual-channel signal generator, an ultrasonic power supply, a four-channel oscilloscope, a high-voltage probe, a high-frequency current probe, a gas source, a water tank, a product tank, a gas pump, a liquid pump, a gas flow meter, a liquid flow meter, an active ingredient detector, a UV-Vis spectrophotometer, and a spectrometer. The gas-liquid-solid three-phase pulsed discharge reactor is the core reaction device. Under the combined action of high-voltage pulses and ultrasound, multiple sets of electrode gaps undergo discharge reactions in a gas, liquid, and solid three-phase environment. The positive and negative high-voltage DC power supplies drive the first and second high-voltage semiconductor high-speed switches through the adjustable drive signals of the signal frequency, pulse width and phase generated by the dual-channel signal generator, so as to realize the conversion and output of electrical energy in the form of positive high-voltage pulse, negative high-voltage pulse and positive and negative complementary high-voltage pulse, and to excite the gas-liquid-solid three-phase pulse discharge reactor to generate discharge. The four-channel oscilloscope acquires and displays voltage waveforms during high-voltage power supply output and gas-liquid-solid three-phase pulse discharge reactor discharge processes via a high-voltage voltage probe, and acquires and displays current waveforms during reactor discharge processes via a high-frequency current probe. The gas source is a mixture of oxygen and nitrogen, which provides the gas phase required for the reaction in the gas-liquid-solid three-phase pulse discharge reactor. The water tank provides the liquid phase required for the reaction and is transported to the reactor through relevant pipelines; The product box is used to collect the liquid and gas phases generated by the gas-liquid-solid three-phase pulse discharge reactor. The gas flow meter and the liquid flow meter are used to precisely control the gas flow rate and liquid flow rate entering the gas-liquid-solid three-phase pulse discharge reactor, respectively. The air pump and the liquid pump are used to adjust the relevant parameters of the air circuit and the water circuit, respectively. The first high-voltage semiconductor high-speed switch and the second high-voltage semiconductor high-speed switch serve as control switches for generating positive high-voltage pulses, negative high-voltage pulses, and positive and negative complementary high-voltage pulses. They are driven by a dual-channel signal generator with adjustable signal frequency, pulse width, and phase to realize the conversion and output of electrical energy in the form of positive high-voltage pulses, negative high-voltage pulses, and positive and negative complementary high-voltage pulses. The ultrasonic power supply provides electrical energy to the ultrasonic transducer in the gas-liquid-solid three-phase pulsed discharge reactor, drives the ultrasonic transducer to work, generates ultrasonic vibration, and realizes combined acoustic and optical catalysis. The active ingredient detector detects the active ingredients in the solution after the gas-liquid-solid three-phase pulsed discharge reactor reaction. The UV-Vis spectrophotometer uses ultraviolet-visible spectrophotometry to detect the absorption of ultraviolet-visible light by substances in the solution after the reaction. The spectrometer is used to analyze the spectral properties of substances during or after the reaction. The gas-liquid-solid three-phase pulse discharge reactor includes: an air inlet, a water inlet, an air outlet, a water outlet, an ultrasonic transducer, a high-voltage electrode, an insulating shell, and a porous medium; The porous medium is a small spherical catalytic material filled with C3N4, C3N5 or Al2O3 and Cu2O or Cu2O-SnO2 composite combination, and CQDs of different concentrations are attached to its surface; The water tank outlet is connected to the liquid pump inlet, the liquid pump outlet is connected to the liquid phase flow meter inlet, and the liquid phase flow meter outlet is connected to the water inlet of the gas-liquid-solid three-phase discharge reactor. The air source is connected to the inlet of the air pump, the outlet of the air pump is connected to the inlet of the gas phase flow meter, and the outlet of the gas phase flow meter is connected to the air inlet of the gas-liquid-solid three-phase discharge reactor. The first interface of the first high-voltage semiconductor high-speed switch and the second high-voltage semiconductor high-speed switch are connected to a positive high-voltage DC power supply; the third interface of the first high-voltage semiconductor high-speed switch and the second high-voltage semiconductor high-speed switch are connected to a negative high-voltage DC power supply. The second interface of the first high-voltage semiconductor high-speed switch is connected to the high-voltage pulse input interface of the gas-liquid-solid three-phase discharge reactor, and the fourth interface of the first high-voltage semiconductor high-speed switch is used to input the drive signal. The first channel of the dual-channel signal generator is connected to the fourth interface of the first high-voltage semiconductor high-speed switch, and the second channel of the dual-channel signal generator is connected to the fourth interface of the second high-voltage semiconductor high-speed switch. The second interface of the first and second high-voltage semiconductor high-speed switches is connected to the high-voltage pulse input interface of the gas-liquid-solid three-phase discharge reactor. The first interface of the first high-voltage semiconductor high-speed switch is connected to the first interface of the second high-voltage semiconductor high-speed switch; the third interface of the first high-voltage semiconductor high-speed switch is connected to the third interface of the second high-voltage semiconductor high-speed switch. The output interface of the ultrasonic power supply is connected to the ultrasonic transducer on the outside of the gas-liquid-solid three-phase discharge reactor. The high-voltage probe of the first channel of the four-channel oscilloscope is connected to the connection line between the first interface of the first high-voltage semiconductor high-speed switch and the first interface of the second high-voltage semiconductor high-speed switch; the high-voltage probe of the second channel is connected to the connection line between the third interface of the first high-voltage semiconductor high-speed switch and the third interface of the second high-voltage semiconductor high-speed switch; the high-frequency current probe of the third channel is connected to the cable of the second interface of the second high-voltage semiconductor high-speed switch; and the high-frequency current probe of the fourth channel is connected to the cable of the second interface of the first high-voltage semiconductor high-speed switch. The upper output port of the gas-liquid-solid three-phase discharge reactor is connected to the inlet of the product box, and the outlet of the product box is connected to the active ingredient detector and the UV-Vis spectrophotometer. The spectrometer's spectral detection port is connected to the window of the gas-liquid-solid three-phase discharge reactor.

[0007] The methods include: Step S1: Set fixed gas phase flow rate and liquid phase flow rate, adjust the voltage of the high voltage DC power supply, the pulse width and phase relationship of the dual-channel signal generator, and control the high voltage semiconductor switch through the two output channels of the signal generator to achieve high voltage discharge through three excitation modes: positive pulse, negative pulse and positive-negative complementary pulse. By detecting the electrical parameters and the concentration of active ingredients, calculate the energy conversion efficiency, and screen out the combination of voltage, pulse width and excitation mode with the highest energy conversion efficiency as the optimal electrical parameters. Step S2: Based on the optimal electrical parameters of pulsed discharge determined in Step S1, a carbon quantum dot composite catalyst material is selected, the concentration of carbon quantum dots in the composite catalyst material is adjusted, and the wavelength and intensity of light irradiation are adjusted. Combined with the detection results of the concentration of active ingredients in the liquid phase, the optimal carbon quantum dot concentration, catalyst type, light irradiation wavelength and intensity are determined to form the optimal activation parameters. Step S3: Based on the optimal electrical parameters in Step S1 and the optimal activation parameters in Step S2, adjust the flow ratio of the gas phase and the liquid phase and the gas phase composition to change the gas content and flow rate of the fluid in the reaction system. Simultaneously adjust the power and frequency of the ultrasonic transducer. By detecting the concentration of the active ingredient and the reaction efficiency, determine the optimal fluid flow rate, gas content, ultrasonic frequency and power to form the optimal diffusion parameters. Step S4: The wastewater to be treated is introduced into the product tank, and the reaction system is operated according to the optimal electrical parameters, optimal activation parameters, and optimal diffusion parameters determined in steps S1 to S3, so that the wastewater to be treated circulates and reacts in the system to achieve efficient nitrogen fixation or pollutant degradation in the liquid phase.

[0008] Furthermore, step S1 includes: Step S1-1: Set the voltage adjustment range of the positive high voltage DC power supply and the negative high voltage DC power supply, the pulse width adjustment range of the dual-channel signal generator, fix the discharge frequency, maintain a fixed gas phase flow rate and liquid phase flow rate, and determine the three excitation methods of positive pulse, negative pulse and positive-negative complementary pulse as test variables. Step S1-2: With a fixed pulse width, adjust the voltage according to the set step size. Under each parameter combination, use three excitation methods to carry out the discharge reaction. Record the voltage and current waveforms and the concentration of active ingredients after each reaction. Step S1-3: Based on the voltage and current waveforms recorded in step S1-2, the power supply energy is calculated using the full width at half maximum (FWHM) method, and the energy conversion efficiency is calculated in combination with the concentration of active ingredients. After two consecutive step size adjustments, the energy conversion efficiency decreases in the second step compared to the first step, and the parameters in the first step are marked as local optima. Step S1-4: Integrate the energy conversion efficiency data of all parameter combinations, calculate the approximate partial derivatives of energy conversion efficiency with respect to voltage and pulse width, and find the extreme points where the partial derivatives are approximately zero. Step S1-5: If there is more than one extreme point, calculate the energy consumption corresponding to the extreme point, and select the voltage, pulse width and excitation method corresponding to the extreme point with the lowest energy consumption and the highest energy conversion efficiency as the optimal electrical parameters.

[0009] Furthermore, step S2 includes: Step S2-1: Based on the optimal electrical parameters determined in step S1, select a variety of carbon quantum dot composite catalytic materials and carry out discharge reactions under the same experimental conditions. Detect and compare the active ingredient concentration and energy conversion efficiency corresponding to different catalysts, and screen out the catalyst type with the highest active ingredient concentration and the best energy conversion efficiency as the target catalyst. Step S2-2: For the target catalyst determined in step S2-1, adjust the concentration of carbon quantum dots according to the set step size, carry out the discharge reaction at each concentration, detect the concentration of active ingredients and energy conversion efficiency, and select the carbon quantum dot concentration corresponding to the highest energy conversion efficiency. Step S2-3: Based on the band gap of the target catalyst selected in step S2-1, calculate the incident light wavelength threshold using the formula, replace different narrowband filters to achieve specific wavelength irradiation, detect the concentration of active ingredients at each wavelength, and select the wavelength with the highest concentration as the preferred wavelength. Step S2-4: Under the preferred wavelength determined in step S2-3, gradually adjust the light intensity according to the set gradient. Monitor the change in the concentration of active ingredient after each adjustment. When the concentration of active ingredient no longer increases with the increase of light intensity, determine the light intensity at this time. Step S2-5: Activation parameter integration. The target catalyst type determined in step S2-1, the carbon quantum dot concentration determined in step S2-2, and the light parameters determined in steps S2-3 and S2-4 are combined to form the optimal activation parameters.

[0010] Furthermore, step S3 includes: Step S3-1: Load the optimal electrical parameters of step S1 and the optimal activation parameters of step S2, adjust the gas-liquid flow rate according to the set step size to change the fluid velocity and gas content, detect the diffusion uniformity and reaction efficiency of the active ingredient under each parameter combination, and select the flow rate and gas content with the best diffusion effect and the highest reaction efficiency. Step S3-2: Under the optimal fluid parameters determined in step S3-1, test the average bubble size in the reaction system, calculate the theoretical optimal ultrasonic frequency using the Minnaert resonance frequency formula, adjust the frequency in steps towards both high and low frequencies with the theoretical frequency as the center, detect the diffusion rate of the active ingredient at each frequency, and determine the optimal ultrasonic frequency. Step S3-3: Based on the optimal ultrasonic frequency determined in step S3-2, adjust the power supply of the ultrasonic transducer according to the set gradient. After each adjustment, detect the concentration of the active ingredient. When the concentration of the active ingredient reaches its maximum and no longer changes, determine the optimal ultrasonic power. Step S3-4: Combine the fluid parameters determined in step S3-1 with the ultrasonic parameters determined in steps S3-2 and S3-3 to form the optimal diffusion parameters.

[0011] Furthermore, step S4 includes: Step S4-1: Import the wastewater to be treated into the product tank, and start the high-voltage pulse power supply, air pump, liquid pump and ultrasonic transducer according to the optimal parameters determined in steps S1-5, S2-4 and S3-4. Monitor the voltage and current waveforms in real time through a digital oscilloscope. Step S4-2: Monitor the concentration of active ingredients in real time using an active ingredient detector and record the data changes; Step S4-3: Periodically sample and test the yield of active ingredients or the degradation efficiency of pollutants in the water. If the yield or degradation rate continues to decline, adjust the fluid flow rate or gas content according to the optimization logic determined in step S3-1 to optimize the mass transfer effect. Step S4-4: Continue monitoring and adjusting steps S4-1 to S4-3 until the wastewater pollutant concentration drops to the discharge standard, then stop the system operation.

[0012] Compared with the prior art, the beneficial effects of the present invention are: 1. Through carbon nitride ( or ) or aluminum oxide ( )and or By forming photocatalytic materials, photocatalytic activity is effectively improved. Utilizing the broad-spectrum absorption and electron storage characteristics of CQDs, combined with acousto-optic synergy, the types and dosages of active ingredients are effectively controlled, significantly increasing the generation and utilization rate of active ingredients compared to traditional pulsed discharge technology. This provides an optimized control parameter model for the activation control reaction rate of liquid-phase nitrogen fixation and water pollutant degradation. Simultaneously, through the synergistic control of optimal electrical parameters, activation parameters, and diffusion parameters, the reaction diffusion rate is effectively enhanced, not only shortening the reaction time but also improving the utilization rate of active ingredients, providing an optimized control parameter model for the diffusion reaction rate of liquid-phase nitrogen fixation and water pollutant degradation.

[0013] 2. By accurately calculating the power supply energy using the full width at half maximum (WWHM) method, coupled with a dynamic feedback control mechanism, ineffective energy loss is effectively reduced, resulting in a significant improvement in energy conversion efficiency compared to existing technologies. The generation and utilization rate of active ingredients per unit energy are greatly increased. In addition, by optimizing the matching of ultrasonic power and frequency, and precisely matching light intensity with catalyst spectrum, energy waste is avoided, and the total energy consumption of the system is significantly reduced. While ensuring the treatment effect, the goal of energy saving and consumption reduction is achieved. 3. It supports flexible switching between three excitation modes: positive pulse, negative pulse, and positive-negative complementary pulse. At the same time, it monitors in real time, effectively avoiding the problem of sharp drop in processing efficiency caused by parameter mismatch in traditional technologies. During continuous operation of the system, the types of active ingredients generated can be selected as either active nitrogen-based or active oxygen-based, providing options for efficient application in subsequent liquid-phase nitrogen fixation and degradation of pollutants in water. Attached Figure Description

[0014] Figure 1 This is a schematic diagram of the experimental device for enhancing pulsed discharge activity using acousto-optic combined catalysis, as described in this invention. Figure 2 This is a schematic diagram of the gas-liquid-solid three-phase pulsed discharge reactor of the experimental device for enhancing pulsed discharge activity using combined acoustic-optical catalysis according to the present invention. Figure 3 This is a schematic flowchart of the method for enhancing pulsed discharge activity using acousto-optic combined catalysis according to the present invention; The diagram is labeled as follows: 1-Gas-Liquid-Solid Three-Phase Pulse Discharge Reactor; 2-Positive High Voltage DC Power Supply; 3-Four-Channel Oscilloscope; 4-Air Source; 5-Water Tank; 6-Product Tank; 7-Air Pump; 8-Liquid Pump; 9-Gas Flow Meter; 10-Liquid Flow Meter; 11-First High Voltage Semiconductor High-Speed ​​Switch; 12-Second High Voltage Semiconductor High-Speed ​​Switch; 13-Ultrasonic Power Supply; 14-Active Ingredient Detector; 15-UV-Vis Spectrophotometer; 16-Spectrometer; 17-Computer; 18-First Switch; 19-Second Switch; 20-First Interface of First High Voltage Semiconductor High-Speed ​​Switch; 21-Second Interface of First High Voltage Semiconductor High-Speed ​​Switch; 22-Third Interface of First High Voltage Semiconductor High-Speed ​​Switch; 23-First High Voltage... 24 - Fourth interface of semiconductor high-speed switch; 25 - First interface of second high-voltage semiconductor high-speed switch; 26 - Fourth interface of second high-voltage semiconductor high-speed switch; 27 - Third interface of second high-voltage semiconductor high-speed switch; 28 - First channel of four-channel oscilloscope; 29 - Second channel of four-channel oscilloscope; 30 - Third channel of four-channel oscilloscope; 31 - Fourth channel of four-channel oscilloscope; 32 - Spectrometer detection port; 33 - Negative high-voltage DC power supply; 34 - Ultrasonic power supply; 1a - Air inlet; 1b - Water inlet; 1c - Air outlet; 1d - Water outlet; 1e - Ultrasonic transducer; 1f - High-voltage electrode; 1g - Insulating shell; 1h - Porous medium. Detailed Implementation

[0015] 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, and 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.

[0016] Example: Figure 1 , Figure 2 and Figure 3 As shown, the present invention provides a technical solution, employing an experimental apparatus and method for enhancing pulsed discharge activity through combined acousto-optic catalysis. The apparatus includes a gas-liquid-solid three-phase pulse discharge reactor, a positive high-voltage DC power supply, a negative high-voltage DC power supply, a dual-channel signal generator, a four-channel oscilloscope, a high-voltage probe, a high-frequency current probe, a gas source, a water tank, a product tank, a gas pump, a liquid pump, a gas phase flow meter, a liquid phase flow meter, a first high-voltage semiconductor high-speed switch, a second high-voltage semiconductor high-speed switch, an ultrasonic power supply, an active ingredient detector, a UV-Vis spectrophotometer, and a spectrometer. The gas-liquid-solid three-phase pulsed discharge reactor is the core reaction device. Under the combined action of high-voltage pulses and ultrasound, multiple sets of electrode gaps undergo discharge reactions in a gas, liquid, and solid three-phase environment. The positive and negative high-voltage DC power supplies drive the first and second high-voltage semiconductor high-speed switches through the adjustable drive signals of the signal frequency, pulse width and phase generated by the dual-channel signal generator, so as to realize the conversion and output of electrical energy in the form of positive high-voltage pulse, negative high-voltage pulse and positive and negative complementary high-voltage pulse, and to excite the gas-liquid-solid three-phase pulse discharge reactor to generate discharge. The four-channel oscilloscope acquires and displays voltage waveforms during high-voltage power supply output and reactor discharge processes via a high-voltage voltage probe, and acquires and displays current waveforms during reactor discharge processes via a high-frequency current probe. The gas source is a mixture of oxygen and nitrogen, which provides the gas phase required for the reaction in the gas-liquid-solid three-phase pulse discharge reactor. The water tank provides the liquid phase required for the reaction and is transported to the reactor through relevant pipelines; The product box is used to collect the liquid and gas phases generated by the gas-liquid-solid three-phase pulse discharge reactor. The gas flow meter and the liquid flow meter are used to precisely control the gas flow rate and liquid flow rate entering the gas-liquid-solid three-phase pulse discharge reactor, respectively. The air pump and the liquid pump are used to adjust the relevant parameters of the air circuit and the water circuit, respectively. The first high-voltage semiconductor high-speed switch and the second high-voltage semiconductor high-speed switch serve as control switches for generating positive high-voltage pulses, negative high-voltage pulses, and positive and negative complementary high-voltage pulses. They are driven by a dual-channel signal generator with adjustable signal frequency, pulse width, and phase to realize the conversion and output of electrical energy in the form of positive high-voltage pulses, negative high-voltage pulses, and positive and negative complementary high-voltage pulses. The ultrasonic power supply provides electrical energy to the ultrasonic transducer in the gas-liquid-solid three-phase pulsed discharge reactor, drives the ultrasonic transducer to work, generates ultrasonic vibration, and realizes combined acoustic and optical catalysis. The active ingredient detector detects the active ingredients in the solution after the gas-liquid-solid three-phase pulsed discharge reactor reaction. The UV-Vis spectrophotometer uses ultraviolet-visible spectrophotometry to detect the absorption of ultraviolet-visible light by substances in the solution after the reaction. The spectrometer is used to analyze the spectral properties of substances during or after the reaction. The gas-liquid-solid three-phase pulse discharge reactor includes: an air inlet, a water inlet, an air outlet, a water outlet, an ultrasonic transducer, a high-voltage electrode, an insulating shell, and a porous medium; The porous medium is filled with carbon nitride ( or ) or aluminum oxide ( )and or Composite photocatalytic media incorporating and attaching CQDs; The water tank outlet is connected to the liquid pump inlet, the liquid pump outlet is connected to the liquid phase flow meter inlet, and the liquid phase flow meter outlet is connected to the water inlet of the gas-liquid-solid three-phase discharge reactor. The air source is connected to the inlet of the air pump, the outlet of the air pump is connected to the inlet of the gas phase flow meter, and the outlet of the gas phase flow meter is connected to the air inlet of the gas-liquid-solid three-phase discharge reactor. The first interface of the first high-voltage semiconductor high-speed switch and the second high-voltage semiconductor high-speed switch are connected to a positive high-voltage DC power supply; the third interface of the first high-voltage semiconductor high-speed switch and the second high-voltage semiconductor high-speed switch are connected to a negative high-voltage DC power supply. The second interface of the first high-voltage semiconductor high-speed switch is connected to the high-voltage pulse input interface of the gas-liquid-solid three-phase discharge reactor, and the fourth interface of the first high-voltage semiconductor high-speed switch is used to input the drive signal. The first channel of the dual-channel signal generator is connected to the fourth interface of the first high-voltage semiconductor high-speed switch, and the second channel of the dual-channel signal generator is connected to the fourth interface of the second high-voltage semiconductor high-speed switch. The second interface of the first and second high-voltage semiconductor high-speed switches is connected to the high-voltage pulse input interface of the gas-liquid-solid three-phase discharge reactor. The first interface of the first high-voltage semiconductor high-speed switch is connected to the first interface of the second high-voltage semiconductor high-speed switch; the third interface of the first high-voltage semiconductor high-speed switch is connected to the third interface of the second high-voltage semiconductor high-speed switch. The output interface of the ultrasonic power supply is connected to the ultrasonic transducer on the outside of the gas-liquid-solid three-phase discharge reactor. The high-voltage probe of the first channel of the four-channel oscilloscope is connected to the connection line between the first interface of the first high-voltage semiconductor high-speed switch and the first interface of the second high-voltage semiconductor high-speed switch; the high-voltage probe of the second channel is connected to the connection line between the third interface of the first high-voltage semiconductor high-speed switch and the third interface of the second high-voltage semiconductor high-speed switch; the high-frequency current probe of the third channel is connected to the cable of the second interface of the second high-voltage semiconductor high-speed switch; and the high-frequency current probe of the fourth channel is connected to the cable of the second interface of the first high-voltage semiconductor high-speed switch. The upper output port of the gas-liquid-solid three-phase discharge reactor is connected to the inlet of the product box, and the outlet of the product box is connected to the active ingredient detector and the UV-Vis spectrophotometer. The spectrometer's spectral detection port is connected to the window of the gas-liquid-solid three-phase discharge reactor.

[0017] The methods include: Step S1: Set fixed gas phase flow rate and liquid phase flow rate, adjust the voltage of the high voltage DC power supply, the pulse width and phase relationship of the dual-channel signal generator, and control the high voltage semiconductor switch through the two output channels of the signal generator to achieve high voltage discharge through three excitation modes: positive pulse, negative pulse and positive-negative complementary pulse. By detecting the electrical parameters and the concentration of active ingredients, calculate the energy conversion efficiency, and screen out the combination of voltage, pulse width and excitation mode with the highest energy conversion efficiency as the optimal electrical parameters. Step S2: Based on the optimal electrical parameters of pulsed discharge determined in Step S1, a carbon quantum dot composite catalyst material is selected, the concentration of carbon quantum dots in the composite catalyst material is adjusted, and the wavelength and intensity of light irradiation are adjusted. Combined with the detection results of the concentration of active ingredients in the liquid phase, the optimal carbon quantum dot concentration, catalyst type, light irradiation wavelength and intensity are determined to form the optimal activation parameters. Step S3: Based on the optimal electrical parameters in Step S1 and the optimal activation parameters in Step S2, adjust the flow ratio of the gas phase and the liquid phase and the gas phase composition to change the gas content and flow rate of the fluid in the reaction system. Simultaneously adjust the power and frequency of the ultrasonic transducer. By detecting the concentration of the active ingredient and the reaction efficiency, determine the optimal fluid flow rate, gas content, ultrasonic frequency and power to form the optimal diffusion parameters. Step S4: The wastewater to be treated is introduced into the product tank, and the reaction system is operated according to the optimal electrical parameters, optimal activation parameters, and optimal diffusion parameters determined in steps S1 to S3, so that the wastewater to be treated circulates and reacts in the system to achieve efficient nitrogen fixation or pollutant degradation in the liquid phase.

[0018] Furthermore, step S1 includes: Step S1-1: Set the voltage adjustment range of the positive high voltage DC power supply and the negative high voltage DC power supply to 2.0kV to 10.0kV and -2.0kV to -10kV respectively, with an adjustment step of 2.0kV. The pulse width adjustment range is 100.0-1000.0ns, with an adjustment step of 50ns to 200.0ns. The fixed discharge frequency is 1.0kHz. Set the fixed gas phase flow rate to 9.0LPM and the liquid phase flow rate to 1.0LPM. Keep the gas phase flow rate and liquid phase flow rate constant. Operate using positive pulse, negative pulse, and positive-negative complementary pulse as excitation mode variables. Steps S1-2: With a fixed pulse width of 200 ns, adjust the voltage in 2.0 kV steps, sequentially at 2.0 kV, 4.0 kV, 6.0 kV, 8.0 kV, and 10.0 kV. At each voltage, use three excitation methods: positive pulse excitation, negative pulse excitation, and complementary positive-negative pulse excitation. The reaction time is 20 minutes. After each reaction, record the voltage and current waveforms using a four-channel oscilloscope. Detect the concentration of the active ingredient using an active ingredient detector. The active ingredient detection target is... , and Repeat the operation, adjusting the pulse width in 200ns increments, with the adjustment sequence being 200ns, 400ns, 600ns, 800ns, and 1000ns, to complete the test of all parameter combinations. Step S1-3: Based on the recorded voltage and current waveforms, calculate the power supply energy using the full width at half maximum (FWHM) method. The formula is as follows: , where P i The peak power of the power supply cycle, t i This represents the time duration of the half-peak power. When the voltage is 6.0kV, the pulse width is 500ns, and the excitation is a negative pulse, the seven peak-to-peak power values ​​within a single power supply cycle are 23.8kW, 20.7kW, 17.2kW, 12.8kW, 8.1kW, 39.0kW, and 1.1kW, respectively, corresponding to half-peak times of 32.2ns, 40.3ns, 35.8ns, 47.6ns, 28.3ns, 48.7ns, and 20.6ns. Substituting these values ​​into the formula... The energy obtained for a single cycle is 0.00498 J. Combined with the concentration of the active ingredient, the energy conversion efficiency formula is applied. Calculate the energy conversion efficiency EER, where c0 is the initial concentration, c1 is the concentration after the reaction, and V1 is the liquid volume; Steps S1-4: Integrate the EER data of all parameter combinations, plot the "voltage-pulse width-EER" response plane, and filter out the parameter combinations with higher EER by comparing the EER values ​​of different parameter combinations. Step S1-5: Verification results of the highest concentration of active ingredient under negative pulse excitation. By comparing with the selected parameter combinations with higher EER, the optimal electrical parameters are determined to be: voltage 6.0kV, pulse width 500.0ns, negative pulse excitation, and frequency 5.0kHz.

[0019] Furthermore, step S2 includes: Step S2-1: Based on the optimal electrical parameters in step S1, select... , , , , , , , Eight carbon quantum dot composite catalytic materials were filled into the reactor to carry out discharge reactions; the concentration of active components and EER of different catalysts were detected and compared, and the catalyst with the highest concentration of active components and the best EER was screened. Step S2-2: For the screened catalyst, adjust the CQDs concentration in 0.5wt% increments, with the adjustment order being 0.5wt%, 1.0wt%, ..., 5.0wt%, and conduct discharge reactions at each concentration; determine the optimal CQDs concentration by detecting the concentration of active ingredients and EER. Step S2-3: Given Forbidden Bandwidth , Forbidden Bandwidth , Forbidden Bandwidth , Forbidden Bandwidth , Forbidden Bandwidth According to the wavelength threshold formula Calculate the corresponding wavelength; by replacing the narrowband filter, detect the concentration of active ingredients at different wavelengths to determine the preferred wavelength of the external irradiation source; Step S2-4: At the preferred wavelength, adjust the light intensity according to the gradient, based on the carrier generation rate formula. , where α is the light absorption coefficient, I is the light intensity, and hν is the photon energy, and the data on the change in the concentration of active ingredients under different light intensities are recorded; Step S2-5: The optimal activation parameters are: the optimal concentration of the target catalyst and its CQDs, the preferred wavelength, and the corresponding intensity modulation range.

[0020] Furthermore, step S3 includes: Step S3-1: Load the optimal electrical and activation parameters, adjust the gas-liquid flow rate in steps, and apply the fluid velocity formula. Q G Q is the gas phase flow rate. L S is the liquid phase flow rate. T S is the total cross-sectional area of ​​the reactor. C Formula for gas content as the area occupied by the catalyst Adjust the parameters; adjust the gas-liquid flow rate to stabilize the gas content at 0.9, at which point the active ingredients diffuse evenly and the reaction efficiency is the highest. Determine the optimal fluid parameters as a gas content of 0.9 and a suitable flow rate. Step S3-2: Under optimal fluid parameters, test the average bubble radius R. e =300μm, according to the Minnaert resonant frequency formula In water, ρ = 1000 kg / m³ 3 p h =1.013×105Pa. Calculate the theoretical frequency range, adjust the frequency by step size, and detect the diffusion rate of active ingredients to determine the optimal ultrasonic frequency. Step S3-3: At the optimal ultrasonic frequency, set the power adjustment gradient, test the concentration and diffusion efficiency of the active ingredient at different powers, and record the data changes; Step S3-4: Integrate the parameters from steps S3-1 to S3-3 to form the optimal combination of diffusion parameters: gas content 0.9, suitable flow rate, ultrasonic frequency 10kHz and corresponding ultrasonic power adjustment range.

[0021] Furthermore, step S4 includes: Step S4-1: Import the wastewater to be treated into the product tank, and start the high-voltage pulse power supply, air pump, liquid pump, ultrasonic transducer and halogen light source according to the optimal parameters determined in steps S1, S2 and S3. Monitor the voltage and current waveforms in real time through a digital oscilloscope. Step S4-2: Monitor the concentration in real time using an active ingredient detector and record the data changes; Step S4-3: Take samples periodically to detect the value of nitrogen oxides and other pollutants in the water, and calculate the production rate of active ingredients and the degradation rate of pollutants; if the production rate of active ingredients and the degradation rate of pollutants continue to decrease, adjust the gas-liquid flow rate according to the fluid parameter optimization logic in step S3-1 to keep the gas content stable at 0.9, and optimize the diffusion and mass transfer effect in the reactor. Step S4-4: Continue monitoring and adjusting steps S4-1 to S4-3 until the concentration of nitrogen oxides or pollutants in the water reaches the predetermined standard, then stop the system operation.

[0022] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

Claims

1. An experimental apparatus for enhancing pulsed discharge activity using a combination of acoustic and optical catalysis, characterized in that: The device includes a gas-liquid-solid three-phase pulse discharge reactor, a positive high-voltage DC power supply, a negative high-voltage DC power supply, a dual-channel signal generator, a high-voltage probe, a high-frequency current probe, a four-channel oscilloscope, a gas source, a water tank, a product tank, a gas pump, a liquid pump, a gas phase flow meter, a liquid phase flow meter, a first high-voltage semiconductor high-speed switch, a second high-voltage semiconductor high-speed switch, an ultrasonic power supply, an active ingredient detector, a UV-Vis spectrophotometer, and a spectrometer. The gas-liquid-solid three-phase pulsed discharge reactor is the core reaction device. Under the combined action of a positive high-voltage DC power supply, a negative high-voltage DC power supply, a dual-channel signal generator, a high-voltage semiconductor switch, and ultrasound, the gas, liquid, and solid phases react. The positive and negative high-voltage DC power supplies generate polarity-adjustable high-voltage pulse power supplies through a dual-channel signal generator and a high-voltage pulse switch, providing positive and negative pulse high-voltage power supply to the gas-liquid-solid three-phase pulse discharge reactor, and exciting the discharge gap in the reactor to generate pulse discharge. The four-channel oscilloscope is used to acquire and display the voltage and current waveforms transmitted from the high-voltage power supply to the electrode terminals of the gas-liquid-solid three-phase pulse discharge reactor. The air source provides the gas phase required for the reaction in the gas-liquid-solid three-phase pulse discharge reactor. The water tank provides the liquid phase required for the reaction and is transported to the reactor through relevant pipelines; The product box is used to collect the liquid phase generated by the gas-liquid-solid three-phase pulse discharge reactor. The gas flow meter and the liquid flow meter are used to precisely control the gas flow rate and liquid flow rate entering the gas-liquid-solid three-phase pulse discharge reactor, respectively. Liquid flow rate; The air pump and the liquid pump are used to adjust the relevant parameters of the air circuit and the water circuit, respectively. The first high-voltage semiconductor high-speed switch and the second high-voltage semiconductor high-speed switch serve as high-voltage switches to control the positive pulse, negative pulse, or positive-negative complementary pulse applied to the gas-liquid-solid three-phase pulse discharge reactor. The ultrasonic power supply provides electrical energy to the ultrasonic transducer in the gas-liquid-solid three-phase pulsed discharge reactor, drives the ultrasonic transducer to work, generates ultrasonic vibration, and realizes combined acoustic and optical catalysis. The active ingredient detector detects the active ingredients in the solution after the gas-liquid-solid three-phase pulsed discharge reactor reaction. The UV-Vis spectrophotometer uses ultraviolet-visible spectrophotometry to detect the absorption of ultraviolet-visible light by the products in the solution after the reaction. The spectrometer is used to observe the spectral characteristics of the discharge and analyze the active components in the discharge region.

2. The experimental apparatus for enhancing pulsed discharge activity using combined acousto-optic catalysis according to claim 1, characterized in that: The gas-liquid-solid three-phase pulse discharge reactor includes: an air inlet, a water inlet, an air outlet, a water outlet, an ultrasonic transducer, a high-voltage electrode, an insulating shell, and a porous medium; The porous medium is a medium filled with CQDs composite catalyst support.

3. The experimental apparatus for enhancing pulsed discharge activity using combined acousto-optic catalysis according to claim 2, characterized in that: The water tank outlet is connected to the liquid pump inlet, the liquid pump outlet is connected to the liquid phase flow meter inlet, and the liquid phase flow meter outlet is connected to the water inlet of the gas-liquid-solid three-phase discharge reactor. The air source is connected to the inlet of the air pump, the outlet of the air pump is connected to the inlet of the gas phase flow meter, and the outlet of the gas phase flow meter is connected to the air inlet of the gas-liquid-solid three-phase discharge reactor. The positive high voltage DC power supply is connected to the first interface of the first high voltage semiconductor high speed switch and the first interface of the second high voltage semiconductor high speed switch; the negative high voltage DC power supply is connected to the third interface of the first high voltage semiconductor high speed switch and the third interface of the second high voltage semiconductor high speed switch. The first channel of the dual-channel signal generator is connected to the fourth interface of the first high-voltage semiconductor high-speed switch, and the second channel of the dual-channel signal generator is connected to the fourth interface of the second high-voltage semiconductor high-speed switch. The second interface of the first and second high-voltage semiconductor high-speed switches is connected to the high-voltage pulse input interface of the gas-liquid-solid three-phase discharge reactor. The first interface of the first high-voltage semiconductor high-speed switch is connected to the first interface of the second high-voltage semiconductor high-speed switch; the third interface of the first high-voltage semiconductor high-speed switch is connected to the third interface of the second high-voltage semiconductor high-speed switch. The output interface of the ultrasonic power supply is connected to the ultrasonic transducer on the outside of the gas-liquid-solid three-phase discharge reactor. The high-voltage probe of the first channel of the four-channel oscilloscope is connected to the connection line between the first interface of the first high-voltage semiconductor high-speed switch and the first interface of the second high-voltage semiconductor high-speed switch; the high-voltage probe of the second channel is connected to the connection line between the third interface of the first high-voltage semiconductor high-speed switch and the third interface of the second high-voltage semiconductor high-speed switch; the high-frequency current probe of the third channel is connected to the cable of the second interface of the second high-voltage semiconductor high-speed switch; and the high-frequency current probe of the fourth channel is connected to the cable of the second interface of the first high-voltage semiconductor high-speed switch. The upper output port of the gas-liquid-solid three-phase discharge reactor is connected to the inlet of the product box, and the outlet of the product box is connected to the active ingredient detector and the UV-Vis spectrophotometer. The spectrometer's spectral detection port is connected to the window of the gas-liquid-solid three-phase discharge reactor.

4. A method for enhancing pulsed discharge activity using acousto-optic combined catalysis, applied to the experimental apparatus for enhancing pulsed discharge activity using acousto-optic combined catalysis as described in any one of claims 1-3, characterized in that: Includes the following steps: Step S1: Set fixed gas phase flow rate and liquid phase flow rate, adjust the voltage of the high voltage DC power supply, the pulse width and phase relationship of the signal generator, and control the high voltage semiconductor switch through the two output channels of the signal generator to achieve high voltage discharge through three excitation modes: positive pulse, negative pulse and positive-negative complementary pulse. By detecting the electrical parameters and the concentration of active ingredients, calculate the energy conversion efficiency, and screen out the combination of voltage, pulse width and excitation mode with the highest energy conversion efficiency as the optimal electrical parameters. Step S2: Based on the optimal electrical parameters of pulsed discharge determined in Step S1, a carbon quantum dot composite catalyst material is selected, the concentration of carbon quantum dots in the composite catalyst material is adjusted, and the wavelength and intensity of light irradiation are adjusted. Combined with the detection results of the concentration of active ingredients in the liquid phase, the optimal carbon quantum dot concentration, catalyst type, light irradiation wavelength and intensity are determined to form the optimal activation parameters. Step S3: Based on the optimal electrical parameters in Step S1 and the optimal activation parameters in Step S2, adjust the flow ratio of the gas phase and the liquid phase and the gas phase composition to change the gas content and flow rate of the fluid in the reaction system. Simultaneously adjust the power and frequency of the ultrasonic transducer. By detecting the concentration of the active ingredient and the reaction efficiency, determine the optimal fluid flow rate, gas content, ultrasonic frequency and power to form the optimal diffusion parameters. Step S4: The wastewater to be treated is introduced into the product tank, and the experimental device is run according to the optimal electrical parameters, optimal activation parameters, and optimal diffusion parameters determined in steps S1 to S3, so that the wastewater to be treated circulates and reacts in the experimental device to achieve efficient nitrogen fixation or pollutant degradation in the liquid phase.

5. The method for enhancing pulsed discharge activity using acousto-optic combined catalysis according to claim 4, characterized in that: Step S1 includes: Step S1-1: Set the voltage adjustment range of the positive high voltage DC power supply and the negative high voltage DC power supply, the pulse width adjustment range of the dual-channel signal generator, fix the discharge frequency, maintain a fixed gas phase flow rate and liquid phase flow rate, and determine the three excitation methods of positive pulse, negative pulse and positive-negative complementary pulse as test variables. Step S1-2: With a fixed pulse width, adjust the voltage according to the set step size. Under each parameter combination, use three excitation methods to carry out the discharge reaction. Record the voltage and current waveforms and the concentration of active ingredients after each reaction. Step S1-3: Based on the voltage and current waveforms recorded in step S1-2, the power supply energy is calculated using the full width at half maximum (FWHM) method, and the energy conversion efficiency is calculated in combination with the concentration of active ingredients. After two consecutive step size adjustments, the energy conversion efficiency decreases in the second step compared to the first step, and the parameters in the first step are marked as local optima. Step S1-4: Integrate the energy conversion efficiency data of all parameter combinations, calculate the approximate partial derivatives of energy conversion efficiency with respect to voltage and pulse width, and find the extreme points where the partial derivatives are approximately zero. Step S1-5: If there is more than one extreme point, calculate the energy consumption corresponding to the extreme point, and select the voltage, pulse width and excitation method corresponding to the extreme point with the lowest energy consumption and the highest energy conversion efficiency as the optimal electrical parameters.

6. The method for enhancing pulsed discharge activity using acousto-optic combined catalysis according to claim 4, characterized in that: Step S2 includes: Step S2-1: Based on the optimal electrical parameters determined in step S1, select a variety of carbon quantum dot composite catalytic materials and carry out discharge reactions under the same experimental conditions. Detect and compare the active ingredient concentration and energy conversion efficiency corresponding to different catalysts, and screen out the catalyst type with the highest active ingredient concentration and the best energy conversion efficiency as the target catalyst. Step S2-2: For the target catalyst determined in step S2-1, adjust the concentration of carbon quantum dots according to the set step size, carry out the discharge reaction at each concentration, detect the concentration of active ingredients and energy conversion efficiency, and select the carbon quantum dot concentration corresponding to the highest energy conversion efficiency. Step S2-3: Based on the band gap of the target catalyst selected in step S2-1, calculate the incident light wavelength threshold using the formula, replace different narrowband filters to achieve specific wavelength irradiation, detect the concentration of active ingredients at each wavelength, and select the wavelength with the highest concentration as the preferred wavelength. Step S2-4: Under the preferred wavelength determined in step S2-3, gradually adjust the light intensity according to the set gradient. Monitor the change in the concentration of active ingredient after each adjustment. When the concentration of active ingredient no longer increases with the increase of light intensity, determine the light intensity at this time. Step S2-5: Activation parameter integration. The target catalyst type determined in step S2-1, the carbon quantum dot concentration determined in step S2-2, and the light parameters determined in steps S2-3 and S2-4 are combined to form the optimal activation parameters.

7. The method for enhancing pulsed discharge activity using acousto-optic combined catalysis according to claim 4, characterized in that: Step S3 includes: Step S3-1: Load the optimal electrical parameters of step S1 and the optimal activation parameters of step S2, adjust the gas-liquid flow rate according to the set step size to change the fluid velocity and gas content, detect the diffusion uniformity and reaction efficiency of the active ingredient under each parameter combination, and select the flow rate and gas content with the best diffusion effect and the highest reaction efficiency. Step S3-2: Under the optimal fluid parameters determined in step S3-1, test the average bubble size in the reaction system, calculate the theoretical optimal ultrasonic frequency using the Minnaert resonance frequency formula, adjust the frequency in steps towards both high and low frequencies with the theoretical frequency as the center, detect the diffusion rate of the active ingredient at each frequency, and determine the optimal ultrasonic frequency. Step S3-3: Based on the optimal ultrasonic frequency determined in step S3-2, adjust the power supply of the ultrasonic transducer according to the set gradient. After each adjustment, detect the concentration of the active ingredient. When the concentration of the active ingredient reaches its maximum and no longer changes, determine the optimal ultrasonic power. Step S3-4: Combine the fluid parameters determined in step S3-1 with the ultrasonic parameters determined in steps S3-2 and S3-3 to form the optimal diffusion parameters.

8. The method for enhancing pulsed discharge activity using acousto-optic combined catalysis according to claim 4, characterized in that: Step S4 includes: Step S4-1: Import the wastewater to be treated into the product tank, and start the high-voltage pulse power supply, air pump, liquid pump and ultrasonic transducer according to the optimal parameters determined in steps S1-5, S2-4 and S3-4. Monitor the voltage and current waveforms in real time through a digital oscilloscope. Step S4-2: Monitor the concentration of active ingredients in real time using an active ingredient detector and record the data changes; Step S4-3: Periodically sample and test the yield of active ingredients or the degradation efficiency of pollutants in the water. If the yield or degradation rate continues to decline, adjust the fluid flow rate or gas content according to the optimization logic determined in step S3-1 to optimize the mass transfer effect. Step S4-4: Continue monitoring and adjusting steps S4-1 to S4-3 until the wastewater pollutant concentration drops to the discharge standard, then stop the system operation.

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