A method for optimizing the regulation of active substances in a glow discharge for water treatment

Abstract

The present application relates to the technical field of electrochemical oxidation, and discloses a glow discharge active substance optimization control method for water treatment, which comprises the following steps: initial parameters are provided by calculating the synergistic quenching coefficient, pH buffer capacity and matrix type autocatalytic potential matrix, and establishing a water quality dynamic evolution model through applying logarithmically increasing calibration pulses; a stable microcosmic reaction basis is constructed by adjusting the active substance dynamic proportion through a degradation path, and the stable microcosmic reaction basis is constructed by implementing pulse front slope control, mixed gas component fine adjustment, intrinsic magnetic field and external magnetic field same direction superposition and afterglow period frequency matching alternating electric field; the active substance proportion is adjusted, group pulse timing optimization, periodic high concentration active substance impact and energy efficiency target function control are implemented, and real-time operation feedback is carried out; the electrode interface state is detected, local reverse cleaning, passivation film classification cleaning, electrode surface micro-morphology active control and by-product source control are implemented, and full-dimensional closed-loop adaptive operation of the system from water quality to electrode is realized.

Description

Technical Field

[0001] This invention relates to the field of electrochemical oxidation technology, and more specifically to a method for optimizing and controlling glow discharge active materials for water treatment. Background Technology

[0002] With its advantages of generating a variety of highly active oxygen and nitrogen species in situ and requiring no secondary reagents, glow discharge water treatment technology has shown broad application prospects in the fields of recalcitrant organic wastewater and microbial inactivation. However, existing technologies have systemic and fundamental defects in the precise control of active substances, which restricts their transformation from laboratory pilot-scale to large-scale industrial application.

[0003] Existing technologies lack sufficient characterization of the intrinsic properties of water quality. Setting initial operating conditions based on conductivity and pH fails to identify the synergistic quenching effect between chloride ions and quenchers such as bicarbonate ions, leading to significant deviations in initial power settings. They completely ignore the irreversible impact of water pH buffering capacity on the active substance generation pathway, and cannot distinguish the catalytic characteristics of different autocatalytic intermediates, nor predict the dynamic evolution of water quality parameters during treatment, resulting in substantial energy waste and fluctuating treatment effectiveness. While optimizing electrode structure and macroscopic flow field to improve discharge effects, they cannot control the nucleation and growth of nanobubbles within the vapor sheath. Furthermore, they neglect the influence of charge distribution at the gas-liquid interface on the active substances. The selective enrichment of reactive substances does not utilize the synergistic effect of the intrinsic magnetic field and external magnetic field of glow discharge; the energy transfer process of metastable atoms during the pulse afterglow period has not been developed, resulting in low overall energy conversion efficiency; the statically fixed proportion of active substances cannot be adjusted according to the specific degradation pathway of pollutants; it cannot distinguish between effective consumption and ineffective self-recombination consumption of active substances; continuous exposure to low concentrations of active substances can easily induce drug resistance in microorganisms; electrode maintenance uses a fixed-frequency overall reverse cleaning method, which cannot identify local passivation differences and the semiconductor characteristics of the passivation film; by-products rely on end-of-pipe treatment, and it cannot inhibit the generation of nitrates and halogenated organic compounds from the source;

[0004] Therefore, there is a need to provide a method for optimizing and controlling glow discharge active materials for water treatment. Summary of the Invention

[0005] The purpose of this invention is to provide a method for optimizing and controlling glow discharge active materials for water treatment, constructing a precise control system for glow discharge active materials that encompasses multi-dimensional characterization of intrinsic water quality, multi-field coupled microscopic reaction regulation, dynamic matching of degradation pathways, and adaptive electrode lifecycle. To solve the aforementioned problems in the prior art, this invention achieves this through the following technical solution:

[0006] In a first aspect, the present invention provides a method for optimizing and controlling glow discharge active materials for water treatment, which specifically includes the following steps:

[0007] Step 1: By applying logarithmically increasing calibration pulses, pre-set spectral absorption data and current-time waveforms are collected. The synergistic quenching coefficient, pH buffer capacity, and autocatalytic potential matrix of different types are calculated to establish a dynamic water quality evolution model and provide initial parameters.

[0008] Step 2: Based on the initial parameter matching results, multi-physics field detection is carried out, and alternating electric fields with pulse front slope control, mixed gas composition fine-tuning, intrinsic magnetic field and external magnetic field superposition in the same direction and afterglow frequency matching are implemented. A stable micro-reaction basis is constructed by dynamically controlling the proportion of active substances in the degradation path.

[0009] Step 3: Based on the stable microscopic reaction, monitor the degradation process in real time, adjust the proportion of active materials, implement group pulse timing optimization, periodic high-concentration active material impact and energy efficiency objective function regulation, and provide real-time operational feedback for the full life cycle adaptive regulation of the electrode interface state.

[0010] Step 4: Based on real-time operational feedback, detect the state of the electrode interface, implement local reverse cleaning, passivation film classification cleaning, active regulation of electrode surface micromorphology, and control of by-product sources, so as to realize the full-dimensional closed-loop adaptive operation of the system from water quality to electrodes.

[0011] Secondly, the glow discharge active material optimization and control system for water treatment provided by the embodiments of the present invention specifically includes the following modules:

[0012] Characterization matching module: By applying logarithmically increasing calibration pulses, it collects preset spectral absorption data and current-time waveforms, calculates the synergistic quenching coefficient, pH buffer capacity, and autocatalytic potential matrix of different types, and provides initial parameters to establish a dynamic water quality evolution model.

[0013] Coupling matching module: Combining the initial parameter matching results, multi-physics field detection is performed, and alternating electric fields with pulse front slope regulation, mixed gas composition fine-tuning, intrinsic magnetic field and external magnetic field superposition in the same direction and afterglow frequency matching are implemented. Stable micro-reaction basis is constructed through dynamic proportion regulation of active substances in the degradation path.

[0014] Tracking and processing module: Based on stable micro-reaction, it monitors the degradation process in real time, adjusts the proportion of active materials, implements group pulse timing optimization, periodic high-concentration active material impact and energy efficiency objective function regulation, and provides real-time operational feedback on the adaptive regulation of the electrode interface state throughout its entire life cycle.

[0015] Sensing and control module: Combining real-time operation feedback, it detects the state of the electrode interface and implements local reverse cleaning, passivation film classification cleaning, active control of electrode surface micromorphology, and by-product source control, so as to realize the full-dimensional closed-loop adaptive operation of the system from water quality to electrodes.

[0016] The beneficial effects of this invention are:

[0017] 1. A logarithmically increasing calibration pulse combined with high-frequency current spectrum analysis technology solves the problem of not being able to identify the synergistic quenching effect of quenchers such as chloride ions and bicarbonate ions. By calculating the synergistic quenching coefficient, a categorized autocatalytic potential matrix and a water quality dynamic evolution model are established, addressing issues such as the dependence of initial parameters on empirical values, the influence of pH buffering capacity on active nitrogen conversion, insufficient utilization of autocatalytic intermediates, and arc discharge caused by water quality evolution. A spatiotemporal precise control method of multi-field coupling between bubbles, vapor sheath, and magnetic field is proposed to reduce the microsecond-level fluctuations in the amount of active substances generated due to random breakdown of nanobubbles within the vapor sheath. By controlling the slope of the pulse leading edge to suppress nanobubble nucleation, fine-tuning the mixed gas composition to achieve selective enrichment of active substances at the interface, and extending the free radical lifetime by superimposing the intrinsic magnetic field and the external magnetic field in the same direction, the alternating electric field with frequency matching during the afterglow period excites metastable atomic energy transfer, solving the problems of interface active substance loss, magnetic field cancellation effect, and afterglow energy waste.

[0018] 2. Establish a dynamic ratio control system for active substances that combines degradation path tracking to solve the problem that static fixed ratios cannot match the degradation needs of pollutants; adjust the ratio of active oxygen and nitrogen in stages according to the degradation path, implement grouped pulse timing optimization to reduce ineffective self-recombination consumption, and periodically bombard with high concentrations of active substances to prevent microbial resistance; develop dynamic sensing and full life cycle adaptive control technology for electrode interface state to solve the problem that fixed-frequency overall cleaning cannot handle local passivation; identify local passivation areas by scanning Kelvin probes, classify cleaning according to the semiconductor characteristics of the passivation film, actively control the density of nano-peaks on the electrode surface, and inhibit the formation of nitrates and halogenated organic compounds. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 This is a flowchart of the steps in an embodiment 1 of the present invention for optimizing and controlling glow discharge active materials for water treatment;

[0021] Figure 2 This is a schematic diagram of the structure of a glow discharge active material optimization and control system for water treatment provided in Embodiment 2 of the present invention. Detailed Implementation

[0022] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. 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 should fall within the scope of protection of the present invention.

[0023] Example 1: As Figure 1 As shown in the figure, the method for optimizing and controlling glow discharge active materials for water treatment provided by the present invention specifically includes the following steps:

[0024] Step 1: By applying logarithmically increasing calibration pulses, pre-set spectral absorption data and current-time waveforms are collected. The synergistic quenching coefficient, pH buffer capacity, and autocatalytic potential matrix of different types are calculated to establish a dynamic water quality evolution model and provide initial parameters.

[0025] It should be noted that the core parameters of the glow discharge reactor used are as follows: the working electrode is a titanium alloy rod electrode with a diameter of 10 mm and a surface roughness Ra=0.8μm; the counter electrode is a 316L stainless steel plate with a side length of 50 mm and a thickness of 2 mm; the electrode spacing is fixed at 5 mm; the effective volume of the reactor is 1 L; the total flow rate of the mixed gas is controlled at 100 mL / min; the wastewater to be treated is continuously injected at a flow rate of 50 mL / min.

[0026] In a specific embodiment, wastewater to be treated is injected into the reactor to a preset level, and the distance between the working electrode and the counter electrode is kept at a preset distance. A gradient pulse calibration experiment is performed by sequentially applying eight sets of calibration pulses with a constant voltage of 1200 volts and a width increasing logarithmically from 0.5 microseconds to 50 microseconds. After each set of pulses is applied, preset spectral absorption data within a preset wavelength range are immediately collected using a UV-Vis-NIR full-spectrum spectrophotometer, and the complete current-time waveform and voltage fluctuation curve during the discharge process of each set of pulses are recorded.

[0027] Analyze the high-frequency component characteristics of the current-time waveform and extract the power spectral density within the preset frequency band. Different types of quenchers will cause changes in the power spectral density in different frequency bands.

[0028] For example, chloride ions lead to an increase in power spectral density in the 30 MHz to 50 MHz band, bicarbonate ions lead to an increase in power spectral density in the 60 MHz to 80 MHz band, and humic acid leads to an increase in power spectral density in the 10 MHz to 20 MHz band.

[0029] A standard database was established. This database was created by preparing standard solutions of a single quencher and measuring the power spectral density increments at different concentrations in corresponding frequency bands under the same experimental conditions. A linear relationship curve between concentration and power spectral density increments was then fitted. For the wastewater to be tested, the power spectral density increments in three frequency bands—[10MHz, 20MHz], [30MHz, 50MHz], and [60MHz, 80MHz]—were calculated separately. This was the power spectral density of the wastewater to be tested minus the blank value of deionized water. The increments of each frequency band were then substituted into the corresponding standard curves to obtain the individual contributions of humic acid, chloride ions, and bicarbonate ions.

[0030] The method for calculating the synergistic quenching coefficient is as follows: determine the total quenching efficiency of the three quenching agents after mixing them according to their individual contribution ratios, then subtract the sum of the individual quenching efficiencies of the three quenching agents, and finally divide by the sum of the individual quenching efficiencies of the three quenching agents to obtain the synergistic quenching coefficient.

[0031] For example, if the sum of the individual quenching efficiencies is 40%, and the total quenching efficiency after mixing is 60%, then the synergistic quenching coefficient is (60%-40%) / 40%=0.5.

[0032] By comparing the power spectral density of each frequency band with the standard database, the individual contribution and synergistic quenching coefficient of each major quencher are calculated.

[0033] To analyze the pH buffering capacity curve, hydrochloric acid and sodium hydroxide solution were added dropwise to the wastewater, and the pH value was recorded as the amount added was recorded. The pH buffering capacity curve was plotted, and the buffering capacity in the pH range of 3 to 9 was calculated. The larger the buffering capacity, the stronger the ability of the wastewater to resist pH changes and the higher the stability of the active substance generation pathway during the treatment process.

[0034] The types and potential of autocatalytic intermediates are analyzed by differentiating different types of autocatalytic intermediates through the changes in absorption intensity at four characteristic wavelengths (254 nm, 280 nm, 360 nm, and 420 nm) in the preset spectral absorption data.

[0035] A categorized autocatalytic potential matrix was constructed, with a dimension of 4 rows and 2 columns. The rows correspond to aromatic, peroxide, quinone, and aldehyde intermediates, respectively. The first column represents the potential amount of product, and the second column represents the catalytic efficiency.

[0036] The potential amount of product is calculated by substituting the absorbance of each characteristic wavelength into a pre-established standard curve to obtain the initial concentration, and then multiplying it by the maximum conversion rate of this type of intermediate product under glow discharge conditions; the catalytic efficiency is determined by standard experiments.

[0037] It should be noted that 254 nm corresponds to aromatic compounds, 280 nm corresponds to peroxide intermediates, 360 nm corresponds to quinone intermediates, and 420 nm corresponds to aldehyde intermediates. When adjusting the staged active substance generation strategy according to the autocatalytic potential matrix, the preset accumulation concentration of quinone intermediates is 0.1 mmol / L. When the concentration of peroxide intermediates reaches 0.3 mmol / L, a chain reaction is triggered. The concentration of aldehyde intermediates needs to be maintained below 0.05 mmol / L to avoid over-oxidation.

[0038] Calculate the potential amount of each intermediate product and its catalytic efficiency to obtain a categorized autocatalytic potential matrix.

[0039] A preliminary experiment on the dynamic evolution of water quality was conducted. Ten consecutive main discharge pulses were applied, and the changes in pH, conductivity, and hydrogen peroxide concentration of the wastewater were recorded after each pulse. A dynamic evolution model of water quality in the form of multiple linear regression was established using the 10 sets of data. The cumulative discharge energy was used as the independent variable, and pH, conductivity, and hydrogen peroxide concentration were used as the dependent variables. The least squares method was used to estimate the model parameters and predict the changing trends of pH and conductivity during the treatment process.

[0040] The energy density distribution of the initial discharge pulse is adjusted according to the synergistic quenching coefficient. When the synergistic quenching coefficient is greater than the preset synergistic quenching threshold, a peak-platform composite pulse waveform is adopted. The peak voltage of 2000 volts is reached within 0.1 microseconds of the pulse leading edge, generating a momentary high concentration of active material to overcome the synergistic effect of the quencher. Subsequently, the voltage drops to 1200 volts to maintain a stable vapor sheath layer. The peak-platform composite pulse waveform improves the effective utilization rate of active material and avoids energy waste caused by increasing the average power.

[0041] The initial nitrogen ratio of the mixed gas is adjusted according to the pH buffer capacity. When the pH buffer capacity is greater than the preset buffer capacity, the initial volume ratio of nitrogen is increased to the preset adjustment ratio. The wastewater with high buffer capacity maintains an acidic environment, which is conducive to the conversion of active nitrogen species into peroxynitroso anions with strong oxidizing properties.

[0042] When the pH buffer capacity is less than the preset buffer capacity, the initial volume ratio of nitrogen is reduced to the preset adjustment ratio; otherwise, it is not changed. This is to prevent the conversion of reactive nitrogen species into nitrates, which would cause a sharp drop in pH and damage the stability of the vapor sheath.

[0043] The staged active substance generation strategy is adjusted according to the autocatalytic potential matrix. For wastewater with high quinone autocatalytic potential, a large amount of hydrogen peroxide is generated in the initial stage. After the quinone intermediates accumulate to the preset accumulation concentration, the amount of hydrogen peroxide generated is reduced, and hydroxyl radicals are generated by the autocatalytic reaction of quinones and hydrogen peroxide.

[0044] For wastewater with high autocatalytic potential of peroxides, a large number of hydroxyl radicals are generated in the initial stage, triggering a chain reaction of peroxide intermediates; for wastewater with high autocatalytic potential of aldehydes, a low concentration of active substances is maintained throughout the process to prevent aldehyde intermediates from being over-oxidized into carbon dioxide and losing their autocatalytic ability.

[0045] The initial parameters are adjusted proactively based on the water quality dynamic evolution model. If it is predicted that the pH value will drop by more than 2 units during the treatment process, the nitrogen ratio is increased in the initial stage to generate nitrate in advance to buffer the drop in pH value.

[0046] If it is predicted that the conductivity will increase by more than 50% during the processing, the discharge power will be reduced in the initial stage to avoid the discharge mode from turning into arc discharge due to excessive conductivity in the later stage.

[0047] Step 2: Based on the initial parameter matching results, multi-physics field detection is carried out, and alternating electric fields with pulse front slope control, mixed gas composition fine-tuning, intrinsic magnetic field and external magnetic field superposition in the same direction and afterglow frequency matching are implemented. A stable micro-reaction basis is constructed by dynamically controlling the proportion of active substances in the degradation path.

[0048] It should be noted that the laser-induced fluorescence imaging technology was implemented under the following conditions: excitation wavelength 488 nm, fluorescence emission wavelength for detecting hydroxyl radicals 520 nm, sampling frequency 10 kHz, and imaging area covering the entire vapor sheath layer; the three-dimensional Hall sensor array consisted of four Hall sensors, which were arranged around the reactor at a distance of 10 mm from the center of the electrode, with a sampling accuracy of 0.1 mT and a sampling frequency of 1 kHz; the time-resolved emission spectroscopy technology had a spectral resolution of 0.1 nm, a time resolution of 1 μs, and a detection wavelength range of [200 nm, 800 nm].

[0049] In a specific embodiment, laser-induced fluorescence imaging technology was used to observe the distribution of nanobubbles inside the vapor sheath, and the nucleation density, growth rate and distribution uniformity of nanobubbles inside the vapor sheath were recorded under different discharge parameters.

[0050] It should be noted that the nucleation density of nanobubbles is directly related to the temperature gradient within the vapor sheath; the greater the temperature gradient, the higher the nucleation density of nanobubbles.

[0051] The surface potential of the gas-liquid interface is detected in real time using a surface potential meter. Different gas mixtures and discharge parameters will cause changes in the surface potential of the gas-liquid interface. When the surface potential is positive, negatively charged active substances are enriched at the interface; when the surface potential is negative, positively charged active substances are enriched at the interface.

[0052] A three-dimensional Hall sensor array is used to detect the three-dimensional magnetic field distribution inside the reactor. The three-dimensional magnetic field distribution includes: the intrinsic magnetic field generated by the glow discharge itself and the external magnetic field generated by the external permanent magnet. The direction of the intrinsic magnetic field is perpendicular to the direction of the discharge current, and the intensity is proportional to the discharge current. By adjusting the position and direction of the external permanent magnet, the external magnetic field and the intrinsic magnetic field are superimposed in the same direction in the vapor sheath region and canceled in opposite directions in the liquid phase bulk region.

[0053] Time-resolved emission spectroscopy was used to detect the changes in emission spectral intensity of different active species over time during the afterglow period, and to identify the main active substance generation pathways during the afterglow period; the decay curve of emission spectral intensity can reflect the lifetime and energy transfer efficiency of metastable atoms.

[0054] Suppressing nanobubble nucleation within the vapor sheath by precisely controlling the leading edge slope of the pulse: Based on the results of laser-induced fluorescence imaging, the leading edge slope of the main discharge pulse is adjusted within a preset range;

[0055] When the leading edge slope is a preset standard slope, the temperature gradient inside the vapor sheath is the most uniform, the nucleation density of nanobubbles is the lowest, and the stability of the vapor sheath is the best.

[0056] Selective enrichment of active substances at the gas-liquid interface is achieved by fine-tuning the composition of the mixed gas: when it is necessary to enrich negatively charged active substances, a preset proportion of sulfur hexafluoride is added to the mixed gas. Sulfur hexafluoride undergoes a decomposition reaction at the gas-liquid interface to generate negatively charged fluoride ions, which makes the interface surface potential positive.

[0057] When it is necessary to enrich positively charged active substances, a predetermined proportion of ammonia is added to the mixed gas. The ammonia undergoes a protonation reaction at the gas-liquid interface to generate positively charged ammonium ions, which makes the interfacial surface potential negative.

[0058] By maximizing the effect of magnetic field on extending the lifespan of active material through the co-directional superposition of intrinsic magnetic field and external magnetic field, the angle of external permanent magnet is adjusted in real time according to the detection results of three-dimensional Hall sensor array, so that the external magnetic field is superimposed with intrinsic magnetic field in the vapor sheath region, and the total magnetic field strength reaches the preset standard magnetic field strength.

[0059] In the liquid phase bulk region, the magnetic field cancels out the intrinsic magnetic field in the opposite direction, and the total magnetic field strength is close to zero, which prolongs the lifetime of hydroxyl radicals in the vapor sheath and prevents the active substances in the liquid phase bulk from agglomerating and quenching under the action of the magnetic field.

[0060] Energy transfer of metastable atoms is excited by an alternating electric field with frequency matching during the afterglow period. Based on the results of time-resolved emission spectra, an alternating electric field with a frequency of 333 Hz and an electric field strength of 50 volts per centimeter is applied during the afterglow period.

[0061] It should be noted that the 333 Hz alternating electric field matches the energy transfer frequency of the metastable argon atoms, exciting them to collide with water and oxygen molecules to generate hydroxyl radicals and superoxide anions. If helium is used as the carrier gas, the alternating electric field frequency is adjusted to 400 Hz; if nitrogen is used as the carrier gas, the alternating electric field frequency is adjusted to 250 Hz.

[0062] Step 3: Based on the stable microscopic reaction, monitor the degradation process in real time, adjust the proportion of active materials, implement group pulse timing optimization, periodic high-concentration active material impact and energy efficiency objective function regulation, and provide real-time operational feedback for the full life cycle adaptive regulation of the electrode interface state.

[0063] It should be noted that the in-situ liquid chromatography-mass spectrometry technique uses a C18 column, the mass spectrometry uses an electrospray ionization source, and the detection mode is positive ion; the electron spin resonance spectroscopy technique uses DMPO as a spin trapping agent, and the detection time is 10 seconds after pulse discharge; the flow cytometry uses SYTO9 / PI dual fluorescence staining.

[0064] In a specific embodiment, in-situ liquid chromatography-mass spectrometry is used to monitor the degradation intermediates of pollutants in real time. By comparing the mass spectra of the intermediates with the standard database, the main degradation intermediates and degradation pathways are identified, and the branch ratio of each degradation pathway is calculated. The branch ratio is equal to the generation rate of the first intermediate on the pathway divided by the sum of the generation rates of all intermediates, thus determining the main degradation pathway and the secondary degradation pathway.

[0065] The concentration of different active substances in the liquid phase was detected in real time using electron spin resonance spectroscopy. By adding different spin trapping agents, hydroxyl radicals, superoxide anions, peroxynitroso anions and nitric oxide were captured respectively, and the real-time concentration curves of each active substance were obtained.

[0066] Calculate the generation rate, total consumption rate, effective consumption rate, and ineffective consumption rate for each active substance; where the effective consumption rate is equal to the sum of the generation rates of intermediate products on the main degradation pathway multiplied by the corresponding reaction stoichiometry; the ineffective consumption rate is equal to the total consumption rate minus the effective consumption rate, including self-recombination reactions, non-target reactions, and reactions with quenchers.

[0067] Flow cytometry was used to detect the activity and drug resistance of microorganisms in water in real time, with a sampling interval of 1 hour. Fluorescent staining was used to distinguish between live cells, dead cells, and sublethal cells, and the mortality and sublethal rates of the microorganisms were calculated. Simultaneously, the activity of antioxidant enzymes in the microorganisms was detected to assess the level of drug resistance.

[0068] The ratio of active substances is dynamically adjusted according to the requirements of the main degradation pathway. If the main degradation pathway is the hydroxyl radical oxidation pathway, the ratio of hydroxyl radicals to hydrogen peroxide is controlled between 1:3 and 1:10. If the main degradation pathway is the peroxynitrosoanion oxidation pathway, the ratio of reactive oxygen species to reactive nitrogen species is controlled between 3:1 and 10:1. For pollutants that are mainly degraded by hydroxyl radical oxidation of the benzene ring, the ratio of hydroxyl radicals to hydrogen peroxide is maintained at 1:5 in the early stage of degradation to quickly open the benzene ring. In the middle stage of degradation, the ratio is adjusted to 1:10 to utilize the autocatalytic reaction between hydrogen peroxide and intermediate products. In the later stage of degradation, the ratio is adjusted to 1:3 to completely degrade carboxylic acid intermediate products.

[0069] For pollutants that are mainly degraded by the oxidation of heterocycles by peroxynitroso anions, the ratio of reactive oxygen to reactive nitrogen is maintained at 3:1 in the early stage of degradation to rapidly break down heterocycles; in the middle stage of degradation, the ratio is adjusted to 5:1 to avoid excessive formation of nitrates by reactive nitrogen; and in the later stage of degradation, the ratio is adjusted to 10:1 to utilize hydroxyl radicals to degrade the final intermediate products.

[0070] The timing of pulsed discharge was optimized based on the consumption characteristics of active substances. The original continuous pulsed discharge was changed to grouped pulsed discharge. Each group contains 3 main discharge pulses and 1 interval period. The main discharge pulses are used to generate high concentrations of active substances, and the interval period is used for the active substances to fully react with pollutants.

[0071] The length of the interval is adjusted according to the effective consumption rate; the faster the effective consumption rate, the shorter the interval; the slower the effective consumption rate, the longer the interval.

[0072] To prevent microorganisms from developing drug resistance, a periodic high-concentration active substance shock strategy is adopted. Every 24 hours of operation, a set of high-power shock pulses is applied, with the power of the shock pulses being 5 times that of the normal power.

[0073] High concentrations of active substances can quickly kill all microorganisms in a sublethal state, avoiding the development of drug resistance. During the shock pulse, the proportion of active nitrogen should be appropriately increased.

[0074] A dynamic control objective function combining energy efficiency is established. The energy consumption per unit of pollutant removal is calculated by dividing the cumulative electrical energy consumed by the cumulative mass of pollutants removed. The energy consumption per unit of pollutant removal is calculated in real time, and minimizing the energy consumption is taken as the final control objective. If the energy consumption decreases after adjusting the proportion of active substances, the adjustment continues in that direction; if the energy consumption increases, the adjustment is reversed.

[0075] Step 4: Based on real-time operation feedback, detect the state of the electrode interface, implement local reverse cleaning, passivation film classification cleaning, active regulation of electrode surface micromorphology, and control of by-product sources, so as to realize the full-dimensional closed-loop adaptive operation of the system from water quality to electrodes.

[0076] In a specific embodiment, a scanning Kelvin probe microscope is used to detect the surface work function distribution in different regions of the electrode surface in situ. The change in surface work function reflects the passivation degree and composition change of the electrode surface. The higher the passivation degree, the larger the surface work function. Passivation films with different compositions have different characteristic surface work functions.

[0077] By comparing the surface work function distribution of the electrode surface with the initial state, a local passivation distribution map of the electrode surface is drawn to identify areas with severe local passivation.

[0078] In-situ ultraviolet photoelectron spectroscopy was used to detect the band gap and valence band structure of the passivation film to determine its semiconductor properties. Passivation films with a band gap of less than 3 electron volts were classified as semiconductor passivation films, while those with a band gap of more than 3 electron volts were classified as insulating passivation films.

[0079] The microstructure of the electrode surface was periodically examined using atomic force microscopy, and changes in surface roughness, peak density, and peak height were measured. The correlation between the microstructure parameters of the electrode surface and the bubble nucleation density and vapor sheath stability was established.

[0080] The concentration of by-products in water was detected in real time using ion chromatography. The by-products in water included nitrates, nitrites and halogenated organic compounds. A correlation model was established between the formation rate of by-products in water and the state of the electrode surface, the proportion of active materials and discharge parameters.

[0081] Local reverse cleaning technology was used to specifically repair the local passivation areas on the electrode surface. Based on the detection results of scanning Kelvin probe microscopy, the areas with severe local passivation were identified.

[0082] By adjusting the position of the working electrode so that the severely passivated area is directly opposite the counter electrode, a set of high-energy local reverse cleaning pulses are applied. The local reverse cleaning pulses repair the passivated area and avoid damaging the electrode surface of the cleaning area.

[0083] Different cleaning strategies are selected based on the semiconductor characteristics of the passivation film. For semiconductor passivation films, a low-voltage, long-pulse chemical reduction cleaning method is used, and the passivation film is reduced to metal by hydrogen ion implantation.

[0084] For insulating passivation films, a high-voltage, short-pulse physical sputtering cleaning method is used to peel the passivation film off the electrode surface through cathode sputtering.

[0085] The microstructure of the electrode surface is actively controlled by the reverse cleaning pulse parameters: an appropriate positive pulse component is added to the reverse cleaning pulse, and the positive pulse produces tiny melting and recrystallization on the electrode surface, forming uniformly distributed nanoscale peaks.

[0086] By adjusting the number and energy of the positive pulses, the peak density on the electrode surface is controlled within a preset peak density range, which simultaneously ensures the optimal electric field concentration effect and bubble nucleation density.

[0087] To control the generation of byproducts at the source, based on the correlation model of byproduct generation rate, when the nitrate generation rate exceeds the threshold, the proportion of nitrogen in the mixed gas is reduced, the work function of the electrode surface is increased, and the dissociation reaction of nitrogen is suppressed.

[0088] When the rate of formation of halogenated organic compounds exceeds the threshold, the peak voltage of the main discharge pulse is reduced, the number of high-energy electrons is decreased, and the oxidation reaction of chloride ions is suppressed.

[0089] The full life cycle adaptive regulation simultaneously covers five dimensions: water quality characteristics, vapor sheath state, active material ratio, electrode interface state, and by-product generation; a digital twin model is established by collecting multi-source data from these five dimensions in real time.

[0090] The digital twin model adopts a modular architecture, which includes: water quality unit, vapor sheath unit, active material unit, electrode unit, and by-product unit. Each unit interacts in real time through a data interface. Input parameters include: water quality parameters, discharge parameters, magnetic field parameters, and gas parameters. Output parameters include: pollutant removal rate, energy efficiency, electrode lifetime, and by-product concentration. The model updates its operating status every 30 seconds, predicts the system operating trend for the next hour, simulates the system's operating status, predicts potential problems, and adjusts operating parameters in advance.

[0091] Example 2: As Figure 2 As shown in the figure, the glow discharge active material optimization and control system for water treatment provided by this embodiment of the invention specifically includes the following modules:

[0092] Characterization matching module: By applying logarithmically increasing calibration pulses, it collects preset spectral absorption data and current-time waveforms, calculates the synergistic quenching coefficient, pH buffer capacity, and autocatalytic potential matrix of different types, and provides initial parameters to establish a dynamic water quality evolution model.

[0093] Coupling matching module: Combining the initial parameter matching results, multi-physics field detection is performed, and alternating electric fields with pulse front slope regulation, mixed gas composition fine-tuning, intrinsic magnetic field and external magnetic field superposition in the same direction and afterglow frequency matching are implemented. Stable micro-reaction basis is constructed through dynamic proportion regulation of active substances in the degradation path.

[0094] Tracking and processing module: Based on stable micro-reaction, it monitors the degradation process in real time, adjusts the proportion of active materials, implements group pulse timing optimization, periodic high-concentration active material impact and energy efficiency objective function regulation, and provides real-time operational feedback on the adaptive regulation of the electrode interface state throughout its entire life cycle.

[0095] Sensing and control module: Combining real-time operation feedback, it detects the state of the electrode interface and implements local reverse cleaning, passivation film classification cleaning, active control of electrode surface micromorphology, and by-product source control, so as to realize the full-dimensional closed-loop adaptive operation of the system from water quality to electrodes.

[0096] The above provides a detailed description of one embodiment of the present invention, but the content described is only a preferred embodiment of the present invention and should not be considered as limiting the scope of the present invention. The above formulas are all dimensionless numerical calculations, and the formulas are derived from software simulations based on a large amount of collected data to obtain the most recent real-world situation. The preset parameters in the formulas are set by those skilled in the art based on actual conditions and historical experience, and can be adjusted according to actual conditions. The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. All equivalent changes and improvements made in accordance with the scope of the present invention should still fall within the patent coverage of the present invention.

Claims

1. A method for optimizing and controlling glow discharge active materials for water treatment, characterized in that, Includes the following steps: By applying logarithmically increasing calibration pulses, pre-set spectral absorption data and current-time waveforms are collected, and the synergistic quenching coefficient, pH buffer capacity, and autocatalytic potential matrix of different types are calculated to establish a dynamic water quality evolution model and provide initial parameters. Based on the initial parameter matching results, multi-physics field detection is carried out, and alternating electric fields with pulse front slope regulation, mixed gas composition fine-tuning, intrinsic magnetic field and external magnetic field superposition in the same direction and afterglow frequency matching are implemented. A stable micro-reaction basis is constructed by dynamically regulating the proportion of active substances in the degradation path. Based on stable microscopic reactions, the degradation process is monitored in real time, the proportion of active materials is adjusted, and the group pulse timing optimization, periodic high-concentration active material impact and energy efficiency objective function regulation are implemented to provide real-time operational feedback for the adaptive regulation of the electrode interface state throughout its entire life cycle. By combining real-time operational feedback, detecting the state of the electrode interface, implementing local reverse cleaning, passivation film classification cleaning, active regulation of electrode surface micromorphology, and control of by-product sources, the system achieves closed-loop adaptive operation across all dimensions from water quality to electrodes.

2. The method for optimizing and controlling glow discharge active materials for water treatment according to claim 1, characterized in that, The method for calculating the synergistic quenching coefficient is as follows: Eight sets of calibration pulses with constant voltage and logarithmically increasing width were applied sequentially, and the complete current-time waveform of each set of pulses was recorded. The high-frequency component characteristics of the current-time waveform were analyzed, the power spectral density within the preset frequency band was extracted, the differences between the power spectral density of each frequency band and the standard database were compared, and the individual contribution and synergistic quenching coefficient of each major quencher were calculated.

3. The method for optimizing and controlling glow discharge active materials for water treatment according to claim 1, characterized in that, The method for providing initial parameters is as follows: Ten consecutive main discharge pulses were applied, and the changes in pH, conductivity, and hydrogen peroxide concentration of the wastewater were recorded after each pulse. Based on the 10 sets of data, an evolution model of water quality parameters with discharge energy input was established to predict the changing trends of pH and conductivity during the treatment process.

4. The method for optimizing and controlling glow discharge active materials for water treatment according to claim 1, characterized in that, The method for implementing pulse leading edge slope control is as follows: Laser-induced fluorescence imaging was used to observe the distribution of nanobubbles inside the vapor sheath, and the nucleation density, growth rate and distribution uniformity of nanobubbles inside the vapor sheath were recorded under different discharge parameters. The nucleation of nanobubbles within the vapor sheath is suppressed by precisely controlling the slope of the pulse leading edge. Based on the results of laser-induced fluorescence imaging, the slope of the leading edge of the main discharge pulse is adjusted within a preset range.

5. The method for optimizing and controlling glow discharge active materials for water treatment according to claim 1, characterized in that, The method for superimposing the intrinsic magnetic field and the external magnetic field in the same direction is as follows: A three-dimensional Hall sensor array is used to detect the three-dimensional magnetic field distribution inside the reactor, including the intrinsic magnetic field generated by the glow discharge itself and the external magnetic field generated by the external permanent magnet. Based on the detection results of the three-dimensional Hall sensor array, the angle of the external permanent magnet is adjusted in real time so that the external magnetic field and the intrinsic magnetic field are superimposed in the same direction in the vapor sheath region and canceled out in the opposite direction in the liquid phase bulk region.

6. The method for optimizing and controlling glow discharge active materials for water treatment according to claim 1, characterized in that, The method for frequency matching of the alternating electric field during the afterglow period is as follows: Time-resolved emission spectroscopy was used to detect the changes in emission spectral intensity of different active species over time during the afterglow period, and to identify the main active substance generation pathways during the afterglow period. Energy transfer of metastable atoms is excited by an alternating electric field with frequency matching during the afterglow period. Based on the time-resolved emission spectrum, an alternating electric field with a frequency of 333 Hz and an electric field strength of 50 volts per centimeter is applied during the afterglow period.

7. The method for optimizing and controlling glow discharge active materials for water treatment according to claim 1, characterized in that, The method for implementing grouped pulse timing optimization is as follows: The continuous pulse discharge was changed to grouped pulse discharge, with each group containing 3 main discharge pulses and 1 interval period; Electron spin resonance spectroscopy is used to detect the concentration of different active substances in the liquid phase in real time and calculate the effective consumption rate of each active substance; the length of the interval is adjusted according to the effective consumption rate.

8. The method for optimizing and controlling glow discharge active materials for water treatment according to claim 1, characterized in that, The method of periodic high-concentration reactive substance impact is as follows: The activity and drug resistance of microorganisms in water were detected in real time using flow cytometry, with a sampling interval of 1 hour. Every 24 hours of operation, a set of high-power shock pulses was applied, with the power of the shock pulses being 5 times that of the normal power. During the shock pulses, the proportion of nitrogen in the mixed gas was increased.

9. The method for optimizing and controlling glow discharge active materials for water treatment according to claim 1, characterized in that, The method for implementing local reverse cleaning is as follows: The surface work function distribution in different regions of the electrode surface was detected in situ using a scanning Kelvin probe microscope. The difference between the surface work function distribution of the electrode surface and the initial state was compared to draw a local passivation distribution map of the electrode surface and identify areas with severe local passivation. Adjust the position of the working electrode so that the severely passivated area is directly opposite the counter electrode, and apply a set of high-energy local reverse cleaning pulses.

10. The method for optimizing and controlling glow discharge active materials for water treatment according to claim 1, characterized in that, The method for classifying and cleaning the passivation film is as follows: In-situ ultraviolet photoelectron spectroscopy was used to detect the band gap and valence band structure of the passivation film, and to determine the semiconductor properties of the passivation film. For semiconductor passivation films with a bandgap of less than 3 electron volts, a low-voltage, long-pulse chemical reduction cleaning method is used. For insulating passivation films with a bandgap greater than 3 electron volts, a high-voltage, short-pulse physical sputtering cleaning method is used.

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