Sulfate radical sterilization process parameter regulation and control method and system

Abstract

The invention relates to the technical field of water treatment regulation and control, in particular to a sulfate radical sterilization process parameter regulation and control method and system.The method comprises the following steps that electrochemical response characteristics of a metal activator in aquaculture tail water are monitored on line, and electrochemical response characteristic data are obtained; based on the electrochemical response characteristic data and preset calibration data or model for representing the corresponding relation between the electrochemical response characteristics of the metal activator in different organic ligand complexing states and the persulfate catalytic activation efficiency of the metal activator; evaluating the real-time attenuation degree of the effective catalytic activity caused by the complexation of the metal activator and the organic ligand in the tail water to obtain a real-time attenuation degree evaluation result; the electrochemical response characteristics are monitored on line, the attenuation degree of the activator is evaluated, and the dosage is adjusted according to the evaluation result, so that the problems that the efficiency of the activator is reduced due to organic ligand complexation and the activator cannot be accurately evaluated and adjusted in the prior art are solved.

Description

Technical Field

[0001] This invention relates to the field of water treatment control technology, and in particular to a method and system for controlling process parameters of sulfate free radical sterilization. Background Technology

[0002] In intensive aquaculture, the efficient treatment of aquaculture wastewater is crucial for ensuring water environment safety and promoting the sustainable development of the industry. Sulfate radical advanced oxidation technology (SR-AOPs) is applied to the disinfection of aquaculture wastewater due to its ability to efficiently degrade organic pollutants and kill pathogenic microorganisms. This technology generates highly oxidizing sulfate radicals (SO4·-) in situ by adding persulfate (such as potassium peroxymonosulfate compound salt) and metal ion activators (such as ferrous sulfate). Process operators or automated systems adjust the persulfate concentration, ferrous sulfate dosage, pH value, and reaction contact time based on monitoring conventional water quality parameters such as chemical oxygen demand (COD), ammonia nitrogen concentration, and turbidity, as well as periodic testing results of microbial indicators such as total coliforms, to achieve microbiological safety standards for wastewater discharge or reuse.

[0003] However, in actual aquaculture, to maintain water quality, promote growth, or prevent disease, farmers often add water conditioners, nutrients, or veterinary drugs containing organic acids or their salts (such as citric acid, oxalic acid, tartaric acid, and EDTA). Some dissolved organic matter enters the SR-AOPs treatment unit with the wastewater. These organic acids contain functional groups such as carboxyl and hydroxyl groups, which can complex with metal ions. When ferrous sulfate is added to wastewater containing such organic ligands, ferrous ions or their oxidation product, ferric ions, will form water-soluble organometallic complexes. The change in the form of iron ions significantly reduces their catalytic activity as activators, leading to a reduction in the generation of sulfate free radicals. This degree of inhibition is dynamically affected by factors such as the type and concentration of organic ligands and the pH of the water, exhibiting irregular fluctuations.

[0004] Current process parameter control is typically based on calculations or empirical adjustments of the total iron dosage. When the concentration of organic ligands in the effluent increases, even with conventional ferrous sulfate addition, the actual effective concentration of iron ions participating in activation may be far lower than expected, leading to a decrease in the rate and concentration of free radical generation and substandard sterilization. The root cause is that the activation process itself is hindered (change in activator form), rather than the competitive consumption of free radicals. If operators or automatic control systems fail to recognize this underlying cause of reduced activator efficiency and only observe deterioration in effluent microbial indicators, they may misjudge it as insufficient persulfate dosage or excessive consumption of free radicals by high-concentration organic matter in the effluent. Based on this misjudgment, the conventional response is to increase the total dosage of persulfate and ferrous sulfate. However, in the presence of high concentrations of organic ligands, simply increasing the ferrous sulfate dosage cannot effectively increase the concentration of free iron ions to restore its activation efficiency; most of the newly added iron ions will still be complexed by excess organic ligands. This not only fails to increase free radical generation, but also leads to the accumulation of total iron concentration, increasing the amount of sludge generated and the treatment cost of subsequent treatments (such as sedimentation and filtration), and causing waste of chemicals.

[0005] More complexly, some formed iron-organic complexes may interfere with the accuracy of conventional water quality monitoring indicators (such as COD) or affect the performance of online monitoring sensors, leading to distorted monitoring information and further exacerbating the difficulty of parameter regulation. Currently, the system lacks a means to accurately assess in real time the dynamic changes in activator effectiveness caused by the complexation of specific organic ligands in the effluent, and to adjust activator dosing strategies or activation conditions accordingly. This is to address the challenges posed by the introduction and dynamism of specific organic ligands, their primary mechanism of influence on activators being complexation inhibition, the ineffectiveness of existing control methods, and the high discriminative requirements of the control targets, among other scenario-specific characteristics.

[0006] To address the aforementioned issues, existing technologies urgently need improvement. Summary of the Invention

[0007] The purpose of this invention is to address the shortcomings of existing technologies by proposing a method and system for controlling the process parameters of sulfate free radical sterilization.

[0008] In a first aspect, the present invention provides a method for controlling process parameters of sulfate radical sterilization, the method comprising the following steps: The electrochemical response characteristics of metal activators in aquaculture wastewater were monitored online to obtain the electrochemical response characteristic data. Based on the electrochemical response characteristic data and the preset calibration data or model characterizing the relationship between the electrochemical response characteristics of the metal activator in different organic ligand complexation states and its catalytic activation efficiency of persulfate, the real-time attenuation degree of the effective catalytic activity of the metal activator due to complexation with organic ligands in the tailwater is evaluated, and the real-time attenuation degree evaluation result is obtained. Based on the real-time attenuation assessment results, adjust the dosage of the metal activator and, optionally, the persulfate.

[0009] The core innovation of this application lies in the introduction of a technical means to monitor the electrochemical response characteristics of metal activators online, and based on the preset correspondence between electrochemical characteristics and catalytic activity decay, thereby achieving online and real-time evaluation of the degree of effective catalytic activity decay of metal activators caused by organic ligand complexation. This enables targeted adjustment of the dosage of activator and persulfate to compensate for the decline in activator efficiency, ensure stable sterilization effect, and avoid waste of reagents.

[0010] Secondly, a sulfate radical sterilization process parameter control system is provided, the system comprising: The monitoring module is used to monitor the electrochemical response characteristics of metal activators in aquaculture wastewater online and obtain the electrochemical response characteristic data. The evaluation module is used to evaluate the real-time attenuation of the effective catalytic activity of the metal activator due to complexation with organic ligands in the tailwater based on the electrochemical response characteristic data and the preset calibration data or model characterizing the relationship between the electrochemical response characteristics of the metal activator in different organic ligand complexation states and its catalytic activation efficiency of persulfate, and obtain the evaluation result of the real-time attenuation. The control module is used to adjust the dosage of the metal activator and, optionally, persulfate, based on the real-time attenuation assessment results.

[0011] Compared with the prior art, the present invention has the following beneficial effects: By monitoring the electrochemical response characteristics online and assessing the degree of activator decay, and adjusting the dosage based on the assessment results, this technology solves the problem in existing technologies where the activator efficiency is reduced due to the complexation of organic ligands and cannot be accurately assessed and adjusted. It has the advantages of being able to accurately assess the degree of decay of the effective catalytic activity of metal activators in real time and dynamically adjust the dosage accordingly, thereby improving the stability of sterilization treatment effect and agent utilization efficiency. Attached Figure Description

[0012] Figure 1 This is a flowchart of the method of the present invention.

[0013] Figure 2 This is a schematic diagram of the system structure of the present invention.

[0014] In the diagram: 201, monitoring module; 202, evaluation module; 203, control module. Detailed Implementation

[0015] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0016] The terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the stated features. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0017] like Figure 1 The method shown is a method for controlling the process parameters of sulfate radical sterilization, which includes the following steps: S101. Monitor the electrochemical response characteristics of metal activators in aquaculture wastewater online and obtain electrochemical response characteristic data; S102. Based on the electrochemical response characteristic data and the pre-set calibration data or model that characterizes the relationship between the electrochemical response characteristics of the metal activator in different organic ligand complexation states and its catalytic activation efficiency of persulfate, evaluate the real-time decay of the effective catalytic activity of the metal activator due to complexation with organic ligands in the tailwater, and obtain the real-time decay assessment result. S103. Adjust the dosage of metal activator and optional persulfate based on the real-time decay assessment results.

[0018] Online monitoring refers to the continuous and real-time acquisition of water quality parameters or technical characteristics during the treatment of aquaculture wastewater. This can be achieved using various online sensors or analytical instruments, such as electrochemical sensors and spectrometers, primarily to obtain data reflecting the real-time state of the wastewater. Electrochemical response characteristics refer to the electrical signal properties exhibited by metal activators under specific electrochemical conditions, such as current, potential, charge, or their time / potential variation curves. These can be obtained using electrochemical measurement techniques such as voltammetry, chronoamperometry, and potentiometry, mainly to characterize the form and activity of metal activators in the wastewater. Electrochemical response characteristic data refers to the raw or pre-processed dataset obtained through online monitoring that records the electrochemical response characteristics of metal activators. This data primarily provides input information for subsequent evaluation steps. Pre-defined calibration data or models characterizing the relationship between the electrochemical response characteristics of metal activators in different organic ligand complexation states and their catalytic activation efficiency of persulfate refer to data established experimentally or through simulation under controlled conditions. These models reflect how the electrochemical response characteristics of metal activators change when complexed with different types and concentrations of organic ligands, and how these complexation states affect their catalytic activation of persulfate to generate free radicals. The efficiency correlation information set or mathematical expression can exist in the form of lookup tables, regression models, machine learning models, etc., and is mainly used to transform the real-time monitored electrochemical response characteristic data into an assessment of the effective catalytic activity of the activator. Assessing the real-time attenuation of the effective catalytic activity of the metal activator due to complexation with organic ligands in the tailwater refers to using the above-mentioned calibration data or model, based on the real-time acquired electrochemical response characteristic data, to quantify the proportion or degree of decrease in the catalytic efficiency of the metal activator in the tailwater due to complexation with organic ligands relative to its free or highly active form. This is mainly for accurate... The assessment determines the real-time status of the activator's effectiveness impairment. The real-time attenuation assessment result refers to the quantitative value or status indication output by the assessment step, reflecting the real-time attenuation of the effective catalytic activity of the metal activator. This mainly provides a direct basis for subsequent dosage adjustments. Adjusting the dosage of the metal activator and optional persulfate refers to dynamically changing the amount of metal activator and / or persulfate added to the effluent based on the real-time attenuation assessment result. This can be achieved by adjusting the flow rate of the metering pump, changing the dosage frequency, etc., mainly to compensate for the decrease in activator activity caused by complexation and maintain a stable free radical generation rate and sterilization effect.

[0019] This application's solution acquires real-time data reflecting the electrochemical response characteristics of metal activators in aquaculture wastewater by monitoring their properties online. Since the complexation of metal activators with organic ligands in the wastewater alters their chemical form and thus affects their electrochemical behavior, the electrochemical response characteristics can sensitively reflect this complexation state and its degree. Based on this real-time acquired electrochemical response characteristic data, and referring to pre-established calibration data or models characterizing the relationship between electrochemical characteristics under different complexation states and the catalytic activation efficiency of persulfate, the system can assess the real-time attenuation of the effective catalytic activity of the metal activator due to complexation. This assessment directly targets the activator's efficiency loss, distinguishing between two different failure mechanisms: a decrease in the activator's ability to generate free radicals and the consumption of free radicals. Finally, based on the real-time attenuation results obtained from the assessment, the system dynamically adjusts the dosage of the metal activator and, optionally, persulfate. This adjustment is based on the assessment of the actual effective activity of the activator, and can accurately compensate for the activity loss caused by complexation. It ensures that even with dynamic changes in the types and concentrations of organic ligands in the effluent, a stable free radical generation rate can still be maintained, guaranteeing the sterilization effect. At the same time, it avoids the waste and increased costs caused by blindly increasing the total dosage when the activator's effectiveness is impaired. The entire process forms a closed-loop control, realizing intelligent and precise management of the metal activator dosage.

[0020] As one embodiment of the present invention, when electrochemical response characteristic data indicates the presence of multiple organic ligands co-complexing with the metal activator, the step of evaluating the real-time attenuation of the effective catalytic activity of the metal activator due to its complexation with organic ligands in the effluent, based on the electrochemical response characteristic data and a preset calibration data or model characterizing the relationship between the electrochemical response characteristics of the metal activator in different organic ligand complexation states and its catalytic activation efficiency of persulfate, includes: Extract composite electrochemical characteristic parameters that characterize the co-complexation state of multiple organic ligands from electrochemical response characteristic data; Based on the composite electrochemical characteristic parameters and the correspondence between the electrochemical response characteristics of metal activators under the combined action of multiple organic ligands contained in the preset calibration data or model, the degree of overall effective catalytic activity decay under the combined action of multiple organic ligands is determined, and the degree of overall effective catalytic activity decay is taken as the real-time decay of the effective catalytic activity caused by the complexation of metal activators with organic ligands in the tailwater.

[0021] Electrochemical response characteristic data refers to the raw or pre-processed signal data obtained by online monitoring of the electrochemical behavior of metal activators in the tailwater environment using electrochemical methods (such as cyclic voltammetry, differential pulse voltammetry, electrochemical impedance spectroscopy, etc.). This data can be presented in the form of current-potential curves, impedance spectra, charge transfer resistance values, etc., aiming to capture the real-time electrochemical state of the metal activator under specific water conditions. Pre-defined calibration data or models characterizing the electrochemical response characteristics of metal activators in different organic ligand complexation states and their catalytic activation efficiency of persulfate refer to the electrochemical response characteristics generated when different types and concentrations of organic ligands complex with metal activators are experimentally measured under laboratory or controlled conditions. Simultaneously, the catalytic activation efficiency of persulfate by the metal activator in these complexation states (e.g., free radical generation rate, target pollutant degradation efficiency, etc.) is measured to establish a quantitative relationship between electrochemical characteristics and the degree of catalytic efficiency decay. This data can be stored or expressed using lookup tables, regression equations, neural network models, support vector machine models, etc., aiming to provide a basis for future research. This provides a basis for continuous real-time evaluation; composite electrochemical characteristic parameters refer to the combination of multiple parameters extracted from the original electrochemical response characteristic data, which can comprehensively reflect the influence of multiple organic ligands on the electrochemical behavior of metal activators when they coexist. They can be represented by the potential difference of multiple peaks, peak current ratio, curve integral area, impedance modulus and phase angle combination at a specific frequency, or feature vectors obtained by dimensionality reduction through principal component analysis, independent component analysis, etc. The purpose is to capture complex complexation state information that is difficult to characterize with a single parameter; the co-complexation state of multiple organic ligands refers to the simultaneous presence of two or more organic substances with complexing ability in the effluent, which together undergo complexation reactions with the metal activator to form multiple complexes and have a superimposed or synergistic effect on the electrochemical behavior of the metal activator. The purpose is to describe the complexity of the effluent environment; the degree of comprehensive effective catalytic activity decay refers to the overall decrease in the efficiency of the metal activator in catalytic activation of persulfate under the combined action of multiple organic ligands, relative to its efficiency in the absence of complexation or in the baseline state. The purpose is to quantify the comprehensive impact of complex complexation environment on activator efficiency.

[0022] The proposed solution extracts composite electrochemical characteristic parameters from electrochemical response data to characterize the complexation state of multiple organic ligands. This is because when multiple organic ligands are present in the effluent, their complexation with the metal activator generates complex electrochemical response signals. A single electrochemical parameter is often insufficient to accurately depict this complexation state under the combined action of multiple components. By extracting composite electrochemical characteristic parameters, the electrochemical signal characteristics under the combined influence of multiple organic ligands can be captured more comprehensively and precisely, thus more accurately reflecting the true complexation state of the metal activator. It is precisely because composite characteristic parameters reflecting complex complexation states are extracted that the degree of overall effective catalytic activity decay under the combined action of multiple organic ligands can be determined based on these parameters and in conjunction with pre-set calibration data or models specifically designed for the combined action of multiple organic ligands. The pre-set calibration data or models include the correspondence between the electrochemical response characteristics of the metal activator and the decay of catalytic activity under different composite complexation states. This correspondence is established based on a large amount of experimental data, considering the mutual influence and superposition effects when multiple organic ligands coexist. By inputting the real-time extracted composite electrochemical characteristic parameters into this model, the overall effective catalytic activity decay of the metal activator under the current complex complexation environment can be obtained. Using this overall decay as the real-time decay of the effective catalytic activity of the metal activator due to complexation can provide an accurate basis for subsequent adjustments to the metal activator dosage. Compared to methods that rely solely on a single organic ligand or simple parameters for evaluation, this application, by extracting composite characteristics and utilizing calibration relationships established for complex systems, can more accurately assess the effective activity of the metal activator in real, complex wastewater environments. This overcomes the problem of inaccurate assessment in existing technologies when dealing with the coexistence of multiple organic ligands, making dosage control based on the assessment results more precise and effective.

[0023] As one embodiment of the present invention, the step of extracting composite electrochemical characteristic parameters characterizing the co-complexation state of multiple organic ligands from electrochemical response characteristic data includes: Acquire electrochemical response characteristic data; Identify the characteristics of interference signals or background noise generated by non-target components in the tailwater in the electrochemical response characteristic data; Based on the characteristics of the identified interference signals or background noise, the electrochemical response characteristic data is processed to suppress the interference signals or background noise, resulting in interference-suppressed electrochemical response data. Composite electrochemical characteristic parameters were extracted from interference-suppressed electrochemical response data.

[0024] Identifying the characteristics of interference signals or background noise generated by non-target components in the electrochemical response feature data refers to analyzing the electrochemical response data and determining the properties of the signal components caused by non-target components. Specifically, this can be achieved by performing time-domain, frequency-domain, or time-frequency-domain analysis on the electrochemical response data, such as Fourier transform and wavelet analysis, to determine the frequency range, amplitude, duration, waveform pattern, or statistical characteristics of the interference signal. The purpose is to understand the nature of the interference and provide a basis for subsequent suppression processing. Processing the electrochemical response feature data based on the identified interference signal or background noise characteristics to suppress the interference signal or background noise refers to using appropriate signal processing techniques to weaken or remove these interference components according to the determined properties of the interference signal or background noise. Specifically, filtering techniques, such as digital filters and adaptive filters, or noise reduction algorithms, such as wavelet denoising, independent component analysis, and machine learning noise reduction models, can be used to process the original electrochemical response data. The purpose is to improve the signal-to-noise ratio of the electrochemical response data, making the effective signal reflecting the complexation state of the metal activator more prominent.

[0025] The proposed method first acquires raw electrochemical response characteristic data, which includes complexation information between the metal activator and organic ligands, and may also be superimposed with interference signals or background noise from non-target components in the effluent. Next, the acquired data is analyzed to identify the specific characteristics of these interference signals or background noise, such as their frequency, amplitude, or time-domain pattern. Based on these identified interference characteristics, targeted signal processing methods are used to process the raw data to effectively suppress or remove these interfering components, thereby obtaining purer, interference-suppressed electrochemical response data. Finally, composite electrochemical characteristic parameters characterizing the co-complexation state of multiple organic ligands are extracted from the processed electrochemical response data with a higher signal-to-noise ratio. Because of the effective interference suppression before parameter extraction, the extracted composite electrochemical characteristic parameters can more accurately reflect the true complexation state of the metal activator and organic ligands, thus providing a more reliable data basis for subsequent assessment of the activity decay of the metal activator. This treatment process, which involves first suppressing interference and then extracting characteristic parameters in complex water quality environments, combined with a scheme that assesses the degree of activity decay by extracting composite electrochemical characteristic parameters when multiple organic ligands are present, effectively solves the problem of inaccurate parameter extraction caused by interference from non-target components in the effluent. This improves the accuracy and reliability of activity decay assessment, and makes the control of metal activator addition based on the assessment results more precise and effective, avoiding waste of reagents or substandard treatment results due to misjudgment.

[0026] As one embodiment of the present invention, when the real-time attenuation assessment results or electrochemical response characteristic data indicate a change in the type of dominant complexed organic ligands in aquaculture tailwater, the step of adjusting the dosage of the metal activator and optionally persulfate according to the real-time attenuation assessment results includes: Identify indicative information related to the dominant complexed organic ligand types in current aquaculture tailwater from real-time attenuation assessment results or electrochemical response characteristic data; Based on the identified indication information and referring to the preset adjustment rules for the dosage ratio of metal activator and persulfate corresponding to different dominant complexed organic ligand types, the target dosage ratio applicable to the current dominant complexed organic ligand type is determined; Based on the real-time attenuation assessment results and the determined target dosage ratio, the adjusted dosages of the metal activator and persulfate were determined respectively.

[0027] Specifically, indicating a change in the type of dominant complexed organic ligands in aquaculture effluent based on real-time attenuation assessment results or electrochemical response characteristic data refers to analyzing specific patterns, peak shapes, peak positions, or intensity changes in electrochemical response characteristic data, or specific trends or numerical ranges in real-time attenuation assessment results. These changes correspond to the known influence characteristics of different dominant complexed organic ligand types on the electrochemical behavior of metal activators, aiming to determine whether the main complexed organic ligand type in the current effluent has changed. Identifying indications related to the dominant complexed organic ligand type in the current aquaculture effluent from real-time attenuation assessment results or electrochemical response characteristic data refers to the indications being able to... The identification can be based on specific parameters or combinations thereof from the electrochemical response curve, or numerical values ​​or patterns reflecting complexation characteristics extracted from real-time decay assessment results. Identification can be achieved through pattern recognition algorithms, machine learning models, or threshold comparisons. Its purpose is to distinguish the main types of complexed organic ligands in the current effluent, providing a basis for subsequent adjustments to the dosage ratio. The preset adjustment rules for the metal activator and persulfate dosage ratios corresponding to different dominant complexed organic ligand types refer to the adjustment rules, which can be a lookup table, a set of formulas, or a decision tree model. These rules record the direction and magnitude of adjustments relative to the baseline dosage ratio under different dominant complexed organic ligand types, or directly provide recommendations. The target dosage ratios are established by studying the effects of different organic ligand types on the activation efficiency of metal activators under laboratory or pilot-scale conditions, and optimizing the balance between sterilization effect and reagent cost. The aim is to guide how to adjust the dosage ratio based on the dominant complexed organic ligand type to achieve the best sterilization effect. The target dosage ratio applicable to the current dominant complexed organic ligand type refers to the mass ratio or molar ratio that the metal activator and persulfate should maintain to achieve the expected sterilization effect under the currently identified dominant complexed organic ligand type. This ratio is determined based on the identified indication information and by consulting or calculating the preset adjustment rules, with the purpose of providing a basis for subsequent accurate calculations. The dosage of the reagents provides a basic proportional relationship; combined with the real-time attenuation assessment results and based on the determined target dosage ratio, the adjusted dosage of the metal activator and the persulfate are determined respectively. This means taking into account the current attenuation of the effective catalytic activity of the metal activator. Based on the determined target dosage ratio, it is possible to calculate how much additional metal activator is needed to restore its effective activity under the current attenuation level, and how much persulfate needs to be adjusted according to the new ratio. The purpose is to accurately calculate the dosage of metal activator and persulfate that needs to be adjusted, thereby compensating for the decrease in free radical generation efficiency caused by complexation, and ensuring that the sterilization effect is stably maintained under the condition of fluctuation in organic ligand concentration.

[0028] This application's solution assesses the real-time decay of the effective catalytic activity of metal activators by monitoring their electrochemical response characteristics online. Based on this, it further identifies changes in the dominant complexed organic ligand types in aquaculture wastewater. When a change in the dominant complexed organic ligand type is detected, the solution no longer simply adjusts the dosage according to the original reagent ratio. Instead, it determines a target dosage ratio suitable for the current complexing environment based on the identified dominant complexed organic ligand type and a pre-defined adjustment rule. Subsequently, combining the real-time assessment of the decay of the metal activator's effective activity with this new target dosage ratio, the required adjustments to the dosage of both the metal activator and persulfate are precisely calculated. This approach allows the reagent dosing strategy to dynamically adapt to changes in the dominant complexed organic ligand types in the wastewater, thereby maintaining optimal sterilization effects under different aquaculture cycles or water quality variations. Compared to methods that adjust the dosage solely based on the total decay rate, this approach, by considering the influence of the dominant complexed organic ligand type on the optimal reagent ratio, can more precisely address complex changes in the effluent environment. This solves the problem that adjusting the dosage solely based on the total decay rate cannot address changes in the dominant complexed organic ligand type, thus improving the stability of the sterilization effect and the efficiency of reagent utilization.

[0029] As one embodiment of the present invention, the step of identifying indication information related to the type of dominant complexed organic ligands in the current aquaculture tailwater from real-time attenuation assessment results or electrochemical response characteristic data includes: Obtain real-time assessment results of decay degree or electrochemical response characteristic data; Online monitoring of at least one non-complexed water quality parameter in aquaculture wastewater to obtain the real-time parameter value of at least one non-complexed water quality parameter; Based on the real-time parameter value of at least one non-complexing water quality parameter and the preset correction data used to determine the adjustment of the real-time attenuation degree assessment result or electrochemical response characteristic data based on the real-time parameter value, the obtained real-time attenuation degree assessment result or electrochemical response characteristic data is adjusted to generate corrected data that has compensated for the influence of fluctuations in non-complexing water quality parameters. Identify indicative information from the corrected data that relates to the dominant complexed organic ligand types in current aquaculture wastewater.

[0030] Among them, the real-time attenuation assessment results or electrochemical response characteristic data refer to the raw data obtained by monitoring the electrochemical response characteristics of metal activators in aquaculture effluent, or the attenuation degree of the effective catalytic activity of the activator assessed based on the raw data. This can be achieved using an electrochemical workstation, a specially designed electrochemical sensor, and a data acquisition unit. Its purpose is to provide basic information reflecting the state of the metal activator in the effluent. Non-complexing water quality parameters refer to water quality indicators in aquaculture effluent that do not directly complex with the metal activator, but whose concentration or state changes affect the electrochemical response signal or attenuation assessment results. These can be pH, temperature, salinity, dissolved oxygen concentration, etc., and their purpose is to identify environmental factors that may interfere with the measurement results. Real-time parameter values ​​refer to the current values ​​of non-complexing water quality parameters obtained in real time through online monitoring equipment. This can be achieved using online pH meters, temperature sensors, conductivity meters, dissolved oxygen sensors, etc., and its purpose is to provide real-time basis for assessing and compensating for interference. Calibration data refers to a pre-established dataset or model that establishes a correspondence between real-time parameter values ​​characterizing non-complexing water quality parameters and adjustments made to real-time attenuation assessment results or electrochemical response characteristic data. It can be stored and represented using lookup tables, mathematical function models, machine learning models, etc. Its purpose is to quantify the impact of non-complexing water quality parameters on measurement results and provide a basis for data adjustment. Corrected data refers to data obtained by adjusting the acquired real-time attenuation assessment results or electrochemical response characteristic data based on the real-time parameter values ​​of non-complexing water quality parameters and the calibration data. Its purpose is to eliminate interference caused by fluctuations in non-complexing water quality parameters and obtain more accurate information reflecting the dominant complexed organic ligand types. Indicative information refers to characteristic signals or parameters extracted from the corrected data that characterize the dominant complexed organic ligand types or their relative content in the current aquaculture tailwater. These can include specific electrochemical peak positions, peak areas, signal intensity ratios, attenuation rate changes, etc., and their purpose is to provide a basis for subsequently determining the dosage ratio.

[0031] This application's solution uses real-time attenuation assessment results or electrochemical response characteristic data as a basis, while simultaneously monitoring the real-time values ​​of at least one non-complexing water quality parameter online. Monitoring non-complexing water quality parameters is necessary because changes in these parameters directly or indirectly affect the accuracy of electrochemical measurement signals or attenuation assessments, thus interfering with the determination of the dominant complexed organic ligand type. Due to the interference of these non-complexing parameters, relying solely on the original real-time attenuation assessment results or electrochemical response characteristic data to identify the dominant complexed organic ligand type may lead to bias. Therefore, this application further adjusts the acquired original data based on the real-time parameter values ​​of the non-complexing water quality parameters and preset correction data, generating corrected data that compensates for the influence of fluctuations in the non-complexing water quality parameters. The existence of the correction data allows the system to quantify and eliminate the interference of non-complexing water quality parameters on the measurement results, thereby obtaining purer and more accurate information reflecting the dominant complexed organic ligand type. Finally, the system identifies indication information related to the dominant complexed organic ligand type in the current aquaculture wastewater from the corrected data. This method of improving the accuracy of indications through data correction enables more reliable identification of the type of dominant complexed organic ligands in the complex and dynamically changing environment of aquaculture wastewater. This more reliable identification capability further enhances the effectiveness of strategies for adjusting the dosage ratio of metal activators and persulfates based on the type of dominant complexed organic ligands. This allows for more precise matching of dosage adjustments to actual needs, thereby maintaining a stable sterilization effect even when the type of organic ligand changes, and avoiding waste of reagents or substandard treatment results due to misjudgment.

[0032] As one embodiment of the present invention, the step of constructing the pre-set correction data for adjusting the real-time attenuation degree assessment results or electrochemical response characteristic data based on the real-time parameter values ​​of at least one non-complexing water quality parameter includes: Obtain the actual response value of the real-time attenuation degree assessment result or electrochemical response characteristic data under different combinations of preset non-complexing water quality parameters. Determine the impact of independent changes in each non-complexing water quality parameter on the real-time attenuation assessment results or electrochemical response characteristic data; Based on the independent effects of various non-complexed water quality parameters, the expected response value obtained by superimposing the independent effects of each non-complexed water quality parameter under different combinations of values ​​is calculated. By comparing the actual response values ​​with the expected response values, the coupling effects existing under different combinations of various non-complexing water quality parameters are determined. Based on the independent influence and determined coupling influence of various non-complexed water quality parameters, a comprehensive adjustment value for the real-time attenuation assessment results or electrochemical response characteristic data is jointly determined under different combinations of values ​​of various non-complexed water quality parameters. Construct preset calibration data, which includes different combinations of values ​​for various non-complexed water quality parameters and their corresponding comprehensive adjustment values.

[0033] Among them, the preset correction data used to adjust the real-time attenuation degree assessment results or electrochemical response characteristic data based on the real-time parameter value of at least one non-complexing water quality parameter refers to a data structure that records the relationship between different combinations of values ​​of various non-complexing water quality parameters and the corresponding adjustment amounts. It can be implemented using lookup tables, mathematical models or algorithms. Among them, obtaining the actual response value of the real-time attenuation degree assessment result or electrochemical response characteristic data under different combinations of preset non-complexing water quality parameters refers to obtaining the system output data under a specific combination of water quality parameters through experimental measurement or simulation calculation, which can be achieved by laboratory controlled experiments, on-site data acquisition or numerical simulation. Among them, determining the impact of each non-complexed water quality parameter on the real-time attenuation assessment results or electrochemical response characteristic data when each parameter changes independently refers to quantifying the change in the system response caused by the change of a single water quality parameter. This can be achieved by using single-factor variable experiments, regression analysis, or sensitivity analysis. Among them, the expected response value obtained by superimposing the independent influence effects of each non-complexed water quality parameter under different combination values ​​refers to the prediction of the system response when multiple parameters change simultaneously based on the linear superposition or other simple combination model of the independent influence of each parameter. It can be realized by linear superposition calculation, simple function model calculation or prediction model calculation based on independent influence. Among them, determining the coupling effects under different combinations of various non-complexed water quality parameters by comparing the actual response value with the expected response value refers to identifying the difference between the actual system response and the response predicted based on independent effects. This difference reflects the interaction between parameters and can be achieved by difference calculation, residual analysis or interaction term analysis. Among them, the comprehensive adjustment value for the real-time attenuation degree assessment results or electrochemical response characteristic data under different combinations of values ​​of various non-complexed water quality parameters, based on the independent influence and determined coupling influence of multiple non-complexed water quality parameters, refers to the final correction amount calculated to correct the real-time response of the system by comprehensively considering the individual effects of each parameter and their interactions. It can be achieved by using a multivariate regression model, a neural network model, or a combination of calculations based on independent influence and coupling influence. Among them, constructing preset calibration data, which includes different combinations of non-complexed water quality parameters and corresponding comprehensive adjustment values, refers to organizing the calculated comprehensive adjustment values ​​under different parameter combinations into a data structure that can be queried or calculated in real time. This can be achieved by constructing multidimensional lookup tables, fitting parameters of mathematical models, or establishing algorithm rules.

[0034] This application's scheme systematically acquires actual response data under various combinations of non-complexing water quality parameters, providing a foundation for analyzing parameter influences. Based on this, the scheme further quantifies the impact of each non-complexing water quality parameter's independent variation on the response, thereby understanding the individual action patterns of each parameter. Subsequently, based on these independent effects, the scheme calculates the expected response values ​​under different parameter combinations, representing the predicted response in the absence of parameter interactions (coupling). By comparing the actual measured response values ​​with the expected response values ​​obtained based on the superposition of independent effects, the scheme can identify and quantify the coupling effects between various non-complexing water quality parameters, i.e., the additional or nonlinear effects produced by parameter interactions. Finally, the scheme combines the independent effects of each parameter with the identified coupling effects to jointly determine the comprehensive adjustment values ​​for real-time attenuation assessment results or electrochemical response characteristic data under various parameter combinations. These comprehensive adjustment values, along with the corresponding parameter combinations, are organized into pre-defined correction data. Because this correction data fully considers and quantifies the coupling effects between non-complexed water quality parameters, when applied to the above adjustment steps, it can more accurately compensate for the impact of fluctuations in non-complexed water quality parameters on real-time assessment results or electrochemical characteristic data, thereby generating corrected data with reduced bias. This corrected data with reduced bias allows for less misjudgment due to interference from non-complexed parameters when subsequently identifying dominant complexed organic ligand types in aquaculture wastewater, improving the stability of dominant complexed organic ligand type identification. By accurately identifying dominant complexed organic ligand types, the dosage of metal activators and persulfates can be more precisely determined based on the dosage adjustment rules for that type of ligand, effectively addressing the problem of decreased activator efficiency caused by the complexation of specific organic ligands, ensuring stable sterilization effects, and reducing reagent waste.

[0035] As one embodiment of the present invention, it further includes: Obtain the corrected data; Monitor the residual effects caused by fluctuations in non-complexed water quality parameters in the corrected data, and determine whether the residual effects exceed the preset threshold. Based on the residual effects, adjust the correction parameters in the preset correction data to reduce the residual effects.

[0036] The corrected data refers to the data that has undergone preliminary correction, which can be obtained by using lookup tables, mathematical models, or machine learning models. The residual impact caused by fluctuations in non-complexing water quality parameters refers to the deviations in the data that still exist after preliminary correction, caused by changes in non-complexing water quality parameters. These deviations can be monitored using time-series analysis, frequency domain analysis, or statistical analysis. The preset threshold is the boundary value used to determine whether the residual impact is significant. It can be a fixed value, a dynamic value determined based on historical data statistical analysis, or a value set based on expert experience. The correction parameters in the preset correction data refer to data in the form of lookup tables, model coefficients, or correction curves used for preliminary correction of real-time attenuation assessment results or electrochemical response characteristic data. These parameters can be adjusted using optimization algorithms such as least squares, gradient descent, or genetic algorithms.

[0037] The proposed solution first acquires pre-corrected data, which has partially eliminated interference from non-complexing water quality parameters. Next, these corrected data are analyzed in depth to monitor for any residual effects caused by fluctuations in non-complexing water quality parameters that have not been completely eliminated. By comparing this residual effect with a preset threshold, it is determined whether the residual effect is significant enough to affect the accuracy of subsequent judgments and adjustments. If the residual effect exceeds the threshold, it indicates that the current pre-correction effect is insufficient and optimization is needed. At this point, the system adjusts the correction parameters in the preset correction data used for pre-correction based on the degree and characteristics of the monitored residual effect. For example, if it is found that the residual deviation caused by a certain non-complexing parameter is consistently high within a certain value range, the correction coefficient or model parameter corresponding to that parameter within that value range can be adjusted to more effectively compensate for this deviation. Through this feedback adjustment mechanism based on residual effects, the accuracy of the correction data can be continuously optimized, resulting in higher quality data after pre-correction, thus providing a more reliable basis for subsequent identification of dominant complexed organic ligand types and adjustment of dosage. This iterative optimization process enables the entire control system to better adapt to dynamic changes in water quality parameters, improving the accuracy and robustness of control. This mechanism of secondary monitoring and feedback adjustment of preliminary correction results is an improvement over existing methods that rely solely on one-time correction. Based on preliminary correction, it further enhances the precision and adaptability of data processing, thereby more effectively solving the problem of residual interference caused by fluctuations in non-complexed water quality parameters.

[0038] As one embodiment of the present invention, the step of monitoring the residual effects caused by fluctuations in non-complexing water quality parameters in the corrected data and determining whether the residual effects exceed a preset threshold includes: Perform time-series or frequency-domain analysis on the corrected data to obtain its time-series or frequency-domain characteristics; Identify patterns or signal features caused by fluctuations in non-complexed water quality parameters from time-series or frequency-domain characteristics; Based on the pattern or signal characteristics, compare them with a preset threshold to determine whether the residual effect exceeds the preset threshold.

[0039] Time series analysis refers to the study of the patterns of data series changes over time. It can be implemented using methods such as moving averages, autoregressive models, and time series decomposition, aiming to reveal the trends, periodicity, or random fluctuations of data over time. Frequency domain analysis involves transforming data from the time domain to the frequency domain for analysis. It can be implemented using methods such as Fourier transforms and wavelet analysis, aiming to reveal the intensity and distribution of different frequency components in the data. Time series or frequency domain characteristics refer to information extracted from the original data through time series or frequency domain analysis that characterizes the inherent patterns of the data, such as trend slope, periodic frequency, amplitude of specific frequencies, and waveform shape. Identifying patterns or signal characteristics caused by fluctuations in non-complexed water quality parameters is... This refers to the process of distinguishing specific manifestations related to fluctuations in non-complexed water quality parameters from time-series or frequency-domain features using specific algorithms or rules. This can be achieved using techniques such as pattern matching, machine learning classification, and signal filtering. The goal is to separate the target influence from complex background data. Pattern or signal features refer to the regular manifestations of non-complexed water quality parameter fluctuations left in the corrected data, such as specific periodic fluctuations, enhancement or weakening of specific frequency components, or specific waveform changes. Preset thresholds refer to a boundary value set in advance before judgment to measure the acceptability of residual effects. This threshold can be determined based on historical data analysis, experimental results, or process requirements, and its purpose is to provide a judgment standard.

[0040] The proposed solution transforms complex raw data into easily identifiable and analyzable time-series or frequency-domain feature information by performing time-series or frequency-domain analysis on the corrected data. Since fluctuations in non-complexing water quality parameters often leave specific time or frequency imprints in the data, these analytical methods can extract these hidden patterns or signal features. Furthermore, identifying patterns or signal features directly related to fluctuations in non-complexing water quality parameters from these features requires prior knowledge of the typical manifestations that fluctuations in different water quality parameters may produce. Through pattern recognition algorithms or manual analysis, the target influence can be separated from the feature set. Finally, by comparing the identified pattern or signal features with preset thresholds, it can be determined whether the magnitude of the residual influence exceeds an acceptable range. This feature-based judgment method, compared to absolute changes in monitoring data, can effectively distinguish specific residual influences caused by fluctuations in non-complexing water quality parameters from other interfering factors, thereby improving the accuracy of residual influence monitoring. This accurate monitoring and judgment allows subsequent steps to adjust correction parameters based on residual influences to be performed on reliable information, effectively reducing residual influences, improving the accuracy and stability of correction data, and ultimately enhancing the effectiveness of the control method.

[0041] As one embodiment of the present invention, the step of jointly determining the comprehensive adjustment value of the real-time attenuation degree assessment result or electrochemical response characteristic data under different combinations of values ​​of various non-complexing water quality parameters, based on the independent influence and determined coupled influence of various non-complexing water quality parameters, includes: Get the combined values ​​P_current of multiple non-complexed water quality parameters, where the number of types of multiple non-complexed water quality parameters is N, P_current = [p1_current, p2_current, ..., pN_current], where p_i_current is the current value of the i-th non-complexed water quality parameter; Obtain the preset baseline effect value Base_Effect; Based on P_current and according to the preset function or data Ind_Effect_i(p_i) characterizing the independent influence of each non-complexed water quality parameter, determine the independent influence value of each non-complexed water quality parameter. Based on P_current, and according to the preset functions or data Coup_Effect_ij(p_i, p_j) and Coup_Effect_ijk(p_i, p_j, p_k) that characterize the coupling effect between non-complexed water quality parameters, the coupling effect value between non-complexed water quality parameters is determined. The comprehensive adjustment value Delta_total is obtained by superimposing Base_Effect, the independent influence value of each non-complexed water quality parameter, and the coupling influence value between non-complexed water quality parameters.

[0042] Among them, the preset baseline effect value Base_Effect refers to the benchmark value of the real-time attenuation assessment result or electrochemical response characteristic data under standard conditions or without the influence of non-complexing water quality parameters. Its purpose is to ensure that even when the influence of all non-complexing water quality parameters is small, the corrected data can still reflect the true activity state of the metal activator. The preset function or data Ind_Effect_i(p_i) characterizing the independent influence effect of each non-complexing water quality parameter refers to the mathematical model or lookup table describing the influence of the current value p_i of the i-th non-complexing water quality parameter. It can be implemented using polynomial functions, exponential functions, logarithmic functions, or pre-measured and stored data tables. Its purpose is to quickly determine the independent influence value of each parameter, thereby simplifying the calculation process. The preset functions or data Coup_Effect_ij(p_i, p_j) and Coup_Effect_ijk(p_i, p_j, ...) characterizing the coupling influence effect between non-complexing water quality parameters p_k, etc., refer to mathematical models or lookup tables that describe the mutual influences generated when non-complexed water quality parameters work together. They can be implemented using multivariate functions, interaction term models, or pre-measured and stored multidimensional data tables. Their purpose is to more accurately reflect the combined effects of various parameters under actual water quality conditions and avoid correction errors caused by ignoring the interactions between parameters.

[0043] The proposed method obtains a preset baseline influence value by acquiring the combined values ​​of multiple non-complexing water quality parameters. Based on the current parameter combinations and a preset independent influence function or data, the independent influence value of each parameter is determined. The coupling influence value between parameters is determined based on the current parameter combinations and a preset coupling influence function or data. The baseline influence value, independent influence value, and coupling influence value are then superimposed to obtain a comprehensive adjustment value. This method considers both the independent influence and the coupling influence between multiple non-complexing water quality parameters, calculating the comprehensive adjustment value for real-time attenuation assessment results or electrochemical response characteristic data through superposition. This allows the calculated adjustment value to more comprehensively and accurately reflect the combined influence of non-complexing water quality parameters on measurement results under complex water quality conditions. The comprehensive adjustment value determined in this way can be used to correct real-time attenuation assessment results or electrochemical response characteristic data, thereby obtaining more accurate corrected data. This more accurate calibration data provides a reliable basis for the subsequent accurate identification of dominant complexed organic ligand types and precise adjustment of metal activator dosage, overcoming the error problem caused by only considering independent effects while ignoring coupling effects, and improving the accuracy and reliability of the entire regulation method.

[0044] like Figure 2 The system shown is a sulfate radical sterilization process parameter control system, which includes: Monitoring module 201 is used to monitor the electrochemical response characteristics of metal activators in aquaculture wastewater online and obtain electrochemical response characteristic data; Evaluation module 202 is used to evaluate the real-time decay of the effective catalytic activity of the metal activator due to complexation with organic ligands in the tailwater based on electrochemical response characteristic data and preset calibration data or models that characterize the relationship between the electrochemical response characteristics of the metal activator in different organic ligand complexation states and its catalytic activation efficiency of persulfate, and obtain the real-time decay evaluation result. The control module 203 is used to adjust the dosage of metal activator and optional persulfate based on the real-time decay assessment results.

[0045] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A method for controlling process parameters in sulfate radical sterilization, characterized in that, The method includes the following steps: The electrochemical response characteristics of metal activators in aquaculture wastewater were monitored online to obtain the electrochemical response characteristic data. Based on the electrochemical response characteristic data and the preset calibration data or model characterizing the relationship between the electrochemical response characteristics of the metal activator in different organic ligand complexation states and its catalytic activation efficiency of persulfate, the real-time attenuation degree of the effective catalytic activity of the metal activator due to complexation with organic ligands in the tailwater is evaluated, and the real-time attenuation degree evaluation result is obtained. Based on the real-time attenuation assessment results, adjust the dosage of the metal activator and, optionally, the persulfate.

2. The method for controlling process parameters of sulfate radical sterilization according to claim 1, characterized in that, When the electrochemical response characteristic data indicates the presence of multiple organic ligands that collectively complex with the metal activator, the step of evaluating the real-time attenuation of the effective catalytic activity of the metal activator due to complexation with organic ligands in the effluent, based on the electrochemical response characteristic data and a preset calibration data or model characterizing the relationship between the electrochemical response characteristics of the metal activator in different organic ligand complexation states and its catalytic activation efficiency of persulfate, includes: Extract composite electrochemical characteristic parameters characterizing the co-complexation state of multiple organic ligands from the electrochemical response characteristic data; Based on the composite electrochemical characteristic parameters and the correspondence between the electrochemical response characteristics of the metal activator and the catalytic activity decay under the combined action of multiple organic ligands contained in the preset calibration data or model, the degree of overall effective catalytic activity decay under the combined action of multiple organic ligands is determined, and the degree of overall effective catalytic activity decay is taken as the real-time degree of effective catalytic activity decay caused by the metal activator complexing with the organic ligands in the tailwater.

3. The method for controlling process parameters of sulfate free radical sterilization according to claim 2, characterized in that, The step of extracting composite electrochemical characteristic parameters characterizing the co-complexation state of multiple organic ligands from the electrochemical response characteristic data includes: Obtain the electrochemical response characteristic data; Identify the characteristics of interference signals or background noise generated by non-target components in the electrochemical response feature data; Based on the characteristics of the identified interference signals or background noise, the electrochemical response feature data is processed to suppress the interference signals or background noise, resulting in interference-suppressed electrochemical response data. The composite electrochemical characteristic parameters are extracted from the interference-suppressed electrochemical response data.

4. The method for controlling process parameters of sulfate radical sterilization according to claim 1, characterized in that, When the real-time attenuation assessment result or the electrochemical response characteristic data indicates a change in the type of dominant complexed organic ligands in aquaculture tailwater, the step of adjusting the dosage of the metal activator and optionally persulfate based on the real-time attenuation assessment result includes: Identify indicative information related to the dominant complexed organic ligand types in the current aquaculture tailwater from the real-time attenuation assessment results or the electrochemical response characteristic data; Based on the identified indication information and referring to the preset adjustment rules for the dosage ratio of metal activator and persulfate corresponding to different dominant complexed organic ligand types, the target dosage ratio applicable to the current dominant complexed organic ligand type is determined; Based on the real-time attenuation assessment results and the determined target dosage ratio, the adjusted dosage of the metal activator and the adjusted dosage of persulfate are determined respectively.

5. The method for controlling process parameters of sulfate radical sterilization according to claim 4, characterized in that, The step of identifying indication information related to the dominant complexed organic ligand type in the current aquaculture tailwater from the real-time attenuation assessment results or the electrochemical response characteristic data includes: Obtain the real-time attenuation assessment results or the electrochemical response characteristic data; Online monitoring of at least one non-complexed water quality parameter in aquaculture wastewater to obtain the real-time parameter value of at least one non-complexed water quality parameter; Based on the real-time parameter value of at least one non-complexing water quality parameter and preset correction data for determining the adjustment of the real-time attenuation assessment result or the electrochemical response characteristic data based on the real-time parameter value, the obtained real-time attenuation assessment result or electrochemical response characteristic data is adjusted to generate corrected data that has compensated for the influence of fluctuations in non-complexing water quality parameters. Identify indicative information from the corrected data that relates to the dominant complexed organic ligand types in current aquaculture wastewater.

6. The method for controlling process parameters of sulfate radical sterilization according to claim 5, characterized in that, The steps for constructing the pre-defined correction data for adjusting the real-time attenuation assessment result or the electrochemical response characteristic data based on real-time parameter values ​​of at least one non-complexing water quality parameter include: Under different combinations of preset non-complexing water quality parameters, the actual response values ​​of the real-time attenuation assessment results or the electrochemical response characteristic data are obtained. Determine the impact of each non-complexing water quality parameter changing independently on the real-time attenuation assessment results or the electrochemical response characteristic data; Based on the independent effects of various non-complexed water quality parameters, the expected response value obtained by superimposing the independent effects of each non-complexed water quality parameter under different combinations of values ​​is calculated. By comparing the actual response value with the expected response value, the coupling effects existing under different combinations of various non-complexing water quality parameters are determined. Based on the independent influence and determined coupling influence of various non-complexing water quality parameters, a comprehensive adjustment value for the real-time attenuation assessment result or the electrochemical response characteristic data is jointly determined under different combinations of values ​​of various non-complexing water quality parameters. A preset calibration data is constructed, which includes different combinations of values ​​of various non-complexing water quality parameters and their corresponding comprehensive adjustment values.

7. The method for controlling process parameters of sulfate free radical sterilization according to claim 6, characterized in that, Also includes: Obtain the corrected data; Monitor the residual effects caused by fluctuations in the non-complexing water quality parameters in the corrected data, and determine whether the residual effects exceed a preset threshold; Based on the residual effects, the correction parameters in the preset correction data are adjusted to reduce the residual effects.

8. The method for controlling process parameters of sulfate radical sterilization according to claim 7, characterized in that, The step of monitoring the residual effects caused by fluctuations in the non-complexing water quality parameters in the corrected data and determining whether the residual effects exceed a preset threshold includes: Perform time-series analysis or frequency-domain analysis on the corrected data to obtain the time-series or frequency-domain characteristics of the corrected data; Identify patterns or signal features caused by fluctuations in the non-complexed water quality parameters from the time-series or frequency-domain features; Based on the comparison between the pattern or signal characteristics and the preset threshold, it is determined whether the residual effect exceeds the preset threshold.

9. The method for controlling process parameters of sulfate free radical sterilization according to claim 6, characterized in that, The step of determining the comprehensive adjustment value of the real-time attenuation assessment result or the electrochemical response characteristic data under different combinations of values ​​of multiple non-complexing water quality parameters, based on the independent influence and determined coupling influence of multiple non-complexing water quality parameters, includes: Obtain the combined value P_current of multiple non-complexing water quality parameters, wherein the number of types of multiple non-complexing water quality parameters is N, and P_current = [p1_current, p2_current, ..., pN_current], where p_i_current is the current value of the i-th non-complexing water quality parameter; Obtain the preset baseline effect value Base_Effect; Based on P_current and according to the preset function or data Ind_Effect_i(p_i) characterizing the independent influence effect of each non-complexed water quality parameter, determine the independent influence value of each non-complexed water quality parameter. Based on P_current, and according to preset functions or data such as Coup_Effect_ij(p_i, p_j) and Coup_Effect_ijk(p_i, p_j, p_k) that characterize the coupling effect between non-complexed water quality parameters, the coupling effect value between the non-complexed water quality parameters is determined. The comprehensive adjustment value Delta_total is obtained by superimposing the Base_Effect, the independent influence value of each non-complexing water quality parameter, and the coupling influence value between the non-complexing water quality parameters.

10. A sulfate radical sterilization process parameter control system, characterized in that, The system includes: The monitoring module is used to monitor the electrochemical response characteristics of metal activators in aquaculture wastewater online and obtain the electrochemical response characteristic data. The evaluation module is used to evaluate the real-time attenuation of the effective catalytic activity of the metal activator due to complexation with organic ligands in the tailwater based on the electrochemical response characteristic data and the preset calibration data or model characterizing the relationship between the electrochemical response characteristics of the metal activator in different organic ligand complexation states and its catalytic activation efficiency of persulfate, and obtain the evaluation result of the real-time attenuation. The control module is used to adjust the dosage of the metal activator and, optionally, persulfate, based on the real-time attenuation assessment results.

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