Multifunctional modular ozone catalytic oxidation wastewater treatment device and method

Abstract

The present application relates to wastewater treatment technical field, specifically disclose a kind of multifunctional modular ozone catalytic oxidation wastewater treatment device and method.Method is matched with continuous time series analysis to obtain oxidation gain coefficient on liquid phase dosing increment;Identify negative mutation after truncation liquid phase input, extract transient feedback slope and decouple out quenching characteristic component and distortion characteristic component;Based on former, construct in-situ clear residual in silence period, based on latter, reconstruct asynchronous restart dosing of wake-up reference quantity, obtain pretreated water;Then pretreated water is introduced into ultraviolet radiation zone containing solid phase catalyst to carry out three-phase catalytic oxidation, and biochemical degradation filtration is obtained by biological activated carbon filter to obtain final effluent.The device is used to realize modular ozone catalytic oxidation wastewater treatment method.The present application is beneficial to reduce the physical quenching deadlock caused by local excess of liquid phase oxidant, and realize the dynamic adaptation of dosing strategy and system real carrying capacity.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, specifically to a multifunctional modular ozone catalytic oxidation wastewater treatment device and method. Background Technology

[0002] Advanced oxidation processes using ozone and hydrogen peroxide are widely used in the treatment of recalcitrant wastewater because they synergistically generate highly potent hydroxyl radicals. However, in actual engineering operations, while hydrogen peroxide is a highly efficient free radical activator when the dosage is appropriate, it can transform into a free radical scavenger when excessively added locally, resulting in a severe quenching effect and consuming a large number of hydroxyl radicals.

[0003] When the system faces fluctuations in operating conditions, such as a sudden increase in the organic load of the influent, conventional control logic usually simply increases the dosage of oxidant synchronously. Once the hydrogen peroxide concentration exceeds the critical point and triggers a quenching effect, an abnormal chemical paradox occurs: the more hydrogen peroxide is added to the system, the more free radicals are generated and consumed, leading to a sharp drop in the overall oxidation efficiency of the system, and the ORP decreases instead of increasing.

[0004] Traditional automated control systems cannot distinguish whether the current ORP decline is due to "water quality deterioration caused by high concentrations of organic load in the influent" or "free radical quenching caused by excessive liquid-phase oxidant." Lacking the ability to decouple and identify the inhibited mechanism, the system often mistakenly continues to increase the hydrogen peroxide dosage, ultimately dragging the reaction system into a state of physical quenching deadlock. This leads to waste of chemical reagents and causes a large amount of unreacted residual hydrogen peroxide to overflow from the pre-oxidation stage with the water flow, disrupting the stable operation of subsequent advanced treatment modules or biochemical processes.

[0005] Therefore, the present invention provides a multifunctional modular ozone catalytic oxidation wastewater treatment device and method. Summary of the Invention

[0006] The purpose of this invention is to provide a multifunctional modular ozone catalytic oxidation wastewater treatment device and method to solve the aforementioned background problems.

[0007] The objective of this invention can be achieved through the following technical solutions: A multifunctional modular ozone catalytic oxidation wastewater treatment method includes the following steps: Extract the hydraulic mass transfer time delay and continuous time series, perform misaligned time-domain matching analysis on the incremental addition of liquid phase oxidant and the continuous time series to obtain the oxidation gain coefficient; evaluate the performance based on the oxidation gain coefficient, and output an active perturbation command if the negative abrupt change condition of the oxidation gain coefficient is met. In response to active perturbation commands, a transient cutoff operation is performed on the liquid-phase oxidant. Feature parameters within the cutoff window are collected and a transient response dataset is constructed. Potential evolution rate is extracted and trend analysis is performed on the transient response dataset to obtain the slope feature value of the transient feedback. The transient feedback slope eigenvalues ​​are analyzed for polarity and amplitude to obtain the mechanism discrimination intermediate state; based on the mechanism discrimination intermediate state, the hysteresis state separation process is performed on the multiphase oxidation reaction system to obtain the quenching characteristic component and the distortion characteristic component; A quiescent window period is constructed based on quenching characteristic components, and zero addition and clearing residue are maintained during the quiescent window period. The awakening reference quantity of the liquid phase is reconstructed based on the distortion characteristic components. After the quiescent window period ends, the addition is asynchronously restarted based on the awakening reference quantity to obtain pretreated water.

[0008] As a further technical solution of the present invention: the method for extracting the continuous time series is as follows: The water to be treated is introduced into the pre-oxidation reaction zone, and liquid and gaseous oxidants are added simultaneously to establish a multiphase oxidation reaction system. The redox characteristics of the multiphase oxidation reaction system are continuously collected to establish a continuous time series of redox characteristics.

[0009] As a further technical solution of the present invention, the method for performing misaligned time-domain matching analysis is as follows: Obtain the incremental liquid-phase oxidant dosage within the unit evaluation period; A sliding time window is established based on the unit evaluation cycle. Within the sliding time window, the data point of the liquid phase oxidant addition increment is shifted backward along the time axis by one mass transfer time delay cycle, so that the data point and the millivolt-level electrical signal in the continuous time series can complete the misaligned time domain matching on the same effective physical action surface. For the liquid phase oxidant addition increment after misaligned time-domain matching, calculate the input rate of change of the liquid phase oxidant addition increment under the same sliding window step size, and the output rate of change of the corresponding continuous time series values. Extract the non-zero displacement segment of the input rate of change, and calculate the ratio of the output rate of change to the input rate of change within the non-zero displacement segment to obtain the oxidation gain coefficient.

[0010] As a further technical solution of the present invention, the method for extracting the potential evolution rate and analyzing its trend is as follows: First-order time-domain difference processing is performed on the millivolt-level electrical signals in the transient response dataset, that is, the rate of change of electrical signals between adjacent high-frequency sampling periods is calculated point by point; Traverse the rate of change of the electrical signal along the time axis, locate the extreme point where the rate of change of the electrical signal first changes from negative decay or zero plateau to positive change, and define the extreme point as the starting point of the physical response; The millivolt-level electrical signal between the start of the physical response and the end of the truncation window period is extracted as the effective recovered data segment; Linear least squares fitting is performed on the millivolt-level electrical signal and the corresponding timestamp within the effective recovered data segment to calculate the geometric slope of the fitted line; The geometric slope is defined as the slope characteristic value of transient feedback.

[0011] As a further technical solution of the present invention: the transient response dataset is constructed as follows: Upon receiving an active disturbance command, the gaseous oxidant supply to the main reactor is kept constant. The input of liquid-phase oxidant into the pipeline mixer is simultaneously cut off, and the system simultaneously sets the cutoff window period; Millivolt-level electrical signals are extracted within the truncated window period, and the millivolt-level electrical signals within the truncated window period are sequentially spliced ​​according to absolute timestamps to construct a transient response dataset.

[0012] As a further technical solution of the present invention, the method for performing the hysteresis state separation process is as follows: The system calls the pre-calibrated single-phase reference recovery slope stored in the control unit; Based on the single-phase baseline recovery slope, the polarity characteristics in the intermediate state of mechanism discrimination are decoupled and processed to obtain the quenching characteristic component caused by excessive liquid phase oxidant, and the distortion characteristic component caused by the sudden change in influent oxygen consumption load.

[0013] As a further technical solution of the present invention, the method for performing the current splitting and decoupling process is as follows: When the polarity characteristic is positive, the quenching characteristic component is determined by the amplitude characteristic of the intermediate state and the single-phase reference recovery slope based on the mechanism, and the preset basic noise floor constant is assigned as the distortion characteristic component. When the polarity characteristic is negative or zero polarity, the load gap parameters are determined based on the single-phase reference recovery slope and amplitude characteristics, and the distortion characteristic components are determined in combination with the pre-calibrated load conversion coefficient.

[0014] As a further technical solution of the present invention: the method for reconstructing the wake-up reference quantity is as follows: A preset liquid phase safety ratio constant is established, and the distortion characteristic components are multiplied with the liquid phase safety ratio constant to obtain the load compensation increment; Extract the historical baseline injection amount before the system performs the instantaneous truncation operation, introduce a preset penalty attenuation coefficient as a weighting factor, and perform attenuation reduction processing on the historical baseline injection amount to obtain the base injection amount; The base dosage and the load compensation increment are summed to obtain the reconstructed liquid phase wake-up reference quantity.

[0015] As a further technical solution of the present invention, it also includes: Pretreated water is introduced into an ultraviolet radiation zone containing a solid catalyst, and a gaseous oxidant is introduced for three-phase catalytic oxidation treatment to obtain deeply treated water. The deeply treated water is then introduced into a biological activated carbon filter for biochemical degradation filtration to obtain the final effluent.

[0016] A multifunctional modular ozone catalytic oxidation wastewater treatment device includes: Ozone and hydrogen peroxide pre-oxidation module; Ozone-UV catalytic oxidation module; Biological activated carbon filter module.

[0017] The beneficial effects of this invention are as follows: 1. Introducing the water to be treated into the pre-oxidation reaction zone and simultaneously adding a gas-liquid two-phase oxidant to establish a multiphase reaction system helps reduce ineffective decomposition caused by excessively high local concentrations. Breaking the gas-phase oxidant into microbubbles increases the gas-liquid contact surface area and improves the synergistic catalytic efficiency of the gas-liquid-solid multiphase reaction. Staggered time-domain matching of the liquid-phase oxidant addition increment with the continuous time series reduces feedback lag caused by reagent mixing and reaction delays. Obtaining the oxidation gain coefficient helps assess the synergistic catalytic state of the current multiphase oxidation reaction system. Setting negative abrupt change conditions for real-time monitoring of the system's suppressed state helps reduce the possibility of reduced system catalytic efficiency due to excessive local accumulation of reagents or bubble coalescence.

[0018] 2. In response to active perturbation commands, the system synchronously cuts off the input of liquid-phase oxidant, actively blocking the continuous deterioration of the abnormal state by physically cutting off the input source. The system extracts the potential evolution rate from the transient response dataset to obtain the physical response starting point of residual liquid-phase oxidant depletion. By extracting the effective recovery data segment and fitting its timestamp, the geometric slope of the transient feedback is obtained, transforming the internal microscopic reaction mechanism of the system into the trend of the electrical signal evolution rate, which is beneficial for characterizing the true reaction state of the multiphase system after the intervention of excess liquid-phase oxidant. When the polarity characteristic is positive, the quenching characteristic component is established by calculating the ratio of the amplitude characteristic of the intermediate state based on the mechanism to the single-phase reference recovery slope, quantifying the redundant concentration of ineffective liquid-phase oxidant accumulated inside the multiphase oxidation reaction system.

[0019] 3. The distortion characteristic components are combined with the preset liquid phase safety ratio constant to convert into load compensation increments, and the corrected historical benchmark dosage is superimposed to reconstruct a liquid phase wake-up benchmark dosage that reduces the risk of quenching. After the quiescent window ends and the oxidation gain coefficient crosses zero and enters the positive range, the continuous addition of liquid phase oxidant is asynchronously resumed using this benchmark dosage, which is conducive to achieving dynamic adaptation between the addition strategy and the actual load-bearing capacity of the system.

[0020] 4. Pretreated water is introduced into an ozone-UV catalytic oxidation module equipped with an ozone gas distributor and a solid-phase catalyst. Under UV light excitation, ozone in the water decomposes to generate a large number of hydroxyl radicals, enhancing the deep degradation efficiency of residual recalcitrant organic matter in the water. Residual ozone in the water is recycled, extending the reaction cycle of pollutants in a highly oxidizing environment. The deeply oxidized water is then introduced into an upflow biological activated carbon filter module. The physical adsorption properties of activated carbon are used to retain trace amounts of organic matter, while the biochemical degradation filtration effect of the attached microbial community reduces the chemical oxygen demand (COD) of the final effluent. In conjunction with an ozone destruction device, ozone emitted from the exhaust gas is thermally catalytically decomposed into oxygen, reducing the environmental emission pressure caused by system operation. Attached Figure Description

[0021] The invention will now be further described with reference to the accompanying drawings.

[0022] Figure 1 This is a functional module diagram of a multifunctional modular ozone catalytic oxidation wastewater treatment device according to the present invention; Figure 2 This is a flowchart of a multifunctional modular ozone catalytic oxidation wastewater treatment method according to the present invention; Figure 3 This is a flowchart of the flow decoupling process performed in this invention. Detailed Implementation

[0023] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0024] Example 1: Please refer to Figure 1 As shown, a multifunctional modular ozone catalytic oxidation wastewater treatment device includes the following modules: A1. Ozone and Hydrogen Peroxide Pre-oxidation Module: Includes a hydrogen peroxide storage tank, a pipeline mixer, and a pre-oxidation reaction tank; Among them, the hydrogen peroxide storage tank is equipped with a metering pump to realize the addition control of hydrogen peroxide. The addition amount can be determined by small-scale test according to the quality of the influent water, reducing the dual economic losses of reduced free radical efficiency and waste of reagents caused by over-addition; Among them, the pipeline mixer adopts a static mixing structure to ensure that hydrogen peroxide and water to be treated are fully mixed before entering the pre-oxidation reaction tank, and the mixing time is controlled within 5 to 10 seconds. The pre-oxidation reaction tank is a vertical tank with a built-in bidirectional stirring device to enhance the mass transfer reaction of ozone, hydrogen peroxide, and water. The bidirectional stirring device uses a gear structure to achieve reverse blade cutting, which can break ozone bubbles into microbubbles. Monitoring devices are installed on the side wall of the tank to monitor oxidation-reduction potential (ORP), pH, and organic matter concentration (such as UV254 and COD) in real time. A2. Ozone-UV catalytic oxidation module: consists of an ozone generator, multiple sets of UV lamps, and multiple sets of catalyst packing. It should be noted that the ozone generator uses dielectric barrier discharge technology, and the ozone generation rate can be adjusted according to the influent water load. An opening is provided at the top of the module (to facilitate the removal, regeneration, or replacement of the catalyst packing; the regeneration cycle is generally 3 to 6 months). The power of a single UV lamp is 50-100W, and the lamp spacing is controlled at 10-15cm to ensure uniform light intensity. The catalyst packing material is an aluminum-based catalyst; A3. Biological activated carbon filter module: The filter has an upward flow structure and is filled with biological activated carbon. The filter is connected to an ozone destruction device. It should be noted that the bio-activated carbon is coal-based granular carbon with a particle size of 0.8–1.2 mm and a specific surface area ≥1000 m². 2 / g, after domestication, the surface is covered with a microbial community mainly composed of heterotrophic bacteria; Among them, the ozone destruction device uses thermal catalytic decomposition technology to decompose ozone in the exhaust gas into oxygen, thereby reducing the harm of ozone emissions to the environment and human body. An ozone gas distributor is installed above the water inlet area of ​​the biological activated carbon filter module to increase the ozone partial pressure and improve the ozone solubility in the water. After the water enters, the module has multiple reaction tank compartments and a catalyst interlayer. The water flow must pass through the catalyst interlayer to enter the next reaction tank compartment. An ozone microporous aerator is installed at the bottom of the reaction tank (except for the last compartment) to maintain the ozone concentration in the water. The last set of reaction tank compartments is equipped with ultraviolet lamps, and the module outlet water pipe is equipped with a return pipe to return part of the outlet water to the module inlet water pipe.

[0025] Example 2: As Figure 2 As shown, a multifunctional modular ozone catalytic oxidation wastewater treatment method includes the following steps: S10. Introduce the water to be treated into the pre-oxidation reaction zone, and simultaneously add liquid and gaseous oxidants to establish a multiphase oxidation reaction system; continuously collect the redox characteristics of the multiphase oxidation reaction system and establish a continuous time series of redox characteristics. The method of introducing the water to be treated into the pre-oxidation reaction zone and simultaneously adding liquid and gaseous oxidants to establish a multiphase oxidation reaction system is as follows: In some embodiments, the water to be treated is introduced into the pipeline mixer at the front end of the pre-oxidation reaction zone, the metering pump of the liquid phase oxidant storage tank is started, the liquid phase oxidant is injected into the pipeline mixer, and the water to be treated is mixed with the liquid phase oxidant in the pipeline mixer by high-frequency shearing. Preferably, the liquid oxidant is a hydrogen peroxide solution, and its dosage is set to 0.5 mg / L to 5 mg / L (preferably 2.5 mg / L). The mixing time under high-frequency shear mixing is controlled to be 5 to 10 seconds (preferably 7 seconds) to achieve uniform dispersion of the liquid oxidant in the water body and reduce ineffective decomposition caused by excessively high local concentrations. After being mixed evenly, the water flows into the main reaction tank of the pre-oxidation reaction zone. At the same time, the microbubble generator continuously introduces gaseous oxidant into the main reaction tank and cuts the gaseous oxidant into physical bubbles through the bidirectional stirring device. Preferably, the gaseous oxidant is a mixed gas containing ozone, wherein the ozone dosage is controlled at 2 mg / L to 8 mg / L (preferably 5 mg / L); physical bubbles not only increase the contact surface area between the gas and liquid phases, but also prolong the residence and mass transfer time of the gaseous oxidant in the water. Inside the main reaction vessel, micro- and nano-sized ozone bubbles and uniformly dispersed hydrogen peroxide solution undergo synergistic catalysis to establish a heterogeneous oxidation reaction system. A hydraulic retention time of 10 to 20 minutes (preferably 15 minutes) is maintained in a multiphase oxidation reaction system to preliminarily degrade 60% to 70% of the recalcitrant organic matter and odor substances in the water to be treated. The method for continuously collecting redox characteristics of multiphase oxidation reaction systems and establishing a continuous time series of redox characteristics is as follows: Multiple sets of water quality physicochemical monitoring probes are installed below the liquid surface of the multiphase oxidation reaction system and at the water outlet pipeline of the reaction tank. Preferably, the water quality physicochemical monitoring probe includes at least an oxidation-reduction potential probe, a pH probe, and an ultraviolet absorbance probe to reflect the comprehensive physicochemical state of the water body; The multi-channel data acquisition instrument is activated, and the millivolt-level electrical signal output by the redox potential probe installed at the outlet water pipeline of the reaction tank is extracted first as the redox characteristic to characterize the oxidation capacity of the current multiphase oxidation reaction system. It should be noted that the millivolt-level electrical signal of the redox potential was selected as the core redox feature because it can directly reflect whether the overall oxidation process formed by the liquid and gaseous oxidants in the reaction vessel is sufficient to suppress the oxygen-consuming organic load in the influent. The discrete millivolt-level electrical signals extracted within the high-frequency sampling period are time-sequentially spliced ​​and filtered and smoothed according to the absolute timestamp to remove the background high-frequency electrical noise caused by the physical impact of bubbles on the probe surface. Among them, the filtering and smoothing process can be carried out by conventional moving average filtering algorithm or median filtering algorithm; After filtering and smoothing, the millivolt-level electrical signals are correlated one-to-one with the acquisition time axis to establish a data sequence reflecting the dynamic evolution trajectory of oxidation capacity in the pre-oxidation stage, which is defined as a continuous time series of redox characteristics.

[0026] S20. Extract the hydraulic mass transfer time delay, perform misaligned time-domain matching analysis on the incremental addition of liquid phase oxidant and the continuous time series to obtain the oxidation gain coefficient; evaluate the performance based on the oxidation gain coefficient, and output the active perturbation command if the negative abrupt change condition of the oxidation gain coefficient is met. Among them, by combining the hydraulic mass transfer time lag, a misaligned time-domain matching analysis of the liquid-phase oxidant addition increment and the continuous time series is performed to obtain the oxidation gain coefficient as follows: Set a unit evaluation period and obtain the incremental liquid phase oxidant dosage within the unit evaluation period; For example, the unit evaluation period is set to 5% to 10% of the baseline hydraulic mass transfer time delay period, or a fixed duration of 1 to 3 minutes; The system extracts the current influent flow rate and the effective water volume of the main reaction tank, calculates the ratio of the effective water volume to the current influent flow rate, and determines the ratio as the reference hydraulic mass transfer time delay period. The continuous time series output by the redox potential probe installed at the outlet pipeline of the reaction tank is extracted, and the continuous time series is subjected to misaligned time domain matching processing based on the mass transfer time delay period. Preferably, the method for performing misaligned time-domain matching is as follows: a sliding time window is established based on the unit evaluation period. Within the sliding time window, the data point of the liquid phase oxidant addition increment is shifted backward along the time axis by one mass transfer time delay period, so that the data point and the millivolt-level electrical signal in the continuous time series complete misaligned time-domain matching on the same effective physical action surface. For the liquid phase oxidant addition increment after misaligned time domain matching, calculate the input rate of change of the liquid phase oxidant addition increment under the same sliding window step size, and the output rate of change of the corresponding continuous time series value (i.e., millivolt-level electrical signal). In response to the dynamic change of the liquid oxidant addition increment, the non-zero displacement segment of the input change rate is extracted, and the ratio of the output change rate to the input change rate within the non-zero displacement segment is calculated to obtain the redox potential increase contributed by the unit reagent increment, which is defined as the oxidation gain coefficient. Among them, the performance evaluation is based on the oxidation gain coefficient. If the negative abrupt change condition of the oxidation gain coefficient is met, the active perturbation command is output in the following way: Set the baseline operating range for the oxidation gain coefficient under normal synergistic catalysis conditions; The oxidation gain coefficient and the incremental liquid oxidant dosage are compared in real time within the current sliding time window. When any of the following negative abrupt change conditions are detected, the multiphase oxidation reaction system is determined to be in a suppressed state. The negative mutation conditions include: Quenching deviation condition: Under the condition of increasing liquid phase oxidant dosage, if the oxidation gain coefficient drops below zero and enters the negative range for N consecutive evaluation cycles, it indicates that the system has a free radical quenching effect, and the local excess agent is converted into a consumption source of highly active hydroxyl free radicals. Preferably, N=10; Mass transfer passivation conditions: Under the condition of increasing liquid phase oxidant addition, the oxidation gain coefficient undergoes a step decrease in the positive range and continues to approach the zero threshold. The gas-liquid mass transfer resistance of the reaction system surges, and physical bubble coalescence leads to the loss of effective catalytic specific surface area. When any of the above negative mutation conditions are detected, the system generates an active disturbance command and outputs it to the corresponding front-end control device.

[0027] Example 3: Please refer to Figure 2 As shown, a multifunctional modular ozone catalytic oxidation wastewater treatment method further includes the following steps: S30. Respond to the active disturbance command and perform an instantaneous cutoff operation on the liquid phase oxidant, collect the characteristic parameters within the cutoff window period and construct a transient response dataset; extract the potential evolution rate and perform trend analysis on the transient response dataset to obtain the slope characteristic value of the transient feedback; The method for responding to active perturbation commands and performing instantaneous truncation on the liquid-phase oxidant, collecting feature parameters within the truncation window, and constructing a transient response dataset is as follows: Upon receiving an active disturbance command indicating that the multiphase oxidation reaction system is in a suppressed state, the system locks the opening of the microbubble generator inlet valve to maintain a constant load of gaseous oxidant in the main reaction tank. Simultaneously, a zero-point operation command is sent to the metering pump at the front end of the liquid phase oxidant storage tank to physically cut off the input of liquid phase oxidant into the pipeline mixer. The system also sets a cutoff window period of 5 to 10 minutes from the cutoff time. During the cutoff window period, a multi-channel data acquisition instrument is invoked to continuously extract millivolt-level electrical signals output by the redox potential probe at the outlet pipeline of the reaction tank within a high-frequency sampling cycle. The millivolt-level electrical signals during the cutoff window period are then sequentially spliced ​​according to absolute timestamps to construct a transient response dataset. The method for extracting the potential evolution rate and analyzing the trend of the transient response dataset to obtain the slope characteristic value of the transient feedback is as follows: It should be noted that after the system truncation command is executed, there is residual liquid oxidant inside the main reaction tank and pipeline that has not been completely consumed, resulting in residual mass transfer inertia in the first part of the transient response dataset. Therefore, it is necessary to perform potential evolution rate extraction and trend analysis on the transient response dataset. First-order time-domain difference processing is performed on the millivolt-level electrical signals in the transient response dataset, that is, the rate of change of electrical signals between adjacent high-frequency sampling periods is calculated point by point; Traverse the rate of change of the electrical signal along the time axis to locate the extreme point where the rate of change of the electrical signal first changes from negative decay or zero plateau to positive change. Define the extreme point as the physical response starting point where the residual liquid phase oxidant in the multiphase oxidation reaction system is consumed. The millivolt-level electrical signal between the start of the physical response and the end of the truncation window period is extracted as the effective recovered data segment; Linear least squares fitting is performed on the millivolt-level electrical signal and the corresponding timestamp within the effective recovered data segment to calculate the geometric slope of the fitted line; The geometric slope is defined as the slope characteristic value of the transient feedback, serving as the quantitative input source for the response state of the subsequent multiphase oxidation reaction system.

[0028] S40. The polarity and amplitude of the transient feedback slope characteristic value are analyzed to obtain the mechanism discrimination intermediate state; based on the mechanism discrimination intermediate state, the hysteresis state separation process is performed on the multiphase oxidation reaction system to obtain the quenching characteristic component and the distortion characteristic component. Among them, the method of determining the intermediate state of the mechanism by analyzing the polarity and amplitude of the transient feedback slope eigenvalue is as follows: The algebraic sign attribute of the transient feedback slope feature value is extracted and defined as the polarity feature. Among them, the positive characterization potential shows a recovery and upward trend, the negative characterization potential shows a continuous deterioration and decay trend, and the zero characterization potential is at a stagnant plateau. Extract the absolute value of the transient feedback slope feature and define it as the amplitude feature; It should be noted that the amplitude characteristic characterizes the severity of the redox potential evolution rate inside the reaction system after the liquid phase oxidant is cut off; The extracted polarity features and amplitude features are combined to construct a two-dimensional feature vector representing the current system state, which is defined as the mechanism discrimination intermediate state; Among them, the method for separating the quenching characteristic component and the distortion characteristic component by performing hysteresis state separation processing on the heterogeneous oxidation reaction system based on the mechanism of intermediate state discrimination is as follows: The system calls the pre-calibrated single-phase reference recovery slope stored in the control unit; It should be noted that the single-phase baseline recovery slope is the theoretically required rate of positive rise of the redox potential of the system under the current influent flow rate and current gas phase oxidant loading, without the addition of any liquid phase oxidant. Based on the single-phase baseline recovery slope, the polarity characteristics in the intermediate state of mechanism discrimination are decoupled and processed to obtain the quenching characteristic component caused by excessive liquid-phase oxidant, and the distortion characteristic component caused by the sudden change in influent oxygen consumption load: Preferred, such as Figure 2 As shown, the method for performing the flow splitting and decoupling process is as follows: If the polarity characteristic is positive, the dominant mechanism of the current sluggish state of the heterogeneous oxidation reaction system is determined to be free radical quenching caused by excess liquid-phase oxidant. In the presence of free radical quenching, the system performs a ratio calculation between the amplitude characteristics of the mechanism discrimination intermediate state and the single-phase reference recovery slope, and the ratio result is used as the quenching characteristic component. The greater the quenching characteristic component is and the larger the ratio, the higher the concentration of ineffective liquid phase oxidant accumulated inside the multiphase oxidation reaction system. At this time, the preset base noise constant in the system is assigned as the distortion characteristic component, and the base noise constant is set to zero. If the polarity characteristic is negative or zero polarity, it indicates that after the liquid phase oxidant is cut off and the residual reagent is exhausted, the gas phase oxidant alone cannot reverse the downward trend of the oxidation-reduction potential. It is determined that the dominant mechanism of the current sluggish state of the multiphase oxidation reaction system is the water quality deterioration distortion caused by the impact of high concentration of organic load in the influent. In the presence of water quality deterioration and distortion, the system sums the absolute value of the single-phase baseline recovery slope with the amplitude characteristics of the intermediate state to obtain the load gap parameter characterizing the degree of oxidation capacity deficit. Extract the pre-set load conversion coefficient, multiply the load gap parameter with the load conversion coefficient, and use the product result as the distortion feature component; Preferably, the load conversion factor is set as follows: before the system is put into operation, under the baseline operating condition of only a stable gaseous oxidant is introduced, a standard oxygen-consuming pollutant of known unit equivalent is introduced into the pre-oxidation reaction tank at one time; The steady-state negative decay slope of the redox potential was measured after being subjected to a standard oxygen-consuming pollutant shock. The ratio of the unit equivalent of standard oxygen-consuming pollutants to the absolute value of the steady-state negative decay slope is used as the load conversion coefficient.

[0029] S50. Construct a quiescent window period based on quenching characteristic components and maintain zero addition and clearing residue during the quiescent window period; reconstruct the awakening reference amount of the liquid phase based on the distortion characteristic components, wait for the quiescent window period to end, and asynchronously restart the addition based on the awakening reference amount to obtain pretreated water; The method for constructing a quiescent window based on quenching feature components and maintaining zero addition and clearing residue within the quiescent window is as follows: The system obtains the current effective hydraulic volume and influent flow rate of the pre-oxidation reactor, and calculates the quotient of the two to obtain the basic hydraulic renewal cycle. The quenching characteristic component is multiplied by the basic hydraulic renewal cycle to calculate the physical time required for the system to consume redundant liquid phase oxidant, which is defined as the quiescent window period. The system generates a lock command and sends it to the metering pump of the liquid phase oxidant storage tank. During the entire quiet window period, the metering pump is kept in a zero-position shutdown state, and the gas phase oxidant is continuously supplied according to the original load. The existing high concentration of pollutants in the water body and the continuously injected gaseous oxidant are used as physical consumption sources to remove excess liquid oxidant remaining in the reaction system in situ. The method for obtaining pretreated water is as follows: The awakening reference quantity of the liquid phase is reconstructed based on the distortion feature components. The addition is then asynchronously restarted based on the awakening reference quantity after the quiet window period ends. By introducing a preset liquid phase safety ratio constant, the distortion characteristic components are multiplied with the liquid phase safety ratio constant to obtain the load compensation increment; It should be noted that the liquid phase safety ratio constant is obtained by means of an offline titration test before the system is put into operation. The value of the liquid phase safety ratio constant is equal to the baseline consumption of liquid phase oxidant required for a single degradation of a unit equivalent of characteristic pollutant. Extract the historical baseline dosage before the system performs the instantaneous truncation operation, multiply it by the preset penalty attenuation coefficient, and obtain the base dosage. For example, the default method for the penalty attenuation coefficient is as follows: the penalty attenuation coefficient is a dimensionless empirical constant with a value range of 0.5-0.8, which is used to reduce the historical dosage that induces quenching effect in the early stage of pressure drop; The base dosage and the load compensation increment are summed to obtain the liquid phase wake-up reference amount after the quenching risk has been removed. After the window period ends and the system recovers its positive oxidation gain, the liquid-phase oxidant addition will be asynchronously restarted using this baseline amount: When the forced silence window ends, the system re-extracts the current potential evolution rate of the reaction system as an evaluation index. If the current potential evolution rate is still in the negative range or at the zero plateau, the silence time is extended by the set time step until the potential evolution rate crosses zero and enters the positive polarity range. Once it is confirmed that the potential evolution rate is stable in the positive polarity range, it is determined that the physical quenching deadlock of the heterogeneous oxidation reaction system has been completely released, and the system cancels the lock command. The metering pump's dosing parameters are directly set to the liquid phase wake-up reference amount calculated above, and the continuous dosing of liquid phase oxidant is asynchronously restored to rebuild a stable multiphase synergistic catalytic equilibrium. The final effluent is the pretreated water.

[0030] Example 4: Please refer to Figure 2 As shown, a multifunctional modular ozone catalytic oxidation wastewater treatment method further includes the following steps: S60. The pretreated water is introduced into the ultraviolet radiation zone containing a solid catalyst, and a gaseous oxidant is continuously introduced for three-phase catalytic oxidation treatment to obtain deeply treated water; the deeply treated water is introduced into a biological activated carbon filter for biochemical degradation filtration to obtain the final effluent. The process for obtaining deeply treated water is as follows: Pre-oxidized water flows into the ozone-UV catalytic oxidation module, where ozone is continuously introduced through a bottom microbubble generator (dosage is 3-10 mg / L, preferably 6 mg / L), and ozone is added through a top gas distributor to maintain the ozone concentration in the upper region at 45-60 g / Nm³. 3 ; Water flows through the catalyst interlayer into the next reaction tank compartment, where ozone in the water fully reacts with the catalyst, decomposing to generate a large amount of ·OH, which regenerates the catalyst packing (e.g., by acid washing-activation) or replaces it to ensure catalytic efficiency. The last set of ultraviolet lamps in the compartments is turned on, emitting ultraviolet light of a fixed wavelength to irradiate the water, with the light intensity controlled at 10–20 mW / cm². 2 (Preferred value: 15mW / cm) 2 Ozone is excited and decomposed under photocatalysis and reacts with water to generate ·OH; the overall reaction time is controlled at 50-70 min (preferably 60 min), and a return pipe is set to return part of the effluent to the module inlet pipe, which can both recover residual ozone in the water and further remove pollutants in the water; The final water output is obtained through the following method: Water that has undergone ozone-ultraviolet catalytic oxidation enters the biological activated carbon filter and passes through the activated carbon layer from top to bottom at a filtration rate of 5-10 m / h (preferably 7 m / h). Activated carbon physically adsorbs trace organic matter and pigments, and its surface microorganisms degrade the adsorbed organic matter, further reducing the COD and other indicators of the effluent, so that the effluent finally meets the standards for drinking water or reclaimed water. The ozone exhaust gas generated during the process (mainly from the exhaust gas of the ozone generator and the ozone emitted from each reaction unit) is introduced into the ozone destruction device and decomposed into oxygen under thermocatalytic conditions of 300-400℃ (preferably 350℃) to meet emission standards.

[0031] The foregoing has provided a detailed description of one embodiment of the present invention, but this description is merely a preferred embodiment and should not be construed as limiting the scope of the invention. All equivalent variations and modifications made within the scope of the present invention should still fall within the scope of the present invention.

Claims

1. A multifunctional modular ozone catalytic oxidation wastewater treatment method, characterized in that, Includes the following steps: Extract the hydraulic mass transfer time delay and continuous time series, perform misaligned time-domain matching analysis on the incremental addition of liquid phase oxidant and the continuous time series to obtain the oxidation gain coefficient; evaluate the performance based on the oxidation gain coefficient, and output an active perturbation command if the negative abrupt change condition of the oxidation gain coefficient is met. In response to active perturbation commands, a transient cutoff operation is performed on the liquid-phase oxidant. Feature parameters within the cutoff window are collected and a transient response dataset is constructed. Potential evolution rate is extracted and trend analysis is performed on the transient response dataset to obtain the slope feature value of the transient feedback. The transient feedback slope eigenvalues ​​are analyzed for polarity and amplitude to obtain the intermediate state for mechanism discrimination; Based on the mechanism of intermediate state discrimination, the hysteresis state separation process is performed on the multiphase oxidation reaction system to obtain quenching characteristic components and distortion characteristic components. A quiescent window period is constructed based on quenching characteristic components, and zero dosage and clearing residue are maintained during the quiescent window period; The awakening reference quantity of the liquid phase is reconstructed based on the distortion feature components. After the quiescent window period ends, the addition is asynchronously restarted based on the awakening reference quantity to obtain pretreated water.

2. The multifunctional modular ozone catalytic oxidation wastewater treatment method according to claim 1, characterized in that: The method for extracting the continuous time series is as follows: The water to be treated is introduced into the pre-oxidation reaction zone, and liquid and gaseous oxidants are added simultaneously to establish a multiphase oxidation reaction system. The redox characteristics of the multiphase oxidation reaction system are continuously collected to establish a continuous time series of redox characteristics.

3. The multifunctional modular ozone catalytic oxidation wastewater treatment method according to claim 1, characterized in that: The method for performing misaligned time-domain matching analysis is as follows: Obtain the incremental liquid-phase oxidant dosage within the unit evaluation period; A sliding time window is established based on the unit evaluation cycle. Within the sliding time window, the data point of the liquid phase oxidant addition increment is shifted backward along the time axis by one mass transfer time delay cycle, so that the data point and the millivolt-level electrical signal in the continuous time series can complete the misaligned time domain matching on the same effective physical action surface. For the liquid phase oxidant addition increment after misaligned time-domain matching, calculate the input rate of change of the liquid phase oxidant addition increment under the same sliding window step size, and the output rate of change of the corresponding continuous time series values. Extract the non-zero displacement segment of the input rate of change, and calculate the ratio of the output rate of change to the input rate of change within the non-zero displacement segment to obtain the oxidation gain coefficient.

4. The multifunctional modular ozone catalytic oxidation wastewater treatment method according to claim 1, characterized in that: The method for extracting and analyzing the potential evolution rate is as follows: First-order time-domain difference processing is performed on the millivolt-level electrical signals in the transient response dataset, that is, the rate of change of electrical signals between adjacent high-frequency sampling periods is calculated point by point; Traverse the rate of change of the electrical signal along the time axis, locate the extreme point where the rate of change of the electrical signal first changes from negative decay or zero plateau to positive change, and define the extreme point as the starting point of the physical response; The millivolt-level electrical signal between the start of the physical response and the end of the truncation window period is extracted as the effective recovered data segment; Linear least squares fitting is performed on the millivolt-level electrical signal and the corresponding timestamp within the effective recovered data segment to calculate the geometric slope of the fitted line; The geometric slope is defined as the slope characteristic value of transient feedback.

5. The multifunctional modular ozone catalytic oxidation wastewater treatment method according to claim 4, characterized in that: The transient response dataset is constructed as follows: Upon receiving an active disturbance command, the gaseous oxidant supply to the main reactor is kept constant. The input of liquid-phase oxidant into the pipeline mixer is simultaneously cut off, and the system simultaneously sets the cutoff window period; Millivolt-level electrical signals are extracted within the truncated window period, and the millivolt-level electrical signals within the truncated window period are sequentially spliced ​​according to absolute timestamps to construct a transient response dataset.

6. The multifunctional modular ozone catalytic oxidation wastewater treatment method according to claim 1, characterized in that: The method for performing the hysteresis state separation process is as follows: The system calls the pre-calibrated single-phase reference recovery slope stored in the control unit; Based on the single-phase baseline recovery slope, the polarity characteristics in the intermediate state of mechanism discrimination are decoupled and processed to obtain the quenching characteristic component caused by excessive liquid phase oxidant, and the distortion characteristic component caused by the sudden change in influent oxygen consumption load.

7. The multifunctional modular ozone catalytic oxidation wastewater treatment method according to claim 6, characterized in that: The method for performing the aforementioned decoupling process is as follows: When the polarity characteristic is positive, the quenching characteristic component is determined by the amplitude characteristic of the intermediate state and the single-phase reference recovery slope based on the mechanism, and the preset basic noise floor constant is assigned as the distortion characteristic component. When the polarity characteristic is negative or zero polarity, the load gap parameters are determined based on the single-phase reference recovery slope and amplitude characteristics, and the distortion characteristic components are determined in combination with the pre-calibrated load conversion coefficient.

8. The multifunctional modular ozone catalytic oxidation wastewater treatment method according to claim 1, characterized in that: The method for reconstructing the wake-up reference value is as follows: A preset liquid phase safety ratio constant is established, and the distortion characteristic components are multiplied with the liquid phase safety ratio constant to obtain the load compensation increment; Extract the historical baseline injection amount before the system performs the instantaneous truncation operation, introduce a preset penalty attenuation coefficient as a weighting factor, and perform attenuation reduction processing on the historical baseline injection amount to obtain the base injection amount; The base dosage and the load compensation increment are summed to obtain the reconstructed liquid phase wake-up reference quantity.

9. The multifunctional modular ozone catalytic oxidation wastewater treatment method according to claim 1, characterized in that: Also includes: Pretreated water is introduced into an ultraviolet radiation zone containing a solid catalyst, and gaseous oxidant is continuously introduced for three-phase catalytic oxidation treatment to obtain deeply treated water. The deeply treated water is introduced into a biological activated carbon filter for biochemical degradation and filtration to obtain the final effluent.

10. A multifunctional modular ozone catalytic oxidation wastewater treatment device, used to implement a multifunctional modular ozone catalytic oxidation wastewater treatment method.

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