An advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water bodies

Abstract

This invention relates to the field of water treatment technology and discloses an advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water. The system includes a reaction module, a sensing module, a dosing module, a power supply module, and a control module. The reaction module is filled with a composite packing material composed of carbon-coated copper-doped two-dimensional titanium carbide catalyst particles, graphite particles, and quartz sand particles, and a three-dimensional volume electrode is constructed using a flow distribution network. The sensing module acquires redox potential and dissolved oxygen concentration data. The control module calculates the spatial decay gradient to determine the state of reaction path obstruction. By adjusting the opening frequency of the pulse dosing valve and the asymmetric pulse waveform output by the power supply module, which includes both cathode and anodic polarization output stages, divalent copper ions on the surface of the composite packing material are reduced by electron injection, and nascent oxygen is precipitated by water electrolysis, achieving spatiotemporal decoupling and reconstruction. This invention solves the problems of reduced treatment efficiency caused by catalytic activity passivation and uneven oxygen source distribution.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, specifically to an advanced oxidation treatment system for the broad-spectrum removal of organic pollutants from water. Background Technology

[0002] Advanced oxidation technologies based on persulfate are widely used in the treatment of recalcitrant organic wastewater. Existing advanced oxidation systems typically employ fixed-bed reactors, which are filled with transition metal-doped carbon-based catalysts. When the organic wastewater and persulfate solution flow through the fixed-bed reactor, the catalyst activates the persulfate to generate free radicals and non-free radicals, thereby completing the degradation of organic pollutants.

[0003] Existing fixed-bed advanced oxidation systems suffer from a technical drawback: a gradual decline in processing efficiency during long-term continuous operation. During the activation of persulfate, the valence state of transition metal active centers increases. Due to the lack of an effective in-situ electron compensation mechanism within the fixed-bed reactor, high-valence metal ions cannot be reduced in time, leading to gradual passivation of active sites on the catalyst surface. As the degradation reaction proceeds, dissolved oxygen within the fixed-bed reactor is rapidly consumed. Due to the mass transfer limitations of the fixed-bed structure, external oxygen cannot effectively diffuse into the reactor, resulting in localized hypoxia. This hypoxic environment blocks oxygen vacancy-mediated electron transfer processes and inhibits non-radical reaction pathways.

[0004] When organic wastewater flows inside a fixed-bed reactor, the concentrations of oxidant and pollutants gradually decrease along the flow direction, leading to differences in the redox microenvironment at different depths within the reactor. Conventional advanced oxidation treatment systems typically employ a single, monolithic dosing method or apply a continuous DC electric field. A continuous DC electric field easily causes charge accumulation on the electrode surfaces. Conventional systems cannot detect spatial gradient changes in the microenvironment within the fixed-bed reactor, making it difficult to intervene based on the degree of catalyst passivation and anoxic conditions at different reaction stages. Conventional systems cannot reconcile the conflicting spatial and temporal demands of free radical and non-free radical pathways, resulting in weak adaptability to fluctuations in influent water quality and poor long-term broad-spectrum removal efficiency for organic pollutants in water. Therefore, this invention proposes an advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water to address the shortcomings of existing technologies. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an advanced oxidation treatment system for the broad-spectrum removal of organic pollutants from water. It solves the problems of easy passivation of active sites of catalysts and the obstruction of non-radical reactions due to local hypoxia in existing fixed-bed reactors. At the same time, it solves the problem that conventional advanced oxidation treatment systems cannot sense and intervene in the spatial gradient differences of the microenvironment in different reaction stages, resulting in conflicts between the temporal and spatial distribution of free radical degradation pathways and non-radical degradation pathways.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution: an advanced oxidation treatment system for broad-spectrum removal of organic pollutants in water, comprising a reaction module, a sensing module, a dosing module, a power supply module, and a control module; The reaction module is divided into multiple reaction segments along the longitudinal height direction, filled with a composite filler consisting of carbon-coated copper-doped two-dimensional titanium carbide catalyst particles, graphite particles and quartz sand particles, and a three-dimensional volume electrode is constructed at the junction of the segments using a flow distribution network. The sensing module includes a potential sensor and an oxygen sensor distributed at the flow distribution and collection network. The sensing module is connected to the control module and is used to transmit the collected potential data and dissolved oxygen data to the control module. The dosing module includes an inlet pump and a pulse dosing valve. The inlet pump is used to pump in the organic wastewater to be treated, and the pulse dosing valve is used to pass a sulfate solution. The power module is connected to the current distribution network and is used to apply an asymmetric pulse current to the three-dimensional volume electrode through the current distribution network to trigger the electrochemical oxidation-reduction reaction on the surface of the composite filler. The control module uses a built-in spatial gradient calculation model to calculate the ratio of the data difference to the height difference between adjacent monitoring points and obtains the spatial decay gradient of oxidation-reduction potential and the spatial decay gradient of dissolved oxygen. The microenvironment diagnostic engine determines the blocked state of the reaction path based on the spatial decay gradient of oxidation-reduction potential and the spatial decay gradient of dissolved oxygen. By adjusting the opening frequency of the pulse dosing valve and the pulse waveform of the power module, the spatiotemporal decoupling reconstruction of the degradation path is realized.

[0007] Preferably, the volume ratio of each component in the composite filler meets the percolation threshold condition, the graphite particles are physically in contact with each other in three-dimensional space and connect with adjacent flow distribution and collection networks to form a macroscopic three-dimensional conductive framework, and the carbon-coated copper-doped two-dimensional titanium carbide catalyst particles are physically connected to the macroscopic three-dimensional conductive framework through the in-situ amorphous carbon coating on the surface of the carbon-coated copper-doped two-dimensional titanium carbide catalyst particles.

[0008] Preferably, the reaction module adopts a modular vertical stacking design, which is composed of multiple standardized reaction column segments connected together; the flow distribution and collection network is clamped at the flange connection of two adjacent reaction column segments, and an insulating sealing gasket is provided at the sealing point between the flow distribution and collection network and the reaction column segment, and the insulating sealing gasket is disposed between adjacent reaction column segments.

[0009] Preferably, the flow distribution and collection network is a titanium mesh with a noble metal oxide coating on its surface. The flow distribution and collection network acts as a fluid distributor, using the local hydraulic resistance provided by the metal mesh to redistribute the fluid across the cross section, and acts as an electrochemical current collector to perform electron injection and current collection.

[0010] Preferably, the measuring ends of the potential sensor and the oxygen sensor are covered with a porous shielding protective sleeve made of polytetrafluoroethylene; the porous shielding protective sleeve uses a microporous structure to allow water phase permeation and prevent solid particles in the composite filler and macroscopic bubbles generated by in-situ electrolysis from contacting the sensor surfaces of the potential sensor and the oxygen sensor.

[0011] Preferably, the microenvironment diagnostic engine determines the state of blocked reaction paths by: if the absolute value of the spatial decay gradient of the redox potential exceeds a preset potential decay threshold, then the reaction segment is determined to be in a state of blocked free radical paths; if the actual measured dissolved oxygen concentration is lower than a preset minimum oxygen concentration limit and the absolute value of the spatial decay gradient of the dissolved oxygen exceeds a preset oxygen decay threshold, then the reaction segment is determined to be in a state of blocked non-free radical paths.

[0012] Preferably, the control module instructs the power module to output a pulse waveform including a cathode polarization output stage, an anodic polarization output stage, and a dead zone buffer time set during the switching between positive and negative polarities, according to the state of the blocked reaction path; the cathode polarization output stage corresponds to the cathode polarization pulse width, and uses electron injection to reduce divalent copper ions on the surface of the composite filler to cuprous ions; the anodic polarization output stage corresponds to the anodic polarization pulse width, and uses electrolysis of water to precipitate nascent oxygen.

[0013] Preferably, the control module calculates the energy ratio between the anodic polarization output stage and the cathodic polarization output stage to obtain an asymmetric energy factor, and allocates unequal voltage amplitudes and unequal pulse durations between the anodic polarization output stage and the cathodic polarization output stage according to the asymmetric energy factor.

[0014] Preferably, the control module collects the instantaneous pulse voltage parameters and response current parameters output by the power module in real time to calculate the dynamic impedance parameters; when the dynamic impedance parameters are lower than the preset safety impedance threshold and a physical particle bridging short circuit is determined to have occurred, the control module instructs the power module to cut off the current output and triggers the backwashing procedure of the reaction module.

[0015] This invention provides an advanced oxidation treatment system for the broad-spectrum removal of organic pollutants from water. It offers the following advantages: 1. This invention uses the cathode polarization pulse output by the power module to reduce the divalent copper ions on the surface of the composite packing to cuprous ions, thereby achieving in-situ regeneration of the catalytic active sites, solving the passivation problem caused by the evolution of valence state during the reaction process, maintaining the catalytic activity of the composite packing, and extending the service life of the composite packing.

[0016] 2. This invention utilizes a sensing module in conjunction with a spatial gradient calculation model to acquire real-time data on the redox potential and dissolved oxygen distribution of different reaction zones. The control module instructs the power supply module to perform water electrolysis during the anodic polarization stage and generate nascent oxygen. This in-situ oxygen supply method eliminates the reaction blind zone caused by oxygen mass transfer resistance inside the fixed bed, ensuring the synergistic efficiency of free radical and non-free radical pathways.

[0017] 3. This invention achieves decoupled reconstruction of the degradation path in both time and space by adjusting the opening frequency of the pulse dosing valve and the pulse waveform of the power module. The advanced oxidation treatment system can dynamically compensate for fluctuations in influent water quality and changes in the internal reaction microenvironment. Through the synergistic effect of physical intervention and chemical dosing, the advanced oxidation treatment system improves the removal efficiency of different types of organic pollutants while reducing energy consumption and reagent loss. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the system architecture of the present invention; Figure 2 This is a schematic diagram of the overall method flow of the present invention; Figure 3 This is a schematic diagram of the time-division multiplexed asymmetric alternating pulse waveform of the present invention; Figure 4 This is a schematic diagram comparing the pollutant removal rates after 120 hours of continuous operation according to the present invention; Figure 5 This is a schematic diagram comparing the cross-sectional spatial gradient before and after the intervention of the present invention. Detailed Implementation

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Please see Figure 1 This invention provides an advanced oxidation treatment system for the broad-spectrum removal of organic pollutants from water, comprising a reaction module, a sensing module, a dosing module, a power supply module, and a control module.

[0021] The reaction module is divided into multiple reaction segments along its longitudinal height, each segment filled with a composite filler. The composite filler is composed of carbon-coated copper-doped two-dimensional titanium carbide catalyst particles, graphite particles, and quartz sand particles mixed in a specific volume ratio. The graphite particles are in contact with each other within the composite filler, forming a conductive network. At the physical interface between adjacent reaction segments, a transverse current distribution and collection network is installed. This network is electrically connected to the composite filler, constructing each reaction segment as an independently controlled three-dimensional volume electrode.

[0022] The sensing module includes potential sensors and oxygen sensors distributed at the elevation of the flow distribution and collection network. The potential and oxygen sensors penetrate the sidewalls of the reaction module to acquire redox potential data and dissolved oxygen concentration data for each reaction section. The sensing module transmits the collected data to the control module.

[0023] The dosing module includes an inlet pump located at the bottom of the reaction module and pulse dosing valves corresponding to each reaction section. The inlet pump pumps the organic wastewater to be treated and the initial persulfate solution into the reaction module. The pulse dosing valves replenish the corresponding reaction section with persulfate solution according to the control module's instructions.

[0024] The power module output is connected to the current distribution and collection network at each elevation. Controlled by the control module, the power module outputs asymmetric pulsed current to the selected reaction zone. The power module performs electronic compensation for the valence state of the catalytically active sites on the composite packing surface and in-situ electrochemical oxygen desorption intervention.

[0025] The control module receives the data collected by the sensing module. Redox potential of each cross section and the Dissolved oxygen concentration at each cross section The control module processes data using a built-in spatial gradient calculation model. The spatial gradient calculation model calculates the first... Spatial decay gradient of redox potential within the reaction zone of each cross section The calculation formula is as follows: ; Spatial gradient calculation model calculates the first Dissolved oxygen spatial decay gradient within the reaction zone of each cross section The calculation formula is as follows: ; in, and Representing the The first cross section and the second The physical elevation of the reaction zone boundary at each cross section. The control module determines the elevation based on the spatial decay gradient of the redox potential. Spatial decay gradient with dissolved oxygen The numerical value determines the state of the blocked reaction path.

[0026] The control module outputs control signals to the dosing module and the power supply module. By adjusting the opening frequency of the pulse dosing valve and the duty cycle and polarity of the pulse output from the power supply module, the system decouples and reconstructs the free radical degradation pathway and the non-free radical degradation pathway in both time and space dimensions.

[0027] This invention provides a workflow for an advanced oxidation treatment system for the broad-spectrum removal of organic pollutants from water, the operation steps of which are described below: During system startup and flow initialization, the influent pump mixes wastewater containing organic pollutants with persulfate solution and pumps it into the reaction module from the bottom. The wastewater flows upwards through each reaction section within the module, contacting the composite packing material. The graded composite packing material, through its surface copper active sites, undergoes electron transfer with the persulfate solution, triggering advanced oxidation reactions. Because the reaction module employs a longitudinal fixed-bed structure, the active sites at the bottom preferentially contact the high-concentration reagent during wastewater flow, resulting in spatial differences in the valence state circulation rate and oxygen consumption rate on the catalyst surface in different sections.

[0028] Real-time data acquisition and synchronous monitoring by the sensing module. The potential sensor collects redox potential data at each elevation section within the reaction module, and the oxygen sensor collects dissolved oxygen concentration data at each elevation section. The collected electrical signals are transmitted to the control module.

[0029] The spatial gradient model is used for calculation. The control module substitutes the received discrete data into the built-in spatial gradient calculation model. The spatial gradient calculation model obtains the dynamic state characteristics of the reaction process by calculating the ratio of the parameter difference between adjacent sections to the physical height difference.

[0030] In the reaction path obstruction diagnosis, the control module compares the calculated gradient value with a preset logic threshold. The preset logic threshold is obtained by performing a blank benchmark test on the system. That is, during the steady-state operation period when the catalyst activity is optimal and the effluent indicators meet the standards, the initial gradient value of each stage is recorded as a benchmark, and the threshold range is determined by combining it with a preset percentage of efficiency reduction deviation.

[0031] Define the potential decay threshold as The oxygen decay threshold is The minimum oxygen concentration limit is In practical engineering applications, The value range is typically 50–200 mV / m. The value range is 0.5−2.0mg / (L·m). The concentration was set at 2.0 mg / L. If the redox potential spatial decay gradient... The absolute value exceeds the potential decay threshold. Then determine the first In a reaction segment of a catalyst cross section, the free radical pathway is blocked, and the accumulation rate of divalent copper ions on the catalyst surface exceeds the reduction rate. If the dissolved oxygen concentration... Below the minimum oxygen concentration limit And the dissolved oxygen spatial decay gradient The absolute value exceeds the oxygen decay threshold. Then determine the first The reaction layer of each cross section is in a state of blocked non-radical pathways, at which point the molecular oxygen concentration in the water is insufficient to maintain the oxygen vacancy activation reaction.

[0032] Spatiotemporal decoupling adaptive intervention involves the control module issuing compensation commands to the dosing and power modules based on diagnostic results. For the pulse dosing valve in the dosing module, the control module adjusts the opening frequency to replenish the chemical agent. For the power module, the system employs a time-division multiplexed pulse electric field strategy to perform physical intervention. By utilizing spatially independent electric field addressing and temporally switching pulses, spatiotemporal decoupling reconstruction of the degradation path is achieved. When both free radical and non-free radical paths are simultaneously blocked, the power module outputs an asymmetric pulse voltage to the corresponding reaction segment. The following waveform will be output: ; in, The representative control module is in At all times towards the first The instantaneous pulse voltage value output by the reaction section of each cross section; This represents the cathode polarization voltage, with a value range of 100mV-500mV; This represents the anodic polarization voltage, with a value range of 1.5V-2.5V; Representing the The pulse duration for cathodic polarization of the reaction layer segment in each cross section; This represents the dead zone buffer time during the switching process between positive and negative polarities. Representing the The pulse duration for anodic polarization is performed on the reaction layer segment of each cross section; Represents the pulse control period, in seconds. The duration of the cathode polarization pulse anodic polarization pulse duration And the dead zone buffer time required for two polarity switching The sum of the values.

[0033] exist In this stage, the power module injects electrons into the copper active sites on the two-dimensional titanium carbide surface through the graphite skeleton in the graded composite conductive filler, reducing divalent copper ions to cuprous ions. to During this phase, the power module switches to the anode potential, utilizing the active sites on the surface of the composite packing to electrolyze water and release nascent oxygen, thereby activating the oxygen vacancy pathway. Through time-dimensional pulse switching, the system alternately completes electron compensation and oxygen source replenishment within the same reaction layer, avoiding charge accumulation and side reaction interference that would occur under a DC electric field.

[0034] Steady-state monitoring and recovery are implemented, with treated purified water discharged from the top of the reaction module. The control module continuously monitors the effluent parameters and gradient changes at each stage. When the spatial gradient returns to the preset operating range, the control module instructs the power supply module to reduce the pulse duty cycle or stop the electric field output. For the voltage accuracy control of the power supply module and the pump speed regulation of the dosing module, those skilled in the art can use conventional industrial automation control methods, the implementation of which is well-known technology and will not be described in detail here.

[0035] See attached document Figure 2 The specific structure and assembly implementation of the reaction module of this invention are described as follows: The main structure of the reaction module adopts a modular, vertically stacked design, consisting of multiple standardized reaction columns connected sequentially along a vertical axis. The reaction columns are made of chemically resistant and high-strength insulating engineering plastics or 304 stainless steel with an inner insulating layer. The interior of each reaction column forms a physical space to accommodate the liquid-solid two-phase mass transfer. The use of insulating materials in the reaction columns prevents short-circuit losses caused by applied current along the sidewalls of the reaction module. Each reaction column has standard flange interfaces at both ends, and adjacent flange interfaces are mechanically fixed and tightened using bolt assemblies, forming a connected vertical fluid channel.

[0036] At the flange connection between two adjacent reaction column sections, a flow distribution and collection mesh is laterally clamped. The flow distribution and collection mesh is made of titanium mesh coated with a noble metal oxide coating, such as titanium mesh coated with ruthenium-iridium oxide or iridium-tantalum oxide. Uncoated pure titanium readily forms an insulating titanium dioxide passivation film under anodic potential, while the noble metal oxide coating ensures that the flow distribution and collection mesh maintains stable electron conductivity during frequent alternations between anodic and cathodic polarization. The mesh size is set in the range of 40-100 mesh. The flow distribution and collection mesh serves two engineering functions: as a fluid distributor, it utilizes the local hydraulic resistance provided by the metal mesh to redistribute the fluid from bottom to top across the cross-section, eliminating channeling and dead zones generated after the fluid passes through the lower composite packing layer, thus homogenizing the fluid velocity distribution entering the next stage of the reaction column; as an electrochemical current collector, the flow distribution and collection mesh is in direct physical contact with the composite packing inside the reaction column, serving as the end plate of a three-dimensional volume electrode, undertaking the functions of electron injection and current collection.

[0037] An insulating gasket, made of polytetrafluoroethylene (PTFE) or fluororubber, is installed between the flow distribution network and the flange sealing surface of the reaction column. The gasket's geometry matches the flange sealing surface of the reaction column. Under bolt preload, the gasket undergoes elastic deformation, achieving fluid sealing while simultaneously creating an electrical isolation barrier between adjacent reaction column shells. This electrical isolation barrier electrically divides the longitudinally continuous composite packing into multiple independent impedance ranges, preventing a large ohmic voltage drop caused by excessive longitudinal bed thickness when applying an electric field to the entire reaction module, thereby reducing the terminal voltage output load of the power supply module.

[0038] Each current distribution grid has a titanium-based conductive lead-out terminal welded to its edge. These terminals extend outside the reaction module through pre-drilled holes in the insulating sealing gasket or dedicated openings in the sidewall of the reaction column. The contact area between the conductive lead-out terminal and the reaction column is sealed with an insulating sleeve and resin potting structure to prevent internal fluid leakage. These externally extending conductive leads serve as independent electrical nodes, independently connected to the corresponding output channel of the power module, enabling independent addressing and control of the power module's application of potential to any layer of composite filler.

[0039] A rigid support grid is installed below the bottom layer of the flow distribution and collection network. This grid, made of polypropylene sheet with an open area of ​​60%-80%, is used to withstand the mechanical loads from the upper composite packing and fluid. A clamping ring is installed above the top layer of the flow distribution and collection network to prevent small particles from being lost with the effluent. Through this structural design, the reaction module is physically divided into several independent hydraulic and electrical boundaries. For the torque standards of flange connections and the sealing pressure testing procedures, those skilled in the art can refer to the standard specifications for chemical equipment installation engineering; further details are omitted here.

[0040] See attached document Figure 2 The specific implementation method of the composite filler composition and conductive network construction of the present invention is described as follows: The composite packing consists of a catalytically active phase, a macroscopically electronically conductive phase, and a fluidly dispersed phase mixed in a predetermined volume ratio. The catalytically active phase uses carbon-coated copper-doped two-dimensional titanium carbide particles, the macroscopically electronically conductive phase uses porous graphite particles, and the fluidly dispersed phase uses quartz sand particles. The average particle size of the quartz sand particles and the porous graphite particles must be consistent; in conventional engineering applications, a particle size range of 1 mm to 3 mm is preferred to prevent hydraulic stratification and bed collapse under fluid scouring. The catalytically active phase, the macroscopically electronically conductive phase, and the fluidly dispersed phase form a fixed bed with porosity within the reaction zone, allowing the waste liquid to flow from bottom to top.

[0041] The catalytically active phase provides the microscopic interface for triggering advanced oxidation reactions. The carbon-coated copper-doped two-dimensional titanium carbide particles comprise a two-dimensional titanium carbide substrate, copper active sites distributed on the surface and between layers of the two-dimensional titanium carbide substrate, and an in-situ amorphous carbon coating encapsulating the surface of the two-dimensional titanium carbide substrate. The in-situ amorphous carbon coating maintains the chemical stability of the copper active sites while imparting microscopic electrical conductivity to the carbon-coated copper-doped two-dimensional titanium carbide particles.

[0042] The macroscopic electronically conductive phase is used to reconstruct macroscopic electron transport channels within an insulating fluid dispersion phase. Insulating quartz sand particles provide hydrodynamic support and limit the system's back pressure, preventing physical stacking and pore blockage of carbon-coated copper-doped two-dimensional titanium carbide particles. Quartz sand particles are insulators; excessive doping can disrupt electron transport between catalytically active phases. The introduction of porous graphite particles into the composite filler bridges the electrical percolation threshold. These porous graphite particles physically contact each other in three-dimensional space, connecting adjacent flow distribution networks and constructing a macroscopically interconnected three-dimensional conductive framework. The porous graphite particles possess a well-developed pore structure, providing electron conduction pathways without adding additional hydraulic resistance within the reaction layer.

[0043] To ensure the integrity of the conductive pathway, the volume ratio of each component in the composite filler meets the percolation threshold condition. The volume of the carbon-coated copper-doped two-dimensional titanium carbide particles is set to... The volume of porous graphite particles is The volume of the quartz sand particles is Total volume of composite packing The calculation formula is as follows: ; The volume fraction of porous graphite particles is defined as follows: The formula for calculating the volume percentage is as follows: ; To establish a macroscopic three-dimensional conductive framework, the volume ratio of porous graphite particles is... Greater than or equal to the percolation threshold critical point Percolation threshold critical point The value is affected by the sphericity of the particles and the porosity of the packing. In engineering implementation, The exact volume percentage is determined by measuring the abrupt change in resistivity at both ends of a fixed bed. This is achieved by gradually increasing the proportion of porous graphite particles in the bed; the volume percentage at which the macroscopic resistivity of the bed decreases by an order of magnitude is the accurate measurement. In actual industrial loading, the permeation threshold is critical. The value range is typically between 15% and 30%. To ensure the reaction processing load, the volume percentage of carbon-coated copper-doped two-dimensional titanium carbide particles is set between 5% and 15%, with the remaining volume filled by quartz sand particles. When the following conditions are met... At this time, carbon-coated copper-doped two-dimensional titanium carbide particles dispersed in the pores of the macroscopic three-dimensional conductive framework physically connect with porous graphite particles through the in-situ amorphous carbon coating on the surface. This physical connection directly integrates the microscopic catalytically active phase into the macroscopic electron conduction network.

[0044] When the power module is not connected, the composite packing acts as a multiphase fluid contact medium in the reaction zone. The composite packing activates the persulfate through the chemical properties of the surface of the copper-doped two-dimensional titanium carbide particles coated with carbon. When the power module applies a polarization potential to a specific reaction zone through the current distribution network, electrons are transported along the current distribution network to the macroscopic three-dimensional conductive framework composed of porous graphite particles, and then transported to the copper active sites through the in-situ amorphous carbon coating. The transport path based on the physical overlap of the framework is a low-impedance conduction, reducing the ohmic voltage drop loss during electron injection. At this time, the clamped composite packing is electrically transformed into a three-dimensional volume electrode. The three-dimensional volume electrode extends the electrochemical oxygen evolution reaction or electron compensation reaction, which originally only occurred on the surface of the two-dimensional electrode plate, to the entire three-dimensional space of the fixed bed, eliminating external gas-liquid mass transfer resistance. For the filling and mixing process of quartz sand and porous graphite particles, as well as the washing and sieving steps, those skilled in the art can use conventional solid particle mixing and fixed bed filling methods. The specific operation steps are well known in the art and will not be described in detail here.

[0045] See attached document Figure 2 The specific implementation method of the present invention regarding the formation mechanism of the in-situ electrochemical actuation interface of the catalyst on the composite filler surface is described as follows: In a purely chemical catalytic interface without an external electric field, during the period when the power module stops outputting electrical signals, the composite packing material inside the reaction layer behaves as a chemical catalytic fixed bed. Carbon-coated copper-doped two-dimensional titanium carbide particles exposed in the liquid microenvironment experience collisions between monovalent cuprous ions and persulfate molecules. The monovalent cuprous ions donate electrons to the persulfate, causing the peroxy bond to break, generating sulfate radicals and hydroxyl radicals. During electron transfer, the monovalent cuprous ions lose electrons and transform into divalent copper ions. Oxygen vacancies on the surface of the carbon-coated copper-doped two-dimensional titanium carbide particles capture dissolved oxygen molecules in the water, converting them into singlet oxygen via a non-radical pathway. This chemical reaction process is highly dependent on the reagent concentration distribution and initial catalyst activity; as the reaction time progresses, the active sites gradually become ineffective because their valence states cannot be restored in time.

[0046] The intervention of a physical electric field and the formation of an electrochemical interface lead to a spatial reconstruction of the charge distribution within the composite filler when the power module applies a potential to the reaction layer through the current distribution network. Current flows from the macroscopic conductive framework composed of porous graphite particles into the in-situ amorphous carbon coating on the surface of carbon-coated copper-doped two-dimensional titanium carbide particles. This in-situ amorphous carbon coating possesses microscopic conductivity and establishes a continuous electrochemical double layer at the solid-liquid interface. The formation of this electrochemical double layer provides a locally high-intensity micro-electric field at the solid-liquid interface, altering the activation energy of the surface reactants. The divalent copper ions and oxygen vacancies at the solid-liquid interface transform from chemical contact points into electrochemical execution nodes driven by the applied physical electric field.

[0047] Based on in-situ remediation of free radical pathways using cathode polarization, when the free radical yield decreases due to the large accumulation of divalent copper ions within the reaction zone, the control module instructs the power supply module to output cathode polarization voltage. Electrons are injected into the passivated divalent copper ions through the in-situ amorphous carbon coating, forcing the divalent copper ions to capture electrons and undergo a reduction reaction, transforming them into monovalent cuprous ions that regain the ability to activate persulfate. The absolute value range is set to 0.1 volts - 0.5 volts. The specific value is determined by testing the reduction peak potential range of the target catalyst using cyclic voltammetry. Those skilled in the art can ensure that effective reduction of copper ions occurs while avoiding [further degradation / damage] by determining the reduction peak potential range using cyclic voltammetry. The hydrogen desorption potential beyond that of water is exceeded, thus preventing the formation of a large number of hydrogen bubbles on the electrode surface that would reduce the reaction area. The electrochemical reduction reaction removes the charge accumulation on the surface of the carbon-coated copper-doped two-dimensional titanium carbide particles, restoring the continuous generation cycle of free radicals.

[0048] Based on the in-situ reconstruction of the non-radical pathway using anodic polarization, when the dissolved oxygen concentration in the reaction zone is depleted, causing the singlet oxygen generation reaction to stagnate, the control module instructs the power supply module to switch the output anodic polarization voltage. In-situ amorphous carbon coating will The transfer to the carbon-coated copper-doped two-dimensional titanium carbide particle substrate drives water molecules in the liquid microenvironment to lose electrons near the catalytic site, undergoing an oxidation reaction. The water molecules in the liquid microenvironment release hydrogen ions, generating nascent nano-oxygen molecules within the micropores. The value range is set to 1.5 volts - 2.5 volts. The specific value is determined by testing the oxygen evolution overpotential of the target catalyst using a linear sweep voltammetry method. Those skilled in the art can determine the oxygen evolution overpotential using a linear sweep voltammetry method and ensure the set anodic polarization voltage. It is higher than the thermodynamic oxygen evolution potential and lower than the chlorine evolution potential to prevent the production of toxic free chlorine byproducts when treating chlorinated water.

[0049] The in-situ oxygen evolution reaction occurs within the micropores on the surface of carbon-coated copper-doped two-dimensional titanium carbide particles. The nascent nano-oxygen molecules generated are directly captured and activated by adjacent oxygen vacancies before coalescing into macroscopic bubbles. This in-situ gas-liquid mass transfer mechanism within the microscopic space eliminates the mass transfer resistance and bed gas resistance problems present in conventional external aeration.

[0050] Microscopic corrosion protection through in-situ amorphous carbon coating. At the output anodic polarization voltage. During this period, high-potential environments can easily induce anodic dissolution of transition metal elements or low-valence metal oxides. An in-situ amorphous carbon coating encapsulated on the exterior of a two-dimensional titanium carbide substrate forms a physical barrier and an electronic conduction barrier.

[0051] The in-situ amorphous carbon coating maintains electronic conductivity between the carbon-coated copper-doped two-dimensional titanium carbide particles and the external porous graphite framework through the quantum tunneling effect. Simultaneously, the dense carbon structure physically prevents free water molecules in the liquid microenvironment from directly contacting and etching the internal copper active sites, ensuring the structural stability of the composite filler under long-term electrochemical alternating polarization conditions. For the precursor synthesis and surface carbonization treatment of the carbon-coated copper-doped two-dimensional titanium carbide particles, those skilled in the art can choose chemical vapor deposition or hydrothermal carbonization calcination processes. Specific material synthesis steps are well-known techniques in the field and will not be elaborated here.

[0052] See attached document Figure 2 The specific implementation methods of the sensing module and the dosing module of this invention are described as follows: The sensing module includes a potential sensor and an oxygen sensor, which are discretely arrayed along the height of the reaction module. At the physical elevation of each flow distribution network, a sensor mounting hole is provided on the sidewall corresponding to the reaction section. The measuring ends of the potential sensor and the oxygen sensor penetrate the sidewall of the reaction section to enter the main fluid flow zone inside the fixed bed. This spatially discrete deployment transforms the conventional two-point monitoring mode of fixed bed inlet and outlet water into one-dimensional longitudinal gradient monitoring along the liquid flow direction.

[0053] The reaction module contains an external alternating electric field and a three-phase gas-liquid-solid flow. To acquire local state data, the measuring ends of the potential and oxygen sensors are encased in porous PTFE shielding sleeves with micropore diameters ranging from 10 to 50 micrometers. These micropores allow the aqueous phase and dissolved redox ions to freely permeate through capillary action, while physically preventing solid particles from the composite packing from entering the sensitive membrane of the internal friction sensor. The microporous structure also prevents macroscopic bubbles generated during in-situ electrolysis from directly adhering to the sensor surface and causing gas resistance insulation. The mounting bases of the potential and oxygen sensors are securely fixed to the sidewalls of the reaction section using double-layer fluororubber sealing rings to prevent leakage of pressurized liquid from the reaction section.

[0054] A potential sensor measures the macroscopic apparent potential of the relative concentrations of oxidant and reductant in the liquid-phase microenvironment within the fixed bed, while an oxygen sensor measures the actual molecular oxygen retention within the fixed bed. The acquired spatial gradient data reflects the spatial decay characteristics of the reaction kinetics due to reagent consumption or passivation of active sites on the catalyst surface. This spatial gradient data is transmitted to the control module, providing raw measurement data to support the module's segmented state diagnosis and stratified independent intervention.

[0055] The bottom-point centralized dosing mode can easily lead to excessively high local concentrations of supersulfate at the inlet. This excessively high initial concentration causes self-quenching side reactions between supersulfate molecules, generating low-activity sulfate ions and oxygen. In other words, the high concentration of oxidant molecules undergoes ineffective chemical decomposition before contacting organic pollutants, resulting in reduced absolute utilization efficiency of the reagent. Therefore, the dosing module adopts a bypass multi-point supersulfate pulse injection physical structure. A bypass dosing main pipe is led out from the side of the main water supply pipeline of the inlet pump. The bypass dosing main pipe is connected to the lateral inlet of each reaction section through multiple parallel pulse dosing valves. The lateral inlets are located in the lower half of the corresponding reaction section, with the outlet direction of the lateral inlets facing the fluid dispersion section of the upper distribution and collection network.

[0056] The pulse dosing valves utilize precision electromagnetic proportional valves resistant to strong oxidation and corrosion. The control module independently adjusts the opening frequency and duration of each pulse dosing valve based on the attenuation of local parameters fed back by the sensing module. When the redox potential attenuation within a certain reaction zone exceeds the normal operating threshold, and a cathodic polarization voltage is applied... If the ideal potential spatial distribution cannot be restored, the control module determines that the concentration of persulfate reagent in the corresponding reaction section is depleted. The control module outputs a digital electrical signal to the drive coil of the corresponding pulse dosing valve. With the pulse dosing valve energized, it replenishes the corresponding reaction section laterally with a high-concentration persulfate solution in the form of a high-voltage pulse jet.

[0057] The quantitative replenishment logic of the pulse dosing valve is based on the feedback deviation of the spatial decay gradient. The control module calculates the amount of feed to the first... The theoretical persulfate pulse dosage injected into the reaction zone of each cross section . The calculation formula is as follows: ; in, Represents the first operation within a single operation cycle. The mass of persulfate injected into the reaction section of each cross section, in grams; Representing the The reagent compensation ratio coefficient for each cross-section of the reaction layer. The value is obtained by calibration using the response curve of the injected persulfate mass and the change in local potential gradient. Those skilled in the art can determine it through multiple step titration experiments. The conventional value range is 0.1-0.5. This represents the upper limit of the absolute value of the spatial decay gradient of the ideal redox potential preset by the system. The settings are based on the average historical gradient data recorded during continuous steady-state operation of the system at its optimal pollutant removal efficiency; Represents the first [unit / item] measured and calculated by the sensing module. The absolute value of the actual decay gradient in the actual redox potential space of each cross section; This represents the main pipeline liquid volumetric flow rate provided by the inlet pump. Representing the The duration of a single opening of a pulse dosing valve in each cross-section. Greater than When this occurs, it indicates a shortage of reagents in the corresponding layer, and the system initiates positive reagent compensation.

[0058] The bypass multi-point pulse injection mode distributes the total reagent load, originally concentrated at the bottom of the reaction module, evenly across the various independent reaction sections along the longitudinal direction. Multi-point dispersed dosing avoids the self-quenching loss of persulfate in a single section. The pulse jet utilizes jet kinetic energy to enhance the radial diffusion mixing rate of persulfate on the cross-section of the corresponding reaction section. Combined with the hydraulic division and redistribution effect of the flow distribution network, this ensures uniform contact between the supplemented persulfate molecules and the active sites on the composite packing surface. For industrial selection of pulse dosing valves, valve response time calibration, and sealing performance testing, those skilled in the art can consult industrial pipe and valve equipment selection manuals. Valve selection, configuration, and installation are well-known techniques in this field and will not be elaborated upon here.

[0059] See attached document Figure 2 The specific implementation of the computational logic of the first-order forward difference model in space in this invention is described as follows: The control module receives discrete state parameters transmitted by the sensing module according to a preset sampling period. Within the reaction module, there is a strong alternating electromagnetic field and three-phase flow of gas, liquid, and solid. The raw electrical signals output by the potential and oxygen sensors are superimposed with high-frequency fluctuation noise. The small spatial height difference calculation amplifies the high-frequency fluctuation noise of the local electrical signals, leading to diagnostic misjudgments by the control module. Before performing the first-order forward difference calculation in space, the control module calls a moving average filtering algorithm to preprocess the raw electrical signals for noise reduction. To balance data smoothness and system response real-time performance, the filtering window width of the moving average filtering algorithm is set to 5 to 20 consecutive sampling points. The total acquisition time span of these sampling points must be less than the average hydraulic residence time of the liquid phase within a single reaction layer.

[0060] After noise reduction preprocessing, the control module invokes the first-order forward difference model in space. This model quantifies the rate of change of reaction kinetics within a local space by using the ratio of the data difference between two adjacent discrete monitoring points along the fluid flow direction to the difference in physical spatial distance. From a macroscopic reaction engineering perspective, since the wastewater maintains a stable, unidirectional upward flow within the reaction module, the increase in physical spatial height is mathematically equivalent to an extension of reaction time. The calculation of the spatial gradient essentially transforms the chemical reaction rate, which is difficult to measure directly, into a physically calculable difference distribution in real time. The control module then calculates the... Forward spatial gradient of redox potential in the reaction zone of each cross section The calculation formula is as follows: ; in, For the first The forward spatial gradient of redox potential calculated for each cross-section of the reaction layer; For the first Redox potential of each cross section; For the first Redox potential of each cross section; Representing the The physical elevation of the boundary of the reaction section of each cross section; Representing the The physical elevation of the boundary of the reaction zone section at each cross-section. Because the waste liquid flows unidirectionally from bottom to top. The physical space elevation value is always greater than The physical space elevation value.

[0061] Similarly, the control module calculates the first... Dissolved oxygen forward spatial gradient of the reaction zone at each cross section The calculation formula is as follows: ; in, Representing the The forward spatial gradient of dissolved oxygen calculated for each cross-section of the reaction layer; Representing the The actual dissolved oxygen concentration at each cross section; Representing the The actual dissolved oxygen concentration of each cross section.

[0062] The forward spatial gradient output by the first-order forward difference model has a clear indication of reaction engineering physics. If the forward spatial gradient of the redox potential... A negative value with an absolute value exceeding the system's steady-state operating limit indicates that the liquid microenvironment... elevation Within the physical region where elevation advances, highly oxidizing free radicals or persulfate agents undergo rapid chemical consumption. The control module forwards the redox potential spatial gradient. With dissolved oxygen forward spatial gradient As basic feature inputs, these are passed to the microenvironment diagnostic engine to perform subsequent obstruction state determination. For the moving average filtering algorithm for discrete data and the microprocessor's store-and-recall mechanism, those skilled in the art can use standard digital signal processing programs and conventional automated programming methods. Specific software engineering implementation details are well-known in the field and will not be elaborated upon here.

[0063] See attached document Figure 2 The specific implementation of the mathematical diagnostic criteria for blocked reaction pathways in this invention is described below: The microenvironment diagnostic engine of the control module has a built-in multi-dimensional diagnostic threshold matrix, which includes potential decay thresholds. Oxygen decay threshold and minimum oxygen concentration limit The potential decay threshold is With oxygen decay threshold The values ​​were obtained through continuous and stable operation tests of the reaction module at its optimal organic pollutant removal efficiency. Those skilled in the art, after setting the system to achieve the target pollutant removal rate, collected historical spatial gradient data covering at least three complete hydraulic retention cycles or more than 72 hours of continuous operation as the basic statistical sample. The control module calculated the mathematical expectation value of the historical spatial gradient data and added three times the standard deviation to the mathematical expectation value as the corresponding attenuation threshold. This calculation method of adding three times the standard deviation to the mathematical expectation value effectively accommodates reasonable measurement errors caused by normal water quality fluctuations and sensor background noise, preventing frequent false triggering interventions by the control module.

[0064] The control module performs a free radical pathway obstruction diagnosis. The control module extracts the first... Forward spatial gradient of redox potential in the reaction zone of each cross section The absolute value, and The absolute value and the potential decay threshold are Numerical comparison is performed. The control module outputs free radical path diagnostic status parameters. The calculation formula is as follows: ; in, Representing the The free radical path diagnostic state parameters calculated from the reaction section of each cross section; This indicates that the free radical pathway is blocked. This indicates that the free radical pathway is functioning normally.

[0065] when The output is At that time, macroscopic physicochemical principles indicated that the first The reduction reaction of divalent copper ions to monovalent cuprous ions on the surface of the composite packing inside the reaction layer of each cross section is halted, and a large amount of charge accumulates at the catalytic active sites. As a result, persulfate cannot be continuously converted into sulfate radicals and hydroxyl radicals with strong oxidizing properties, and the local free radical generation rate lags far behind the pollutant consumption rate.

[0066] The control module performs non-radical pathway obstruction diagnosis. The continuous operation of non-radical pathways is highly dependent on the absolute value of molecular oxygen concentration and the rate of molecular oxygen concentration decay in the liquid microenvironment. The control module extracts the first... Dissolved oxygen forward spatial gradient of the reaction zone at each cross section The absolute value and the first Actual dissolved oxygen concentration at each cross section The control module performs a Boolean logic union operation on the actual measured concentration parameters and preset thresholds, outputting non-radical path diagnostic status parameters. The calculation formula is as follows: ; in, Representing the The non-radical path diagnostic state parameters of the reaction layer segment calculated for each cross section; This indicates that the non-radical pathway is blocked. This indicates that the non-radical pathway is functioning normally. Represents the absolute value of the forward spatial gradient of dissolved oxygen; This represents the oxygen decay threshold.

[0067] The principle behind this formula is that a high dissolved oxygen decay rate simply indicates extremely vigorous local non-radical reactions, and does not necessarily mean that the reaction is blocked; only when the absolute molecular oxygen content simultaneously approaches the lower limit boundary does it truly represent a resource shortage in the reaction network. When the non-radical pathway diagnostic state parameters... The output is When, it indicates the first The absolute amount of molecular oxygen inside the reaction layer of each cross section has been depleted. The remaining molecular oxygen cannot maintain the continuous consumption rate at which oxygen vacancies on the surface of carbon-coated copper-doped two-dimensional titanium carbide particles convert dissolved oxygen into singlet oxygen. The non-radical oxidation process shows a tendency to stagnate.

[0068] The control module will calculate the free radical path diagnostic state parameters. Diagnostic state parameters of non-radical pathways The state matrix is ​​composed of two parts. This matrix provides the fundamental mathematical logic for triggering the pulse injection action of the dosing module and the cathode / anode polarity switching action of the power supply module. Based on the state matrix, the control module locates the specific physical height and chemical resistance type of the reaction path degradation in three-dimensional space, thereby guiding subsequent operational steps to perform spatially segmented intervention. For the hardware physical construction of the Boolean logic operation unit within the control module and the compilation of the underlying logic judgment program, those skilled in the art can use an industrial programmable logic controller or a conventional microprocessor for configuration. The compilation of microprocessor logic programs is a well-known technology in this field and will not be elaborated upon here.

[0069] See attached document Figure 2 The specific implementation of the unidirectional polarization directional compensation mechanism in the spatiotemporal decoupling intervention module based on the time-division multiplexing asymmetric pulse strategy of this invention is described as follows: The control module receives free radical path diagnostic state parameters and non-free radical path diagnostic state parameters output by the microenvironment diagnostic engine. The reaction module consists of a fixed bed of solid-liquid two-phase mixture, exhibiting high ohmic resistance characteristics in its vertical direction. If a global continuous DC electric field is directly applied to the entire reaction module, the high ohmic resistance characteristic will cause ineffective Joule heat loss and lead to water electrolysis side reactions at the inlet and outlet. The control module uses time-division multiplexing logic to distribute the electric field energy. The time-division multiplexing logic divides the time axis into multiple independent intervention time windows.

[0070] The total length of the intervention time window is determined based on the hydraulic residence time calculated from the liquid phase volumetric flow rate of the influent pump and the effective volume of the reaction module. To ensure that electrochemical polarization can act on the liquid phase microenvironment currently in a specific reaction zone, the length of a single intervention time window is set to one to five percent of the overall hydraulic residence time.

[0071] Within each intervention time window, the power module only connects specific conductive leads, focusing the electric field energy on specific reaction segments where the reaction is hindered. The spatial segmentation of the electric field and the time-division multiplexing of time constitute, in physical essence, the spatiotemporal decoupling and reconstruction of the degradation path of the reaction system.

[0072] Unidirectional cathode polarization compensation for the free radical path. When the control module determines the first... The non-radical path diagnostic state parameters of the reaction section of each cross section are as follows: At this time, the control module issues a cathode pulse output command to the power module. The power module injects electrons into the macroscopic three-dimensional conductive framework inside the specific reaction section through the current distribution network corresponding to the physical height. The electrons are transported to the divalent copper ion sites through the in-situ amorphous carbon coating, driving the divalent copper ions to capture electrons and undergo an electrochemical reduction reaction to regenerate monovalent cuprous ions. The calculation formula is as follows: ; in, Representing the The cathodic polarization pulse width of the reaction layer segment of each cross section performs cathodic polarization; This represents the cathode pulse time compensation coefficient.

[0073] Cathode pulse time compensation coefficient The effective conductive specific surface area of ​​the composite filler is predetermined by the mapping relationship between the amount of charge and Faraday's law of electrolysis. Those skilled in the art can obtain this information by dividing and adjusting the total charge consumed by a known mass of composite filler to reach a completely reduced state in a standard test solution. The value is typically set within the range of 10 s·m / V to 50 s·m / V for industrial applications.

[0074] For unidirectional anodic polarization compensation of non-radical paths, when the control module determines the first The non-radical path diagnostic state parameters of the reaction section of each cross section are as follows: At this time, the control module issues an anode pulse output command to the power supply module. The power supply module outputs a positive polarization potential to a specific reaction section through the current distribution network. The positive polarization potential drives water molecules at the solid-liquid interface to lose electrons and undergo an oxygen evolution reaction, generating nascent oxygen molecules in situ within the pores of the liquid phase microenvironment, thereby replenishing the depleted dissolved oxygen molecules. The control module calculates the anode polarization pulse width. The calculation formula is as follows: ; in, Representing the The anodic polarization pulse width for each cross-section of the reaction layer is used to perform anodic polarization. This represents the anode pulse time compensation coefficient.

[0075] Anode pulse time compensation coefficient The intrinsic oxygen evolution kinetic constant of carbon-coated copper-doped two-dimensional titanium carbide particles was tested for calibration. Those skilled in the art used the constant potential step method to record the amount of oxygen evolved at the micro-interface per unit time and performed equivalent calculations to obtain the anodic pulse time compensation coefficient. The value is typically set within the range of 5 s·L·m / mg to 20 s·L·m / mg for industrial applications.

[0076] The physicochemical essence of the asymmetric pulse strategy is that the activation energy of the electrochemical reduction reaction of divalent copper ions is lower than that of the oxygen evolution reaction of water molecules. To match different reaction kinetic barriers, the absolute potential amplitude of the cathode pulse is set by the control module to be constantly lower than that of the absolute potential amplitude of the anode pulse. Simultaneously, to prevent irreversible anodic oxidation etching or even structural collapse of the two-dimensional titanium carbide substrate due to prolonged high-potential anodic polarization, the control module sets the single-pulse width of the anodic polarization in its underlying logic. Set a forced shutdown threshold. The forced shutdown threshold is usually no more than 5 seconds.

[0077] By matching the potential amplitude differences established through the activation energies of different chemical reactions, and by setting pulse width limitations for anodic oxidation etching, an asymmetric pulse strategy is constituted in the time-division multiplexing logic. This dual asymmetric design of potential amplitude differences and pulse width limitations ensures the restoration of unobstructed chemical reaction paths while maintaining the physical framework stability of the composite filler under long-term operation. For the high-frequency insulated-gate bipolar transistor switch array topology within the power module and the pulse width modulation signal generation program of the programmable logic controller, those skilled in the art can consult conventional power electronic converter design manuals. The specific switch circuit construction and hardware driver programming are well-known techniques in this field and will not be elaborated upon here.

[0078] See attached document Figure 2 The specific implementation method of constructing alternating pulse waveforms in the spatiotemporal decoupling intervention module based on time-division multiplexing asymmetric pulse strategy of the present invention is described as follows: The control module receives multi-dimensional state parameters through the micro-environment diagnostic engine. When the control module determines the first... The free radical path diagnostic state parameters and non-free radical path diagnostic state parameters of the reaction layer of each cross section are simultaneously output as follows: At that time, macroscopic physicochemical principles indicate that in the first... Within the reaction layer of each cross section, the reduction reaction of divalent copper ions and the molecular oxygen generation reaction on the surface of the composite filler simultaneously stall. Unidirectional polarization compensation cannot simultaneously repair two blocked chemical reaction paths. The control module instructs the power module to generate and output a time-division multiplexed asymmetric alternating pulse waveform.

[0079] The time-division multiplexed asymmetric alternating pulse waveform integrates cathode polarization compensation and anode polarization compensation within a single control cycle. Because the activation energy of the reduction reaction where divalent copper ions capture electrons is lower than the activation energy of the oxygen evolution reaction where water molecules lose electrons, the time-division multiplexed asymmetric alternating pulse waveform uses unequal voltage amplitudes and pulse durations in the forward and reverse output ranges. The control module calculates the output up to the [number missing]. Waveform function of the reaction layer section of each cross section The calculation formula is as follows: ; in, The representative control module is in At all times towards the first The instantaneous pulse voltage value output by the reaction section of each cross section; This represents the cathode polarization voltage, with a value range of 100mV-500mV; This represents the anodic polarization voltage, with a value range of 1.5V-2.5V; Representing the The pulse duration for cathodic polarization of the reaction layer segment in each cross section; This represents the dead zone buffer time during the switching process between positive and negative polarities. Representing the The pulse duration for anodic polarization is performed on the reaction layer segment of each cross section; Represents the pulse control period, pulse control period The duration of the cathode polarization pulse anodic polarization pulse duration And the dead zone buffer time required for two polarity switching The sum of the values, that is .

[0080] The composite filler constructs a macroscopic three-dimensional conductive framework in physical space, exhibiting high double-layer capacitance between the framework and the liquid-phase microenvironment. If the power module directly switches from cathode polarization voltage to anodic polarization voltage, the reverse charge accumulated by the double-layer capacitance will generate a transient surge current. This transient surge current will damage the in-situ amorphous carbon coating on the surface of the carbon-coated copper-doped two-dimensional titanium carbide particles. Waveform function Dead buffer time introduced in The power module is forced to output zero potential during polarity switching. The zero-potential output range allows the double-layer capacitance within the macroscopic three-dimensional conductive framework to discharge naturally through the liquid-phase microenvironment. Dead-time buffer. The specific value is determined based on the resistance, capacitance, and time constant of the fixed bed. In engineering applications, the dead zone buffer time... Set to 0.1 to 0.5 seconds.

[0081] The control module calculates the asymmetric energy factor. The energy distribution ratio of the time-division multiplexed asymmetric alternating pulse waveform is verified using the following formula: ; in, Representing the The asymmetric energy factor of the reaction section of each cross section; Represents the anodic polarization voltage; Representing the The pulse duration for anodic polarization is performed on the reaction layer segment of each cross section; Represents the cathode polarization voltage; Representing the The pulse duration for cathodic polarization is performed on the reaction layer segment of each cross section.

[0082] In macroscopic physicochemical processes, the oxygen evolution reaction of water molecules is a slow-kinetic process involving four-electron transfer, while the reduction reaction of divalent copper ions is a fast-kinetic process involving one-electron transfer. This difference in kinetics dictates that the anodic polarization energy required to maintain the non-radical pathway must be higher than the cathodic polarization energy required to maintain the radical pathway. To ensure sufficient dissolved oxygen is generated in situ without triggering anodic oxidation loss in the macroscopic three-dimensional conductive framework, the control module applies an asymmetric energy factor... The dynamic range of values ​​is forcibly clamped between 2.0 and 5.0. When the calculated asymmetric energy factor... When the upper limit of 5.0 is exceeded, the control module prioritizes proportionally reducing the pulse duration of anodic polarization. .

[0083] The alternating electric field, with unequal amplitudes and polarization times of positive and negative polarization voltages constructed to address the differences in activation energies of different chemical reactions within the same reaction space, essentially constitutes a time-division multiplexed asymmetric alternating pulse waveform. This dual asymmetry of voltage and time establishes the priority and energy matching principle for reaction path repair in complex multiphase catalytic systems. Regarding the H-bridge full-bridge inverter circuit structure and dead-time injection logic upon which the time-division multiplexed asymmetric alternating pulse waveform output by the power module depends, those skilled in the art can employ a conventional AC motor drive controller hardware architecture. The specific switching timing of the power switching devices is well-known in the field and will not be elaborated upon here.

[0084] See attached document Figure 2 The specific implementation method of the present invention regarding the targeted repair and short-circuit prevention mechanism for dual-path concurrent obstruction in the spatiotemporal decoupling intervention module based on time-division multiplexing asymmetric pulse strategy is described as follows: The control module locates the physical location where the dual-path concurrency is blocked. When the control module determines the first... The free radical path diagnostic state parameters and non-free radical path diagnostic state parameters of the reaction layer of each cross section are simultaneously output as follows: At that time, the control module locks the first The reaction layer of each section is the target for targeted repair. The control module controls the power module to directionally apply time-division multiplexed asymmetric alternating pulse waveforms to the first section. The flow distribution network of the first cross section and the first Between the current distribution and collection networks of each cross section. The spatially confined electric field loading method ensures that the electrochemical intervention energy is focused only on the specific physical space where the reaction has stalled, avoiding unnecessary charge impact on other normally operating reaction sections.

[0085] The targeted remediation process is based on the alternating polarization of the liquid-phase microenvironment by an alternating electric field. Time-division multiplexing of asymmetric alternating pulse waveforms forces the surface of the composite packing to switch frequently between cathodic and anodic polarization states. The cathodic polarization state drives divalent copper ions to capture electrons and undergo reduction reactions to restore catalytically active sites, while the anodic polarization state promotes anodic oxidation of water molecules at the solid-liquid interface to replenish dissolved oxygen in situ. The high-frequency polarity reversal process disrupts the static concentration boundary layer on the surface of the composite packing, accelerating the mass transfer rate of persulfate reagent molecules and organic pollutant molecules into the micropores of the composite packing, simultaneously removing reaction hindrance from both physical diffusion and chemical oxidation dimensions.

[0086] The introduction of the short-circuit prevention mechanism is based on the intrinsic physical structure characteristics of the solid-liquid multiphase fixed bed. The composite packing material possesses high conductivity, and the composite packing particles form a continuous solid-phase conductive network through physical compression. If the power module outputs a constant DC level, the charge will follow the principle of minimum impedance, preferentially forming an electronic conduction short circuit through the solid-phase conductive network. This prevents electric field energy from penetrating the solid-liquid interface to enter the liquid-phase microenvironment and drive ion reactions. The time-division multiplexed asymmetric alternating pulse waveform contains a high time-voltage change rate. The double layer formed between the macroscopic three-dimensional conductive framework and the liquid-phase microenvironment is equivalent to a capacitive load in the circuit topology. The pulse signal with a high time-voltage change rate can preferentially inject displacement current into the double-layer capacitor, converting electrical energy into the energy required to maintain the electrochemical polarization of the solid-liquid interface, effectively blocking the ohmic short-circuit dissipation path along the solid-phase framework.

[0087] The control module executes a real-time short-circuit protection monitoring algorithm. The control module synchronously acquires and outputs data to the first... The instantaneous pulse voltage parameters and response current parameters of the reaction layer section of each cross section are calculated. The control module calculates the... Dynamic impedance parameters of the reaction section of each cross section The calculation formula is as follows: ; in, Representing the The reaction zone of each cross section is in The dynamic impedance parameter at any given time; The representative control module is in At all times towards the first The instantaneous pulse voltage value output by the reaction section of each cross section; The representative control module is in The flow of data collected at each moment The response current parameter of the reaction layer section of each cross section, in amperes.

[0088] The control module has a built-in safety impedance threshold. Those skilled in the art can measure the background impedance of the fixed bed under compaction by introducing test wastewater with a preset maximum conductivity into the reaction module.

[0089] Those skilled in the art use a scaling factor of 0.5-0.8 to multiply the background impedance value as the safe impedance threshold. The fixed write parameters ensure that the system only triggers an alarm when severe physical compression and bridging of solid particles causes a sharp drop in impedance, effectively filtering out interference caused by fluctuations in water conductivity. With safety impedance threshold Perform numerical comparison.

[0090] When dynamic impedance parameter The value drops and falls below the safe impedance threshold. At that time, the control module determines the first Physical particle bridging short circuits occurred within the reaction layer section of each cross-section. The control module instructed the power module to forcibly cut off the output to the first... The time-division multiplexed asymmetric alternating pulse waveform of the reaction layer section of each cross section, the execution delay time of the control command is limited to between 50 microseconds and 200 microseconds to prevent thermal breakdown of power devices.

[0091] Subsequently, the control module triggers the system's underlying backwashing or gas-liquid disturbance program, applying hydraulic shear force to force the first The composite filler within the reaction layer of each cross section undergoes spatial rearrangement, disrupting abnormal solid-phase conductive pathways. For the high-frequency current sampling circuit within the control module, those skilled in the art can construct it using conventional Hall current sensors and analog-to-digital converter chips. The hardware integration and data conversion algorithms of the Hall current sensor are well-known technologies in this field and will not be elaborated upon here.

[0092] To verify the effectiveness of this invention, this embodiment relies on a spatiotemporally decoupled adaptive pulsed intervention fixed-bed reactor system for the advanced treatment of industrial organic wastewater (such as chemical or pharmaceutical wastewater containing recalcitrant organic matter). The system is filled with a fixed bed containing a copper-based catalyst, and an electrocatalytic advanced oxidation reaction is driven by an externally applied specific electrical signal to achieve continuous removal of organic pollutants from the wastewater.

[0093] Regarding the implementation of time-division multiplexed asymmetric alternating pulse waveforms in catalytic polarization control (combined with...) Figure 3 ):like Figure 3As shown, in the organic wastewater treatment process of this embodiment, the voltage waveform applied across the fixed-bed reactor is a time-division multiplexed asymmetric alternating pulse waveform. The time-division multiplexed asymmetric alternating pulse waveform is used to regulate the valence state cycle of the copper-based catalyst in the bed and the generation of in-situ active oxygen, and it changes in segments within a complete pulse cycle (4.9s).

[0094] The specific operating parameters are set as follows: The system first applies a cathodic polarization potential of -0.3V to the reactor for 1.5s to reduce divalent copper and regenerate catalytic active sites; then it enters the first dead zone stage, where the voltage amplitude drops to 0V for 0.2s; after the first dead zone ends, the system switches to the anodic polarization stage, applying a voltage amplitude of 2.0V for 3.0s to drive in-situ oxygen evolution and the oxidative degradation of organic matter; finally, it enters the second dead zone stage, where the voltage amplitude returns to 0V for 0.2s. During actual wastewater treatment, the reactor outputs electrical signals cyclically according to this 4.9s cycle.

[0095] Experimental verification of the continuous operation stability of the wastewater treatment system (combined with...) Figure 4 ):like Figure 4 As shown, to verify the long-term stability of the fixed-bed reactor system of this invention under actual continuous wastewater treatment conditions, a 120-hour continuous influent degradation test was conducted. The horizontal axis represents the system operating time, and the vertical axis represents the removal rate of organic pollutants in the wastewater. Three parallel treatment systems were set up in the experiment, and the specific operating data are as follows: The removal rate of organic pollutants in control group A (conventional bottom-addition fixed bed) decreased significantly with the extension of operating time. The removal rate was 92% in the initial stage of system startup (0h), which decreased to 55% after 24h of continuous operation due to bed passivation, and finally decreased to 35% by the end of the 120h test.

[0096] The removal rate of control group B (global DC dosing fixed bed) also showed a continuous downward trend. Its initial removal rate was 95%, which dropped to 75% after 24 hours of operation, and then decreased to 39% after 120 hours.

[0097] In the experimental group of this invention (a fixed-bed system employing spatiotemporal decoupling adaptive pulse intervention), the removal rate curve remained stable during a 120-hour continuous influent treatment process, without significant attenuation. The removal rate of organic pollutants consistently fluctuated between 96% and 97.5%, reaching 97% at the end of the 120-hour test, essentially consistent with the initial operating level. This verifies the system's advantages in resisting passivation and ensuring stable operation in long-term industrial wastewater treatment applications.

[0098] The implementation status of the spatial gradient change before and after adaptive intervention within the reactor bed (combined with...) Figure 5 ):like Figure 5 As shown, in the continuous treatment of organic wastewater, the internal reaction of the fixed bed can be hindered due to local dead zones in the flow field or the adhesion of pollutants. In this embodiment, the reactor bed is divided into four segments along the water flow direction (segment L1, segment L2, segment L3, and segment L4), and the changes in the absolute value of the potential spatial attenuation gradient of each segment before and after adaptive intervention are recorded. The upper limit of the normal operation judgment threshold set internally by the system is 150 mV / m.

[0099] Before system intervention (i.e., when the reactor was locally in a state of reaction inhibition), the absolute values ​​of the potential spatial decay gradients in the first to fourth layers were 80 mV / m, 180 mV / m, 160 mV / m, and 90 mV / m, respectively. Among them, the data of the second layer (180 mV / m) and the third layer (160 mV / m) significantly exceeded the upper limit of the threshold of 150 mV / m, and the system determined that the reaction was inhibited in these two specific layers.

[0100] After the system implemented pulse intervention on the obstructed sections (i.e., the reaction path returned to normal), the resistance accumulated within the bed was broken, and the gradient data of each section decreased. The first section decreased to 75 mV / m, the second to 110 mV / m, the third to 120 mV / m, and the fourth to 85 mV / m. After the intervention, the absolute values ​​of the potential spatial decay gradients in all four sections of the reactor returned to within the normal threshold of 150 mV / m, indicating that the local obstruction had been eliminated, the spatial gradient distribution within the system had returned to normal, and the wastewater treatment process had returned to uniformity and efficiency.

Claims

1. An advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water, characterized in that, It includes a reaction module, a sensing module, a dosing module, a power supply module, and a control module; The reaction module is divided into multiple reaction segments along the longitudinal height direction, filled with a composite filler consisting of carbon-coated copper-doped two-dimensional titanium carbide catalyst particles, graphite particles and quartz sand particles, and a three-dimensional volume electrode is constructed at the junction of the segments using a flow distribution network. The sensing module includes a potential sensor and an oxygen sensor distributed at the flow distribution and collection network. The sensing module is connected to the control module and is used to transmit the collected potential data and dissolved oxygen data to the control module. The dosing module includes an inlet pump and a pulse dosing valve. The inlet pump is used to pump in the organic wastewater to be treated, and the pulse dosing valve is used to pass a sulfate solution. The power module is connected to the current distribution network and is used to apply an asymmetric pulse current to the three-dimensional volume electrode through the current distribution network to trigger the electrochemical oxidation-reduction reaction on the surface of the composite filler. The control module uses a built-in spatial gradient calculation model to calculate the ratio of the data difference to the height difference between adjacent monitoring points and obtains the spatial decay gradient of oxidation-reduction potential and the spatial decay gradient of dissolved oxygen. The microenvironment diagnostic engine determines the blocked state of the reaction path based on the spatial decay gradient of oxidation-reduction potential and the spatial decay gradient of dissolved oxygen. By adjusting the opening frequency of the pulse dosing valve and the pulse waveform of the power module, the spatiotemporal decoupling reconstruction of the degradation path is realized.

2. The advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water according to claim 1, characterized in that, The volume ratio of carbon-coated copper-doped two-dimensional titanium carbide catalyst particles, graphite particles, and quartz sand particles in the composite filler meets the percolation threshold condition. The graphite particles are physically in contact with each other in three-dimensional space and connect with adjacent flow distribution and collection networks to construct a macroscopic three-dimensional conductive framework. The carbon-coated copper-doped two-dimensional titanium carbide catalyst particles are physically connected to the macroscopic three-dimensional conductive framework through an in-situ amorphous carbon coating on their surface.

3. The advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water according to claim 1, characterized in that, The reaction module adopts a modular vertical stacking design and is composed of multiple standardized reaction column segments connected together. The flow distribution and collection network is clamped at the flange connection between two adjacent reaction column sections, and an insulating sealing gasket is provided at the sealing point between the flow distribution and collection network and the reaction column section. The insulating sealing gasket is provided between adjacent reaction column sections.

4. The advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water according to claim 1, characterized in that, The flow distribution and collection network is a titanium mesh with a noble metal oxide coating on its surface. As a fluid distributor, the flow distribution and collection network uses the local hydraulic resistance provided by the metal mesh to redistribute the fluid on the cross section, and as an electrochemical current collector, it undertakes electron injection and current collection.

5. The advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water according to claim 1, characterized in that, The measuring ends of the potential sensor and the oxygen sensor are covered with a porous shielding protective sleeve made of polytetrafluoroethylene. The porous shielding sleeve utilizes a microporous structure to allow water phase permeation while blocking solid particles in the composite filler and macroscopic bubbles generated by in-situ electrolysis from contacting the sensor surface.

6. The advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water according to claim 1, characterized in that, The microenvironment diagnostic engine determines the reaction path obstruction state based on the redox potential spatial decay gradient and the dissolved oxygen spatial decay gradient, specifically including: If the absolute value of the redox potential spatial decay gradient exceeds the preset potential decay threshold, the reaction segment is determined to be in a state of blocked free radical pathway.

7. The advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water according to claim 6, characterized in that, The microenvironment diagnostic engine, based on the spatial decay gradient of the redox potential and the spatial decay gradient of dissolved oxygen, further includes the following for determining the blocked reaction path state: If the actual measured dissolved oxygen concentration is lower than the preset minimum oxygen concentration limit and the absolute value of the dissolved oxygen spatial decay gradient exceeds the preset oxygen decay threshold, then the reaction segment is determined to be in a state of non-radical path obstruction.

8. The advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water according to claim 1, characterized in that, The control module instructs the power module to output a pulse waveform that includes a cathode polarization output stage, an anode polarization output stage, and a dead zone buffer time set during the switching of positive and negative polarities, based on the blocked reaction path state. The cathode polarization output stage corresponds to the cathode polarization pulse width, and electron injection is used to reduce the divalent copper ions on the surface of the composite filler to cuprous ions. The anodic polarization output stage corresponds to the anodic polarization pulse width, and nascent oxygen is generated by electrolysis of water.

9. The advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water according to claim 8, characterized in that, The control module calculates the energy ratio between the anodic polarization output stage and the cathodic polarization output stage to obtain the asymmetric energy factor, and allocates unequal voltage amplitudes and unequal pulse durations between the anodic polarization output stage and the cathodic polarization output stage according to the asymmetric energy factor.

10. The advanced oxidation treatment system for broad-spectrum removal of organic pollutants from water according to claim 1, characterized in that, The control module collects the instantaneous pulse voltage parameters and response current parameters output by the power module in real time to calculate the dynamic impedance parameters. When the dynamic impedance parameter is lower than the preset safety impedance threshold and a physical particle bridging short circuit is determined to have occurred, the control module instructs the power module to cut off the current output and triggers the backwashing procedure of the reaction module.

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