Titanium Electrode Group for Wastewater Treatment and Its Application

Abstract

The present invention provides a titanium electrode group for wastewater treatment, which comprises a plurality of titanium electrode units. An insulating layer is provided between two adjacent titanium electrode units. Each titanium electrode unit includes a substrate and a surface coating layer, and the surface coating layer is provided with a microporous nanostructure. The substrate includes titanium and a doped metal. Among them, calculated by weight percentage, the doped metal accounts for 10-30%, and the balance is titanium. The doped metal includes at least one of chromium, nickel, manganese, ruthenium, rhodium, palladium, tantalum, iridium, platinum, and gold. The surface coating layer includes at least one of ruthenium chloride, iridium chloride, tantalum chloride, platinum chloride, palladium chloride, and tungsten chloride. With such a setting, the wastewater treatment effect and treatment efficiency are effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of wastewater treatment, and particularly relates to a titanium electrode group for wastewater treatment and its application. Background Art

[0002] The electrolysis method is a water treatment technology that can effectively decompose harmful substances, remove heavy metals and organic pollutants by triggering redox reactions in wastewater through electrochemical reactions. The electrode group refers to a combined structure including a positive electrode, a negative electrode and a diaphragm in an electrolysis device. The function of the electrode group is to provide a place for chemical reactions, store and release electrical energy through these reactions, and is a key component for charge and ion transfer.

[0003] The titanium electrode group is suitable for application scenarios with high corrosion resistance, long service life and high safety in wastewater treatment. Titanium has extremely strong corrosion resistance, especially in acidic and alkaline environments. Titanium exhibits good mechanical strength and chemical stability under extreme conditions. Even under high temperature or high pressure, the titanium electrode group can still maintain a stable shape and performance and is not easily deformed.

[0004] However, in some wastewater treatment processes (especially wastewater containing high concentrations of chlorides or sulfates), passivation occurs on the surface of the titanium electrode. Passivation forms an oxide protective layer on the electrode surface, resulting in a decrease in the electrochemical activity of the electrode, and as the treatment time increases, the wastewater treatment effect deteriorates and the treatment efficiency decreases. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a titanium electrode group for wastewater treatment and its application, aiming to solve the problem that the wastewater treatment effect of the titanium electrode group deteriorates and the efficiency decreases with the increase of time.

[0006] To solve the above technical problem, the present invention is implemented as follows. A titanium electrode group for wastewater treatment includes a plurality of titanium electrode units. An insulating layer is provided between two adjacent titanium electrode units. Each titanium electrode unit includes a substrate and a surface coating, and the surface coating has a microporous nanostructure;

[0007] The substrate includes titanium and a doped metal. Among them, calculated by weight percentage, the doped metal accounts for 10% - 30%, and the balance is titanium. The doped metal includes at least one of chromium, nickel, manganese, ruthenium, rhodium, palladium, tantalum, iridium, platinum, and gold;

[0008] The surface coating includes at least one of ruthenium chloride, iridium chloride, tantalum chloride, platinum chloride, palladium chloride, and tungsten chloride.

[0009] The present invention provides a preparation method for preparing the titanium electrode group for wastewater treatment as described above. The steps of the preparation method include:

[0010] S1. Prepare a coating sol;

[0011] S2. Perform surface treatment on the substrate;

[0012] S3. Combine the coating sol on the surface of the substrate to form a surface coating, and obtain a titanium electrode unit;

[0013] S4. Assemble a plurality of the titanium electrode units to obtain the titanium electrode group.

[0014] In some embodiments of the present invention, step S1 includes:

[0015] S1.1. Stir and mix a metal salt and an organic solvent to obtain a premixed solution;

[0016] S1.2. Add a surfactant to the premixed solution, and then perform ultrasonic vibration dissolution to obtain the coating sol.

[0017] In some embodiments of the present invention, step S2 includes:

[0018] S2.1. Place the substrate in deionized water, acetone, and ethanol for cleaning in sequence;

[0019] S2.2. Perform sandblasting on the surface of the substrate after cleaning, wherein the sandblasting medium includes at least one of alumina particles, steel sand, and silica particles, and the particle size of the sandblasting medium is 200 - 600 um;

[0020] S2.3. Place the substrate after sandblasting in an etching solution for acid etching to obtain the substrate with surface treatment completed, wherein the etching solution includes at least one of hydrofluoric acid, nitric acid, and hydrochloric acid.

[0021] In some embodiments of the present invention, step S3 includes:

[0022] S3.1. Immerse the substrate with surface treatment completed in the coating sol, and adjust the impregnation temperature to obtain a pre-product;

[0023] S3.2. Place the pre-product in a drying oven for low-temperature drying;

[0024] S3.3. Put the dried pre-product into a high-temperature furnace, set the sintering temperature and time, and cool after sintering to obtain a crude product, wherein the sintering temperature is 300 - 700 °C, and the sintering time is 2 - 4 h;

[0025] S3.4. Place the crude product in deionized water, acetone, and ethanol for cleaning in sequence to obtain the titanium electrode unit.

[0026] In some embodiments of the present invention, step S4 includes:

[0027] S4.1. Control the same size for each of the titanium electrode units and electrically connect the multiple titanium electrode units;

[0028] S4.2. Install an insulating layer between two adjacent titanium electrode units and then fix it on the frame of the titanium electrode group, where the insulating layer includes at least one of polyurethane, silica gel, rubber, and plastic;

[0029] S4.3. Perform encapsulation processing on the multiple titanium electrode units to obtain a titanium electrode group.

[0030] The present invention provides a wastewater treatment device, which is characterized by including an electrolytic cell, a power supply module, a cathode material, and the titanium electrode group for wastewater treatment prepared by the above-mentioned preparation method; wherein,

[0031] A circulating water path and a temperature controller are provided in the electrolytic cell;

[0032] The cathode material includes at least one of graphite, stainless steel, carbon fiber, iron, and nickel;

[0033] The power supply module has the functions of adjusting potential, current, and voltage.

[0034] In some embodiments of the present invention, the power supply module is used to periodically output an oscillation signal to the titanium electrode group and receive the feedback information of the titanium electrode group;

[0035] When the feedback information exceeds the preset range, the power supply module adjusts its initial potential to trigger surface oscillation of the titanium electrode unit to clean the surface coating.

[0036] In some embodiments of the present invention, the preset range is , is the current density under the maximum potential, is the current density under the minimum potential;

[0037] , ; wherein,

[0038] is the current density, is the exchange current density, is the transfer coefficient of the electrode, F is the Faraday constant, R is the gas constant, T is the temperature, is the real-time potential, is the dynamic adjustment part of the DC bias voltage for triggering oscillation, is the amplitude, is the angular frequency.

[0039] Compared with the prior art, the beneficial effects of the titanium electrode group for wastewater treatment and its application in the present invention are as follows:

[0040] The surface of the titanium electrode unit is designed with a microporous nanostructure, which greatly increases the specific surface area of the electrode, thereby increasing the contact area between the electrode and the pollutants in the wastewater, improving the electro-chemical reaction efficiency, and further enhancing the efficiency of wastewater treatment. An insulating layer is provided between adjacent electrode units to prevent short circuits and ensure uniform current distribution. This can reduce side reactions caused by excessive local current and improve the electrolysis efficiency of the entire electrode group.

[0041] The noble metals contained in the surface coating have excellent electrocatalytic activity. These noble metals can effectively promote oxidation-reduction reactions and reduce the formation of passivation films. Noble metals have a low oxidation-reduction potential and are not easily formed into a stable oxide passivation layer. Metal elements with good passivation resistance such as titanium, chromium, and nickel are added to the substrate material. These elements can inhibit the formation of passivation films or keep the passivation films in a relatively loose state under specific conditions, effectively improving the wastewater treatment effect and treatment efficiency. Description of the Drawings

[0042] Figure 1 is a microstructural diagram of the surface layer of the titanium electrode unit in an embodiment of the present invention;

[0043] Figure 2 is a schematic flow chart of the preparation method of the titanium electrode group for wastewater treatment in an embodiment of the present invention;

[0044] Figure 3 is a schematic flow chart of the control method of the wastewater treatment device in an embodiment of the present invention. Detailed Embodiments

[0045] In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0046] Please refer to Figure 1 , the present invention provides a titanium electrode group for wastewater treatment, which includes a plurality of titanium electrode units. An insulating layer is provided between two adjacent titanium electrode units. Each titanium electrode unit includes a substrate and a surface coating, and the surface coating is provided with a microporous nanostructure; the substrate includes titanium and doped metals. Among them, calculated by weight percentage, the doped metals account for 10-30%, and the balance is titanium. The doped metals include at least one of chromium, nickel, manganese, ruthenium, rhodium, palladium, tantalum, iridium, platinum, and gold; the surface coating includes at least one of ruthenium chloride, iridium chloride, tantalum chloride, platinum chloride, palladium chloride, and tungsten chloride.

[0047] The electrode surface is designed with a microporous nanostructure, which greatly increases the specific surface area of the electrode, thereby increasing the contact area between the electrode and the pollutants in the wastewater, enhancing the electro-chemical reaction efficiency, and further improving the efficiency of wastewater treatment. An insulating layer is provided between adjacent electrode units to prevent short circuits and ensure uniform current distribution. This can reduce side reactions caused by excessive local current and improve the electrolysis efficiency of the entire electrode group.

[0048] The noble metals (such as ruthenium, iridium, platinum, etc.) contained in the surface coating have excellent electro-catalytic activity. These noble metals can effectively promote redox reactions and reduce the formation of passivation films. Noble metals have a low redox potential and are not easily formed into stable oxide passivation layers. Anti-passivation metal elements such as titanium, chromium, and nickel are added to the substrate material. These elements can inhibit the formation of passivation films or keep the passivation films in a relatively loose state under specific conditions, making it easy to remove or inhibit their growth through electro-chemical means, effectively improving the wastewater treatment effect and treatment efficiency.

[0049] Please refer to Figure 2 , the present invention proposes a preparation method for preparing a titanium electrode group for wastewater treatment. The steps of the preparation method include:

[0050] S1. Prepare a coating sol.

[0051] S1.1. Stir and mix a metal salt with an organic solvent to obtain a premixed solution; wherein, the metal salt includes at least one of ruthenium chloride, iridium chloride, and tantalum chloride, and the organic solvent includes at least one of ethanol, isopropanol, and n-butanol.

[0052] Through stirring and mixing, the metal salt can be uniformly dispersed in the organic solvent, ensuring the uniformity of the distribution of metal ions during the sol formation process. A uniform solution helps the subsequent uniform deposition of the coating and improves the performance and consistency of the coating. The stirring process not only helps with physical mixing but also promotes the chemical reaction between the metal salt and the organic solvent, forming a stable solution system. This is an important basis for the subsequent formation of the sol and the final coating.

[0053] Metal chlorides are easily soluble in organic solvents such as ethanol or isopropanol. This solubility helps to form a uniform solution, ensuring the uniform distribution of metal ions in the solution and thus their uniform deposition on the substrate surface during the coating preparation process. This is crucial for the uniformity and performance of the final coating.

[0054] During subsequent heat treatment or electro-chemical reactions, metal chlorides can decompose rapidly to form corresponding metal oxides or active metal layers. For example, ruthenium chloride can decompose during heat treatment to form a ruthenium oxide coating with high electro-catalytic activity.

[0055] The by-products generated during the thermal decomposition of metal chlorides are hydrogen chloride or chlorine, which can be removed at relatively low temperatures without leaving a large amount of residue, avoiding problems that affect the quality of the electrode coating. This makes the coating preparation process cleaner and more controllable.

[0056] S1.2. Add a surfactant to the premixed solution, and then perform ultrasonic vibration dissolution to obtain a coating sol. Among them, the surfactant includes at least one of polyethylene glycol, sodium dodecyl sulfate, and polyvinylpyrrolidone.

[0057] The addition of the surfactant can effectively reduce the surface tension in the solution, stabilize the dispersion state of the metal salt, and prevent the particles in the sol from aggregating or settling. This ensures that the sol can remain uniform and stable during the subsequent coating process, which is beneficial to the formation of a uniform coating.

[0058] Ultrasonic vibration can effectively disperse the particles in the solution, further refine the metal oxide particles in the coating, and ensure their uniform deposition on the substrate surface. This helps to form a dense and uniform coating, improving the electrocatalytic activity and corrosion resistance of the electrode surface.

[0059] Ultrasonic vibration can also promote the fine particles in the sol to form a uniform distribution, optimizing the microstructure of the final coating. In this way, a coating with good porosity and structural stability can be formed, thereby improving the performance of the electrode, such as enhancing the current density and reducing the risk of passivation.

[0060] The role of ultrasonic waves can accelerate the dissolution process of metal salts and improve the dissolution efficiency. At the same time, ultrasonic vibration can make the sol more uniform, prevent the problem of local high concentration, and further optimize the quality and performance of the coating.

[0061] S2. Surface treat the substrate.

[0062] S2.1. Place the substrate in deionized water, acetone, and ethanol for cleaning in sequence;

[0063] By using deionized water, acetone, and ethanol in sequence, the oil stains, dust, organic substances, and other impurities on the substrate surface can be effectively removed, ensuring the cleanliness of the substrate surface. This is the prerequisite for the uniform deposition of the coating and can improve the adhesion between the coating and the substrate.

[0064] The use of deionized water can prevent ions or other impurities in the water from adhering to the substrate surface. Acetone and ethanol, as organic solvents, can dissolve oils and organic pollutants and volatilize quickly, avoiding the residue of liquid or sediment on the substrate surface and ensuring the pure state of the surface in subsequent treatments.

[0065] Each cleaning step targets different types of contaminants to prevent the reattachment of residual contaminants to the substrate surface in subsequent steps. For example, grease may still remain on the substrate surface after deionized water cleaning, and this grease is further removed by acetone.

[0066] S2.2. Perform sandblasting on the surface of the cleaned substrate. Among them, the sandblasting medium includes at least one of alumina particles, steel grit, and silica particles, and the particle size of the sandblasting medium is 200 - 600 μm, which can be 300 μm or 500 μm, for example.

[0067] Sandblasting roughens the substrate surface through mechanical impact, creating a microporous structure or micro - protrusions on the substrate surface. This change in surface topography increases the surface area of the substrate, helps the coating adhere more firmly to the substrate surface, and improves the mechanical bonding force of the coating.

[0068] Sandblasting can produce microscopic grooves and textures on the substrate surface. These roughened structures contribute to the physical interlocking of the coating, thereby enhancing the adhesion between the coating and the substrate and reducing the risk of coating peeling during use.

[0069] S2.3. Place the sandblasted substrate in an etching solution for acid etching to obtain a substrate with surface treatment completed. Among them, the etching solution includes at least one of hydrofluoric acid, nitric acid, and hydrochloric acid.

[0070] After sandblasting, acid etching is used to further finely adjust the surface topography, remove the oxide layer or other impurities on the surface, and further increase the surface micro - roughness. This helps to form a surface structure that is more conducive to coating adhesion.

[0071] During the acid etching process, the acid solution can activate the substrate surface, forming a highly reactive surface layer. This surface activity can promote chemical bonding between the metal oxide coating and the substrate during subsequent coating processes, improving the adhesion performance and stability of the coating.

[0072] Etching with one or more of hydrofluoric acid, nitric acid, or hydrochloric acid can effectively remove the natural oxide layer on the titanium substrate surface and simultaneously generate a new activated surface. This activated surface not only improves the physical adhesion of the coating but also provides chemical bonding sites through chemical etching, promoting chemical bonding between the coating and the substrate and further enhancing the durability and electrochemical performance of the electrode.

[0073] S3. Combine the coating sol on the surface of the substrate to form a surface coating, obtaining a titanium electrode unit.

[0074] By using the sol-gel method to deposit a coating sol on the surface of the substrate, a uniform surface coating is formed, which helps to improve the electrochemical performance, corrosion resistance and stability of the electrode. This method is suitable for preparing a thin film layer with a microporous structure, enhancing the catalytic efficiency of the electrode during the wastewater treatment process.

[0075] The sol-gel method can deposit a uniform and dense coating on the surface of a substrate with a complex geometry, and a coating can be formed even in tiny depressions or pores, improving the overall performance of the electrode. The sol-gel method can introduce various functional materials (such as metal oxides, conductive polymers, etc.) into the coating to achieve the multi-functionalization of the coating and meet the requirements in different wastewater treatment environments.

[0076] Compared with other coating preparation methods, the sol-gel method requires a lower temperature and can obtain a good oxide coating at a relatively low sintering temperature, reducing the adverse effects of high temperature on the substrate material. This method can precisely control the microstructure of the coating by adjusting the solution formulation, drying and sintering conditions, especially to form a coating with a nano-porous or microporous structure. This structure helps to enhance the electro-chemical reaction activity of the electrode, especially showing outstanding performance in catalytic and wastewater treatment applications.

[0077] S3.1. Immerse the surface-treated substrate in the coating sol and adjust the dipping temperature to obtain a pre-product. The dipping temperature is 40 - 80°C, which can improve the permeability of the solution and help the coating material to deposit better on the surface of the substrate. However, it should be noted to avoid the rapid volatilization of the solvent, which may cause the coating to be uneven or defective.

[0078] During the dipping process, by adjusting the dipping temperature and time, ensure that the coating sol evenly covers the surface of the substrate, avoiding uneven or too thin or too thick coatings and ensuring the consistency of the electrode performance.

[0079] The control of temperature helps to adjust the viscosity and permeability of the coating sol, thereby affecting the thickness and structure of the coating, enabling the coating to adhere evenly to the surface of the substrate and form a stable pre-product.

[0080] S3.2. Place the pre-product in an oven for low-temperature drying. The temperature for low-temperature drying is 40 - 60°C.

[0081] Low-temperature drying is suitable for avoiding coating cracking or unevenness caused by the rapid volatilization of the solvent. It is especially suitable for use when the coating thickness is relatively thin or the sol viscosity is relatively high. Low-temperature drying can slowly evaporate the organic solvent in the sol, preventing the formation of cracks, bubbles or holes due to rapid evaporation, ensuring the smooth and dense surface of the coating and enhancing the stability of the coating. The nano-scale pore structure in the coating can be retained during the low-temperature drying process, enabling the final coating to have good electrochemical performance, especially improving the catalytic activity and reaction efficiency.

[0082] S3.3. Put the dried pre-product into a high-temperature furnace, set the sintering temperature and time, and cool it after sintering to obtain the crude product. Among them, the sintering temperature is 300 - 700 °C, and the sintering time is 2 - 4 h.

[0083] Sintering at an appropriate temperature can promote chemical reactions in the coating, form a stable oxide coating, enhance the bonding force between the coating and the substrate, and improve the wear resistance and corrosion resistance of the electrode.

[0084] Sintering can cause the particles in the coating to melt and crystallize, forming a dense and stable crystal structure, improving the mechanical strength and electrical conductivity of the coating, and ensuring the long-term use performance of the electrode in wastewater treatment.

[0085] S3.4. Place the crude product in deionized water, acetone, and ethanol for cleaning in sequence to obtain the titanium electrode unit.

[0086] After sintering, some by-products or unreacted substances may remain on the surface. These impurities are removed by sequential cleaning to ensure the cleanliness of the electrode surface and avoid the influence of impurities on the electrode performance during use.

[0087] Through cleaning, while keeping the surface clean, it can also activate the surface, enabling the electrode to play a catalytic and electrolytic role more efficiently during wastewater treatment.

[0088] S4. Assemble multiple titanium electrode units to obtain a titanium electrode group.

[0089] S4.1. Control the same size for each titanium electrode unit and make electrical connections for multiple titanium electrode units.

[0090] Ensuring the same size for each titanium electrode unit can ensure uniform current distribution in each electrode unit, avoiding the situation where the current density is too high or too low in some units due to size deviation, thereby affecting the overall electrolysis efficiency.

[0091] By making electrical connections for multiple electrode units, the working area and electrolysis capacity of the entire electrode group can be increased, meeting the needs of different scales of wastewater treatment and improving the treatment efficiency.

[0092] S4.2. Install an insulating layer between two adjacent titanium electrode units and then fix them on the frame of the titanium electrode group. Among them, the insulating layer includes at least one of polyurethane, silica gel, rubber, and plastic.

[0093] The installation of the insulating layer can effectively prevent short circuits between adjacent electrode units, thus ensuring the safety and stability during the electrolysis process. Selecting materials such as polyurethane, silica gel, rubber, and plastic as the insulating layer, these materials have good corrosion resistance and electrical insulation properties, which are suitable for the harsh environment of wastewater treatment.

[0094] Fixing the titanium electrode units to the frame can maintain the structural stability of the entire electrode group, ensuring that the electrodes do not loosen or displace during the wastewater treatment process, and avoiding failures caused by mechanical vibrations or fluid flows.

[0095] S4.3. Encapsulate multiple titanium electrode units to obtain a titanium electrode group.

[0096] Encapsulation can effectively protect the electrode units and connection structures inside the electrode group from being eroded by the external environment (such as water flow, acidic and alkaline wastewater), and extend the service life of the electrode group.

[0097] Encapsulation can also prevent gases or impurities generated during the electrolysis process from entering the inside of the electrode group, maintain the cleanliness and functional stability of the electrode group, and reduce maintenance work.

[0098] In one embodiment, the present invention also proposes a wastewater treatment device, including an electrolytic cell, a power supply module, a cathode material, and a titanium electrode group for wastewater treatment; wherein, a circulating water path and a temperature controller are provided inside the electrolytic cell; the cathode material includes at least one of graphite, stainless steel, carbon fiber, iron, and nickel; the power supply module has the functions of adjusting potential, current, and voltage.

[0099] The circulating water path ensures the uniform flow of wastewater in the electrolytic cell, avoids excessive pollutant concentration in local areas, and improves the wastewater treatment efficiency. At the same time, the flow can reduce the bubbles and deposits generated on the electrode surface, ensure that the electrode surface is always exposed to the wastewater, and improve the electrolysis efficiency.

[0100] The temperature controller can maintain the temperature inside the electrolytic cell within an appropriate range during the wastewater treatment process, prevent the temperature from being too high or too low from affecting the electro-chemical reaction rate. The temperature controller can also reduce the thermal stress of the electrode material and extend the service life of the equipment.

[0101] Different cathode materials have different electrical conductivities, corrosion resistances, and economic selections. The introduction of these materials enables the device to be customized according to different wastewater treatment requirements. For example, graphite and carbon fiber have good electrical conductivity and corrosion resistance, and stainless steel is widely used due to its high strength and corrosion resistance.

[0102] By adjusting the potential, current, and voltage, the power supply module can optimize the energy consumption and reaction rate during the electrolysis process, and improve the efficiency of wastewater treatment. For example, a higher potential can promote the occurrence of redox reactions and accelerate the degradation of pollutants; while adjusting the current can precisely control the power consumption during the treatment process and avoid waste.

[0103] The requirements for electrolysis conditions in different wastewater treatment scenarios are not the same. By adjusting the power supply parameters, the intelligent and refined control of wastewater treatment can be realized to ensure that the treatment results meet the expected goals.

[0104] During the wastewater treatment process, the titanium electrode group acts as the anode. First, an oxidation reaction occurs. Organic pollutants in the wastewater are oxidized and decomposed into harmless small molecules or carbon dioxide at the anode. Heavy metal ions in the wastewater undergo an oxidation reaction at the anode to form precipitates or other forms for subsequent treatment. A reduction reaction occurs on the cathode material, and some heavy metal ions are reduced to insoluble precipitates at the cathode, facilitating separation and recovery.

[0105] The wastewater in the electrolytic cell is evenly distributed between the titanium electrode group and the cathode material through a circulating water path. At the anode, pollutants are oxidized; at the cathode, side reactions such as hydrogen generation or metal deposition occur. After a period of time, harmful substances in the wastewater are converted into harmless substances or precipitates that are easy to remove, thus achieving a purification effect.

[0106] In an embodiment of the present invention, the power supply module is used to periodically output an oscillation signal to the titanium electrode group and receive feedback information from the titanium electrode group;

[0107] When the feedback information exceeds the preset range, the power supply module adjusts its initial potential to trigger surface oscillation of the titanium electrode unit to clean the surface coating.

[0108] Please refer to Figure 3 , the present invention also proposes a control method for controlling the wastewater treatment device. The steps of the control method include:

[0109] Step 101: Set the initial power supply data of the titanium electrode group, where the initial power supply data includes the initial potential and the current density.

[0110] By setting the initial power supply data of the titanium electrode group, it is ensured that the wastewater treatment device can operate with optimal electrochemical parameters at startup. The selection of the initial potential and the current density can affect the activity of the titanium electrode, thereby improving the degradation efficiency of pollutants and reducing energy consumption.

[0111] Step 102: Set a test period to output an oscillation signal and record the feedback information of the current density, where the feedback information includes the fluctuation amplitude of the current density.

[0112] By setting a test period and outputting an oscillation signal, the working state of the titanium electrode group can be monitored in real time. Recording the feedback information of the current density can capture subtle changes in the electrochemical reaction, which helps to judge the active state of the electrode surface and its impact on the treatment efficiency. This process can ensure that the electrode operates in the best working state and avoid performance degradation or efficiency loss.

[0113] Step 103: Determine whether the feedback information is within the preset range.

[0114] If the feedback information is not within the preset range, step 104 is executed. If the feedback information is within the preset range, step 102 is executed.

[0115] Step 104: Adjust the initial potential to trigger surface oscillations of the titanium electrode unit.

[0116] When the feedback information does not reach the preset range, triggering the oscillation on the surface of the titanium electrode by adjusting the initial potential helps to reactivate the electrode surface and improve its electrochemistry reaction ability. This adjustment mechanism ensures that the electrode can maintain high degradation ability during operation, thereby enhancing the overall effect of wastewater treatment.

[0117] If the feedback information is within the preset range, it indicates that the titanium electrode group is working in an ideal state. Continuing to execute the output and monitoring of the test cycle can stably maintain the performance of the treatment device. This mechanism of continuous monitoring and adjustment ensures the automated operation of the system, making the wastewater treatment process more efficient and reliable.

[0118] Specifically, the preset range is ; where

[0119] , ;

[0120] is the current density, is the current density under the maximum potential, is the current density under the minimum potential, is the exchange current density, is the transfer coefficient of the electrode. In this embodiment, is 0.3 - 0.7, for example, it can be 0.5.

[0121] F is the Faraday constant, F = 96485 C / mol, R is the gas constant, R = 8.314 J / (mol·K), T is the temperature, is the real-time potential, is the dynamic adjustment part of the DC bias voltage, used to trigger oscillations, is the amplitude, is the angular frequency.

[0122] By dynamically adjusting the electrode potential , a time-dependent change in the current density is introduced. This change can be used to enhance the reaction activity on the electrode surface, thereby improving the treatment efficiency of the wastewater treatment device.

[0123] indicates that the electrode potential fluctuates sinusoidally with time, thereby triggering a periodic change in the current density, which may bring about an improvement in the electrochemistry reaction efficiency.

[0124] The intensity of oscillation is adjusted by increasing or decreasing A. This affects the activation degree of the reaction on the electrode surface, thereby regulating the activity of the electrode and the treatment effect. A can be 0.01 - 0.1V, which is dimensionless.

[0125] By adjusting ω, the oscillation frequency can be changed, thereby controlling the change rate of the current density, which can make the response time of the system adapt to different treatment requirements. ω can be 1 - 100 rad / s.

[0126] The adjustment of the oscillation frequency (ω) and amplitude (A) can flexibly respond to different types of wastewater and different concentrations of pollutants. For example, when treating high - concentration organic wastewater, appropriately increasing A and ω can stimulate higher surface activity and accelerate degradation; while in the treatment of low - concentration wastewater, the oscillation parameters can be adjusted to reduce energy consumption. After combining with the microporous nanostructure, the titanium electrode unit can better meet the requirements of different wastewater treatment scenarios and improve the treatment adaptability.

[0127] The periodic fluctuation of the current density (oscillation induced by a sinusoidal potential) makes the surface reaction conditions of the titanium electrode unit change continuously, promoting the periodic adsorption and desorption of the surface activity and reactants (such as organic pollutants, heavy metal ions). After combining with the microporous nanostructure, the titanium electrode unit can accommodate more pollutants into the internal reaction zone of the microporous nanostructure, contributing to a more thorough decomposition and removal of organic pollutants.

[0128] The existence of the microporous nanostructure enables the surface of the titanium electrode unit to maintain a high activity during long - term operation. When the activity of the titanium electrode unit surface decreases due to the accumulation of pollutants or the generation of reaction by - products, the periodic change of the current density caused by the sinusoidal oscillation can promote the self - cleaning and de - passivation of the surface substances, effectively reducing the passivation phenomenon on the surface of the titanium electrode unit. In addition, the microporous nanostructure allows more electrolytes to enter, thereby enhancing the reaction activity and regeneration ability of the titanium electrode unit.

[0129] The microporous nanostructure on the surface of the titanium electrode unit can promote the flow of the electrolyte solution, reducing the probability of depositing pollutants or by - products on the surface of the titanium electrode unit. At the same time, the introduction of periodic oscillation can further prevent the deposition of pollutants on the surface of the titanium electrode unit, effectively reducing the pollution and fouling of the titanium electrode unit and extending the service life of the titanium electrode unit. This is particularly important for wastewater treatment devices operating continuously for a long time.

[0130] For wastewater containing heavy metals, the microporous nanostructure can improve the adsorption capacity of the titanium electrode unit and enhance the electrochemical reduction ability of the titanium electrode unit through oscillation, making it easier for heavy metal ions to be reduced to elemental substances or precipitate on the surface of the titanium electrode unit, and then removed from the water. Oscillation can also promote the renewal of the microenvironment on the surface of the titanium electrode unit, avoiding reaction passivation caused by excessive enrichment of heavy metal ions on the surface of the titanium electrode unit.

[0131] By periodically outputting oscillation signals and recording feedback information, the system can adjust the reaction conditions on the surface of the titanium electrode unit according to the fluctuations of the real-time current density. The combination of the microporous nanostructure makes this adjustment more efficient, and the reaction state on the surface of the titanium electrode unit can quickly respond to the changes of the system, maintaining a long-term stable wastewater treatment effect.

[0132] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A control method for a wastewater treatment device, characterized in that the steps include: Step 101, setting initial power supply data of the titanium electrode group, wherein the initial power supply data includes initial potential and current density; Step 102, setting a test period to output an oscillation signal and recording feedback information of current density, wherein the feedback information includes a fluctuation amplitude of current density; Step 103, determining whether the feedback information is within a preset range, if the feedback information is not within the preset range, executing step 104, if the feedback information is within the preset range, executing step 102; Step 104, adjusting the initial potential to induce surface oscillation of the titanium electrode unit; The default range is ;in, ， ； is the current density, is the current density at maximum potential, is the current density at the minimum potential, is the exchange current density, is the transfer coefficient of the electrode, is 0.3~0.7, F is Faraday constant, F=96485 C / mol, R is gas constant, R=8.314J / (mol·K), T is temperature, is the real-time potential, It is the dynamic adjustment part of DC bias, used to induce oscillation. is the amplitude, is the angular frequency; The wastewater treatment device comprises an electrolytic cell, a power module, a cathode material and a titanium electrode group for wastewater treatment; wherein, The electrolytic cell is provided with a circulating water circuit and a temperature controller; The cathode material includes at least one of graphite, stainless steel, carbon fiber, iron, and nickel; The power module has the function of adjusting potential, current and voltage; The titanium electrode group for wastewater treatment comprises a plurality of titanium electrode units, an insulating layer is provided between two adjacent titanium electrode units, each of the titanium electrode units comprises a substrate and a surface coating, and the surface coating is provided with a microporous nanostructure; The matrix includes titanium and a doping metal, wherein the doping metal accounts for 10-30% by weight, and the balance is the titanium, and the doping metal includes at least one of chromium, nickel, manganese, ruthenium, rhodium, palladium, tantalum, iridium, platinum, and gold; The surface coating includes at least one of ruthenium chloride, iridium chloride, tantalum chloride, platinum chloride, palladium chloride and tungsten chloride.

2. The control method of a wastewater treatment device according to claim 1, characterized in that: The steps of the method for preparing a titanium electrode group for wastewater treatment include: S1, preparing coating sol; S2, performing surface treatment on the substrate; S3, combining the coating sol on the surface of the substrate to form a surface coating to obtain a titanium electrode unit; S4. Assemble a plurality of the titanium electrode units to obtain the titanium electrode group.

3. The control method of a wastewater treatment device according to claim 2, characterized in that: The step S1 comprises: S1.1, stirring and mixing the metal salt and the organic solvent to obtain a premixed solution; S1.

2. Add a surfactant to the premixed solution, and then dissolve it by ultrasonic vibration to obtain the coating sol.

4. The control method of a wastewater treatment device according to claim 3, characterized in that: The step S2 comprises: S2.1, washing the substrate in deionized water, acetone and ethanol in sequence; S2.2, performing sandblasting on the surface of the cleaned substrate, wherein the sandblasting medium comprises at least one of aluminum oxide particles, steel sand, and silicon dioxide particles, and the particle size of the sandblasting medium is 200-600; S2.3, placing the substrate after sandblasting in an etching solution for acid etching to obtain the substrate with surface treatment, wherein the etching solution includes at least one of hydrofluoric acid, nitric acid, and hydrochloric acid.

5. A control method for a wastewater treatment device according to claim 4, characterized in that: The step S3 comprises: S3.1, immersing the substrate after surface treatment into the coating sol, adjusting the immersion temperature, and obtaining a pre-product; S3.2, placing the pre-product in a drying oven for low-temperature drying; S3.3, placing the dried pre-product into a high temperature furnace, setting the sintering temperature and time, and cooling after sintering to obtain a crude product, wherein the sintering temperature is 300-700°C, and the sintering time is 2-4h; S3.

4. The crude product is sequentially washed in deionized water, acetone and ethanol to obtain the titanium electrode unit.

6. A control method for a wastewater treatment device according to claim 5, characterized in that: The step S4 comprises: S4.

1. Control the size of each titanium electrode unit to be the same, and electrically connect the multiple titanium electrode units; S4.2, installing an insulating layer between two adjacent titanium electrode units, and then fixing them on the frame of the titanium electrode group, wherein the insulating layer includes at least one of polyurethane, silicone, rubber, and plastic; S4.

3. Packaging the plurality of titanium electrode units to obtain a titanium electrode group.

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