Titanium electrode group for wastewater treatment and application thereof

Abstract

The invention provides a titanium electrode group for wastewater treatment, which comprises a plurality of titanium electrode units, an insulating layer is arranged between every two adjacent titanium electrode units, each titanium electrode unit comprises a substrate and a surface coating, and the surface coating is provided with a microporous nano structure; the matrix comprises titanium and doped metal, the doped metal accounts for 10-30% by weight, the balance is titanium, and the doped metal comprises at least one of chromium, nickel, manganese, ruthenium, rhodium, palladium, tantalum, iridium, platinum and gold; and the surface coating comprises at least one of ruthenium chloride, iridium chloride, tantalum chloride, platinum chloride, palladium chloride and tungsten chloride. Through the arrangement, the wastewater treatment effect and treatment efficiency are effectively improved.

Description

Technical Field

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

[0002] Electrolysis is a water treatment technology that can effectively decompose harmful substances and remove heavy metals and organic pollutants by inducing redox reactions in wastewater through electrochemical reactions. The electrode group refers to the combined structure of the positive electrode, negative electrode and diaphragm in the 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] Titanium electrode groups are suitable for applications in wastewater treatment that require high corrosion resistance, long life, and high safety. 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 chloride or sulfate), the surface of the titanium electrode will be passivated. Passivation will form an oxide protective layer on the electrode surface, resulting in a decrease in the electrochemical activity of the electrode, resulting in a worsening of the wastewater treatment effect and a decrease in treatment efficiency as the treatment time increases. 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 and efficiency of the titanium electrode group deteriorate with time.

[0006] To solve the above technical problems, the present invention is implemented as follows: a titanium electrode group for wastewater treatment, comprising 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.

[0007] The present invention provides a preparation method for preparing the titanium electrode group for wastewater treatment as described above, the preparation method comprising the steps of: 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.

[0008] In some embodiments of the present invention, 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.

[0009] In some embodiments of the present invention, step S2 includes: 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 μm; S2.3, placing 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.

[0010] In some embodiments of the present invention, step S3 includes: 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.

[0011] In some embodiments of the present invention, step S4 includes: 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.

[0012] The present invention provides a wastewater treatment device, characterized in that it comprises an electrolytic cell, a power module, a cathode material and the titanium electrode group for wastewater treatment made by the preparation method as described above; 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 supply module has the function of adjusting potential, current and voltage.

[0013] In some embodiments of the present invention, the power module is used to periodically output an oscillation signal to the titanium electrode group and receive feedback information from the titanium electrode group; When the feedback information exceeds a preset range, the power module adjusts its initial potential to induce surface oscillation of the titanium electrode unit to clean the surface coating.

[0014] In some embodiments of the present invention, the preset range is , is the current density at maximum potential, is the current density at the minimum potential; , ;in, 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, It is the dynamic adjustment part of DC bias, used to induce oscillation. is the amplitude, is the angular frequency.

[0015] Compared with the prior art, the titanium electrode group for wastewater treatment and its application in the present invention have the following beneficial effects: 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 efficiency of the electrochemical reaction, and thus improving the efficiency of wastewater treatment. An insulating layer is set 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.

[0016] The precious metals contained in the surface coating have excellent electrocatalytic activity. These precious metals can effectively promote redox reactions and reduce the formation of passivation films. Precious metals have low redox potentials and are not easy to form stable oxide passivation layers. Metal elements with good anti-passivation properties such as titanium, chromium, and nickel are added to the matrix material. These elements can inhibit the formation of passivation films or keep the passivation films in a relatively loose state under certain conditions, effectively improving the wastewater treatment effect and efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is a microscopic structure diagram of the surface layer of the titanium electrode unit in one embodiment of the present invention; Figure 2 is a schematic flow chart of a method for preparing a titanium electrode group for wastewater treatment in one embodiment of the present invention; Figure 3 It is a flow chart of a control method of a wastewater treatment device in one embodiment of the present invention. DETAILED DESCRIPTION

[0018] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0019] Please refer to Figure 1 The present invention provides a titanium electrode group for wastewater treatment, comprising a plurality of titanium electrode units, an insulating layer is provided between two adjacent titanium electrode units, each titanium electrode unit comprises a substrate and a surface coating, the surface coating is provided with a microporous nanostructure; the substrate comprises titanium and a doped metal, wherein, calculated by weight percentage, the doped metal accounts for 10-30%, and the remainder is titanium, and the doped metal comprises at least one of chromium, nickel, manganese, ruthenium, rhodium, palladium, tantalum, iridium, platinum, and gold; the surface coating comprises at least one of ruthenium chloride, iridium chloride, tantalum chloride, platinum chloride, palladium chloride, and tungsten chloride.

[0020] 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, improving the efficiency of the electrochemical reaction, and thus improving the efficiency of wastewater treatment. An insulating layer is set 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.

[0021] The precious metals (such as ruthenium, iridium, platinum, etc.) contained in the surface coating have excellent electrocatalytic activity. These precious metals can effectively promote redox reactions and reduce the formation of passivation films. Precious metals have low redox potentials and are not easy to form stable oxide passivation layers. Metal elements with good anti-passivation properties such as titanium, chromium, and nickel are added to the matrix material. These elements can inhibit the formation of passivation films or keep the passivation films in a relatively loose state under certain conditions, making them easy to remove or inhibit their growth by electrochemical means, effectively improving the wastewater treatment effect and efficiency.

[0022] Please refer to Figure 2 The present invention provides a preparation method for preparing a titanium electrode group for wastewater treatment, and the steps of the preparation method include: S1. preparing coating sol.

[0023] S1.1. Stir and mix the metal salt and the 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.

[0024] By stirring and mixing, the metal salt can be evenly dispersed in the organic solvent, ensuring the uniform distribution of metal ions during the sol formation process. A uniform solution helps the uniform deposition of the subsequent coating and improves the performance and consistency of the coating. The stirring process not only helps physical mixing, but also promotes the chemical reaction between the metal salt and the organic solvent to form a stable solution system. This is an important basis for the subsequent formation of the sol and the final coating.

[0025] Metal chlorides are readily soluble in organic solvents such as ethanol or isopropanol. This solubility helps to form a homogeneous solution, ensuring that the metal ions are evenly distributed in the solution and thus deposited evenly on the substrate surface during the coating preparation process. This is critical to the uniformity and performance of the final coating.

[0026] During subsequent heat treatment or electrochemical reaction, metal chlorides can quickly decompose 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 electrocatalytic activity.

[0027] The byproducts generated by the thermal decomposition of metal chlorides are hydrogen chloride or chlorine gas, which can be removed at a lower temperature without leaving a large amount of residue, thus avoiding the problem of affecting the quality of the electrode coating. This makes the coating preparation process cleaner and more controllable.

[0028] S1.2, adding a surfactant to the premixed solution, and then dissolving it by ultrasonic vibration to obtain a coating sol, wherein the surfactant includes at least one of polyethylene glycol, sodium lauryl sulfate, and polyvinyl pyrrolidone.

[0029] The addition of surfactants 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 conducive to the formation of a uniform coating.

[0030] 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.

[0031] Ultrasonic vibrations can also promote the uniform distribution of fine particles in the sol and optimize 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 increasing the current density and reducing the risk of passivation.

[0032] Ultrasonic waves can accelerate the dissolution process of metal salts and improve dissolution efficiency. At the same time, ultrasonic vibration can make the sol more uniform, prevent the problem of excessive local concentration, and further optimize the quality and performance of the coating. S2. Surface treatment substrate.

[0033] S2.1. Wash the substrate in deionized water, acetone and ethanol in turn; By using deionized water, acetone and ethanol in sequence, oil, dust, organic matter and other impurities on the substrate surface can be effectively removed to ensure the substrate surface is clean. This is the premise for uniform deposition of the coating and can improve the bonding strength between the coating and the substrate.

[0034] The use of deionized water can prevent ions or other impurities in the water from adhering to the surface of the substrate. Acetone and ethanol, as organic solvents, can dissolve grease and organic pollutants and evaporate quickly to avoid residual liquid or sediment on the surface of the substrate, ensuring the purity of the surface in subsequent treatments.

[0035] Each cleaning step targets different types of contaminants to prevent residual contaminants from reattaching to the substrate surface in subsequent steps. For example, after deionized water cleaning, there may still be residual grease on the substrate surface, which is further removed by acetone.

[0036] S2.2. The surface of the cleaned substrate is sandblasted, wherein the sandblasting medium includes at least one of aluminum oxide particles, steel sand, and silicon dioxide particles, and the particle size of the sandblasting medium is 200-600 um, for example, 300 um or 500 um.

[0037] Sandblasting roughens the substrate surface through mechanical impact, creating microporous structures or micro-protrusions on the substrate surface. This change in surface morphology 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.

[0038] Sandblasting can produce microscopic grooves and textures on the surface of the substrate. These roughened structures help the physical embedding of the coating, thereby enhancing the adhesion between the coating and the substrate and reducing the risk of coating peeling during use.

[0039] S2.3, placing the substrate after sandblasting in an etching solution for acid etching to obtain a substrate with a surface treatment, wherein the etching solution includes at least one of hydrofluoric acid, nitric acid, and hydrochloric acid.

[0040] After sandblasting, the surface morphology is further fine-tuned by acid etching to 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.

[0041] During the acid etching process, the acid solution can activate the substrate surface and form a highly active surface layer. This surface activity can promote the chemical bonding between the metal oxide coating and the substrate in the subsequent coating process, improving the adhesion and stability of the coating.

[0042] Etching with one or more of hydrofluoric acid, nitric acid or hydrochloric acid can effectively remove the natural oxide layer on the surface of the titanium substrate and generate a new activated surface. This activated surface not only improves the physical adhesion of the coating, but also provides chemical binding sites through chemical etching, promotes chemical bonding between the coating and the substrate, and further enhances the durability and electrochemical performance of the electrode.

[0043] S3, combining the coating sol on the surface of the substrate to form a surface coating to obtain a titanium electrode unit.

[0044] The coating sol is deposited on the substrate surface by the sol-gel method to form a uniform surface coating, 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 to enhance the catalytic efficiency of the electrode in the wastewater treatment process.

[0045] The sol-gel method can deposit a uniform and dense coating on the surface of a substrate with complex geometry, and can form a coating even in tiny depressions or pores, thereby improving the overall performance of the electrode. The sol-gel method can introduce a variety of functional materials (such as metal oxides, conductive polymers, etc.) into the coating to achieve multifunctionality of the coating and meet the needs of different wastewater treatment environments.

[0046] 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 forming a coating with nanopores or microporous structures. This structure helps to enhance the electrochemical reaction activity of the electrode, especially in catalysis and wastewater treatment applications.

[0047] S3.1. Immerse the surface treated substrate in the coating sol and adjust the immersion temperature to obtain a pre-product. The immersion temperature is 40 ~ 80℃, which can improve the permeability of the solution and help the coating material to deposit better on the substrate surface. However, care should be taken to avoid excessive evaporation of the solvent, which may lead to uneven coating or defects.

[0048] During the impregnation process, the impregnation temperature and time are adjusted to ensure that the coating sol is evenly covered on the substrate surface, avoiding uneven coating or too thin or too thick coating, thereby ensuring the consistency of electrode performance.

[0049] Temperature control helps to adjust the viscosity and permeability of the coating sol, thereby affecting the thickness and structure of the coating, so that the coating can be evenly attached to the surface of the substrate to form a stable pre-product.

[0050] S3.2, place the pre-product in a drying oven for low temperature drying at a temperature of 40-60°C.

[0051] Low temperature drying is suitable for avoiding cracking or uneven coating caused by rapid volatilization of solvent. It is especially suitable for use when the coating thickness is thin or the viscosity of the sol is high. Low temperature drying can slowly evaporate the organic solvent in the sol, prevent rapid evaporation from causing cracking, bubbles or holes in the coating, ensure a smooth and dense coating surface, and enhance the stability of the coating. The nano-scale pore structure in the coating can be retained during the low temperature drying process, so that the final coating has good electrochemical properties, especially improving catalytic activity and reaction efficiency.

[0052] S3.3. Place the dried pre-product into a high-temperature furnace, set the sintering temperature and time, and cool it after sintering to obtain a crude product. The sintering temperature is 300-700°C and the sintering time is 2-4h.

[0053] Sintering at an appropriate temperature can promote chemical reactions in the coating, form a stable oxide coating, and enhance the bonding force between the coating and the substrate, thereby improving the wear resistance and corrosion resistance of the electrode.

[0054] Sintering can melt and crystallize the particles in the coating to form a dense and stable crystal structure, improve the mechanical strength and conductivity of the coating, and ensure the long-term performance of the electrode in wastewater treatment.

[0055] S3.4. Wash the crude product in deionized water, acetone and ethanol in turn to obtain a titanium electrode unit.

[0056] After sintering, some by-products or unreacted substances may remain on the surface. These impurities can be removed by cleaning in sequence to ensure that the electrode surface is clean and avoid impurities affecting the electrode performance during use.

[0057] By cleaning, the surface is kept clean and activated, allowing the electrodes to perform catalytic and electrolytic functions more efficiently during the wastewater treatment process.

[0058] S4. Assemble multiple titanium electrode units to obtain a titanium electrode group.

[0059] S4.1. Control the size of each titanium electrode unit to be the same, and electrically connect the multiple titanium electrode units.

[0060] Ensuring that the size of each titanium electrode unit is consistent can ensure that the current is evenly distributed in each electrode unit, avoiding the situation where the current density of some units is too high or too low due to size deviation, thereby affecting the overall electrolysis efficiency.

[0061] By electrically connecting multiple electrode units, the working area and electrolysis capacity of the entire electrode group can be increased to meet the needs of wastewater treatment of different scales and improve treatment efficiency.

[0062] S4.2. Install an insulating layer between two adjacent titanium electrode units and then fix it on the frame of the titanium electrode group, wherein the insulating layer includes at least one of polyurethane, silicone, rubber, and plastic.

[0063] The installation of the insulating layer can effectively prevent short circuits between adjacent electrode units, thereby ensuring safety and stability during the electrolysis process. Polyurethane, silicone, rubber, plastic and other materials are selected as the insulating layer. These materials have good corrosion resistance and electrical insulation properties and are suitable for the harsh environment of wastewater treatment.

[0064] Fixing the titanium electrode unit to the frame can maintain the structural stability of the entire electrode group, ensuring that the electrodes will not loosen or shift during the wastewater treatment process, avoiding failures caused by mechanical vibration or fluid flow.

[0065] S4.3. Package multiple titanium electrode units to obtain a titanium electrode group.

[0066] Encapsulation can effectively protect the electrode units and connection structures inside the electrode group from erosion by the external environment (such as water flow, acidic and alkaline wastewater), thereby extending the service life of the electrode group.

[0067] Packaging can also prevent gases or impurities generated during the electrolysis process from entering the interior of the electrode group, maintaining the cleanliness and functional stability of the electrode group and reducing maintenance work.

[0068] In one embodiment, the present invention also proposes a wastewater treatment device, comprising an electrolytic cell, a power module, a cathode material and a titanium electrode group for wastewater treatment; wherein a circulating water circuit and a temperature controller are provided in the electrolytic cell; the cathode material comprises at least one of graphite, stainless steel, carbon fiber, iron and nickel; and the power module has the function of adjusting potential, current and voltage.

[0069] The circulating water circuit ensures that the wastewater flows evenly in the electrolytic cell, avoiding excessive concentration of pollutants in local areas and improving the wastewater treatment efficiency. At the same time, the flow can reduce the bubbles and sediments generated on the electrode surface, ensuring that the electrode surface is always exposed to the wastewater, thereby improving the electrolysis efficiency.

[0070] The temperature controller can maintain the temperature in the electrolytic cell within the appropriate range during the wastewater treatment process, preventing the temperature from being too high or too low, which may affect the electrochemical reaction rate. The temperature controller can also reduce the thermal stress of the electrode material and extend the service life of the equipment.

[0071] Different cathode materials have different conductivity, corrosion resistance and economic options. The introduction of these materials allows the device to be customized according to different wastewater treatment needs. For example, graphite and carbon fiber have good conductivity and corrosion resistance, while stainless steel is widely used due to its high strength and corrosion resistance.

[0072] The power module can optimize the energy consumption and reaction rate in the electrolysis process and improve the efficiency of wastewater treatment by adjusting the potential, current and voltage. For example, a higher potential can promote the occurrence of redox reactions and accelerate the degradation of pollutants; while adjusting the current can accurately control the power consumption in the treatment process to avoid waste.

[0073] Different wastewater treatment scenarios have different requirements for electrolysis conditions. By adjusting the power supply parameters, intelligent and refined control of wastewater treatment can be achieved to ensure that the treatment results meet the expected goals.

[0074] In the process of wastewater treatment, the titanium electrode group acts as the anode and first undergoes an oxidation reaction. The organic pollutants in the wastewater are oxidized and decomposed into harmless small molecules or carbon dioxide at the anode. The heavy metal ions in the wastewater undergo an oxidation reaction at the anode to form precipitation or other forms for subsequent treatment. A reduction reaction occurs on the cathode material, and some heavy metal ions are reduced to insoluble precipitation at the cathode, which is easy to separate and recover.

[0075] The wastewater in the electrolyzer is evenly distributed between the titanium electrode group and the cathode material through the circulating water circuit. At the anode, the pollutants are oxidized; at the cathode, side reactions such as hydrogen generation or metal deposition occur. After a period of time, the harmful substances in the wastewater are converted into harmless substances or easily removable precipitation, thus achieving a purification effect.

[0076] In one embodiment of the present invention, the power module is used to periodically output an oscillation signal to the titanium electrode group and receive feedback information from the titanium electrode group; When the feedback information exceeds a preset range, the power module adjusts its initial potential to induce surface oscillation of the titanium electrode unit to clean the surface coating.

[0077] Please refer to Figure 3 The present invention also provides a control method for controlling a wastewater treatment device, the control method comprising the steps of: Step 101: setting initial power supply data of the titanium electrode group, wherein the initial power supply data includes initial potential and current density.

[0078] By setting the initial power supply data of the titanium electrode group, it is ensured that the wastewater treatment device can operate with the best electrochemical parameters at startup. The selection of initial potential and current density can affect the activity of the titanium electrode, thereby improving the degradation efficiency of pollutants and reducing energy consumption.

[0079] Step 102: Set a test period to output an oscillation signal and record feedback information of current density, wherein the feedback information includes a fluctuation amplitude of the current density.

[0080] By setting the test cycle and outputting the oscillation signal, the working state of the titanium electrode group can be monitored in real time. The feedback information of recording the current density can capture the subtle changes in the electrochemical reaction, which helps to determine the active state of the electrode surface and its impact on the processing efficiency. This process ensures that the electrode operates in the best working state and avoids performance degradation or efficiency loss.

[0081] Step 103: Determine whether the feedback information is within a preset range.

[0082] If the feedback information is not within the preset range, then step 104 is performed. If the feedback information is within the preset range, then step 102 is performed.

[0083] Step 104: adjusting the initial potential to induce surface oscillation of the titanium electrode unit.

[0084] When the feedback information does not reach the preset range, the initial potential is adjusted to induce oscillation on the titanium electrode surface, which helps to reactivate the electrode surface and improve its electrochemical reaction capacity. This adjustment mechanism ensures that the electrode can maintain efficient degradation capacity during operation, thereby improving the overall effect of wastewater treatment.

[0085] If the feedback information is within the preset range, it indicates that the titanium electrode group is working in an ideal state, and continuing to perform the output and monitoring of the test cycle can stably maintain the performance of the treatment device. This continuous monitoring and adjustment mechanism ensures the automatic operation of the system, making the wastewater treatment process more efficient and reliable.

[0086] Specifically, the preset 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. In this embodiment, It is 0.3~0.7, for example, it can be 0.5.

[0087] F is Faraday's constant, F=96485 C / mol, R is the gas constant, R=8.314J / (mol\K), T is the 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.

[0088] Through the electrode potential The dynamic adjustment of the current density This change can be used to enhance the reactivity of the electrode surface, thereby improving the treatment efficiency of the wastewater treatment device.

[0089] It means that the electrode potential fluctuates sinusoidally over time, which causes periodic changes in the current density and may lead to an improvement in the efficiency of the electrochemical reaction.

[0090] The intensity of the oscillation can be adjusted by increasing or decreasing A. This will affect the degree of activation of the electrode surface reaction, thereby adjusting the activity of the electrode and the treatment effect. A can be 0.01~0.1V, Is dimensionless.

[0091] By adjusting ω, the frequency of the oscillation can be changed, thereby controlling the speed of change of the current density, which can adapt the response time of the system to different processing requirements. ω can be 1 ~100 rad / s.

[0092] The adjustment of oscillation frequency (ω) and amplitude (A) can flexibly respond to different types of wastewater and pollutants of different concentrations. For example, when treating high-concentration organic wastewater, appropriately increasing A and ω can stimulate higher surface activity and accelerate degradation; while in low-concentration wastewater treatment, the oscillation parameters can be adjusted to reduce energy consumption. After combining with the microporous nanostructure, the titanium electrode unit can better respond to the needs of different wastewater treatment scenarios and improve the adaptability of treatment.

[0093] The periodic fluctuation of current density (oscillation induced by sinusoidal potential) causes the surface reaction conditions of the titanium electrode unit to change continuously, promoting the surface activity and the periodic adsorption and desorption of reactants (such as organic pollutants and 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, which helps to more thoroughly decompose and remove organic pollutants.

[0094] The presence of the microporous nanostructure allows the titanium electrode unit surface to maintain 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 byproducts, the periodic current density changes caused by sinusoidal oscillations can promote the self-cleaning and depassivation of surface materials, effectively reducing the passivation phenomenon on the titanium electrode unit surface. In addition, the microporous nanostructure allows more electrolytes to enter, thereby improving the reaction activity and regeneration ability of the titanium electrode unit.

[0095] The microporous nanostructure on the surface of the titanium electrode unit can promote the flow of electrolyte solution and reduce the probability of pollutants or byproducts deposited on the surface of the titanium electrode unit. At the same time, the introduction of periodic oscillation can further prevent pollutants from depositing on the surface of the titanium electrode unit, effectively reduce the pollution and scaling of the titanium electrode unit, and extend the service life of the titanium electrode unit. This is especially important for wastewater treatment devices that operate continuously for a long time.

[0096] For wastewater containing heavy metals, the microporous nanostructure can improve the adsorption capacity of the titanium electrode unit and enhance the electrochemical reduction capacity of the titanium electrode unit through oscillation, making it easier for heavy metal ions to be reduced to simple substances or precipitated 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 the reaction passivation caused by excessive enrichment of heavy metal ions on the surface of the titanium electrode unit.

[0097] 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 fluctuation of real-time current density. The combination of microporous nanostructures makes this adjustment more efficient, and the reaction state on the surface of the titanium electrode unit can quickly respond to changes in the system and maintain long-term stable wastewater treatment effects.

[0098] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A titanium electrode group for wastewater treatment, characterized in that: It 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. A preparation method, characterized in that: For preparing the titanium electrode group for wastewater treatment according to claim 1, the preparation method comprises the following steps: 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 preparation method 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 preparation method 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 μm; 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. The preparation method 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. The preparation method 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.

7. A wastewater treatment device, characterized in that: It comprises an electrolytic cell, a power module, a cathode material and the titanium electrode group for wastewater treatment prepared by the preparation method according to any one of claims 2 to 6; 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 supply module has the function of adjusting potential, current and voltage.

8. A wastewater treatment device according to claim 7, characterized in that: 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; When the feedback information exceeds a preset range, the power module adjusts its initial potential to induce surface oscillation of the titanium electrode unit to clean the surface coating.

9. The control method according to claim 8, characterized in that: The preset range is , is the current density at maximum potential, is the current density at the minimum potential; , ;in, 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, It is the dynamic adjustment part of DC bias, used to induce oscillation. is the amplitude, is the angular frequency.

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