High-frequency pulse-ultrasonic synergistic electrochemical descaling device and method

Abstract

The invention discloses a high-frequency pulse-ultrasonic synergistic electrochemical descaling device and method, the device is mainly applied to an industrial circulating cooling water system, the device comprises an electrolytic bath body, a composite electrode system, an integrated control cabinet and a cleaning subsystem, and a cathode adopts a gradient porous titanium alloy substrate; a micro-cone array is constructed on the surface and is coated with a carbon nano tube coating, an anode adopts a ruthenium-iridium coating titanium mesh, the micro-scale cavitation effect is remarkably improved, a high-frequency pulse generator and an ultrasonic driver are integrated in a control cabinet, double-effect cooperation of microcrystal scale cavitation stripping and pore residual scale removal is achieved through a time-sharing control strategy, and on the basis of real-time data of a water quality sensor, a water quality sensor is used for detecting the water quality. When delta Ca + gt; and when the current efficiency is reduced by 15% or 50mg / L or the current efficiency is reduced by 15%, cleaning is automatically started and stopped, 2V anode bias voltage is applied after cleaning, and a TiO2 / CaTiO3 passive film is generated to inhibit secondary scaling.

Description

Technical Field

[0001] This invention belongs to the field of industrial water treatment technology, specifically relating to a high-frequency pulse-ultrasound synergistic electrochemical descaling device and method for circulating cooling water systems, suitable for scenarios with high hardness and high scaling risk. Background Technology

[0002] Industrial circulating cooling water systems are a crucial component of industrial production processes, playing a vital role in numerous fields such as metallurgy, chemical engineering, and power generation. However, with the recycling of industrial water, the concentration of scale-forming substances such as dissolved calcium and magnesium ions in the water continuously increases. Under suitable temperature and pH conditions, scale such as calcium carbonate and magnesium hydroxide easily deposits on the surfaces of system equipment, such as heat exchangers, pipes, and cooling towers, leading to serious scaling problems.

[0003] Traditional electrochemical descaling technologies face numerous challenges in application. Early-formed calcium and magnesium microcrystalline scale on the cathode surface exhibits low removal rates. A large amount of microscale residue remains on the cathode surface, gradually accumulating and leading to a decline in cathode performance. Frequent shutdowns are required for scraping and cleaning the cathode. However, this cleaning method not only interrupts industrial production, causing a loss of efficiency, but also damages the porous titanium substrate, affecting electrode lifespan and descaling effectiveness.

[0004] Traditional chemical scale inhibition methods, such as acid washing and complexation cleaning, while effective in inhibiting and removing scale to some extent and widely used in industry, have significant drawbacks. Firstly, the use of chemical scale inhibitors poses a serious risk of chemical contamination. Secondly, chemical agents are corrosive to equipment, shortening its lifespan and increasing maintenance and replacement costs with prolonged use. The high annual maintenance costs of chemical scale inhibition methods represent a substantial burden for businesses.

[0005] To address these issues, this invention proposes a high-frequency pulse-ultrasound synergistic electrochemical descaling device and method, aiming to overcome the shortcomings of traditional technologies through innovative technical means and provide a more efficient, environmentally friendly, and stable solution for scale treatment in industrial circulating cooling water systems. Summary of the Invention

[0006] This invention addresses the scaling problem in industrial circulating cooling water systems by providing a high-frequency pulse-ultrasound synergistic electrochemical descaling device and method. Through innovative electrode structure, dynamic synergistic control, and self-repair mechanism, it solves the problems of incomplete descaling, lack of dynamic response, and short electrode life of traditional technologies.

[0007] This invention discloses a high-frequency pulse-ultrasound synergistic electrochemical descaling device, comprising an electrolytic cell made of 316L stainless steel, with an internal working chamber and an electrode system. The electrode system includes a gradient porous titanium alloy cathode and a ruthenium-iridium coated titanium anode. The surface of the gradient porous titanium alloy cathode is provided with a micro-cone array and coated with a carbon nanotube coating. An ultrasonic transducer and a control cabinet are installed on the walls of the electrolytic cell. The control cabinet integrates the following modules: a high-frequency pulse generator, an ultrasonic driver, a central control PLC, a sensor group, a turbidity meter, and an electrode impedance analysis module. The outputs of the high-frequency pulse generator and the ultrasonic driver are respectively connected to the cathode and the ultrasonic transducer through an impedance matching network. The central control PLC dynamically triggers time-sharing synergistic cleaning based on sensor data.

[0008] Ideally, the substrate of the microcone array is a titanium alloy TIGr5, the carbon nanotube coating thickness is 5μm, and the cone density is 80-100 cones / mm².

[0009] Optimally, the ultrasonic transducer includes a rear drive device, with internal bolt threads connecting the rear drive device to the bolts, internal bolt threads connecting the piezoelectric ceramic to the bolts, the bottom of the piezoelectric ceramic stacked with an electrode plate, internal bolt threads connecting the electrode plate to the bolts, the bottom of the electrode plate stacked with a buffer pad, internal bolt threads connecting the buffer pad to the bolts, the bottom of the buffer pad stacked with the electrode plate, internal bolt threads connecting the electrode plate to the bolts, the bottom of the electrode plate stacked with a front drive device, internal bolt threads connecting the electrode plate to the bolts, the upper end of the front drive device connected with bolt threads, and the lower end connected with a stud welded to the wall of the electrolytic cell via bolt threads.

[0010] Ideally, the ultrasonic driver outputs a 40kHz sinusoidal alternating current, and the alternating voltage is applied to the electrode plates on both sides of the piezoelectric ceramic.

[0011] Optimally, the circuit topology of the high-frequency pulse generator includes: an LLC resonant converter, a base electrolytic voltage; a Boost converter module, a full-bridge IGBT inverter, and an energy storage capacitor bank.

[0012] Ideally, the negative output terminal of the high-frequency pulse generator is connected to the input terminal of the impedance matching network, the output terminal of the impedance matching network is connected to the conductive post on the back of the cathode substrate, and the positive output terminal of the high-frequency pulse generator is directly connected to the anode conductive frame. The anode adopts a floating design and is not grounded with the tank body to avoid corrosion of the electrolytic tank wall.

[0013] To optimize operation in strong electromagnetic environments, the outer layer of the coaxial cable should be grounded with a braided mesh, the cathode terminal should be shielded with a Mu metal cover, and the anode connection should be filled with ceramic insulating sealant.

[0014] Ideally, the online water quality sensor is first encapsulated with insulating ceramic material, and then installed at the corresponding water quality measurement point in the electrolytic cell in an appropriate manner, transmitting the measured water quality information to the online instrument detector.

[0015] This invention also introduces a high-frequency pulse-ultrasound synergistic electrochemical descaling method based on the above-mentioned descaling device, comprising the following stages: Start-up stage: system initialization, calibration of online water quality sensor and impedance analysis module, and application of 3-5V DC power to start basic electrolysis; Operation stage: real-time monitoring of ΔCa². + and scale thickness δ, when ΔCa² + When the concentration is >50mg / L or the current efficiency decreases by 15%, a graded cleaning is triggered. If δ≤0.1mm, 80kHz high-frequency pulse cleaning is activated for 10min. If 0.1mm<δ<1mm, 40kHz pulse + ultrasonic co-cleaning is activated for 10min. If δ≥1mm, 20kHz high-energy pulse + synchronous ultrasonic cleaning is activated for 15min. Cleaning stage: Pulse and ultrasonic work in a time-sharing manner with an interval >100μs, and the slag discharge valve is opened. Self-repair stage: Apply 2V anodic bias voltage for 5min to generate TiO2 / CaTiO3 passivation film.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. Thin scale removal rate: Increased from 47% of traditional technology to 96%, a 104% improvement in removal efficiency, completely solving the problem of early microcrystalline scale (δ<0.1mm) residue. Energy efficiency: Energy consumption per ton of water treated decreased from 1.8kWh / m³ to 0.52kWh / m³, a reduction of 71%, significantly reducing operating costs.

[0017] 2. Electrode lifespan: Electrode lifespan is extended from 6 months to more than 18 months, durability is improved by 200%, and replacement frequency and maintenance costs are reduced.

[0018] 3. Chemical substitution: Completely replaces chemical scale inhibitors, achieving annual cost savings of 267,000 yuan and realizing the goal of zero chemical pollution.

[0019] 4. Intelligent: Dynamic response delay <18ms, turbidity compliance cycle shortened from 21 days to 7 days, improving system control accuracy.

[0020] 5. Economic efficiency: Compatible with existing circulating water systems, the renovation cost is less than 100,000 yuan, and the investment payback period is less than 8 months. Attached Figure Description

[0021] The invention will now be further described with reference to the accompanying drawings; Figure 1 This is an overall structural diagram of the invention; Figure 2 This is a structural diagram of the ultrasonic array, an important component of this invention; Figure 3 This is a schematic diagram illustrating the working principle of the present invention. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, 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.

[0023] like Figures 1-3 As shown in the schematic diagram of the device structure in an embodiment of the present invention, the system includes the following core components: S1. Electrolytic Cell Body 101: Material: 316L stainless steel, thickness 8mm, pressure rating 0.8MPa, volume: 1.5m³, length × width × height = 1.2m × 0.8m × 1.6m. Internal structure: baffle plate 101a with an inclination angle of 15° to ensure a stable water flow rate of 0.8-1.2m / s; cathode mounting rail 101b with a tolerance of ±0.1mm.

[0024] S2. Electrode System: Cathode: Substrate: Titanium alloy TIGr5 (dimensions 1000×800×5mm). Surface treatment: Laser-etched microcone array, cone height 50μm, spacing 100μm, density 85 cones / mm². Coating: Chemical vapor deposition of 5μm carbon nanotubes. Anode: Ruthenium-iridium coated titanium mesh, mesh size 2mm. Effective area ratio: Cathode:Anode = 1.3:1.

[0025] S3, Control Cabinet: Dimensions: 1000×800×600mm Internal modules: High-frequency pulse generator, model / parameter: customized LLC-IGBT topology, function: output 0-600V / 1-100kHz. Ultrasonic driver, model / parameter: DDS signal source + MOSFET power amplifier, function: output 40kHz / ≤20W / cm². Central control PLC, model / parameter: Siemens S7-1200, function: processes sensor data.

[0026] S4, Sensor Group: Ca² +Probe: Range 0-1000 mg / L. Turbidity meter: Range 0-100 NTU. Impedance analysis module: Operating frequency 1 kHz, resolution 0.1 Ω. Connection: The sensor group is connected to the PLC via a 4-20mA signal line; the pulse / ultrasonic output is connected to the electrodes via a shielded cable; the slag discharge valve is controlled by a pneumatic actuator.

[0027] S5, Fouling Status Monitoring Phase Data collection: Read Ca² every 5 minutes + Concentration, real-time calculation of scale thickness: δ = 0.12 × ΔR. Trigger condition judgment: If ΔCa² + >50mg / L or current efficiency <85% → proceed to graded cleaning.

[0028] S6, Graded Cleaning Stage When δ≤0.1mm, enable low-energy high-frequency pulse mode (80kHz, 300V, 10min). When 0.1mm < δ ≤ 1mm, activate the high-energy high-frequency pulse mode: 40kHz, 500V, 10min. When δ>1mm, activate the pulse-ultrasound co-mode: 20kHz pulse 500V + 40kHz ultrasound 20W / cm², 15min.

[0029] S7, Physical Cooperative Clearance Phase Pulsed phase operation: A high-voltage pulse with a rise time of <100ns is applied to induce cavitation of nanobubbles. Ultrasonic phase operation: Ultrasonic waves are initiated 100μs after the pulse ends. Sound intensity distribution: ≥15W / cm² at the edge of the tank, ≥8W / cm² in the central region. S8, Self-repair Conditions: pH = 8.5-9.5, temperature 25-40℃ Operation: Apply a 2V anode bias voltage and a current density of 15mA / cm² for 5 minutes. Film formation verification: XRD detection of CaTiO3 characteristic peak, 2θ=33.2°±0.2°.

[0030] S8. Operation Example (Xinjiang Daquan 450B System) Initial state: Water quality: Ca² + =600mg / L, turbidity =35NTU, δ =1.2mm (ΔR =10Ω). Execution procedure: Trigger δ>1mm mode → 20kHz pulse 500V combined with 40kHz ultrasound 20W / cm² for 15min. Self-repair: 2V anodic bias for 5min to generate a 380nm CaTiO3 film. Standard assessment: Ca² + ≤380mg / L and impedance change ≤20% → End of cycle.

[0031] S9, Maintenance Specifications Sensor calibration: Ca² + The probe is calibrated quarterly using standard solutions (100 / 500 / 1000 mg / L), and the impedance module is returned to the factory for calibration annually. Energy consumption optimization: the δ>1mm mode is limited to operation during off-peak electricity hours (23:00-7:00). Safety measures: ultrasonic start-up hard delay >100μs, electrode over-temperature protection: automatic power-off at ≥80℃.

[0032] Although embodiments of the invention have been described in conjunction with the accompanying drawings, those skilled in the art can make various modifications and variations without departing from the spirit and scope of the invention, and such modifications and variations all fall within the scope defined by the appended claims.

Claims

1. A high-frequency pulse-ultrasound synergistic electrochemical descaling device, characterized in that, The device includes an electrolytic cell body (5), which is made of 316L stainless steel and has a working chamber inside. It includes an electrode system, which includes a gradient porous titanium alloy cathode (1) and a ruthenium-iridium coated titanium anode (2). The surface of the gradient porous titanium alloy cathode is provided with a microcone array and coated with a carbon nanotube coating. The electrolytic cell body is equipped with an ultrasonic transducer (4) and a control cabinet (3). The control cabinet integrates the following modules: a high-frequency pulse generator, an ultrasonic driver, a central control PLC, a sensor group, a turbidity meter, and an electrode impedance analysis module. The output terminals of the high-frequency pulse generator and the ultrasonic driver are respectively connected to the cathode and the ultrasonic transducer (4) through an impedance matching network. The central control PLC dynamically triggers time-sharing collaborative cleaning according to the sensor data.

2. The high-frequency pulse-ultrasound synergistic electrochemical descaling device according to claim 1, characterized in that, The substrate of the microcone array is titanium alloy TIGr5, the carbon nanotube coating thickness is 5μm, and the cone density is 80-100 cones / mm².

3. The high-frequency pulse-ultrasound synergistic electrochemical descaling device according to claim 1, characterized in that, The ultrasonic transducer (4) includes a rear drive unit (405), which is internally connected to a bolt (406) via bolt threads. The piezoelectric ceramic (404) is internally connected to the bolt (406) via bolt threads. The bottom of the piezoelectric ceramic (404) is stacked with an electrode plate (407), which is internally connected to the bolt (406) via bolt threads. The bottom of the electrode plate (407) is stacked with a buffer pad (408), which is internally connected to the buffer pad (408) via bolt threads. The buffer pad (408) is connected to the bolt (406) through the bottom and stacked with the electrode plate (403). The electrode plate (403) is connected to the bolt (406) through the bolt thread inside. The electrode plate (403) is also connected to the front drive device (401) through the bottom and stacked with the front drive device (401). The electrode plate (403) is connected to the bolt (406) through the bolt thread inside. The upper end of the front drive device (401) is connected to the bolt (406) through the bolt thread, and the lower end is connected to the stud welded on the wall of the electrolytic cell (5) through the bolt thread.

4. The high-frequency pulse-ultrasound synergistic electrochemical descaling device according to claim 3, characterized in that, The ultrasonic driver outputs a 40kHz sinusoidal alternating current, and the alternating voltage is applied to the electrode plates (403 / 407) on both sides of the piezoelectric ceramic.

5. The high-frequency pulse-ultrasound synergistic electrochemical descaling device according to claim 1, characterized in that, The circuit topology of the high-frequency pulse generator includes: an LLC resonant converter, a base electrolytic voltage, a Boost converter module, a full-bridge IGBT inverter, and an energy storage capacitor bank.

6. The high-frequency pulse-ultrasound synergistic electrochemical descaling device according to claim 5, characterized in that, The negative output terminal of the high-frequency pulse generator is connected to the input terminal of the impedance matching network, and the output terminal of the impedance matching network is connected to the conductive post on the back of the cathode substrate. The positive output terminal of the high-frequency pulse generator is directly connected to the anode conductive frame. The anode adopts a floating design and is not grounded with the tank to avoid corrosion of the electrolytic tank wall.

7. The high-frequency pulse-ultrasound synergistic electrochemical descaling device according to claim 5, characterized in that, When working in a strong electromagnetic environment, the outer layer of the coaxial cable needs to be grounded with a braided mesh, the cathode terminal should be shielded with a Mu metal cover, and the anode connection should be filled with ceramic insulating sealant.

8. The high-frequency pulse-ultrasound synergistic electrochemical descaling device according to claim 1, characterized in that, The online water quality sensor is first encapsulated with insulating ceramic material, and then installed in an appropriate manner at the corresponding water quality measurement point on the electrolytic cell (5) to transmit the measured water quality information to the online instrument detector.

9. A high-frequency pulse-ultrasound synergistic electrochemical descaling method based on the descaling device described in claims 1-8, characterized in that, The process includes the following stages: Start-up stage: System initialization, calibration of online water quality sensors and impedance analysis modules, and application of 3-5V DC power to start basic electrolysis; Operation stage: Real-time monitoring of ΔCa². + and scale thickness δ, when ΔCa² + When the concentration is >50mg / L or the current efficiency decreases by 15%, a graded cleaning is triggered. If δ≤0.1mm, 80kHz high-frequency pulse cleaning is activated for 10min. If 0.1mm<δ<1mm, 40kHz pulse + ultrasonic co-cleaning is activated for 10min. If δ≥1mm, 20kHz high-energy pulse + synchronous ultrasonic cleaning is activated for 15min. Cleaning stage: Pulse and ultrasonic work in a time-sharing manner with an interval >100μs, and the slag discharge valve is opened. Self-repair stage: Apply 2V anodic bias voltage for 5min to generate TiO2 / CaTiO3 passivation film.

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