A hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method and device

Abstract

The present invention provides a hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method and device. While the cathode reduces dissolved oxygen to generate H2O2, a dual-anode structure with different catalytic properties is utilized. One anode electrolyzes water using a high overpotential material to selectively generate O3, and the other anode electrochemically produces HClO using a chlorine-containing electrolyte. This cleverly integrates the electrocatalytic in-situ synergistic electrosynthesis preparation of the three components within the same reaction device, achieving integrated electrochemical preparation of a highly efficient composite oxidant. The resulting HClO-H2O2-O3 composite solution has far superior performance for sterilization and organic pollutant degradation than either single component, significantly improving the overall efficiency and application areas of electrochemical synthesis technology.

Description

Technical Field

[0001] The present invention relates to the field of electrochemical technology, and in particular to a hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method and device. Background Art

[0002] Hydrogen peroxide (H2O2), ozone (O3), and hypochlorous acid (HClO) are three strong oxidizing agents widely used in the advanced treatment and disinfection of drinking water and wastewater. Traditional synthesis methods primarily utilize liquid-phase chemistry to produce H2O2, high-voltage discharge or photochemical methods to produce O3, and electrolysis of chlorinated water to produce HClO. These processes present challenges such as high energy consumption, significant safety risks, and suboptimal product purity. With increasingly prominent environmental concerns, the development of new, cost-effective, and environmentally friendly production technologies has become a pressing priority.

[0003] Electrochemical synthesis has become an ideal preparation method for oxidizing agents due to its advantages such as a wide range of raw material sources (water, oxygen, chloride ions), simple equipment and process, and controllable product purity. At present, new electrosynthesis processes have been developed, such as using dissolved oxygen in the electrolyte to produce H2O2 by cathode reduction, anodic oxidation of O2 to produce O3, and anodic oxidation of chloride ions to produce HClO, which simplify the process and reduce costs. However, the performance of a single component is still unsatisfactory. Its bactericidal and oxidative properties can be significantly improved by compounding, but mechanical mixing of two or more components poses the risk of secondary contamination and high preparation and storage costs. Therefore, there is an urgent need for a new on-site composite preparation technology that is efficient, environmentally friendly, and economical.

[0004] A major scientific challenge currently lies in achieving the integrated in-situ electrosynthesis and compounding of key components by utilizing a cathode and a multi-electrocatalytic anode within the same reaction device to produce H2O2 through reduction and O3 and HClO through oxidation. This approach is crucial for overcoming the limitations of traditional single-component preparation and mechanical compounding, significantly improving the preparation efficiency, performance, and application areas of oxidizing agents, and promoting the leapfrog development of electrochemical sterilization and disinfection technologies. Summary of the Invention

[0005] One of the objectives of the present invention is to address the shortcomings of the existing technology and provide a hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method and device, which realizes the efficient synergistic electrosynthesis and homogeneous compounding of the three key oxidative sterilization components HClO-H2O2-O3 in the same reaction device, breaking through the limitations of traditional single-component preparation and mechanical compounding. The prepared HClO-H2O2-O3 composite solution has far superior performance in sterilization and degradation of organic pollutants than a single component, which can significantly improve the comprehensive efficiency and application field of electrochemical synthesis technology.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method comprises the following steps:

[0008] S1, an ozone anode component and a hypochlorous acid anode component are respectively arranged in two compartments separated by three cathode components arranged side by side, each anode component and cathode component is configured as a mesh plate, and the three cathodes and two anodes are electrically connected to the positive and negative electrodes of an external power supply respectively;

[0009] S2. Electrolyte is introduced into the electrolysis chamber, and redox reactions occur on the surfaces of the ozone anode component, the hypochlorous acid anode component, and the cathode component, wherein the ozone anode component produces O3, the hypochlorous acid anode component produces HClO, and the cathode component produces H2O2;

[0010] S3. The HClO, H2O2, and O3 produced by the electrolysis reaction in step S2 are directly dissolved in the electrolyte, forming and flowing out an HClO-H2O2-O3 composite solution with a specific ratio at the outlet of the electrolysis chamber.

[0011] Preferably, tap water is used as the electrolyte. During the electrochemical reaction, the electrolyte is driven by a pump to flow through the surfaces of the ozone anode component, the hypochlorous acid anode component and the cathode component and overflow and discharge.

[0012] Preferably, the generation rate and relative proportion of O3 and HClO are controlled by adjusting the voltage value connected to the ozone anode component and the hypochlorous acid anode component to change the current density at the two anodes.

[0013] Preferably, the current density of the cathode component is 10-30 mA / cm 2 The current density of the ozone anode component and the hypochlorous acid anode component is controlled at 20-50mA / cm 2 and 10-30mA / cm 2 , the electrolyte flow rate is 50-150mL / min, and the reaction temperature is 25-40℃.

[0014] Preferably, when the current density at the ozone anode component is controlled to account for 40-60% of the total current density of the dual anodes and the current density of the cathode component is controlled to remain unchanged, after multiple cycles of reaction of the electrolyte, the mass concentration ratio of O3:HClO in the obtained HClO-H2O2-O3 composite solution is 1:3-1:2.

[0015] Preferably, the cathode component adopts a conductive porous substrate A to carry catalyst A, wherein the conductive porous substrate A adopts a conductive carbon-based porous material, and the catalyst A adopts iron-nitrogen-carbon with a carrying amount of 1mg-5mg / cm 2The ozone anode component adopts a conductive porous substrate B carrying a catalyst B, wherein the conductive porous substrate B adopts a material with a wide electrochemical potential window, and the catalyst B adopts a corrosion-resistant metal oxide coating; the hypochlorous acid anode component adopts a conductive porous substrate C carrying a catalyst C, wherein the conductive porous substrate C adopts titanium, and the catalyst C adopts a corrosion-resistant chlorine evolution material.

[0016] Preferably, the conductive carbon-based porous material used in the conductive porous substrate A includes graphite plate or graphite felt; the material with a wide electrochemical potential window used in the conductive porous substrate B includes titanium or glassy carbon; the corrosion-resistant metal oxide coating used in the catalyst B includes lead dioxide, antimony tin oxide, or iridium tantalum tin; and the corrosion-resistant chlorine evolution material used in the catalyst C includes ruthenium iridium oxide or iridium tantalum oxide.

[0017] Preferably, after the electrolyte is circulated for multiple reactions, the concentration of the total oxidant in the HClO-H2O2-O3 composite solution is controlled at 50-200 ppm, and the sterilization rate of the HClO-H2O2-O3 composite solution is greater than 99.99%.

[0018] A second object of the present invention is to provide a hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical production device, comprising a shell portion having a reaction chamber, wherein three cathode components are arranged side by side in the reaction chamber, and an ozone anode component and a hypochlorous acid anode component are respectively arranged in two compartments separated by the three cathode components. The cathode component, the ozone anode component, and the hypochlorous acid anode component are all mesh plates and are electrically connected to the positive and negative electrodes of an external power supply through wiring harnesses. The electrolyte circulates into the reaction chamber to carry out an electrochemical reaction and obtain an HClO-H2O2-O3 composite solution.

[0019] Preferably, the shell portion includes an upper shell and a lower shell that are fixed to each other, the upper shell is provided with a liquid inlet, and the lower shell is provided with a liquid outlet, the electrolyte flows into the reaction chamber from the liquid inlet and flows out of the reaction chamber from the liquid outlet.

[0020] Preferably, the liquid inlet and the liquid outlet are both arranged to be inclined at an acute angle to the electrode plate component.

[0021] Preferably, a limiting rib is convexly provided on the mating surface of the upper shell that is engaged with the lower shell, and a limiting groove is concavely provided on the mating surface of the lower shell that is engaged with the upper shell, and the limiting rib is matched and engaged in the limiting groove.

[0022] Preferably, fixing grooves are provided on the inner top surface of the upper shell and the inner bottom surface of the lower shell, and the cathode component, ozone anode component and hypochlorous acid anode component are correspondingly inserted into the fixing grooves.

[0023] Preferably, it further includes a bracket and carbon felt. A group of brackets and carbon felt are arranged in the gap between the central cathode component and the ozone anode component, and a group of brackets and carbon felt are arranged in the gap between the central cathode component and the hypochlorous acid anode component, so as to separate the reaction chamber into relatively independent O3-H2O2 generation area and HClO-H2O2 generation area, and they not only provide mechanical support, but also have functions such as electrolyte diversion.

[0024] The present invention also provides an application of a hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method, wherein the prepared HClO-H2O2-O3 composite solution having a specific ratio is used in the fields of environmental pollutant removal, deep treatment of drinking water, disinfection of medical wastewater, and standard discharge of industrial wastewater.

[0025] The beneficial effects of the present invention are:

[0026] (1) The core concept of the present invention is to construct a new composite electrochemical device consisting of a common H2O2-producing cathode, a separate O3-producing anode and a HClO-producing anode. The cathode side adopts a conductive porous substrate to load the corresponding catalyst, which has high reaction activity and good selectivity with dissolved oxygen. The anode side is designed with a dual-electrode structure with different active coatings, which are optimized for the generation of O3 and HClO respectively. On the basis of conventional H2O2 cathode reduction preparation, the new electrochemical synergistic function of dual anode partitions made of different materials is creatively introduced, realizing the efficient synergistic electrosynthesis and homogeneous compounding of the three key oxidative sterilization components HClO-H2O2-O3 in the same reaction device, realizing the high coupling of electrochemical in-situ synthesis and compounding of the composite solution, without the need for additional liquid preparation and storage facilities, greatly simplifying the process flow, controlling the product purity, and making it easier to realize intelligent and small modular applications.

[0027] (2) The present invention cleverly integrates the electrocatalytic in-situ synergistic electrosynthesis preparation of three components in the same reaction device. While the cathode reduces dissolved oxygen to generate H2O2, a dual anode structure with different catalytic properties is used. One anode selectively generates O3 through the electrolysis of water using a high-potential material, and the other anode electrochemically generates HClO through a chlorine-containing electrolyte (such as ordinary tap water), thereby realizing the integrated electrochemical preparation of a high-efficiency composite oxidant.

[0028] (3) In the same electrolyte system, the present invention accurately controls the parameters of each electrode through an automatic control system, including adjusting the voltage across the dual anodes and changing the current density at different anodes. This can accurately control the generation rate of O3 and HClO and their relative proportions, thereby achieving precise control of the concentration and proportion of each component in the composite liquid, making the composition of the composite liquid compatible with the treatment environment and treatment object, flexibly matching the treatment requirements under different water quality conditions, and effectively improving the corresponding sterilization and pollutant removal effects.

[0029] (4) The present invention significantly improves the rate and selectivity of cathode reduction of O2 to generate H2O2 by using a conductive porous substrate and a high-efficiency catalyst to construct a reaction cathode. The dual anodes are coated with a specific catalytic layer for the generation of O3 and HClO, and are separated by a bracket to form an O3 generation area and an HClO generation area, forming relatively independent reaction zones, which can effectively avoid interference between components and ensure the independent controllability of different anode reactions.

[0030] (5) The advantage of the preparation method of the present invention over simple mechanical mixing is that the reaction activity of the components generated in situ in the prepared composite liquid is higher. By cleverly utilizing the activation effect of H2O2 synthesized in situ electrochemically at the cathode on O3 and HClO at the anode, a large number of highly active hydroxyl radicals are synergistically generated, so that the oxidation performance of the composite liquid is effectively improved compared with the oxidation performance of conventional single components. The HClO-H2O2-O3 three-component synergistically amplifies, thereby significantly improving the overall efficiency, which can greatly improve the killing efficiency of bacteria, viruses, etc. and the degradation rate of organic pollutants, and there is no risk of secondary pollution of the reaction products.

[0031] (6) The preparation method of the present invention uses water as the electrolyte, the electrochemical reaction process is green and environmentally friendly, the electrocatalytic layer and the electrode matrix have excellent stability and are suitable for long-term continuous operation; the prepared composite solution can be used on-site without storage and transportation risks and secondary pollution.

[0032] (7) The electrochemical device of the present invention adopts a modular, small-scale integrated design, and its production capacity can be flexibly matched to different needs.

[0033] In summary, the present invention has created a new electrochemical synergistic preparation method for high-efficiency composite oxidizing solvents, which has the advantages of compact electrochemical device structure, high electrode utilization, high coupling of in-situ preparation and compounding, no need for complex liquid preparation and mixing process, greatly reduced energy consumption and cost, and synergistic amplification effect of HClO-H2O2-O3. The killing rate of bacteria and viruses and the degradation rate of organic pollutants are increased by more than 2 times. Therefore, the present invention has significant advantages over traditional single-component preparation and mechanical mixing, and will greatly expand the application space of electrochemical sterilization, especially suitable for a wide range of applications in environmental pollutant removal, deep treatment of drinking water, disinfection of medical wastewater, and standard discharge of industrial wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a curve showing the change of HClO-H2O2-O3 content over time during the synergistic electrochemical preparation reaction of the present invention;

[0035] Figure 2 An exploded view of the HClO-H2O2-O3 synergistic electrochemical preparation device of the present invention;

[0036] Figure 3Schematic diagram of the overall structure of the HClO-H2O2-O3 synergistic electrochemical preparation device of the present invention from a front perspective;

[0037] Figure 4 Schematic diagram of the overall structure of the HClO-H2O2-O3 synergistic electrochemical preparation device of the present invention from the rear side;

[0038] Figure 5 Schematic diagram of the arrangement of the bracket and carbon felt in the present invention;

[0039] Figure 6 It is a front view of the HClO-H2O2-O3 collaborative electrochemical preparation device of the present invention;

[0040] Figure 7 It is a transverse cross-sectional view of the HClO-H2O2-O3 collaborative electrochemical preparation device of the present invention;

[0041] Figure 8 It is a longitudinal cross-sectional view of the HClO-H2O2-O3 collaborative electrochemical preparation device of the present invention. DETAILED DESCRIPTION

[0042] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0043] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise" and the like to indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In addition, the terms "first" and "second" are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, "multiple" means two or more, unless otherwise clearly and specifically defined.

[0044] A hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method comprises the following steps:

[0045] S1, an ozone anode component 5 and a hypochlorous acid anode component 6 are respectively arranged in two compartments separated by three cathode components 7 arranged side by side, each anode component and cathode component is configured as a mesh plate, and the three cathodes and two anodes are electrically connected to the positive and negative electrodes of an external power supply respectively;

[0046] S2. Electrolyte is introduced into the electrolysis chamber, and redox reactions occur on the surfaces of the ozone anode component 5, the hypochlorous acid anode component 6, and the cathode component 7, wherein the ozone anode component 5 produces O3, the hypochlorous acid anode component 6 produces HClO, and the cathode component 7 produces H2O2;

[0047] S3. The HClO, H2O2, and O3 produced by the electrolysis reaction in step S2 are directly dissolved in the electrolyte, forming and flowing out an HClO-H2O2-O3 composite solution with a specific ratio at the outlet of the electrolysis chamber.

[0048] During the electrochemical reaction, the electrolyte, driven by the pump, flows through the surface of the ozone anode component 5, the hypochlorous acid anode component 6, and the cathode component 7 and overflows and is discharged. The electrocatalytic reduction reaction of O2 occurs on the surface of the cathode component 7:

[0049] O2+2H + +2e - →H2O2E 0 = 0.68 V;

[0050] At the same time, the anode oxidation potential is changed by the anode catalyst material, and the oxygen-containing electrolyte is oxidized to generate ozone on the surface of the ozone anode component 5. The electrochemical reaction equation is:

[0051] 2H2O→ O3+6H + +6e - E 0 = 1.51 V (direct oxidation of water)

[0052] 3O2→2O3E 0 = 2.07 V (direct oxidation by oxygen)

[0053] On the surface of the hypochlorous acid anode component 6, a corresponding chlorine evolution catalyst is used to combine with chloride ions in the oxidized water to generate hypochlorous acid:

[0054] Cl - +H2O→HClO+H + +2e - E 0 = 1.49 V

[0055] Preferably, tap water is used as the electrolyte.

[0056] Preferably, the generation rate and relative proportion of O 3 and HClO are controlled by adjusting the voltage value connected to the ozone anode component 5 and the hypochlorous acid anode component 6 to change the current density at the two anodes.

[0057] As a preference, under optimal process conditions, the current density of the cathode component 7 is 10-30 mA / cm 2 The current density of the ozone anode component 5 and the hypochlorous acid anode component 6 is controlled at 20-50 mA / cm 2 and 10-30mA / cm 2 , the electrolyte flow rate is 50-150mL / min, and the reaction temperature is 25-40℃.

[0058] Preferably, the current density at the ozone anode component 5 is controlled to account for 40-60%, and the mass concentration ratio of O3:HClO in the obtained reaction product is 1:3-1:2.

[0059] Preferably, the cathode component 7 uses a conductive porous substrate A to carry catalyst A, wherein the conductive porous substrate A is a conductive carbon-based porous material, and the catalyst A is iron-nitrogen-carbon with a loading amount of 1 mg-5 mg / cm 2 ; The ozone anode component 5 adopts a conductive porous substrate B to carry catalyst B, wherein the conductive porous substrate B adopts a material with a wide electrochemical potential window, and the catalyst B adopts a corrosion-resistant metal oxide coating; the hypochlorous acid anode component 6 adopts a conductive porous substrate C to carry catalyst C, wherein the conductive porous substrate C adopts titanium, and the catalyst C adopts a corrosion-resistant chlorine evolution material.

[0060] Preferably, the conductive carbon-based porous material used in the conductive porous substrate A includes graphite plate or graphite felt; the material with a wide electrochemical potential window used in the conductive porous substrate B includes titanium or glassy carbon; the corrosion-resistant metal oxide coating used in the catalyst B includes lead dioxide, antimony tin oxide, or iridium tantalum tin; and the corrosion-resistant chlorine evolution material used in the catalyst C includes ruthenium iridium oxide or iridium tantalum oxide.

[0061] In this embodiment, the specific selection of catalyst B can greatly improve the selectivity of O3 production due to its high electrochemical oxidation potential; the specific selection of catalyst C can effectively combine Cl in the electrolyte. - , oxidized on the electrode surface to produce HClO.

[0062] Preferably, after the electrolyte is circulated for multiple reactions, the concentration of the total oxidant in the HClO-H2O2-O3 composite solution is controlled at 50-200 ppm, and the sterilization rate of the Escherichia coli is greater than 99.99%.

[0063] The present invention also provides an application of a hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method, wherein the prepared HClO-H2O2-O3 composite solution having a specific ratio is used in the fields of environmental pollutant removal, deep treatment of drinking water, disinfection of medical wastewater, and standard discharge of industrial wastewater.

[0064] In this embodiment, after multiple cycles of the electrolyte reaction, the total oxidant concentration can be controlled to 50-200 ppm. This mixed solution can be used not only for water treatment sterilization and organic matter degradation, but also as an environmentally friendly agent for medical device disinfection, surface disinfection, and fabric bleaching.

[0065] In addition, the present invention also develops an online detection and optimization control system based on sensing and automatic control technology, which provides real-time feedback on key parameters such as the electrolyte condition, conductivity, temperature, voltage and current in the reaction system, and realizes closed-loop control of the water pump and the voltage and current of the reaction through a programmable controller, so that the reaction device can operate stably and for a long time in the optimal state, and has water shortage alarm and safety protection functions.

[0066] It is worth mentioning that the difficulty of the synergistic electrochemical preparation method of the present invention lies in balancing the generation of the three components. For anode 1 (generating O3 and HClO): - In the electrolyte, Cl - Oxidation (generating HClO) competes with H2O oxidation (generating O3), and voltage is required to regulate the priority path. High voltage promotes O3 generation, but may lead to Cl - Overoxidation to ClO3 - or ClO4 - (Harmful byproducts). Regarding anode 2 (generating H2O2): H2O reduction to H2O2 requires low voltage. However, if the high voltage at anode 1 interferes with the cathode reaction, the H2O2 yield decreases. Therefore, to control byproduct formation, the voltage distribution must be controlled to achieve a balance between the three components: HClO, H2O2, and O3.

[0067] Example 1

[0068] The electrolyte for preparing the HClO-H2O2-O3 composite solution is tap water, the cathode is preferably a plate or mesh electrode, the conductive substrate is preferably a graphite plate or graphite felt, and the catalyst coating amount is 1-5 mg / cm2; the conductive substrates of the dual anodes are preferably titanium materials, and the shape is preferably a plate or mesh electrode consistent with the cathode, and lead dioxide and ruthenium iridium oxide (molar ratio 1:1) are used on the surface as high-efficiency selective catalysts for ozone evolution and hypochlorous acid evolution, respectively, and the coating thickness is 0.2-2 μm.

[0069] The reaction chamber is square, and anodes with different catalytic activities are placed on the upper and lower sides of the cathode respectively. The inter-electrode distance between the anode and the cathode is preferably between 1 mm and 10 cm. The reaction area is divided into an O3-H2O2 generation area 50 and an HClO-H2O2 generation area 60 by corresponding brackets 3, and the voltage or current density between the electrodes is adjusted in real time by an external control system, thereby regulating the production rate of different products at the electrodes to achieve a suitable mixture ratio.

[0070] The experimental scheme of Example 1 is shown in Table 1. Table 1:

[0071]

[0072] As shown in Table 1, tap water (pH = 7.2, total dissolved solids (TDS) = 150 ppm, total dissolved chlorine 0.6 mg / L) was placed in an external test tank and pumped into the chemical preparation apparatus at a controlled flow rate of 100 mL / min. The cathode was connected to the negative pole of an external power supply, and the positive pole of a dual anode was connected to the positive pole of an external power supply, both powered by 12 V. After a 60-minute cyclic reaction in 1 L of water, a sample of the reaction solution was collected for concentration measurement. H₂O₂ was determined spectrophotometrically using N,N-diethyl-p-phenylenediamine, O₃ was determined iodimetrically, and HClO was determined spectrophotometrically using N,N-diethyl-1,4-phenylenediamine (DPD).

[0073] The results showed that after 60 minutes of reaction, the concentrations of H2O2, O3 and HClO reached 5, 30 and 20 mg / L, respectively, and the reaction device can well produce the corresponding active substances.

[0074] Investigate the bactericidal effect of HClO-H2O2-O3 composite solution on Escherichia coli:

[0075] Take 100ml of the composite solution and 100ml of the single component solution after the reaction is completed, and add about 10 5 CFU / mL Escherichia coli, constant temperature oscillation reaction at 25℃, sampling every 10 minutes, and the colony count and the killing rate of Escherichia coli were determined by plate method as shown in Table 2. Table 2:

[0076]

[0077] Table 2 shows a comparison of the bactericidal effects of various solutions against E. coli. The results show that the HClO-H₂O₂-O₃ composite solution achieved a 99.99% bactericidal rate within 10 minutes. In contrast, the control groups treated with H₂O₂, O₃, or HClO alone achieved bactericidal rates of only 63%, 92%, and 80% within 10 minutes, respectively. This demonstrates that the electrochemically prepared composite solution of the present invention exhibits significant synergistic bactericidal effects.

[0078] Example 2

[0079] The effect of the dual anode current density ratio on the composition of the HClO-H2O2-O3 composite solution and the bacterial killing rate was investigated. The device and operating conditions of Example 1 were used, and the cathode current density was fixed at 20 mA / cm by adjusting the voltage and the effective area of ​​the anode. 2 The total current density of the two anodes is 40 mA / cm 2 The concentrations of various electrolyte components and the killing rate of Escherichia coli were investigated when the ozone anode current density was 20%, 40%, 60% and 80%.

[0080] The experimental scheme of Example 2 is shown in Table 3. Table 3:

[0081]

[0082] The concentrations of the electrolyte components when the ozone anode current density accounts for 20%, 40%, 60%, and 80% are shown in Table 4. Table 4:

[0083]

[0084] The killing rates of E. coli by the concentrations of the various components of the electrolyte are shown in Table 5.

[0085]

[0086] Table 5 shows a comparison of the bactericidal effects of different HClO-H2O2-O3 composite solutions on E. coli. The results show that as the ozone anode current density ratio increases, the O3 concentration gradually increases while the HClO concentration decreases, and the H2O2 concentration remains essentially unchanged. When the ozone anode current density ratio is 20%, 40%, 60%, and 80%, the O3 concentrations are 2, 4, 6, and 8 mg / L, respectively, and the HClO concentrations are 20, 15, 10, and 4 mg / L. The corresponding E. coli kill rates (10 min) are 97.2%, 99.1%, 99.9%, and 99.5%, respectively. When the ozone anode current density ratio is 40-60%, preferably when the O3:HClO mass concentration ratio is in the range of 1:3-1:2, the bactericidal effect is optimal.

[0087] This shows that by controlling the dual anode current density ratio, the composition ratio of the HClO-H2O2-O3 composite solution can be flexibly adjusted to obtain ideal bactericidal and oxidation performance under different water quality conditions.

[0088] The above examples fully demonstrate the excellent performance of the method and system for the electrochemical synergistic preparation of HClO-H2O2-O3 composite liquid of the present invention. The electrochemical device has a novel structure and adopts an integrated design of a common cathode and a separated dual anode to achieve efficient electrosynthesis and compounding of three different active substances. Each electrode uses a stable and efficient catalytic material, and by optimizing the structural parameters and the electrolysis process, the concentration ratio of the HClO-H2O2-O3 composite liquid can be flexibly controlled to obtain the best treatment effect under different water quality conditions. Compared with traditional single-component preparation and mechanical mixing, this technology has obvious advantages in equipment investment, operating costs, product performance, etc., and is expected to lead the innovation of electrochemical sterilization technology and play an important role in the fields of environmental sterilization, pollutant treatment, drinking water disinfection, and medical wastewater treatment.

[0089] Example 3

[0090] This embodiment provides a hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical production device, such as Figure 2-Figure 3 As shown, it includes a shell portion 10 having a reaction chamber, three cathode components 7 are arranged side by side in the reaction chamber, and an ozone anode component 5 and a hypochlorous acid anode component 6 are respectively arranged in two compartments separated by the three cathode components 7. The cathode component 7, the ozone anode component 5, and the hypochlorous acid anode component 6 are all mesh plates and are electrically connected to the positive and negative electrodes of an external power supply through a wiring harness 8. The electrolyte circulates into the reaction chamber to perform an electrochemical reaction and obtain an HClO-H2O2-O3 composite solution.

[0091] As a preference, Figure 3-Figure 4 As shown, the shell portion 10 includes an upper shell 1 and a lower shell 2 that are fixed to each other. The upper shell 1 is provided with a liquid inlet 11 and the lower shell 2 is provided with a liquid outlet 21. The electrolyte flows into the reaction chamber from the liquid inlet 11 and flows out of the reaction chamber from the liquid outlet 21.

[0092] As a preference, Figure 6 As shown, the liquid inlet 11 and the liquid outlet 21 are both arranged to be inclined at an acute angle to the electrode plate component.

[0093] As a preference, Figure 2 As shown, the cathode component 7, the ozone anode component 5, and the hypochlorous acid anode component 6 are all mesh plates, which are distributed with water-permeable holes 72. In addition, a plug 71 for connecting to the wiring harness 8 is provided on one side.

[0094] In this embodiment, by arranging the liquid inlet 11 and the liquid outlet 21 obliquely, not only the engaging area of ​​each electrode component is larger and more stable, but also secondary mixing is performed when the reaction liquid is discharged, thereby improving the homogeneous effect of the composite liquid.

[0095] As a preference, Figure 7 As shown, a limiting rib 13 is convexly provided on the mating surface of the upper shell 1 that is engaged with the lower shell 2, and a limiting groove 23 is concavely provided on the mating surface of the lower shell 2 that is engaged with the upper shell 1, and the limiting rib 13 is matched and engaged in the limiting groove 23.

[0096] As a preference, Figure 8 As shown, fixing grooves 14 are provided on the inner top surface of the upper shell 1 and the inner bottom surface of the lower shell 2 , and the cathode component 7 , the ozone anode component 5 , and the hypochlorous acid anode component 6 are correspondingly inserted into the fixing grooves 14 .

[0097] As a supplementary explanation, the cathode component 7 is made of stainless steel 316L.

[0098] As a supplementary explanation, Figure 2 、 Figure 4 As shown, the wiring harness 8 includes a plug spring 81, a wire buckle 82, and a wire 83, wherein the wire 83 further includes a red wire 84 connected to the cathode component 7 and a black wire 85 connected to the ozone anode component 5 and the hypochlorous acid anode component 6.

[0099] As a preference, Figure 2 As shown, it also includes a bracket 3 and a carbon felt 4, as shown in FIG. Figure 5 As shown, a set of brackets 3 and carbon felt 4 are provided in the interval between the central cathode component 7 and the ozone anode component 5, and a set of brackets 3 and carbon felt 4 are provided in the interval between the central cathode component 7 and the hypochlorous acid anode component 6, so as to separate the reaction chamber into relatively independent O3-H2O2 generation area 50 and HClO-H2O2 generation area 60.

[0100] In this embodiment, O3 is generated on the surface of the ozone anode component 5, and HClO is generated on the surface of the hypochlorous acid anode component 6. Both reactions are generated on the anode surface, that is, the ozone anode component 5 and the cathode component 7 generate O3, and the hypochlorous acid anode component 6 and the cathode component 7 generate HClO. A catalyst is attached to the surface of the carbon felt 4, and a bracket 3 is provided between the carbon felt 4 and the cathode component 7 to ensure that the anode and cathode are not conductive while ensuring the generation of H2O2. As a result, the regions where the three reactions occur are separated from each other, without mutual interference, and the reaction products are mixed with each other.

[0101] It is worth mentioning that the carbon felt 4 is provided in this embodiment to achieve the following effects:

[0102] (1) As a catalyst carrier and enhance electrode catalytic activity: Carbon felt 4 uses porous materials to load highly active catalysts (such as RuO2, Pt nanoparticles), which can enhance Cl - Reaction efficiency of oxidation to HClO or decomposition of H2O to O3;

[0103] (2) Increased specific surface area: The three-dimensional network structure of carbon felt 4 provides more active sites, reduces local current density, reduces electrode passivation, and optimizes electrolyte distribution and mass transfer;

[0104] (3) Uniform fluid distribution: The porous nature of carbon felt 4 promotes uniform flow of electrolyte on the electrode surface, avoiding local concentration polarization (such as Cl - depletion leading to side reactions);

[0105] (4) Core support of membrane-free design: physical isolation is used to replace the semi-permeable membrane, and the partition arrangement of carbon felt 4 (such as separating Cl - enrichment zone and O3 generation zone), reducing component cross-interference and replacing the traditional semi-permeable membrane function.

[0106] 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 scope of protection of the present invention.

Claims

1. A hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method, characterized in that: The following steps are involved: S1, an ozone anode component (5) and a hypochlorous acid anode component (6) are respectively arranged in two compartments separated by three cathode components (7) arranged side by side, and carbon felt (4) is provided between the cathode component (7) in the middle and the anode components on both sides to separate a reaction chamber into an O3-H2O2 generation area (50) and an HClO-H2O2 generation area (60), each anode component and cathode component is provided as a mesh plate, and the three cathodes and two anodes are respectively electrically connected to the positive and negative electrodes of an external power supply; S2. Electrolyte is introduced into the electrolysis chamber, and redox reaction occurs on the surfaces of the ozone anode component (5), the hypochlorous acid anode component (6), and the cathode component (7), wherein the ozone anode component (5) produces O3, the hypochlorous acid anode component (6) produces HClO, and the cathode component (7) produces H2O2; by adjusting the voltage value connected to the ozone anode component (5) and the hypochlorous acid anode component (6), the current density at the two anodes is changed to control the generation rate and relative ratio of O3 and HClO, wherein the current density of the cathode component (7) is controlled to be 10-30 mA / cm 2 The current density of the ozone anode component (5) and the hypochlorous acid anode component (6) are controlled at 20-50 mA / cm 2 and 10-30mA / cm 2 The current density at the ozone anode component (5) accounts for 40-60% of the total current density of the dual anodes; the mass concentration ratio of O3:HClO in the obtained reaction product is 1:3-1:2; S3. The HClO, H2O2, and O3 produced by the electrolysis reaction in step S2 are directly dissolved in the electrolyte, forming and flowing out an HClO-H2O2-O3 composite solution with a specific ratio at the outlet of the electrolysis chamber.

2. The hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method according to claim 1, characterized in that: The electrolyte flow rate was controlled at 50-150 mL / min and the reaction temperature was controlled at 25-40°C.

3. The hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method according to claim 1, characterized in that: The cathode component (7) adopts a conductive porous substrate A to carry catalyst A, wherein the conductive porous substrate A adopts a conductive carbon-based porous material, and the catalyst A adopts iron-nitrogen-carbon, and the carrying amount is 1mg-5mg / cm 2 The ozone anode component (5) adopts a conductive porous substrate B to carry a catalyst B, wherein the conductive porous substrate B adopts a material with a wide electrochemical potential window, and the catalyst B adopts a corrosion-resistant metal oxide coating; the hypochlorous acid anode component (6) adopts a conductive porous substrate C to carry a catalyst C, wherein the conductive porous substrate C adopts titanium, and the catalyst C adopts a corrosion-resistant chlorine evolution material.

4. The hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method according to claim 3, characterized in that: The conductive carbon-based porous material used in the conductive porous substrate A includes graphite plate or graphite felt; the material with a wide electrochemical potential window used in the conductive porous substrate B includes titanium or glassy carbon; the corrosion-resistant metal oxide coating used in the catalyst B includes lead dioxide, antimony tin oxide, or iridium tantalum tin; and the corrosion-resistant chlorine evolution material used in the catalyst C includes ruthenium iridium oxide or iridium tantalum oxide.

5. A hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method according to any one of claims 1 to 4, characterized in that: After the electrolyte is circulated and reacted multiple times, the concentration of the total oxidant in the HClO-H2O2-O3 composite solution is controlled at 50-200 ppm, and its sterilization rate against Escherichia coli is greater than 99.99%.

6. A device using the hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method according to any one of claims 1 to 5, characterized in that: The invention comprises a shell portion (10) having a reaction chamber, wherein three cathode components (7) are arranged side by side in the reaction chamber, wherein an ozone anode component (5) and a hypochlorous acid anode component (6) are respectively arranged in two compartments separated by the three cathode components (7), and carbon felt (4) is arranged between the cathode component (7) in the middle and the anode components on both sides to separate the reaction chamber into an O3-H2O2 generation area (50) and an HClO-H2O2 generation area (60), wherein the cathode component (7), the ozone anode component (5), and the hypochlorous acid anode component (6) are all mesh plates and are respectively electrically connected to the positive and negative electrodes of an external power supply through a wiring harness (8), wherein an electrolyte circulates in the reaction chamber to perform an electrochemical reaction and obtain an HClO-H2O2-O3 composite solution.

7. The hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical production device according to claim 6, characterized in that: The invention also includes a bracket (3) and a carbon felt (4), wherein a group of brackets (3) and carbon felt (4) are arranged in the interval between the cathode component (7) and the ozone anode component (5), and a group of brackets (3) and carbon felt (4) are arranged in the interval between the cathode component (7) and the hypochlorous acid anode component (6).

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