Hypochlorous acid-hydrogen peroxide-ozone synergistic electrochemical preparation method, device and application thereof

Abstract

The invention provides a hypochlorous acid-hydrogen peroxide-ozone synergetic electrochemical preparation method and device and application of the hypochlorous acid-hydrogen peroxide-ozone synergetic electrochemical preparation method, dissolved oxygen is reduced by a cathode to generate H2O2, meanwhile, a double-anode structure with different catalytic characteristics is utilized, one anode electrolyzes water through a high overpotential material to selectively generate O3, and the other anode electrochemically generates HClO through a chlorine-containing electrolyte. Therefore, electro-catalysis in-situ synergistic electro-synthesis preparation of the three components is ingeniously integrated in the same reaction device, integrated electrochemical preparation of the efficient composite oxidizing agent is achieved, and the prepared HClO-H2O2-O3 composite solution is far better than a single component in sterilization, disinfection and organic pollutant degradation performance. The comprehensive efficiency and the application field of the electrochemical synthesis technology can be obviously improved.

Description

Technical Field

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

[0002] Hydrogen peroxide (H2O2), ozone (O3) and hypochlorous acid (HClO) are three strong oxidizing agents, which are widely used in the fields of drinking water, advanced wastewater treatment and disinfection. In traditional synthesis methods, H2O2 is mainly prepared by liquid-phase chemistry, O3 is prepared by high-voltage discharge or photochemistry, and HClO is prepared by electrolyzing chlorine-containing water. There are problems such as high process energy consumption, high safety risks and less-than-ideal product purity. With the increasingly prominent environmental problems, it has become an urgent task to develop a new preparation technology that is economical, efficient, green and environmentally friendly.

[0003] Electrochemical synthesis method has become an ideal preparation route for oxidizing agents due to its advantages such as wide raw material sources (water, oxygen, chloride ions), simple equipment process and controllable product purity. Currently, new electro-synthesis processes such as reducing dissolved oxygen at the cathode in the electrolyte to produce H2O2, oxidizing O2 at the anode to produce O3, and oxidizing chloride ions at the anode to produce HClO have been successively developed, which simplifies the process and reduces the cost. However, the efficacy of using a single component is still not satisfactory. By compounding, the bactericidal and oxidation performance can be significantly improved, but mechanically mixing two or more components has the problems of secondary pollution risk and high preparation and storage and transportation costs. Therefore, there is an urgent need for a new on-site compound preparation technology that is efficient, environmentally friendly and economical.

[0004] How to use the cathode and multiple electrocatalytic anodes in the same reaction device to respectively reduce and produce H2O2, oxidize and produce O3 and HClO, so as to realize the integrated in-situ electro-synthesis and compounding of key components, is a major scientific and technological problem currently faced. This is of great significance for breaking through the limitations of traditional single-component preparation and mechanical compounding, greatly improving the preparation efficiency, performance and application fields of oxidizing agents, and promoting the leapfrog development of electrochemical sterilization and disinfection technology. Summary of the Invention

[0005] One of the purposes of the present invention is to provide a synergistic electrochemical preparation method and device of hypochlorous acid - hydrogen peroxide - ozone in view of the deficiencies of the prior art, which realizes the efficient synergistic electro-synthesis and homogeneous compounding of three key components of HClO - H2O2 - O3 in the same reaction device, breaks through the limitations of traditional single-component preparation and mechanical compounding, and the prepared HClO - H2O2 - O3 composite solution far exceeds single components in terms of bactericidal disinfection and degradation performance of organic pollutants, and can significantly improve the comprehensive efficacy and application fields of electrochemical synthesis technology.

[0006] To achieve the above object, the present invention provides the following technical solutions: A synergistic electrochemical preparation method of hypochlorous acid - hydrogen peroxide - ozone, comprising the following steps: S1. One ozone anode component and one hypochlorous acid anode component are respectively arranged in two intervals separated by three cathode components arranged side by side. Each anode component and cathode component are set 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. An electrolyte is introduced into the electrolysis chamber, and redox reactions occur on the surfaces of the ozone anode component, hypochlorous acid anode component, and cathode component. Among them, O3 is generated by the ozone anode component, HClO is generated by the hypochlorous acid anode component, and H2O2 is generated by the cathode component; S3. The HClO, H2O2, and O3 generated by the electrolysis reaction in step S2 are all directly dissolved in the electrolyte, and a HClO - H2O2 - O3 composite solution with a specific ratio is formed and flows out at the outlet of the electrolysis chamber.

[0007] Preferably, tap water is used as the electrolyte. During the electrochemical reaction, the electrolyte flows on the surfaces of the ozone anode component, hypochlorous acid anode component, and cathode component under the drive of a pump and overflows and discharges.

[0008] Preferably, by adjusting the voltage values connected to the ozone anode component and the hypochlorous acid anode component, the current densities at the two anodes are changed, and the generation rates and relative ratios of O3 and HClO are controlled.

[0009] Preferably, the current density of the cathode component is 10 - 30 mA / cm 2 , and the current densities of the ozone anode component and the hypochlorous acid anode component are respectively controlled at 20 - 50 mA / cm 2 and 10 - 30 mA / cm 2 , the flow rate of the electrolyte is 50 - 150 mL / min, and the reaction temperature is 25 - 40 °C.

[0010] Preferably, the current density at the ozone anode component accounts for 40 - 60% of the total current density of the double anodes. When the current density of the cathode component remains unchanged, after the electrolyte is recycled and reacted multiple times, the mass concentration ratio of O3:HClO in the obtained HClO - H2O2 - O3 composite solution is 1:3 - 1:2.

[0011] Preferably, the cathode component uses a conductive porous substrate A loaded with catalyst A. Among them, the conductive porous substrate A uses a conductive carbon - based porous material, and the catalyst A uses iron - nitrogen - carbon, and the loading amount is 1 mg - 5 mg / cm 2; The ozone anode component uses a conductive porous substrate B carrying catalyst B. Among them, the conductive porous substrate B uses a material with a wide electrochemical potential window, and the catalyst B uses a corrosion-resistant metal oxide coating; the hypochlorous acid anode component uses a conductive porous substrate C carrying catalyst C. Among them, the conductive porous substrate C uses titanium, and the catalyst C uses a corrosion-resistant chlorine evolution material.

[0012] Preferably, the conductive carbon-based porous material used for the conductive porous substrate A includes a graphite plate or a graphite felt; the material with a wide electrochemical potential window used for the conductive porous substrate B includes titanium or glassy carbon; the corrosion-resistant metal oxide coating used for the catalyst B includes lead dioxide, antimony tin oxide, or iridium tantalum tin; the corrosion-resistant chlorine evolution material used for the catalyst C includes ruthenium iridium oxide or iridium tantalum oxide.

[0013] Preferably, 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 bactericidal rate against Escherichia coli is greater than 99.99%.

[0014] The second object of the present invention is to provide a hypochlorous acid - hydrogen peroxide - ozone synergistic electrochemical preparation device, including a housing part with a reaction chamber. Three cathode components are arranged side by side in the reaction chamber. An ozone anode component and a hypochlorous acid anode component are respectively arranged in the two intervals 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 respectively electrically connected to the positive and negative electrodes of an external power supply through wire harnesses. The electrolyte circulates into the reaction chamber for electrochemical reaction to obtain an HClO - H2O2 - O3 composite solution.

[0015] Preferably, the housing part includes an upper shell and a lower shell that are snap-fitted and 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.

[0016] Preferably, both the liquid inlet and the liquid outlet are arranged in an inclined manner at an acute angle to the plate component.

[0017] Preferably, a limiting rib is convexly provided on the mating surface of the upper shell that engages with the lower shell, and a limiting groove is concavely provided on the mating surface of the lower shell that engages with the upper shell. The limiting rib is snap-fitted in the limiting groove.

[0018] Preferably, fixing grooves are opened on the inner top surface of the upper shell and the inner bottom surface of the lower shell. The cathode component, the ozone anode component, and the hypochlorous acid anode component are correspondingly inserted into the fixing grooves.

[0019] Preferably, it further includes a bracket and a carbon felt. A set of bracket and carbon felt are arranged in the interval between the cathode component in the middle and the ozone anode component, and a set of bracket and carbon felt are arranged in the interval between the cathode component in the middle and the hypochlorous acid anode component, so as to divide the reaction chamber into a relatively independent O3-H2O2 generation area and a HClO-H2O2 generation area. It not only plays a mechanical support role, but also undertakes functions such as electrolyte diversion.

[0020] The present invention also provides an application of the synergistic electrochemical preparation method of hypochlorous acid-hydrogen peroxide-ozone. The prepared HClO-H2O2-O3 composite solution with a specific ratio is used in the fields of environmental pollutant removal, advanced treatment of drinking water, disinfection of medical sewage, and up-to-standard discharge of industrial wastewater.

[0021] The beneficial effects of the present invention are as follows: (1) The core concept of the present invention is to construct a novel composite electrochemical device composed of a cathode for co-producing H2O2, a separated anode for producing O3, and an anode for producing HClO. The cathode side uses a conductive porous substrate to load the corresponding catalyst, which has high reactivity and good selectivity with dissolved oxygen. The anode side is designed with a double-electrode structure with different active coatings, which are optimized for the generation of O3 and HClO respectively. On the basis of the conventional cathode reduction preparation of H2O2, a new function of electrochemical synergy with double anodes of different materials is creatively introduced, realizing the efficient co-electrosynthesis and homogeneous compounding of three key components of HClO-H2O2-O3 in the same reaction device, achieving a high degree of coupling between the in-situ electrochemical 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 being more easily realized for intelligent and small modular applications.

[0022] (2) The present invention ingeniously integrates the electrocatalytic in-situ co-electrosynthesis preparation of three components in the same reaction device. While the cathode reduces dissolved oxygen to generate H2O2, a double-anode structure with different catalytic characteristics is used. One anode selectively generates O3 by electrolyzing water with a high-potential material, and the other anode electrochemically generates HClO through a chlorine-containing electrolyte (such as ordinary tap water), realizing the integrated electrochemical preparation of a highly efficient composite oxidant.

[0023] (3) In the same electrolyte system of the present invention, by precisely controlling each electrode parameter through an automatic control system, including adjusting the voltage at both ends of the double anode and changing the current density at different anodes, the generation rates and relative proportions of O3 and HClO can be precisely controlled, realizing the precise control of the concentration and proportion of each component in the composite solution, making the composition of the composite solution adapt to 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.

[0024] (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.

[0025] (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.

[0026] (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.

[0027] (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.

[0028] 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

[0029] 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; Figure 2 An exploded view of the HClO-H2O2-O3 synergistic electrochemical preparation device of the present invention; Figure 3This is a front - view schematic diagram of the overall structure of the HClO - H2O2 - O3 synergistic electrochemical preparation device in the present invention; Figure 4 This is a rear - view schematic diagram of the overall structure of the HClO - H2O2 - O3 synergistic electrochemical preparation device in the present invention; Figure 5 This is the layout diagram of the bracket and carbon felt in the present invention; Figure 6 This is the front view of the HClO - H2O2 - O3 synergistic electrochemical preparation device in the present invention; Figure 7 This is the transverse cross - sectional view of the HClO - H2O2 - O3 synergistic electrochemical preparation device in the present invention; Figure 8 This is the longitudinal cross - sectional view of the HClO - H2O2 - O3 synergistic electrochemical preparation device in the present invention. Detailed implementation manners

[0030] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.

[0031] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus cannot be understood as a limitation of the present invention. In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of such features. In the description of the present invention, "a plurality" means two or more unless otherwise specifically defined.

[0032] A method for synergistic electrochemical preparation of hypochlorous acid - hydrogen peroxide - ozone includes the following steps: S1. In each of the two intervals separated by three cathode components 7 arranged side by side, an ozone anode component 5 and a hypochlorous acid anode component 6 are arranged respectively. Each anode component and cathode component is set 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. An electrolytic solution is introduced into the electrolytic 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. Among them, the ozone anode component 5 generates O3, the hypochlorous acid anode component 6 generates HClO, and the cathode component 7 generates H2O2; S3. The HClO, H2O2, and O3 generated by the electrolytic reaction in step S2 are all directly dissolved in the electrolytic solution, and a HClO - H2O2 - O3 composite solution with a specific ratio is formed and flows out at the outlet of the electrolytic chamber.

[0033] During the electrochemical reaction, the electrolytic solution flows and overflows under the drive of a pump through the surfaces of the ozone anode component 5, the hypochlorous acid anode component 6, and the cathode component 7. An electrocatalytic reduction reaction of O2 occurs on the surface of the cathode component 7: O2 + 2H + + 2e - → H2O2 E 0 = 0.68 V; Meanwhile, by changing the anodic oxidation potential through the anode catalyst material, the oxygen-containing electrolytic solution is oxidized to generate ozone on the surface of the ozone anode component 5, and its electrochemical reaction equation is: 2H2O → O3 + 6H + + 6e - E 0 = 1.51 V (direct oxidation of water) 3O2 → 2O3 E 0 = 2.07 V (direct oxidation of oxygen) On the surface of the hypochlorous acid anode component 6, the corresponding chlorine evolution catalyst is used to combine and oxidize chloride ions in water to generate hypochlorous acid: Cl - + H2O → HClO + H + + 2e - E 0 = 1.49 V Preferably, tap water is used as the electrolytic solution.

[0034] Preferably, by adjusting the voltage values connected to the ozone anode component 5 and the hypochlorous acid anode component 6, the current densities at the two anodes are changed to control the generation rates and relative proportions of O3 and HClO.

[0035] Preferably, under the optimal process conditions, the current density of the cathode component 7 is 10 - 30 mA / cm 2, the current densities of the ozone anode component 5 and the hypochlorous acid anode component 6 are respectively controlled at 20 - 50 mA / cm 2 and 10 - 30 mA / cm 2 , the flow rate of the electrolyte is 50 - 150 mL / min, and the reaction temperature is 25 - 40 °C.

[0036] Preferably, the proportion of the current density at the ozone anode component 5 is controlled at 40 - 60%, and the mass concentration ratio of O3:HClO in the obtained reaction product is 1:3 - 1:2.

[0037] Preferably, the cathode component 7 uses a conductive porous substrate A carrying a catalyst A. Among them, the conductive porous substrate A uses a conductive carbon-based porous material, and the catalyst A uses iron-nitrogen-carbon with a loading amount of 1 mg - 5 mg / cm 2 ; the ozone anode component 5 uses a conductive porous substrate B carrying a catalyst B. Among them, the conductive porous substrate B uses a material with a wide electrochemical potential window, and the catalyst B uses a corrosion-resistant metal oxide coating; the hypochlorous acid anode component 6 uses a conductive porous substrate C carrying a catalyst C. Among them, the conductive porous substrate C uses titanium, and the catalyst C uses a corrosion-resistant chlorine evolution material.

[0038] Preferably, the conductive carbon-based porous material used for the conductive porous substrate A includes graphite plates or graphite felts; the material with a wide electrochemical potential window used for the conductive porous substrate B includes titanium or glassy carbon; the corrosion-resistant metal oxide coating used for the catalyst B includes lead dioxide, stannic oxide antimony, or iridium tantalum tin; the corrosion-resistant chlorine evolution material used for the catalyst C includes ruthenium iridium oxide or iridium tantalum oxide.

[0039] In this embodiment, for the specific selection of the catalyst B, due to its relatively high electrochemical oxidation potential, the selectivity for O3 generation can be greatly improved; for the specific selection of the catalyst C, it can effectively combine Cl - in the electrolyte to oxidize and generate HClO on the electrode surface.

[0040] Preferably, after the electrolyte is recycled 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 bactericidal rate against Escherichia coli is greater than 99.99%.

[0041] The present invention also provides an application of the synergistic electrochemical preparation method of hypochlorous acid - hydrogen peroxide - ozone. The prepared HClO - H2O2 - O3 composite solution with a specific ratio is used in the fields of environmental pollutant removal, advanced treatment of drinking water, disinfection of medical sewage, and up-to-standard discharge of industrial wastewater.

[0042] In this embodiment, after the electrolyte is cycled and reacted multiple times, the total oxidant concentration can be controlled within 50 - 200 ppm. This mixture can be used not only for water treatment disinfection and organic matter degradation, but also as an environmentally friendly agent in the fields of medical device disinfection, surface disinfection, fabric bleaching, etc.

[0043] In addition, the present invention also develops an online detection and optimization control system based on sensing and automatic control technologies, which can real-time feedback key parameters such as the electrolyte condition, conductivity, temperature, voltage, and current in the reaction system, and achieve closed-loop control of the water pump, reaction voltage, and current through a programmable controller. This enables the reaction device to operate stably in the optimal state for a long time and has functions of water shortage alarm and safety protection.

[0044] It is worth supplementing that the difficult point of the synergistic electrochemical preparation method involved in the present invention lies in balancing the generation of three components. For anode 1 (generating O3 and HClO): in the Cl - electrolyte, the oxidation of Cl - (generating HClO) and the oxidation of H2O (generating O3) compete. It is necessary to regulate the priority path through voltage control. High voltage promotes the generation of O3, but may cause the over-oxidation of Cl - to ClO3 - or ClO4 - (harmful by-products). For anode 2 (generating H2O2): it is necessary to reduce H2O to generate H2O2 at a low voltage. However, if the high voltage of anode 1 interferes with the cathode reaction, the H2O2 yield will decrease. Therefore, to control the generation of by-products, it is necessary to control the voltage distribution to achieve the balance of the contents of the three components of HClO - H2O2 - O3.

[0045] Example 1 The electrolyte for preparing the HClO - H2O2 - O3 composite solution uses tap water. The cathode preferably uses a plate-shaped or mesh-shaped electrode, and its conductive substrate preferably uses a graphite plate or graphite felt, with the catalyst coating amount being 1 - 5 mg / cm2; the conductive substrates of the dual anodes preferably use titanium materials respectively, and the shape is preferably a plate-shaped or mesh-shaped electrode consistent with the cathode. The surfaces respectively use lead dioxide and ruthenium iridium oxide (molar ratio 1:1) as efficient selective catalysts for ozone evolution and hypochlorous acid evolution, and the coating thickness is 0.2 - 2 μm for both.

[0046] Among them, the reaction chamber is square. The anodes with different catalytic activities are respectively placed on the upper and lower sides of the cathode. The electrode spacing 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 through the corresponding brackets 3 respectively, and the voltage or current density between the electrodes is adjusted in real time through an external control system, so as to regulate the generation rate of different products at the electrodes to achieve a suitable mixture ratio.

[0047] The experimental scheme of Example 1 is shown in Table 1. Table 1:

[0048] 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 water tank and pumped into the chemical preparation device, and the flow rate was controlled at 100 mL / min. The cathode was connected to the negative pole of the external power supply, and the dual anodes were connected to the positive pole of the external power supply and powered at 12V respectively. After circulating and reacting in 1 L of water for 60 min, the reaction liquid sample was taken for concentration testing. Hydrogen peroxide was determined by N,N - diethyl - p - phenylenediamine spectrophotometry, ozone was determined by iodometry, and hypochlorous acid was determined by N,N - diethyl - 1,4 - phenylenediamine (DPD) spectrophotometry.

[0049] The results showed that after reacting for 60 min, the concentrations of hydrogen peroxide, ozone, and hypochlorous acid reached 5, 30, and 20 mg / L respectively, and the reaction device could produce the corresponding active substances well.

[0050] Examine the bactericidal effect of the HClO - H2O2 - O3 composite solution on Escherichia coli: 100 ml of the composite solution after the reaction and 100 ml of the single - component solution were respectively taken, and about 10 5 CFU / mL of Escherichia coli were added. The reaction was carried out with constant temperature oscillation at 25°C. Samples were taken every 10 min, and the colony count was determined by the plate method. The killing rates of Escherichia coli are shown in Table 2. Table 2:

[0051] The above Table 2 shows the comparison of the bactericidal effects of each solution on Escherichia coli. The results showed that the bactericidal rate of the HClO - H2O2 - O3 composite solution reached 99.99% within 10 min. While for the control groups treated with hydrogen peroxide, ozone, or hypochlorous acid alone, the bactericidal rates within 10 min were only 63%, 92%, and 80% respectively. It can be seen that the composite solution prepared electrochemically in the present invention has a significant synergistic bactericidal effect.

[0052] Example 2 Examine the influence of the dual - anode current density ratio on the composition of the HClO - H2O2 - O3 composite solution and the bactericidal rate. Using the device and operating conditions of Example 1, by adjusting the voltage and the effective area of the anode, the cathode current density was fixed at 20 mA / cm 2 , and the total dual - anode current density was 40 mA / cm 2 . The concentrations of each component in the electrolyte and the bactericidal rate against Escherichia coli were respectively examined when the proportion of the ozone anode current density was 20%, 40%, 60%, and 80%.

[0053] The experimental scheme of Example 2 is shown in Table 3. Table 3:

[0054] When the proportion of ozone anode current density is 20%, 40%, 60%, and 80%, the concentrations of each component in the electrolyte are shown in Table 4. Table 4:

[0055] The killing rates of each component in the electrolyte on Escherichia coli are shown in Table 5. Table 5:

[0056] The above Table 5 shows the comparison of the bactericidal effects of different concentration ratios of the HClO - H2O2 - O3 composite solution on Escherichia coli. The results show that as the proportion of ozone anode current density increases, the O3 concentration gradually increases while the HClO concentration decreases, and the H2O2 concentration remains basically unchanged. When the proportion of ozone anode current density = 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 killing rates of Escherichia coli (10 min) are 97.2%, 99.1%, 99.9%, and 99.5% respectively. When the proportion of ozone anode current density is 40 - 60%, and preferably the mass concentration ratio of O3:HClO is in the range of 1:3 - 1:2, the bactericidal effect is the best.

[0057] This shows that by controlling the ratio of the dual - anode current density, the composition ratio of the HClO - H2O2 - O3 composite solution can be flexibly regulated to obtain ideal bactericidal and oxidation performances under different water quality conditions.

[0058] The above examples fully demonstrate the excellent performance of the method and system for electrochemically synergistically preparing the HClO - H2O2 - O3 composite solution of the present invention. The electrochemical device has a novel structure, adopts an integrated design of a common cathode and separated dual anodes, and realizes the efficient electro - synthesis and compounding of three different active substances. Each electrode uses a stable and efficient catalytic material, and by optimizing the structural parameters and electrolysis process, the concentration ratio of the HClO - H2O2 - O3 composite solution 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 terms of equipment investment, operation cost, product performance, etc., and is expected to lead the innovation of electro - chemical sterilization technology and play an important role in fields such as environmental sterilization, pollutant treatment, drinking water disinfection, and medical wastewater treatment.

[0059] Example 3 This example provides a hypochlorous acid - hydrogen peroxide - ozone synergistic electrochemical preparation device, as Figures 2 - 3As shown in the figure, it includes a housing part 10 with a reaction chamber, in which three cathode components 7 are arranged side by side. An ozone anode component 5 and a hypochlorous acid anode component 6 are respectively arranged in two intervals 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 respectively electrically connected to the positive and negative electrodes of an external power supply through wire harnesses 8. The electrolyte circulates into the reaction chamber for electrochemical reaction, and a HClO-H2O2-O3 composite solution is obtained.

[0060] Preferably, as Figures 3 - 4 shown in the figure, the housing part 10 includes an upper shell 1 and a lower shell 2 that are snap-fitted and fixed to each other. A liquid inlet 11 is arranged on the upper shell 1, and a liquid outlet 21 is arranged on the lower shell 2. The electrolyte flows into the reaction chamber from the liquid inlet 11 and flows out of the reaction chamber from the liquid outlet 21.

[0061] Preferably, as Figure 6 shown in the figure, both the liquid inlet 11 and the liquid outlet 21 are arranged in an inclined manner at an acute angle to the plate components.

[0062] Preferably, as Figure 2 shown in the figure, the fact that the cathode component 7, the ozone anode component 5, and the hypochlorous acid anode component 6 are all mesh plates means that water-permeable holes 72 are distributed on them. In addition, a tab 71 for connecting with the wire harness 8 is arranged on one side of it.

[0063] In this embodiment, by obliquely arranging both the liquid inlet 11 and the liquid outlet 21, not only is the clamping area of each plate component larger and more stable, but also it plays a role of secondary mixing when the reaction liquid exits, thereby improving the homogeneous effect of the composite liquid.

[0064] Preferably, as Figure 7 shown in the figure, a limiting rib 13 is convexly arranged on the mating surface of the upper shell 1 that is snap-fitted with the lower shell 2, and a limiting groove 23 is concavely arranged on the mating surface of the lower shell 2 that is snap-fitted with the upper shell 1. The limiting rib 13 is snap-fitted in the limiting groove 23.

[0065] Preferably, as Figure 8 shown in the figure, fixing grooves 14 are opened on the inner top surface of the upper shell 1 and the inner bottom surface of the lower shell 2. The cathode component 7, the ozone anode component 5, and the hypochlorous acid anode component 6 are correspondingly inserted into the fixing grooves 14.

[0066] As supplementary explanation, the cathode component 7 is made of stainless steel 316L material.

[0067] As supplementary explanation, as Figure 2 、 Figure 4As shown, the wire harness 8 includes a plug spring 81, a wire pressing buckle 82, and a wire 83. 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.

[0068] Preferably, as Figure 2 shown, it further includes a bracket 3 and a carbon felt 4. As Figure 5 shown, a set of bracket 3 and carbon felt 4 are arranged in the interval between the cathode component 7 and the ozone anode component 5 in the middle, and a set of bracket 3 and carbon felt 4 are arranged in the interval between the cathode component 7 and the hypochlorous acid anode component 6 in the middle, so as to divide the reaction chamber into relatively independent O3-H2O2 generation area 50 and HClO-H2O2 generation area 60.

[0069] 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 are generated on the anode surface, that is, O3 is generated between the ozone anode component 5 and the cathode component 7, and HClO is generated between the hypochlorous acid anode component 6 and the cathode component 7. The catalyst is attached to the surface of the carbon felt 4, and there is a bracket 3 between the carbon felt 4 and the cathode component 7, which can ensure that the anode and cathode are not electrically connected and at the same time ensure the generation of H2O2. Thus, the regions where the three reactions occur are separated from each other without mutual interference, while the reaction products are mixed with each other.

[0070] It is worth supplementing that by setting the carbon felt 4 in this embodiment, the following functions are achieved: (1) As a catalyst carrier, enhancing the catalytic activity of the electrode: The carbon felt 4 uses a porous material and loads a highly active catalyst (such as RuO2, Pt nanoparticles), which can improve the reaction efficiency of Cl - being oxidized to HClO or H2O being decomposed into O3; (2) Increasing the specific surface area: The three-dimensional network structure of the carbon felt 4 provides more active sites, reduces the local current density, reduces electrode passivation, and optimizes the electrolyte distribution and mass transfer; (3) Uniform fluid distribution: The porous property of the carbon felt 4 promotes the uniform flow of the electrolyte on the electrode surface, avoiding local concentration polarization (such as side reactions caused by Cl - depletion); (4) The core support for the membrane-free design: Using physical isolation to replace the semi-permeable membrane, through the partition arrangement of the carbon felt 4 (such as separating the Cl - enrichment area and the O3 generation area), reducing the cross-interference of components and replacing the function of the traditional semi-permeable membrane.

[0071] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A synergistic electrochemical preparation method of hypochlorous acid - hydrogen peroxide - ozone, characterized in that, It includes the following steps: S1. An ozone anode component (5) and a hypochlorous acid anode component (6) are respectively arranged in two intervals separated by three cathode components (7) arranged side by side. Each anode component and cathode component are set 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. An electrolytic solution is introduced into the electrolytic 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). Among them, the ozone anode component (5) generates O3, the hypochlorous acid anode component (6) generates HClO, and the cathode component (7) generates H2O2; S3. The HClO, H2O2, and O3 generated by the electrolytic reaction in step S2 are all directly dissolved in the electrolytic solution, and a HClO-H2O2-O3 composite solution with a specific ratio is formed and flows out at the outlet of the electrolytic chamber.

2. The co-electrochemical preparation method of hypochlorous acid - hydrogen peroxide - ozone according to claim 1, wherein By adjusting the voltage values connected to the ozone anode component (5) and the hypochlorous acid anode component (6), the current densities at the two anodes are changed to control the generation rates and relative ratios of O3 and HClO.

3. A synergistic electrochemical preparation method of hypochlorous acid - hydrogen peroxide - ozone according to claim 2, characterized in that, The current density of the cathode component (7) is 10 - 30 mA / cm 2 , and the current densities of the ozone anode component (5) and the hypochlorous acid anode component (6) are controlled at 20 - 50 mA / cm 2 and 10 - 30 mA / cm 2 , the flow rate of the electrolyte is 50 - 150 mL / min, and the reaction temperature is 25 - 40 °C.

4. A synergistic electrochemical preparation method of hypochlorous acid - hydrogen peroxide - ozone according to claim 2, characterized in that, Among them, the current density at the ozone anode component (5) accounts for 40-60% of the total current density of the double anodes, and the mass concentration ratio of O3:HClO in the reaction product obtained is 1:3-1:

2.

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

6. The synergistic electrochemical preparation method of hypochlorous acid-hydrogen peroxide-ozone according to claim 5, characterized in that, The conductive carbon-based porous material used for the conductive porous substrate A includes a graphite plate or a graphite felt; the material with a wide electrochemical potential window used for the conductive porous substrate B includes titanium or glassy carbon; the corrosion-resistant metal oxide coating used for the catalyst B includes lead dioxide, stannic oxide antimony, or iridium tantalum tin; the corrosion-resistant chlorine evolution material used for the catalyst C includes ruthenium iridium oxide or iridium tantalum oxide.

7. A method for synergistic electrochemical preparation of hypochlorous acid - hydrogen peroxide - ozone, according to any one of claims 1 - 6, characterized in that, After the electrolytic solution is subjected to multiple cyclic reactions, the concentration of the total oxidant in the HClO-H2O2-O3 composite solution is controlled at 50-200 ppm, and its bactericidal rate against Escherichia coli is greater than 99.99%.

8. An apparatus for synergistic electrochemical preparation of hypochlorous acid - hydrogen peroxide - ozone, characterized in that, It includes a housing part (10) having a reaction chamber, in which three cathode components (7) are arranged side by side. An ozone anode component (5) and a hypochlorous acid anode component (6) are respectively arranged in two intervals 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 respectively electrically connected to the positive and negative electrodes of an external power supply through wire harnesses (8). The electrolytic solution circulates into the reaction chamber for an electrochemical reaction, and a HClO-H2O2-O3 composite solution is obtained.

9. The synergistic electrochemical preparation device of hypochlorous acid - hydrogen peroxide - ozone according to claim 8, characterized in that, It also includes a bracket (3) and a carbon felt (4). A group of brackets (3) and a carbon felt (4) are arranged in the interval between the middle cathode component (7) and the ozone anode component (5), and a group of brackets (3) and a carbon felt (4) are arranged in the interval between the middle cathode component (7) and the hypochlorous acid anode component (6) to divide the reaction chamber into a relatively independent O3-H2O2 generation area (50) and a HClO-H2O2 generation area (60).

10. Use of a synergistic electrochemical preparation method of hypochlorous acid - hydrogen peroxide - ozone according to any one of claims 1 - 7, characterized in that, The prepared HClO-H2O2-O3 composite solution with a specific ratio is used in the fields of environmental pollutant removal, advanced treatment of drinking water, disinfection of medical sewage, and up-to-standard discharge of industrial wastewater.

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