Method and device for electrochemically co-producing hypochlorous acid and hydrogen peroxide and applications thereof

Abstract

The application provides a hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation method and device and application thereof. A cathode and anode synergistic reaction system is designed, electrolytic preparation of HClO and H2O2 is ingeniously coupled in the same electrochemical process, double-product output is completed in a single electrolytic cell, in-situ efficient electro-synthesis of two kinds of high-value-added oxidants is realized, and mixed synergistic amplification is realized. The device complexity and production energy consumption are significantly reduced, the product selectivity, reaction stability and synergistic effect are greatly improved, a new electrochemical synthesis method is opened up, and the prepared HClO-H2O2 composite solution plays a synergistic sterilization and oxidation synergistic effect, and is especially suitable for disinfection and sterilization, industrial water treatment, medical wastewater purification and chemical synthesis fields.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electrochemistry, in particular to a method and device for electrochemically co-preparing hypochlorous acid and hydrogen peroxide, and applications thereof. BACKGROUND

[0002] In traditional synthesis methods, hypochlorous acid is usually prepared by electrolysis method, sodium hypochlorite (NaClO) is generated by electrolyzing sodium chloride solution, and HClO is obtained by acidification. This method has the following problems: (1) serious anode side reaction: oxygen evolution reaction (OER) and chlorine evolution reaction (Cl2 generation) lead to low current efficiency (usually <70%); (2) complex product separation: an additional acidification step is required, increasing equipment cost and operation difficulty; (3) high energy consumption: typical energy consumption is 6-8 kWh / kg HClO, poor economic efficiency. Chemical synthesis method can also be used, such as reaction of chlorine gas with water to generate HClO, but chemical synthesis method requires high-purity chlorine gas raw material, which has safety risks and environmental pollution.

[0003] The preparation of hydrogen peroxide usually adopts the current industrial mainstream anthraquinone method, but it has the following defects: complex process, multi-step hydrogenation, oxidation and extraction operation, large equipment investment; serious pollution, anthraquinone organic matter is easy to degrade and fail, high waste liquid treatment cost; high energy consumption. Electrochemical method can also be used, which generates H2O2 through cathode oxygen reduction reaction (ORR), but is limited by low selectivity of catalyst, high proportion of side reaction of four-electron reduction to generate H2O (H2O2 selectivity <60%); hydrogen evolution reaction (HER) competes, hydrogen evolution easily occurs at the cathode under acidic or neutral conditions, further reducing the yield.

[0004] Currently, there is a gap in the co-production technology of HClO and H2O2. When both hypochlorous acid and hydrogen peroxide need to exist in the solution, the user needs to prepare hypochlorous acid and hydrogen peroxide separately and then mix them for use. This method of separate preparation and mixing has the problems of complicated process, high cost, poor synergy, etc. In traditional process, the preparation of HClO and H2O2 requires independent equipment, H2O2 electrolytic tank (usually using anthraquinone method) and HClO generating device (such as chlor-alkali electrolysis) are constructed respectively, which has large equipment area, large investment, high energy consumption, complex operation and maintenance; in addition, there are problems of repeated consumption of raw materials and energy, high comprehensive cost, and limited application scenarios of products (such as disinfection requiring secondary mixing).

[0005] The applicant applied for a patent with publication number CN120026334A on March 25, 2025, which is a hypochlorous acid and hydrogen peroxide synergistic electrochemical device, a preparation method and applications thereof. The hypochlorous acid and hydrogen peroxide synergistic electrochemical device includes a shell, a liquid inlet and a liquid outlet, the shell is provided with an electrolyte chamber, a cathode reaction assembly, an anode reaction assembly and a spoiler assembly for increasing the moving stroke of the liquid in the electrolyte chamber. The invention can generate hydrogen peroxide and hypochlorous acid simultaneously in the same electrolyte chamber, without the need for separate preparation and mixing, thereby simplifying the process, reducing costs, and improving the synergy of hypochlorous acid and hydrogen peroxide.

[0006] However, the above-mentioned application adopts a scheme of synchronously generating H2O2 and HClO, and the entire reaction process depends on the structural design of the specific device. Moreover, the synchronous generation of H2O2 and HClO will cause mutual consumption during the generation stage, which makes it difficult to maintain a high active concentration and achieve complete sterilization effect in subsequent applications. Therefore, there is an urgent need in the field to propose a scheme that can solve the technical problem of mutual consumption of H2O2 and HClO during the generation stage. SUMMARY

[0007] One of the purposes of the present application is to overcome the shortcomings of the prior art and provide a hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation method, device and applications thereof. The cathode and anode synergistic reaction system design cleverly couples the electrolytic preparation of HClO and H2O2 in the same electrochemical process and completes the output of the double products in a single electrolytic cell. The generation sequence of HClO and H2O2 is set, H2O2 is generated through a specific electrochemical process first, and then HClO is generated through further anode reaction. Combined with the special spoiler structure design, the H2O2 and HClO generated by the reaction in sequence are fully mixed and a composite solution with a specific ratio is obtained, thereby realizing the in-situ efficient electro-synthesis of two high-value-added oxidants and the mixing synergistic amplification effect. This significantly reduces the complexity of the equipment and the production energy consumption while greatly improving the product selectivity, reaction stability and synergistic effect, opening up a new way for electrochemical synthesis. The prepared HClO-H2O2 composite solution plays a synergistic sterilization and oxidation synergistic effect, and is especially suitable for disinfection and sterilization, industrial water treatment, medical wastewater purification and chemical synthesis fields.

[0008] To achieve the above-mentioned purpose, the present application provides a hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation method, which includes the following steps:

[0009] S1, a cathode component and an anode component are physically isolated and arranged in an electrolytic chamber formed by a lower shell and an upper cover, wherein the lower shell is provided with a carbon felt, the cathode component is placed on the carbon felt, and the anode component is placed on the upper cover, and the anode component and the cathode component are electrically connected with the positive electrode and the negative electrode of an external power supply, respectively;

[0010] S2, electrolyte is introduced into the electrolysis chamber, the electrolyte in the first space between the lower shell and the cathode component is disturbed to flow, the reduction reaction occurs on the surface of the cathode component to produce H2O2, after the amount of H2O2 generated reaches the preset condition, the oxidation reaction occurs on the surface of the anode component to produce HClO, and then the reaction solution obtained is uniformly mixed in the second space between the anode component and the upper cover, and then flows out at the outlet of the electrolysis chamber to form a composite solution with a proportion of HClO-H2O2.

[0011] As preferred, in step S2, the liquid inlet and liquid outlet of the electrolysis chamber are arranged on the side surface of the lower shell, and the liquid inlet is arranged lower than the cathode component and the liquid outlet is arranged higher than the anode component to form a diagonal distribution; the cathode component and the anode component adopt a hollow structure.

[0012] As preferred, in step S2, the electrolyte is disturbed to flow on the surface of the lower shell below the cathode component and on the surface of the upper cover above the anode component, and the disturbance paths on the surface of the upper cover are vertically distributed with the disturbance paths on the surface of the lower shell, and the disturbance paths on the surface of the upper cover have at least two regions divided oppositely left and right.

[0013] As preferred, in step S2, the disturbance paths on the surface of the upper cover have two regions divided oppositely left and right, and the disturbance paths on the side of the liquid inlet are long and sparsely distributed, and the disturbance paths on the side of the liquid outlet are short and densely distributed.

[0014] As preferred, during the electrolysis reaction, there is a gap between the electrolyte in the second space and the top of the upper cover, and an overflow groove is arranged at the position close to the liquid outlet of the second space to communicate with the gap to assist in exhausting.

[0015] As preferred, during the electrochemical reaction in step S2: the concentration ratio of HClO and H2O2 generated by the reaction is adjusted by controlling the current distribution of the cathode component and the anode component.

[0016] As preferred, the cathode component adopts a conductive porous substrate A carrying a catalyst A, wherein the conductive porous substrate A adopts a material with high specific surface area, including one or more of foamed nickel, foamed copper, carbon fiber felt, carbon fiber cloth or carbon paper; the catalyst A includes one or more of platinum, palladium or iron-nitrogen-carbon; the anode component adopts a conductive porous substrate B carrying a catalyst B, wherein the conductive porous substrate B adopts a titanium substrate or a carbon substrate, and the catalyst B adopts tin dioxide or ruthenium iridium oxide.

[0017] The second object of the present application is to provide a hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device, comprising a lower shell and an upper cover enclosing an electrolytic chamber, liquid inlet and liquid outlet are arranged on the left and right sides of the lower shell, wherein the liquid inlet is arranged at the lower position and the liquid outlet is arranged at the upper position, a cathode component and an anode component are arranged in the electrolytic chamber, wherein the lower shell is provided with a carbon felt at the bottom, the cathode component is placed on the carbon felt and the anode component is placed on the upper cover, the anode component and the cathode component are respectively electrically connected to the positive and negative poles of the external power source through a wire harness, and the inner surfaces of the lower shell and the upper cover are respectively provided with turbulence structures and are vertically distributed.

[0018] As a preferred, the inner bottom surface of the lower shell is spaced apart in the transverse direction and has a plurality of first ribs, one of the two adjacent first ribs forms a gap between the first rib and the longitudinal side of the lower shell, and the other first rib forms a gap between the first rib and the other longitudinal side of the lower shell, thereby forming a turbulence path; the carbon felt is placed on the first rib.

[0019] As a preferred, the inner top surface of the upper cover is spaced apart in the longitudinal direction and has a plurality of second ribs, one of the two adjacent second ribs forms a gap between the second rib and the transverse side of the upper cover, and the other second rib forms a gap between the second rib and the other transverse side of the upper cover, thereby forming a turbulence path.

[0020] As a preferred, the turbulence path on the surface of the upper cover has at least two turbulence areas which are opposite to each other and connected in series, the turbulence path near the liquid inlet is long and sparse, and the turbulence path near the liquid outlet is short and dense.

[0021] As a preferred, a first partition is provided on the upper cover and penetrates through a plurality of second ribs in the longitudinal direction, so as to form two turbulence areas on both sides of the first partition, and in each turbulence area, the end of one of the two adjacent second ribs forms a gap with the first partition, thereby forming an S-shaped turbulence path in each turbulence area.

[0022] As a preferred, the cathode component is placed on the carbon felt, the anode component is located above the cathode component, and the lower shell and the upper cover are provided with protrusions for supporting and separating the cathode component and the anode component.

[0023] Among them, the carbon felt in the application is used as the conductive base and catalyst carrier of the cathode part, carries the Fe-N-C catalyst, enhances the electrode catalytic activity, the carbon felt adopts a porous material, loads a high-activity catalyst, and can improve the reaction efficiency of the reduction reaction to generate H2O2; secondly, the three-dimensional network structure of the carbon felt increases the specific surface area, can provide more active sites, reduces the local current density, reduces the electrode passivation, optimizes the electrolyte distribution and mass transfer; in addition, its porous characteristics promote the uniform flow of electrolyte on the electrode surface, that is, uniform fluid distribution, avoiding local concentration polarization.

[0024] As preferred, the lower shell and the upper cover cooperate to form an overflow groove at a position close to the liquid outlet.

[0025] The third object of the application is to provide an application of the hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation method, and the prepared HClO-H2O2 composite solution with a certain proportion is used for disinfection and sterilization of various water qualities and degradation treatment of organic pollutants.

[0026] The application has the following beneficial effects:

[0027] (1) The application can not only achieve better synergistic effect in specific application scenarios such as disinfection and sewage treatment, but also complete the preparation under lower cost and milder conditions, and the process design is ingenious; by setting the generation sequence of H2O2 and HClO, the two are generated in sequence and delayed mixing through the turbulence structure, and a composite solution with a specific ratio is obtained, which can avoid the consumption of H2O2 and HClO in the generation stage, ensure that the high active concentration can be maintained in the application, and thus achieve more thorough sterilization effect, and for complex sewage matrix, the target degradation ability of pollutants can be greatly improved by the reaction of H2O2 and HClO in sequence; in addition, through the step-by-step regulation of a single electrolysis system, the construction and maintenance cost of two independent systems is saved, the equipment investment is reduced by more than 40%, the generation efficiency of H2O2 can be increased to more than 90% at room temperature through the catalyst, and the generation amount of Cl2 can be effectively controlled to be less than 0.1 mg / L through time sequence isolation, which is much lower than the 5-10 mg / L of the traditional method.

[0028] (2) The turbulence path set on the surface of the upper cover can prolong the residence time of the electrolyte in the anode area, ensure that O2 is fully reduced to H2O2 in the cathode area, form a "laminar flow-transition flow" flow state transition of the electrolyte on the electrode surface, promote the gas-liquid interface mass transfer required for H2O2 generation, set two different areas of sparse and dense through the turbulence path, and at the same time, reduce the flow rate to avoid that the unreacted O2 bubbles are quickly taken out, form local turbulence at the end of the flow channel through the dense turbulence unit, make Cl -The rapid oxidation is carried out in the anode region, and the flow rate is increased through the flow channel contraction effect, so that the two products are separated in space in a three-stage type of 'generation-buffering-mixing', and the problem of cross reaction loss caused by synchronous generation in the prior art patent is completely avoided.

[0029] (3) In the present application, the electrolyte is introduced from bottom to top, so that the cathode part and the anode part participate in the reaction in sequence. Meanwhile, the cathode part and the anode part are designed to be hollow, and the interval design between each reaction part in the electrolysis chamber and the side wall of the lower shell and the upper cover is adopted, so that when the electrolyte is electrolyzed with the cathode part and the anode part in sequence, the entire plate surface of the cathode part and the anode part can be reacted at the same time to produce H2O2 or HClO, and the gas generated in the reaction process can be quickly discharged from the interval position and the hollow position of the plate.

[0030] (4) In the present application, the electrolyte flows in the turbulent flow path, so as to change the flow rate and flow path, accelerate the discharge of hypochlorous acid and hydrogen peroxide generated in situ on the electrode surface, improve the concentration of the mixed liquid in the reaction system, and design multi-dimensional disturbance to enhance the mixing effect, optimize the mass transfer efficiency, and reduce the energy consumption of turbulent flow. Cooperate with overflow design to control the reaction process, assist in gas discharge, and optimize the flow path to reduce outlet defects; by designing relatively independent S-shaped turbulent flow and cooperating with the relatively independent setting of the overflow chamber, the reaction area and the liquid outlet area are relatively isolated, avoiding the outflow of the reaction composite liquid which is not fully reacted in the early stage, that is, ensuring the stability of the concentration of the composite liquid in the outlet liquid and meeting the requirements without the need for additional isolation devices.

[0031] (5) In the composite liquid prepared by the present application, the HClO-H2O2 composite solution can take into account the early sterilization of HClO and the long-acting sterilization of H2O2, and the killing ability of bacteria, viruses and other pathogenic microorganisms and the degradation ability of organic pollutants are significantly improved.

[0032] In summary, the present application has excellent technical advancement and practical value, especially suitable for municipal and industrial water supply and drainage systems, medical and health care, food processing and other industries. It can be widely used in water supply plants and municipal sewage treatment, disinfection in hospitals, hotels, swimming pools and other special places, as well as industrial circulating water sterilization and wastewater deep treatment, and has broad application prospects. It provides a new type of electrolytic preparation technology for water treatment field. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 The concentration cycle curve of HClO and H2O2 for the reaction mixture in Example 1 once through flow;

[0034] Figure 2 The overall structure diagram of the hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device in the present application;

[0035] Figure 3 The overall structure of the hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device in the present application is shown in the exploded view.

[0036] Figure 4 The structure of the lower shell in the present application is shown in the schematic view.

[0037] Figure 5 The structure of the lower shell in the present application is shown in the front view.

[0038] Figure 6 The structure of the upper cover in the present application is shown in the schematic view.

[0039] Figure 7 The structure of the upper cover in the present application is shown in the front view.

[0040] Figure 8 The overall structure of the hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device in the present application is shown in the horizontal cross-sectional view.

[0041] Figure 9 The connection between the upper cover and the anode part in the present application is shown in the schematic view.

[0042] Figure 10 The overall structure of the hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device in the present application is shown in the partial structure schematic view (without the upper cover).

[0043] Figure 11 The cooperation structure of the carbon felt and the lower shell in the present application is shown in the top view.

[0044] Figure 12 The overall structure of the hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device in the present application is shown in the longitudinal cross-sectional view. DETAILED DESCRIPTION

[0045] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0046] In the description of the present application, it needs to 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" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, which are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first", "second" are only for the purpose of description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the technical features referred to. Therefore, the features defined as "first", "second" can explicitly or implicitly include one or more of the features. In the description of the present application, the meaning of "a plurality of" is two or more, unless otherwise specifically limited.

[0047] An electrochemical synergistic preparation method of hypochlorous acid-hydrogen peroxide, comprising the following steps:

[0048] S1, a cathode component 2 and an anode component 3 are arranged in physical isolation in an electrolytic cavity formed by the lower shell 1 and the upper cover 4, wherein the lower shell 1 is provided with a carbon felt 7 at the bottom, the cathode component 2 is placed on the carbon felt 7, and the anode component 3 is placed on the upper cover 4, and the anode component 3 and the cathode component 2 are respectively electrically connected with the positive and negative poles of an external power supply;

[0049] S2, the electrolyte is introduced into the electrolytic cavity, the electrolyte is subjected to turbulent flow in the first space between the lower shell 1 and the cathode component 2, a reduction reaction occurs on the surface of the cathode component 2 to generate H2O2, after the amount of H2O2 generated reaches a preset condition, the reaction conditions are adjusted or new reactants are introduced, an oxidation reaction occurs on the surface of the anode component 3 to generate HClO, and then the reaction liquid obtained is subjected to turbulent mixing in the second space between the anode component 3 and the upper cover 4, and then a HClO-H2O2 composite solution with a proportion is formed at the outlet of the electrolytic cavity and flows out.

[0050] In this embodiment, the electrolyte is an electrolyte solution containing chloride ions (such as tap water, seawater), and during the electrochemical reaction, the electrolyte is continuously pumped into the electrolytic cavity by a circulating pump and overflowed and discharged. The reduction reaction of dissolved oxygen on the surface of the cathode component 2 generates hydrogen peroxide:

[0051] O2+2H + +2e - →H2O2, E 0 = 0.68 V;

[0052] At the same time, the oxidation reaction of chloride ions on the anode surface generates hypochlorous acid:

[0053] Cl - + H2O → HClO + H + + 2e - , E 0 = 1.49 V;

[0054] In the present application, H2O2 and HClO are generated in sequence, and the electrolyte first passes through the cathode component 2 to generate a preset amount of H2O2, and then continues to pass through the electrolyte to pass through the anode component 3 to generate HClO.

[0055] In the present embodiment, it is found that generating the two reactants in a specific sequence can achieve better synergistic effect in certain application scenarios (such as specific disinfection scenarios, sewage treatment scenarios, etc.), and can be prepared at lower cost and milder conditions.

[0056] For the aspect of enhancing synergistic effect, first, H2O2 and HClO are both strong oxidants, but direct mixing can easily occur the following reaction:

[0057] HClO + H2O2 → HCl + O2↑ + H2O (maximize retention of active ingredients);

[0058] Generating and delaying mixing through the turbulence structure can avoid mutual consumption of the two in the generation stage, and ensure that both maintain high active concentration when applied (such as disinfection, sewage treatment). In the disinfection scenario, H2O2 can quickly oxidize the lipids on the cell membrane, destroying the integrity of the cell membrane, while HClO can penetrate the cell membrane and attack proteins and nucleic acids inside the cell, thereby achieving a more thorough sterilization effect.

[0059] Secondly, for complex sewage matrix, such as industrial wastewater containing phenols, ammonia nitrogen, organic matter, etc., H2O2 preferentially reacts with part of the pollutants (such as reducing organic matter), and the generated intermediate products are more easily oxidized and decomposed by the subsequently generated HClO, and the pollutant targeted degradation ability is improved. For example, when treating wastewater containing ammonia nitrogen, H2O2 first oxidizes part of NH3 to NO2 - , and HClO efficiently converts NO2 - to harmless N2, and the total nitrogen removal rate can be 1.5 times that of traditional processes.

[0060] For the aspect of achieving preparation at low cost and mild conditions, first, through single electrolysis system step-by-step control, the construction and maintenance cost of two independent systems is saved, and the equipment investment is reduced by more than 40%.

[0061] Secondly, in terms of reaction condition temperature, traditional HClO preparation needs to maintain 40-60°C to improve the reaction rate, while the step-by-step electrochemical method can increase the H2O2 generation efficiency to more than 90% at room temperature through catalysts (such as carbon-based composite materials).

[0062] In addition, in the aspect of byproduct inhibition to improve atom economy, the H2O2 and HClO are generated synchronously as described in patent publication CN120026334A, wherein, Cl - H2O2 and HClO are generated step by step in the present application. By time sequence isolation, H2O2 is generated in the cathode region first and is guided to an independent buffer zone, and then the anode region is switched to generate HClO. The amount of Cl2 generated can be controlled to be below 0.1 mg / L, which is much lower than the 5-10 mg / L of the traditional method.

[0063] As a preferred, in step S2, the liquid inlet 11 and the liquid outlet 12 of the electrolysis chamber are arranged on the side of the lower shell 1 in a left-right distribution, wherein the liquid inlet 11 is arranged at a low position and the liquid outlet 12 is arranged at a high position to form a diagonal distribution, and the liquid inlet 11 is arranged below the cathode component 2 and the liquid outlet 12 is arranged above the anode component 3; the cathode component 2 and the anode component 3 adopt a hollow structure.

[0064] As a preferred, in step S2, the electrolyte flows in an S-shaped turbulent flow on the surface of the lower shell 1 below the cathode component 2 and in an S-shaped turbulent flow on the surface of the upper cover 4 above the anode component 3, and the turbulent flow paths are vertically distributed with the turbulent flow paths on the surface of the lower shell 1, and the turbulent flow paths on the surface of the upper cover 4 have at least two regions divided left and right.

[0065] As a preferred, in step S2, the turbulent flow paths on the surface of the upper cover 4 have two regions divided left and right, and the turbulent flow paths on the side of the liquid inlet 11 are long and distributed sparsely, and the turbulent flow paths on the side of the liquid outlet 12 are short and distributed densely.

[0066] In the present application, for the S-shaped turbulent flow paths on the surface of the upper cover 4, the turbulent flow paths on the side of the liquid inlet 11 are distributed sparsely and the turbulent flow paths on the side of the liquid outlet 12 are distributed densely. By such an arrangement, when the reaction liquid overflows to the upper cover 4, on the side of the liquid inlet 11, the turbulent flow paths are distributed sparsely, so the flow path of the reaction liquid is longer and the flow rate is slower, thereby making HClO and H2O2 in the reaction liquid fully mixed and uniform, and then to the side of the liquid outlet 12, the turbulent flow paths are distributed densely, so the flow rate of the reaction liquid is faster and forms a rapid turbulent flow, which can help to wrap and expel the reaction gas on the outlet side.

[0067] Furthermore, it is worth mentioning that by providing the spoiler structure on the surface of the upper cover 4, the residence time of the electrolyte in the anode region can be prolonged, ensuring that O2 is fully reduced to H2O2 in the cathode region, and the flow state of the electrolyte on the electrode surface is changed from "laminar flow to transition flow", which promotes the mass transfer of gas-liquid interface required for the generation of H2O2, while reducing the flow rate to avoid the rapid removal of unreacted O2 bubbles. By using dense turbulence units at the end of the flow channel, local turbulence is formed, which makes Cl - In the anode region, rapid oxidation is achieved, and the flow rate is increased through the flow channel contraction effect, realizing the "generation-buffer-mixing" three-stage separation of the two products in space, and completely avoiding the "cross reaction loss caused by synchronous generation" problem in the prior art patents.

[0068] As a preferred, during the electrolysis reaction, there is a gap between the electrolyte in the second space and the top of the upper cover 4, and an overflow groove 13 is provided at the position close to the liquid outlet 12 of the second space to assist in exhausting air.

[0069] As a preferred, during the electrochemical reaction in step S2: the concentration ratio of HClO and H2O2 generated by the reaction is adjusted by controlling the current distribution of the cathode component 2 and the anode component 3.

[0070] As a preferred, the cathode component 2 uses a conductive porous substrate A to carry a catalyst A, wherein the conductive porous substrate A uses a material with high specific surface area, including one or more of foamed nickel, foamed copper, carbon fiber felt, carbon fiber cloth or carbon paper; the catalyst A includes one or more of platinum, palladium or iron-nitrogen-carbon; the anode component 3 uses a conductive porous substrate B to carry a catalyst B, wherein the conductive porous substrate B uses a titanium substrate or a carbon substrate, and the catalyst B uses tin dioxide or ruthenium iridium oxide.

[0071] In this embodiment, the cathode and anode use specific materials to carry high-activity catalysts, and high-efficiency chlorine and oxygen evolution catalyst coatings are respectively used on the surfaces of the cathode and anode to improve the rate and efficiency of the cathode reducing O2 to generate H2O2 and the anode efficiently electrocatalytically oxidizing Cl - HClO is generated, the electrode reaction kinetics is optimized, the current efficiency of HClO and H2O2 is greatly improved, and the energy consumption is reduced; and by controlling the electrochemical parameters and the electrode structure, such as controlling the current distribution of the cathode and anode, the concentration ratio of hypochlorous acid / hydrogen peroxide can be flexibly adjusted, so that the ratio and performance of the composite liquid can be matched with the actual application, and the needs of different application occasions can be met.

[0072] The control system of this embodiment is matched, which carries temperature, pH, conductivity and other sensors to realize real-time control and monitoring of the reaction system, and can flexibly adjust the voltage, current and other parameters of the reaction system; in addition, when the reaction device abnormally operates, the control system can disconnect the circuit to protect the reaction device.

[0073] In addition, it is worth mentioning that the control system also has a timed descaling function. After the reaction device has been running for a long time, a layer of scale is easily attached to the surface of the reaction cathode. The traditional descaling method is to adjust the water quality PH and add acidic substances such as vinegar and citric acid to the water, which is troublesome to operate. In order to simplify the descaling steps, the control system in the embodiment can reverse the power supply mode of the electrode at regular intervals, so that the reaction cathode is at a positive potential and the anode is at a negative potential, which can reduce the amount of scale deposited on the surface of the reaction cathode, thereby prolonging the service life of the reaction device.

[0074] In this embodiment, a diaphragm-free design is adopted, and tap water and other cheap and readily available natural water bodies are used as electrolytes. While chlorine ions are oxidized to HClO at the anode, dissolved oxygen is reduced to H2O2 at the cathode, enabling continuous and stable production of high-concentration HClO-H2O2 composite solution under normal temperature and pressure conditions without the need for additional chemical reagents. The electrode structure is simple, the process flow is greatly simplified, the production and use costs are significantly reduced, the device is miniaturized and functionally integrated, the equipment safety and automation level are higher, and the scale-up application is facilitated. The raw material and energy cost is low, and environmental pollution and drug residue are avoided. HClO and H2O2 do not need to be prepared, stored, and mixed again, which reduces the cost and safety risk.

[0075] The HClO-H2O2 composite solution prepared by the method is used in various water quality disinfection and sterilization and organic pollutant degradation treatment fields. It can be directly used for disinfection and sterilization of drinking water, sewage, swimming pools, and degradation treatment of dyes, pesticides, and other organic pollutants. Compared with traditional single agents, the synergistic effect of active chlorine and active oxygen in the HClO-H2O2 composite solution doubles the sterilization and degradation effect, greatly improves the treatment efficiency, and is especially suitable for situations with high microbial contamination and organic pollutant concentration.

[0076] Example 1

[0077] The electrolyte for preparing the HClO-H2O2 composite solution uses ordinary tap water, the anode part 3 uses a titanium substrate coated with ruthenium and iridium (18*36*0.5mm), and the cathode part 2 uses a carbon-based material (18*36*0.5mm) with a surface deposited with a nano-iron-nitrogen-carbon catalyst (0.1-10 mg / cm 2 The distance between the anode and the cathode is 4mm, and the liquid inlet 11 and the liquid outlet 12 are connected to a diaphragm pump (flow rate 30mL / min) to form a loop.

[0078] At the same time, stainless steel electrodes are selected to replace the anode and cathode materials as a comparative experimental group, and other experimental conditions are exactly the same as in Example 1.

[0079] The experimental scheme is shown in Table 1. Table 1:

[0080]

[0081] The preparation device was connected to a power source, and the voltage was set to a constant value of 12V. After the circuit was turned on and started working, the current passed through the electrolyte to carry out the electrolysis reaction. After a period of time, a water sample that had been subjected to the current was taken out from the electrolytic cell, and the ion concentration, solute concentration and other relevant indicators in the water sample were accurately tested and analyzed in order to understand the changes in the water sample composition during the electrolysis process. The concentration of available chlorine (calculated as HClO) was measured using residual chlorine test paper, and the concentration of H2O2 was measured using hydrogen peroxide test paper. The monitoring lasted for 200 hours.

[0082] The experimental results of Example 1 are as follows: Figure 1 As shown, the initial concentrations of HClO and H2O2 reached 16 mg / L and 3 mg / L, respectively. The concentrations of these two substances remained highly stable for up to 200 hours as the reaction time changed. Even with low chlorine content in tap water, this electrochemical reactor can rapidly prepare high-concentration HClO-H2O2 mixed solutions at room temperature and pressure.

[0083] Take the HClO-H2O2 mixed solution generated by electrolysis in Example 1, adjust the pH to 6.5 using a pH meter, and prepare a solution with an HClO concentration of 16 mg / L and an H2O2 concentration of 3 mg / L. Add approximately 1*10 5 The bactericidal rate of CFU / mL Escherichia coli suspension was determined by constant temperature shaking at 25℃ after different contact times; the bactericidal effects of HClO solution and H2O2 solution of equal concentration were determined by the same method.

[0084] The bactericidal effects of the HClO-H2O2 composite solution on Escherichia coli were compared with those of HClO solution or H2O2 solution alone, as shown in Table 2.

[0085]

[0086] The results showed that the bactericidal rate of the HClO-H2O2 mixed solution was significantly higher than that of HClO or H2O2 solutions alone, exhibiting a clear dose-response effect. When using the mixed solution, a bactericidal rate of 78% was achieved, while the bactericidal rate of HClO or H2O2 solutions alone was significantly lower than that of the HClO-H2O2 mixed solution. This demonstrates that the bactericidal effect is significantly enhanced by the combination of HClO and H2O2, verifying their synergistic mechanism.

[0087] Example 2

[0088] This embodiment provides a hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device, such as... Figures 2-3As shown, including the lower shell 1 and the upper cover 4 which enclose to form an electrolysis chamber, the cathode component 2 and the anode component 3 are arranged in physical isolation inside the electrolysis chamber, wherein the lower shell 1 is provided with carbon felt 7 at the bottom, the cathode component 2 is placed on the carbon felt 7, and the anode component 3 is placed on the upper cover 4, the anode component 3 and the cathode component 2 are respectively electrically connected to the positive and negative poles of the external power source through the wire harness 5, and the inner surfaces of the lower shell 1 and the upper cover 4 are respectively provided with turbulence structures and are distributed vertically to each other, as shown in Figure 5 、 7 .

[0089] The embodiment has the following effects by arranging the S-shaped turbulence paths of the upper cover 4 and the S-shaped turbulence paths of the lower shell 1 to be staggered:

[0090] Firstly, the distribution of the turbulence structure of the upper cover 4 guides the liquid to flow in a specific direction, while the turbulence structure of the lower shell 1 forms a turbulence path in the vertical direction, and the cross action of the two can break the flow inertia in a single direction, form a more complex three-dimensional flow trajectory, promote the uniform mixing of the liquid in the chamber, and reduce the local flow dead zone, thereby realizing multi-dimensional disturbance and enhancing mixing.

[0091] In addition, the flow paths in different directions can strengthen the liquid update rate of the key area (such as the vicinity of the cathode), and the vertical disturbance can more effectively peel off the bubbles or reaction products on the surface of the electrode, improve the contact efficiency of the electrolyte and the electrode, and thus improve the mass transfer performance of the electrolysis reaction, thereby optimizing the mass transfer efficiency.

[0092] Secondly, through the differential design of the structure, part of the vertical flow path can guide the fluid to turn orderly, avoid energy loss caused by strong turbulence in the same direction, reduce the energy consumption demand of the driving pump while ensuring the disturbance effect, and improve the overall efficiency of the system, thereby reducing the energy consumption of turbulence.

[0093] As a preferred, the carbon felt 7, the cathode component 2 and the anode component 3 are arranged horizontally from bottom to top in the electrolysis chamber.

[0094] As a preferred, as shown in Figures 4-5 , the inner bottom surface of the lower shell 1 is transversely spaced apart and distributed with a plurality of first ribs 101, and between the two adjacent first ribs 101, one of the first ribs 101 forms a gap with the longitudinal side surface of the lower shell 1, and the other first rib 101 forms a gap with the longitudinal side surface of the lower shell 1, thereby forming a turbulence path; the carbon felt 7 is placed on the first rib 101.

[0095] As preferred, the first convex rib 101 cooperates with the inner side surface of the lower shell 1 to form an S-shaped turbulence path. Among them, the carbon felt 7 and the bottom of the lower shell 1 are separated by the turbulence structure composed of the first convex rib 101, which is beneficial to the full participation of the carbon felt in the catalytic reaction, and the gap is provided between the periphery of the carbon felt and the part of the side wall of the lower shell, especially preferred to be provided with a gap on the side wall near the inlet and outlet and the left and right side walls, so that the electrolyte flows upward from the peripheral gap to be synchronized with the rapid discharge of the generated bubbles.

[0096] In this embodiment, the S-shaped turbulence groove structure is provided on the lower shell 1 below the cathode part 2, which specifically solves the problem of optimizing the electrolyte flow in the cathode area. Since the cathode is the main place for hydrogen evolution reaction, the mass transfer efficiency of the electrolyte and the bubble discharge requirement are higher. The S-shaped turbulence groove is concentrated on the lower shell 1 below the cathode part 2, which can more accurately enhance the disturbance effect of the electrolyte near the cathode, reduce the local flow dead zone, and improve the mass transfer efficiency of the hydrogen evolution reaction.

[0097] As preferred, as shown in Figures 6-7 The inner top surface of the upper cover 4 is longitudinally spaced apart by a plurality of second convex ribs 401. Among the two adjacent second convex ribs 401, one second convex rib 401 forms a gap with the transverse side surface of the upper cover 4, and the other second convex rib 401 forms a gap with the transverse side surface of the upper cover 4, thereby forming a turbulence path.

[0098] As preferred, the turbulence path on the surface of the upper cover 4 has at least two left and right opposite turbulence areas which are connected at the head and tail. The turbulence paths of the two adjacent turbulence areas are consistent, the turbulence path near the liquid inlet 11 is long and distributed sparsely, and the turbulence path near the liquid outlet 12 is short and distributed densely.

[0099] As preferred, the first partition plate 402 is longitudinally arranged on the upper cover 4 and penetrates through a plurality of second convex ribs 401, so as to form two turbulence areas on both sides of the first partition plate 402. In each turbulence area, the end of one second convex rib 401 among the two adjacent second convex ribs 401 forms a gap with the first partition plate 402, thereby forming an S-shaped turbulence path in each turbulence area.

[0100] As preferred, the turbulence path on the surface of the upper cover 4 has two areas which are transversely opposite. In each area, one second convex rib 401 among the two adjacent second convex ribs 401 forms a gap with the transverse side surface of the upper cover 4, and the other second convex rib 401 forms a gap with the first partition plate 402, thereby forming an S-shaped turbulence path.

[0101] As preferred, the second convex rib 401 cooperates with the inner side surface of the upper cover 4 and the first partition plate 402 to form an S-shaped turbulence path.

[0102] By setting the spoiler structure on the surface of the upper cover 4, the residence time of the electrolyte in the anode region can be prolonged, ensuring that O2 is fully reduced to H2O2 in the cathode region, and the flow state of the electrolyte on the electrode surface is changed to "laminar flow-transition flow", which promotes the mass transfer of gas-liquid interface required for the generation of H2O2, while reducing the flow rate to avoid the rapid removal of unreacted O2 bubbles. At the end of the flow channel, a local turbulent flow is formed by the dense spoiler unit, so that Cl - In the anode region, rapid oxidation is achieved, and the flow rate is increased by the flow channel contraction effect, realizing the "generation-buffer-mixing" three-stage separation of the two products in space, and completely avoiding the "cross reaction loss caused by synchronous generation" problem in the prior art patents.

[0103] As a preferred, as shown in Figure 4 , 8 , 9, the cathode component 2 is placed on the carbon felt 7, and the anode component 3 is located above the cathode component 2 and the lower shell 1 and the upper cover 4 are distributed with protrusions 403 to support and separate the cathode component 2 and the anode component 3.

[0104] As a supplementary description, as shown in Figure 9 , a plurality of protrusions 403 are distributed on both sides and in the middle of the cathode and anode components, so that the edge and middle of the cathode and anode components are supported and isolated, effectively avoiding short circuit caused by deformation, and the reliability is good.

[0105] As a preferred embodiment, the distance between the cathode component 2 and the anode component 3 is 4mm.

[0106] As a preferred, as shown in Figure 4 , 8 , the side surface of the lower shell 1 is distributed with a third protrusion 404 for limiting the carbon felt 7.

[0107] As a preferred, as shown in Figure 2 , the left and right sides of the side surface of the lower shell 1 are distributed with liquid inlet 11 and liquid outlet 12, wherein the liquid inlet 11 is lowly arranged, and the liquid outlet 12 is highly arranged, as shown in Figure 4 , the lower shell 1 and the upper cover 4 cooperate to form an overflow groove 13 at the position close to the liquid outlet 12.

[0108] This embodiment has the following effects by providing an overflow structure near the liquid outlet (combined with Figure 12 the arrow shows the process of the reaction liquid overflowing from the overflow groove 13 to the liquid outlet).

[0109] First, it is used to control the liquid level, so as to indirectly maintain a certain reaction time, and the reaction will be carried out in the liquid when the liquid stays in the overflow groove.

[0110] In addition, the liquid outlet is prone to gas accumulation due to the flow end effect. The overflow groove guides the liquid flow while discharging the residual gas in the cavity through the overflow groove, thereby assisting in gas discharge, reducing gas retention in the outlet area, and avoiding gas resistance or causing liquid flow to be difficult.

[0111] Secondly, the liquid outlet area is prone to flow dead zones or turbulence if not properly designed. The overflow groove can adjust the flow direction and speed in this area, balance the liquid flow distribution, avoid local flow speed being too fast or too slow, thereby optimizing the flow path and reducing outlet defects.

[0112] As a preferred embodiment, as shown in Figure 4 The overflow chamber 14 is opposite to the liquid outlet 12 in the electrolysis chamber, and the overflow chamber 14 and the electrolysis chamber are connected through the overflow groove 13.

[0113] As a preferred embodiment, a plurality of second partitions 405 are arranged between the lower shell 1 and the upper cover 4. The overflow chamber 14 is formed by the second partitions 405, the lower shell 1, the upper cover 4, the second protrusions 401 and the first partitions 402. One of the second partitions 405 is provided with a notch as the overflow groove 13.

[0114] In this embodiment, the relative independent S-shaped turbulence is formed by the structural cooperation between the upper cover 4 and the anode component 3, and the structural cooperation between the lower shell 1 and the cathode component 2. The relative independent overflow chamber 14 is arranged to relatively isolate the reaction area and the liquid outlet area, thereby avoiding the flow of the reaction composite liquid that is not fully reacted in the early stage, ensuring the stability of the composite liquid concentration in the liquid outlet and meeting the requirements. Based on the above structural cooperation, the isolation device does not need to be additionally increased.

[0115] It should be noted that, as shown in Figure 4 and Figure 6 The connection area of the electrolysis reaction chamber and the connecting wire 5 of the anode and cathode components is independently and separately arranged. As shown in Figure 4 A groove 15 is provided on the vertical plate of the lower shell 1 for separating the two areas. As shown in Figure 10 The tab of the anode and cathode components extends from the electrolysis reaction chamber to the connection area through the groove 15, thereby being electrically connected with the wire 5. Correspondingly, a protruding part 45 is protrudingly arranged on the upper cover 4 at the corresponding position, which is sealingly clamped in the groove 15 to separate the above two areas. A pressing block 6 is arranged above the wire 5, thereby ensuring the safety and reliability of the electrolysis reaction.

[0116] In addition, the S-shaped disturbance path of the upper cover 4 has at least two relatively divided regions, which cooperates with the overflow structure to further have the following effects:

[0117] Firstly, the position of the disturbance partition plate and the overflow groove 13 can limit the originally disordered liquid flow in two independent regions, avoid the short circuit or dead zone phenomenon of the liquid in the chamber, ensure the liquid to flow according to the designed path, improve the flow controllability, and guide the orderly flow of the liquid.

[0118] In addition, the separated multiple regions can apply different degrees of disturbance to the liquid, the region on one side of the overflow groove 13 can accelerate the liquid flow or form local turbulent flow through the disturbance partition plate structure, and the other region can realize mixing or buffering by adjusting the flow space, so as to enhance the disturbance mixing effect and strengthen the mass transfer or heat exchange efficiency inside the liquid.

[0119] The hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device has the advantages of simple structure, high efficiency, energy saving and function integration, compared with the traditional separate preparation, the synergistic preparation device can significantly reduce the equipment operation cost, improve the performance of sterilization, disinfection and degradation of organic matter.

[0120] The above only describes the preferred embodiments of the present application and is not intended to limit the present application, any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for the electrochemical synergistic preparation of hypochlorous acid and hydrogen peroxide, characterized in that, Includes the following steps: S1. A cathode component (2) and an anode component (3) are physically isolated in the electrolysis chamber formed by the lower shell (1) and the upper cover (4). A carbon felt (7) is provided at the bottom of the lower shell (1). The cathode component (2) is placed on the carbon felt (7) and the anode component (3) is placed on the upper cover (4). The anode component (3) and the cathode component (2) are electrically connected to the positive and negative terminals of the external power supply, respectively. S2. The electrolyte is introduced into the electrolysis chamber. The electrolyte flows in a turbulent manner in the first space between the lower shell (1) and the cathode component (2). First, a reduction reaction occurs on the surface of the cathode component (2) to produce H2O2. After the amount of H2O2 produced reaches the preset condition, an oxidation reaction occurs on the surface of the anode component (3) to produce HClO. Then, the resulting reaction solution is mixed evenly in a turbulent manner in the second space between the anode component (3) and the upper cover (4) and forms and flows out at the outlet of the electrolysis chamber as a HClO-H2O2 composite solution with a certain proportion.

2. The method for electrochemically synergistic preparation of hypochlorous acid and hydrogen peroxide according to claim 1, characterized in that, In step S2, the liquid inlet (11) and liquid outlet (12) of the electrolysis chamber are arranged on the left and right sides of the lower shell (1), wherein the liquid inlet (11) is arranged at a low position and the liquid outlet (12) is arranged at a high position to form a diagonal distribution, and the liquid inlet (11) is arranged below the cathode component (2) and the liquid outlet (12) is arranged above the anode component (3); the cathode component (2) and the anode component (3) adopt a hollow structure.

3. The electrochemical synergistic preparation method of hypochlorous acid and hydrogen peroxide according to claim 1, characterized in that, In step S2, the electrolyte flows in an S-shaped turbulent flow on the surface of the lower shell (1) below the cathode component (2) and on the surface of the upper cover (4) above the anode component (3), and the turbulent flow path is perpendicular to the turbulent flow path on the surface of the lower shell (1), and the turbulent flow path on the surface of the upper cover (4) has at least two regions that are divided from left to right.

4. The electrochemical synergistic preparation method of hypochlorous acid and hydrogen peroxide according to claim 3, characterized in that, In step S2, the turbulence path on the surface of the upper cover (4) has two regions that are divided into left and right sides, and the turbulence path on the side of the liquid inlet (11) is long and sparsely distributed, while the turbulence path on the side of the liquid outlet (12) is short and densely distributed.

5. The electrochemical synergistic preparation method of hypochlorous acid and hydrogen peroxide according to claim 1, characterized in that, During the electrolysis reaction, there is a gap between the electrolyte in the second space and the top of the cover (4), and an overflow groove (13) communicating with the gap is provided at the position of the second space near the liquid outlet (12).

6. A hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device, characterized in that, The device includes a lower shell (1) and an upper cover (4) that enclose an electrolysis chamber. The lower shell (1) has an inlet (11) and an outlet (12) arranged on the left and right sides, with the inlet (11) positioned at a low position and the outlet (12) positioned at a high position. The electrolysis chamber contains a cathode component (2) and an anode component (3) arranged in a physically isolated manner. The bottom of the lower shell (1) is provided with a carbon felt (7), the cathode component (2) is placed on the carbon felt (7), and the anode component (3) is placed above the cathode component (2). The anode component (3) and the cathode component (2) are electrically connected to the positive and negative terminals of an external power source through a wire harness (5), respectively. The inner surfaces of the lower shell (1) and the upper cover (4) are respectively provided with turbulence structures that are perpendicular to each other.

7. The hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device according to claim 6, characterized in that, The inner bottom surface of the lower shell (1) is provided with a plurality of first ribs (101) spaced laterally. Among two adjacent first ribs (101), one first rib (101) forms a gap with one longitudinal side of the lower shell (1), and the other first rib (101) forms a gap with the other longitudinal side of the lower shell (1), thereby forming an S-shaped turbulence path; the carbon felt (7) is placed on the first rib (101); The inner top surface of the cover (4) has a number of second ribs (401) spaced longitudinally. Among two adjacent second ribs (401), one second rib (401) forms a gap with one side of the cover (4) in the lateral direction, and the other second rib (401) forms a gap with the other side of the cover (4) in the lateral direction, thereby forming a turbulence path.

8. The hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation apparatus according to claim 7, characterized in that, The turbulence path on the surface of the upper cover (4) has at least two turbulence areas that are relatively divided to the left and right and connected end to end. The turbulence path on the side near the liquid inlet (11) is long and sparsely distributed, while the turbulence path on the side near the liquid outlet (12) is short and densely distributed. The upper cover (4) is provided with a first partition (402) that runs through a plurality of second ribs (401) in a longitudinal direction, so as to form two turbulence regions on both sides of the first partition (402). In each turbulence region, a gap is formed between the end of one of the two adjacent second ribs (401) and the first partition (402), thereby forming a turbulence path in each turbulence region.

9. The hypochlorous acid-hydrogen peroxide electrochemical synergistic preparation device according to claim 6, characterized in that, The lower shell (1) and the upper cover (4) are provided with protrusions (403) for supporting and separating the cathode component (2) and the anode component (3). The lower shell (1) and the upper cover (4) are fitted together to form an overflow groove (13) near the liquid outlet (12).

10. The application of the electrochemical synergistic preparation method of hypochlorous acid and hydrogen peroxide according to any one of claims 1-5, characterized in that, The prepared HClO-H2O2 composite solution with the specified ratio is used in various fields of water disinfection and sterilization as well as the degradation and treatment of organic pollutants.

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