Bdd electrolytic ozone generation module with front electrochemical pretreatment structure and application method thereof

Abstract

This invention relates to the field of ozone electrolysis generation modules, specifically a BDD ozone electrolysis generation module with a pre-electrochemical pretreatment structure and its application method. The module includes a shell, a main electrolysis unit, and a pre-electrochemical pretreatment structure. A main flow channel and adjacent electrolysis chambers are formed within the shell. The main electrolysis unit includes a BDD anode, a proton exchange membrane, and a main cathode. The pre-electrochemical pretreatment structure includes a pre-cathode, distinct from the main cathode. The pre-cathode is located before the main electrolysis region, at least partially forming the common boundary between the main flow channel and the electrolysis chambers, and has multiple through holes to allow limited fluid communication between the two. Water to be treated enters the pre-electrochemical pretreatment space through the through holes, and after electrochemical action by the pre-cathode, reaches the main electrolysis region for ozone generation. This invention can regulate the electrochemical and mass transfer states of the fluid before it enters the main electrolysis region, reduce scaling on the main cathode and proton exchange membrane, and improve ozone output stability and module lifespan.

Description

Technical Field

[0001] This invention relates to the field of ozone electrolysis generation module technology, specifically a BDD ozone electrolysis generation module with a pre-electrochemical pretreatment structure and its application method. Background Technology

[0002] Electrolytic ozone generators using proton exchange membranes typically include an anode, a cathode, and a proton exchange membrane disposed between the anode and cathode. Among them, using boron-doped diamond electrodes as anodes can generate ozone through the electrochemical reaction of water. They have the characteristics of high ozone purity, compact structure, and easy continuous ozone water preparation, and are therefore used in drinking water treatment, cleaning and disinfection, and miniaturized ozone water preparation equipment.

[0003] However, when the aforementioned electrolytic ozone generator uses tap water or other non-pure water containing calcium and magnesium hardness ions as feed water and operates continuously for a long period, a reduction reaction occurs at the cathode, creating a localized alkaline environment near its interface. Calcium and magnesium hardness ions from the main water flow continuously into the cathode area as the water is replenished, easily forming insoluble deposits such as calcium carbonate and magnesium hydroxide, which gradually accumulate at the cathode and adjacent proton exchange membranes. As these deposits accumulate, the membrane electrode interface resistance increases, negatively impacting local water replenishment, bubble removal, and heat transfer. This leads to increased cell voltage, decreased ozone output capacity, and affects the long-term operational stability of the electrolytic ozone generator.

[0004] To address the issues of fluid transport, electrode heat dissipation, and scaling in ozone electrolysis devices, existing technologies have proposed various improvement solutions.

[0005] For example, CN112813452A discloses an electrolytic cell structure in which an anode plate and a cathode plate are arranged inside the electrolysis chamber, a cathode chamber is formed between the cathode plate and the outer shell, a water-passing chamber is formed between the anode plate and the cathode plate, and several through holes are provided on the cathode plate at the position corresponding to the proton exchange membrane. These through holes increase the water-receiving area of ​​the proton exchange membrane, improve the heat dissipation conditions of the membrane and the anode encapsulation area, and facilitate the timely discharge of ozone generated during electrolysis with the water flow.

[0006] The aforementioned structure primarily improves the electrolysis operation by addressing water intake, heat dissipation, and fluid transport conditions within the main electrolysis zone. Its through-holes still primarily serve to renew the water and remove ozone within the main electrolysis zone. During long-term treatment of water containing calcium and magnesium hardness ions, the main feed water continues to participate in the water renewal process within the main electrolysis zone. Therefore, the area where the main cathode is located will continue to receive hardness ions from the main feed water during operation. As the operating time increases, inorganic deposits may gradually accumulate at the main cathode and adjacent proton exchange membranes.

[0007] For example, CN111304678A discloses an electrolytic ozone generator, which has through holes on the positive electrode and / or negative electrode, and forms an annular flow channel around the positive electrode, negative electrode and membrane. At the same time, a water flow distribution space is set so that the inlet water flows through the electrode through holes and the outer flow channel respectively. The flow velocity difference and pressure difference between different flow paths are used to increase the fluid flow speed, so as to promote ozone output and electrode heat dissipation.

[0008] The improvement of this scheme mainly focuses on enhancing ozone output and heat dissipation by strengthening fluid exchange between the main electrolysis zone and the peripheral flow channels. For continuous hard water treatment operations, while enhanced water exchange facilitates the removal of bubbles, heat, and ozone, it also allows calcium and magnesium ions from the main feed water to enter the main cathode area along with the continuously replenished water. Therefore, its effectiveness in reducing the cumulative hardness ion load on the main cathode throughout its entire operating lifespan remains limited.

[0009] For example, CN115433955A discloses a three-electrode low-pressure electrolytic ozone generator, which adds a third electrode to the original ozone electrolysis electrode and treats the scale formed on the electrode surface through a corresponding electrochemical circuit, so that the deposits are transferred or removed, thereby improving the operating status after the electrode is scaled.

[0010] The above solution can mitigate the impact of existing scale on electrode operation to some extent, but a corresponding descaling process is still required, along with maintenance or cleaning of the third electrode. The key technical focus is on the subsequent treatment of existing inorganic deposits, without altering the fundamental operational mode of continuous ozone generation where the main feed water continuously participates in the renewal of the main electrolysis zone. Therefore, there is still room for further reduction in the cumulative hardness ion load borne by the main cathode throughout its entire working lifespan.

[0011] In summary, existing electrolytic ozone generators have improved their operation by increasing the electrode water-receiving area, improving fluid transport and heat dissipation, increasing ozone output efficiency, and treating scale through additional electrodes. However, when continuously treating non-pure water containing calcium and / or magnesium ions, the main electrolysis zone faces mutually restrictive operational requirements: on the one hand, to maintain normal electrolysis, the main electrolysis zone needs adequate water renewal to promptly remove bubbles and heat, and to ensure the effective transfer of generated ozone and / or ozone-containing water to the main water flow; on the other hand, the continuous mass exchange between the main influent and the main electrolysis zone continuously replenishes the area where the main cathode, such as calcium and magnesium ions, are located, causing inorganic deposits to gradually accumulate at the main cathode and adjacent proton exchange membrane over time. Simply reducing the fluid exchange between the main water and the main electrolysis zone can reduce the number of hardness ions entering the main electrolysis zone to some extent, but it may also lead to insufficient water renewal and affect bubble removal, heat exchange, and the mass transfer and output of ozone into the main water flow.

[0012] Therefore, the technical problem that existing continuous BDD electrolytic ozone generators still need to solve is: under the condition of long-term continuous operation in water containing calcium ions and / or magnesium ions, how to reduce the cumulative contact and continuous replenishment of hardness ions between the main cathode and the main feed water during the working life, while maintaining the necessary fluid renewal in the main electrolysis area and the effective mass transfer and stable output of ozone into the main water flow, so as to take into account the scaling control of the main cathode and proton exchange membrane, the stability of ozone output, and the long-term operating life of the BDD electrolytic ozone generator module. Summary of the Invention

[0013] The purpose of this invention is to provide a BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure and its application method, so as to solve the technical problems mentioned in the background art.

[0014] Based on the above ideas, the present invention provides the following technical solution:

[0015] A BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure.

[0016] Includes the shell, main electrolysis unit, and pre-electrochemical pretreatment structure;

[0017] The shell contains a main channel for the flow of water to be treated and an electrolysis chamber adjacent to the main channel.

[0018] The main electrolysis unit is disposed in the electrolysis chamber. The main electrolysis unit includes a BDD anode, a proton membrane, and a main cathode. The BDD anode and the main cathode are respectively disposed on both sides of the proton membrane.

[0019] The pre-electrochemical pretreatment structure includes a pre-cathode that is distinct from the main cathode, and a fluid treatment path along the main channel of the water to be treated to the main electrolysis region where the main cathode is located. The pre-cathode is located before the main electrolysis region.

[0020] The front cathode at least partially constitutes the common boundary between the main channel and the electrolysis chamber, and together with the adjacent structures of the electrolysis chamber, defines a pre-electrochemical pretreatment space located before the main electrolysis region.

[0021] The front cathode is provided with multiple through holes, and the main flow channel and the electrolysis chamber are connected by the through holes to form a limited fluid communication, so that the water to be treated in the main flow channel enters the pre-electrochemical pretreatment space through the through holes, and reaches the main electrolysis area where the main cathode is located after passing through the electrochemical action of the front cathode.

[0022] Preferably, the main channel is located at the upper part of the electrolysis chamber, and the front cathode is disposed between the main channel and the electrolysis chamber, forming at least a portion of the cover plate of the electrolysis chamber facing the main channel.

[0023] The precathode and the adjacent structure of the electrolysis chamber together form a semi-enclosed electrochemical pretreatment and electrolysis space.

[0024] Preferably, the front cathode also serves as:

[0025] Electrode components used to apply electrochemical action to the water to be treated entering the pre-electrochemical pretreatment space;

[0026] A partition member for separating the main channel from the electrolysis chamber; and

[0027] A fluid exchange component that controls the fluid exchange between the main flow channel and the electrolysis chamber through the through hole.

[0028] Preferably, the plurality of through holes are distributed on the front cathode;

[0029] By setting the aperture size, distribution density, and aperture ratio of the through holes, the fluid connectivity between the main channel and the electrolysis chamber, as well as the exchange rate of the water to be treated entering the pre-electrochemical pretreatment space, can be adjusted.

[0030] Preferably, the front cathode is an auxiliary cathode;

[0031] The BDD anode is a composite diamond film anode;

[0032] The proton membrane is a proton membrane;

[0033] The main cathode is a titanium composite cathode;

[0034] The auxiliary cathode, composite diamond film anode, proton exchange membrane, and titanium composite cathode are sequentially arranged along the internal space of the shell to form the pre-electrochemical pretreatment structure and the main electrolysis unit.

[0035] Preferably, the module further includes an anode conductive sheet, which is configured to cooperate with the composite diamond film anode for planar clamping of the composite diamond film anode and supplying power to the composite diamond film anode;

[0036] The composite diamond film anode, proton exchange membrane, and titanium composite cathode are stacked together, with the proton exchange membrane located between the composite diamond film anode and the titanium composite cathode.

[0037] Preferably, the module further includes a ceramic insulating washer and a metal level flat washer;

[0038] The ceramic insulating gasket is disposed between adjacent components that require electrical isolation to form an insulating barrier;

[0039] The metal leveling pad is disposed at the assembly position of the main electrolysis unit to balance the height difference formed by the assembly of each electrode of the main electrolysis unit.

[0040] Preferably, the housing includes a plastic support and a plastic lower shell, the plastic support and the plastic lower shell are connected to form the internal fluid space of the module, and the plastic lower shell is provided with water inlet and outlet interfaces;

[0041] The module also includes a hexagonal nut and an electrode fixing screw. The hexagonal nut cooperates with the electrode fixing screw to assemble and fix the auxiliary cathode, anode conductive sheet, composite diamond film anode, proton exchange membrane and titanium composite cathode.

[0042] An application method for a BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure, applied to the aforementioned BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure, the method comprising:

[0043] S1. The water to be treated is introduced into the main channel of the module, so that the water to be treated flows along the main channel;

[0044] S2. At least a portion of the water to be treated in the main channel is allowed to enter the pre-electrochemical pretreatment space through the through hole on the pre-cathode, and the fluid exchange between the main channel and the electrolysis chamber is restricted by the through hole.

[0045] S3. Put the pre-cathode into working state and perform electrochemical action on the water to be treated entering the pre-electrochemical pretreatment space, so that the water to be treated after the pre-electrochemical action forms a reaction state that is different from the original water to be treated in the main channel.

[0046] S4. The water to be treated, after passing through the pre-electrochemical pretreatment space, continues to reach the main electrolysis area where the main cathode is located, and undergoes main electrolysis reaction through the BDD anode, proton membrane and main cathode to generate ozone.

[0047] S5. The fluid exchange between the main channel and the electrolysis chamber is maintained through the through hole, and the ozone generated by electrolysis is output with the water flow.

[0048] Preferably, the water to be treated is water containing calcium ions and / or magnesium ions;

[0049] By setting the aperture size, distribution density, and aperture ratio of the through holes on the pre-cathode, the water flow exchange rate between the main channel and the electrolysis chamber, as well as the amount of water to be treated entering the pre-electrochemical pretreatment space, are adjusted so that the water to be treated undergoes pre-electrochemical treatment before reaching the main cathode, thereby reducing scaling on the main cathode and proton exchange membrane and maintaining ozone water output.

[0050] The technical solution of the present invention may include the following beneficial effects:

[0051] This invention uses an enclosed structure and a pre-cathode to relatively separate the main electrolysis zone from the main flow channel of the main water. A through-hole on the pre-cathode establishes controlled fluid exchange between the main flow channel and the pre-electrochemical pretreatment space. This allows not all the water entering the module to enter the main electrolysis zone; at least a portion can continue flowing towards the outlet along the main flow channel. The water entering the main electrolysis zone enters the pre-electrochemical pretreatment space through the through-hole on the pre-cathode and reaches the main electrolysis zone only after being electrochemically treated by the pre-cathode. This distinguishes the main water flow from the water actually involved in electrolysis in the main electrolysis zone, reducing the amount of water directly in contact with the main feed water during its continuous operating life and the cumulative load of calcium and magnesium hardness ions continuously replenished by the feed water. This slows down the formation and accumulation of inorganic deposits at the main cathode and adjacent proton exchange membranes.

[0052] Meanwhile, this invention does not reduce hardness ion supply by completely isolating the main channel from the main electrolysis zone. The through-holes on the pre-cathode still maintain the necessary fluid exchange between the main channel, the pre-electrochemical pretreatment space, and the main electrolysis zone. Ozone and / or ozone-containing water generated during the main electrolysis process can enter the main channel through the through-holes and undergo mass transfer and mixing with the main water flowing along the main channel. The water, bubbles, and heat in the main electrolysis zone can also be renewed and transferred through the above-mentioned fluid exchange process. Therefore, this invention can reduce the long-term cumulative load of hardness ions on the main cathode while maintaining the water renewal required for normal electrolysis in the main electrolysis zone and the effective output of ozone into the main water flow, avoiding the insufficient water renewal, bubble retention, heat accumulation, and decreased ozone output capacity that may be caused by simply reducing the water intake to the main electrolysis zone.

[0053] Furthermore, the pre-cathode in this invention is not merely used as an additional electrode independent of the main electrolysis unit, but simultaneously serves as a pre-electrochemical pretreatment device, a spatial separator between the main flow channel and the main electrolysis region, and a fluid exchange regulator. The non-penetrating region of the pre-cathode, together with the enclosing structure, defines the fluid path for the bulk water to enter the main electrolysis region, while the through holes constitute the fluid exchange channels for the water to be treated to enter the pre-electrochemical pretreatment space and for the transfer of ozone and / or ozone-containing water from the main electrolysis region to the main flow channel. This ensures that the pre-cathode, the enclosing structure, and the through holes complement each other in terms of spatial structure and electrochemical function. This creates a continuous treatment process where the main water is continuously transported along the main channel, some of the water to be treated enters the main electrolysis zone after undergoing pre-electrochemical treatment at the pre-cathode, and the ozone and / or ozone-containing water generated by the main electrolysis is returned to the main water flow. This reduces the degree of continuous scaling on the main cathode and proton exchange membrane, while mitigating the increase in interfacial resistance, local heating, and deterioration of mass transfer conditions caused by scaling, maintaining the stability of ozone output, and improving the long-term operational stability and service life of the BDD electrolytic ozone generation module. Attached Figure Description

[0054] Figure 1 This is a schematic diagram of the exploded structure of the BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure according to the present invention.

[0055] Figure 2 This is a cross-sectional schematic diagram of the BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure according to the present invention.

[0056] Figure 3 This is a flowchart illustrating the application method of the BDD electrolytic ozone generator module with a pre-electrochemical pretreatment structure according to the present invention.

[0057] Figure 4 Comparison diagram of component status after electrolysis operation of BDD electrolytic ozone generating modules with and without a front cathode and with an insulated front cathode structure.

[0058] Figure 5 The graph shows the cell voltage versus electrolysis time for BDD electrolytic ozone generating modules with a front cathode, without a front cathode, with an insulated front cathode structure, and a simple three-electrode structure.

[0059] Figure 6 The graph shows the ozone concentration versus electrolysis time for BDD electrolytic ozone generating modules with a front cathode, no front cathode, an insulated front cathode structure, and a simple three-electrode structure.

[0060] Figure 7 Comparison of the BDD anode and its local surface condition after operation of BDD electrolytic ozone generation modules with and without a front cathode.

[0061] Figure 8 The graph shows the cell voltage versus electrolysis time for BDD ozone generation modules with different front cathode opening ratios.

[0062] Figure 9 The graph shows the ozone concentration versus electrolysis time for BDD electrolytic ozone generating modules with different front cathode opening ratios.

[0063] Figure 10 This is a graph showing the relationship between the slope of the cell voltage change in the BDD electrolytic ozone generator module and the opening ratio of the front cathode.

[0064] Figure 11 This is a partial decomposition diagram of another BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure in Example 3.

[0065] Figure 12 This is a cross-sectional view of the BDD electrolytic ozone generating module shown in Example 3.

[0066] Explanation of reference numerals in the attached drawings: 1. Hexagonal nut; 2. Plastic bracket; 3. Auxiliary cathode; 4. Ceramic insulating washer; 5. Metal level flat washer; 6. Anode conductive sheet; 7. Composite diamond film anode; 8. Proton exchange membrane; 9. Titanium composite cathode; 10. Electrode fixing screw; 11. Plastic lower shell.

[0067] a. Flow reaction chamber; b. Pre-cathode; c. Electrolytic cathode; d. Proton exchange membrane; e. Electrolytic anode; f. Sealed base plate. Detailed Implementation

[0068] Example 1

[0069] This embodiment provides a BDD electrolytic ozone generator module with a pre-electrochemical pretreatment structure and its application method. It is mainly used for non-pure water containing hardness ions such as calcium and magnesium, and is particularly suitable for the continuous production of ozone water under municipal tap water conditions. Figure 1-7 As shown, this embodiment sets up a pre-cathode, which is different from the main cathode, between the main channel and the main electrolysis region. This pre-cathode has the functions of electrochemical action, spatial separation, and controlled fluid exchange. Before reaching the main electrolysis region where the main cathode is located, part of the water to be treated in the main channel passes through the pre-electrochemical pretreatment space formed by the pre-cathode and then participates in the BDD main electrolysis reaction.

[0070] like Figure 1 As shown, the BDD electrolytic ozone generating module of this embodiment includes a hexagonal nut 1, a plastic bracket 2, an auxiliary cathode 3, a ceramic insulating washer 4, a metal level flat washer 5, an anode conductive sheet 6, a composite diamond film anode 7, a proton exchange membrane 8, a titanium composite cathode 9, electrode fixing screws 10, and a plastic lower shell 11. In this embodiment, the auxiliary cathode 3 constitutes the front cathode, the titanium composite cathode 9 constitutes the main cathode, and the composite diamond film anode 7 is the BDD anode.

[0071] A plastic support 2 is positioned above the lower plastic shell 11, and the plastic support 2 and the lower plastic shell 11 cooperate to form the main shell structure of the module. The lower plastic shell 11 is provided with inlet and outlet ports for the water to be treated to flow in and out, and an internal fluid space for water flow is formed between the plastic support 2 and the lower plastic shell 11. Figure 2 As shown, the internal fluid space includes a main channel for conveying water to be treated and an electrolysis chamber located below the main channel. The main channel and the electrolysis chamber do not form a completely open, continuous space, but are separated by a front cathode 3 disposed between them. The original customer instructions specified that the electrolysis chamber be located below the main channel, so that some water can remain in the electrolysis chamber, thereby continuously wetting the proton exchange membrane 8.

[0072] The pre-cathode 3 is positioned between the main flow channel and the electrolysis chamber, and at least partially forms the common boundary between them. The pre-cathode 3 and the corresponding structure of the plastic lower shell 11 together define a semi-enclosed electrolysis space, within which the composite diamond film anode 7, proton exchange membrane 8, and titanium composite cathode 9 are disposed. Therefore, the pre-cathode 3 is not a typical third electrode suspended in the main flow channel; it serves as both an electrode participating in electrochemical reactions and a partition structure between the main flow channel and the electrolysis chamber. The overall structural relationship established in the existing disclosure is as follows: a pre-cathode, distinct from the main cathode, is positioned outside the main electrolysis unit composed of the BDD anode, proton exchange membrane, and main cathode. The pre-cathode and its surrounding structure define the electrochemical pretreatment space before the main electrolysis, while simultaneously making the pre-cathode the common boundary between the main flow channel and the electrolysis chamber.

[0073] Multiple through holes are provided on the front cathode 3, extending along the thickness direction of the front cathode 3 to create a limited fluid connection between the main flow channel and the electrolysis chamber. When the water to be treated flows along the main flow channel, only a portion of the water enters the electrochemical pretreatment space defined by the front cathode 3 and its surrounding structure through the through holes, while the remaining water in the main flow channel continues to flow along it. This prevents all the water in the main flow channel from directly and continuously flowing into the main electrolysis area, thus limiting the contact and replenishment of hardness ions such as calcium and magnesium in the main cathode 9 with the main body water throughout the entire working cycle. The original disclosure further points out that the purpose of this flow path design is to separate the main flow channel from the electrolysis chamber, maintain necessary mass transfer between them through the openings, and create a relatively independent BDD electrolysis environment in the electrolysis chamber.

[0074] It should be noted that the "limited fluid connectivity" described in this embodiment does not mean that the main flow channel and the electrolysis chamber are completely isolated, but rather that the main water flow exchange between the two is constrained by the through-holes on the pre-cathode 3. The through-holes allow water from the main flow channel to enter the electrolysis chamber, and also allow continuous exchange between the ozone water, bubbles formed during electrolysis, and the water within the electrolysis chamber and the main flow channel. Therefore, the through-holes on the pre-cathode 3 simultaneously constitute the mass transfer control interface in the pre-electrochemical pretreatment structure.

[0075] In this embodiment, the aperture ratio of the front cathode 3 is defined as the ratio of the sum of the projected areas of all through holes on the front cathode 3 to the total projected area of ​​the front cathode 3 when projected along a direction perpendicular to the surface of the front cathode plate. Example 1 does not limit the specific optimal aperture ratio, but only illustrates that the degree of fluid exchange between the main flow channel and the electrolysis chamber can be changed by altering the size, number, or distribution of the through holes. The specific impact of the aperture ratio on scaling, tank voltage, and ozone output stability, and its optimal settings, will be further explained in subsequent embodiments.

[0076] Within the electrolysis chamber, the main electrolysis unit comprises a composite diamond membrane anode 7, a proton exchange membrane 8, and a titanium composite cathode 9. The proton exchange membrane 8 is positioned between the composite diamond membrane anode 7 and the titanium composite cathode 9 to facilitate proton conduction and maintain the membrane electrode reaction interface. The composite diamond membrane anode 7 performs anodic electrochemical reactions and generates ozone under energized conditions, while the titanium composite cathode 9 performs cathodic reactions. The water to be treated enters the electrolysis chamber along the main flow path and ultimately reaches the area where the titanium composite cathode 9 is located. The pre-cathode 3 is positioned before the titanium composite cathode 9, thus ensuring that the water entering the main electrolysis zone undergoes pre-electrochemical processes and controlled mass transfer before participating in the main electrolysis reaction.

[0077] The anode conductive plate 6 is configured in conjunction with the composite diamond film anode 7. The anode conductive plate 6 serves two purposes: firstly, it acts as a conductive component of the composite diamond film anode 7, supplying power to it; secondly, it provides planar clamping for the composite diamond film anode 7 and provides assembly constraints for the stacked structure formed by the composite diamond film anode 7, the proton exchange membrane 8, and the titanium composite cathode 9. This clamping relationship helps maintain the adhesion between the membrane electrodes, reducing the interfacial gap caused by dimensional changes in the proton exchange membrane 8 due to water absorption expansion and water loss contraction, thereby preventing an increase in contact resistance and a deterioration in mass transfer and conductivity conditions. This function is also clearly described in the original technical disclosure.

[0078] Ceramic insulating washers 4 are placed between adjacent conductive components requiring electrical isolation to maintain insulation between conductive components of different polarities; metal leveling washers 5 are used to compensate for the height difference formed by the assembly on both sides of the module, ensuring that the stacked electrodes remain relatively flat in the locked state. Hexagonal nuts 1 cooperate with electrode fixing screws 10 to position and lock the plastic bracket 2, front cathode 3, anode conductive sheet 6, and main electrolysis unit. Through the above assembly relationship, each electrode maintains its predetermined spatial position, while maintaining the semi-enclosed space defined by the front cathode 3 and the lower plastic shell 11.

[0079] In terms of electrical connection, the composite diamond film anode 7 is connected to the anode power supply side via the anode conductive plate 6. Both the pre-cathode 3 and the titanium composite cathode 9 are in cathode operation during electrolysis. After energization, the pre-cathode 3 generates an electrochemical effect on the water to be treated that enters the pre-electrochemical pretreatment space through its through-hole, while the titanium composite cathode 9 continues to participate in the electrolysis reaction as the main cathode in the BDD main electrolysis unit. Therefore, the pre-cathode 3 differs from the main cathode 9 in its position, structural identity, and functional stage, which is different from the structure of simply adding a third electrode to a conventional electrolytic cell.

[0080] In practical applications, such as Figure 3 As shown, this embodiment includes steps S1-S5.

[0081] S1. The water to be treated is introduced into the main channel and flows along the main channel.

[0082] S2. Part of the water to be treated enters the pre-electrochemical pretreatment space through the through hole of the pre-cathode 3. Because the main flow channel and the electrolysis chamber are separated by the pre-cathode 3, the water flow needs to pass through the through hole to carry out the main material exchange between the two areas. Therefore, the amount of water entering the electrolysis chamber and the water turnover rate are constrained by the through hole structure.

[0083] S3. The pre-cathode 3 is put into operation to electrochemically process the water entering the pre-electrochemical pretreatment space, causing the water before entering the main electrolysis zone to undergo an electrochemical and mass transfer process different from the original influent in the main channel. For water containing calcium and magnesium hardness ions, in this process, the electrochemical action of the pre-cathode 3, together with the spatial constraints and mass transfer conditions formed by the through holes, alters the hardness ion replenishment, fluid renewal, and interfacial reaction conditions in the area where the main cathode 9 is located.

[0084] S4. The water to be treated, which has passed through the pre-electrochemical pretreatment space, reaches the main electrolysis area where the titanium composite cathode 9 is located. The main electrolysis reaction is carried out through the composite diamond film anode 7, the proton exchange membrane 8 and the titanium composite cathode 9, generating ozone on the side of the composite diamond film anode 7 and forming ozone-containing water.

[0085] S5. Water exchange between the main channel and the electrolysis chamber is continuously maintained through the through hole on the front cathode 3, so that the ozone water generated in the electrolysis chamber exchanges and mixes with the water in the main channel, and is finally output from the water outlet of the module with the water flow of the main channel.

[0086] As can be seen from the above operation process, the pre-cathode 3 does not aim to concentrate and deposit a large amount of scale on its surface. Its main function is to cooperate with the pretreatment space it forms and the controlled mass transfer structure of the through holes to form a pre-electrochemical process before water enters the main electrolysis area where the main cathode 9 is located. For ordinary electrochemical descaling structures, the additional cathode is usually used as a location for scale deposition and collection. However, in this embodiment, the pre-cathode 3 also serves as the common boundary between the main channel and the electrolysis chamber and the fluid exchange control interface. The existing creative description also clearly defines "distinguished from the main cathode, before the main electrolysis, also serving as a partition structure, with limited connectivity through holes, and the pretreated fluid entering the main electrolysis area" as the overall structural relationship.

[0087] To verify the actual effect of the aforementioned pre-cathode structure, four groups of 040 modules were set up under the same conditions of influent water quality, flow rate, current and operating time for 120 hours of continuous electrolysis control. These included a control group without a pre-cathode, a complete pre-cathode scheme group, an insulated pre-cathode structure control group with an insulating component replacing the pre-cathode, and a simple three-electrode control group that simply added an additional cathode without forming the aforementioned pretreatment space and controlled mass transfer relationship. Figure 4 The diagram shows the physical state of the front structure, cathode, and proton exchange membrane of a portion of the control module after it has been put into operation.

[0088] After continuous operation, the deposits on the main cathode, proton exchange membrane, and pre- or additional components were weighed, and the following results were obtained:

[0089]

[0090] The above-mentioned original experimental data show that the total scale content of the module with complete precathode structure decreased from 354.6 mg without precathode structure to 169.6 mg, a reduction of about 52.2%; the scale content of the main cathode decreased from 306.9 mg to 141.7 mg, a reduction of about 53.8%; and the scale content of the proton exchange membrane decreased from 47.7 mg to 20.8 mg, a reduction of about 56.4%.

[0091] Furthermore, the total scale difference between the module without a precathode and the module with a complete precathode is 185.0 mg, while the precathode 3 in the complete structure only has 7.1 mg of scale attached, which is only about 3.8% of the aforementioned reduction. Therefore, the experimental results show that this embodiment does not simply transfer the scale originally deposited on the main cathode 9 and the proton exchange membrane 8 to the precathode 3, but rather significantly reduces the total amount of scale formation in the entire module.

[0092] The control group with an insulated pre-cathode structure retained similar partition positions, chamber spaces, through holes, and fluid paths to the complete design, but replaced the pre-cathode 3 with an insulating component, rendering this component devoid of the electrochemical effects of a pre-cathode. The total scale in this group still reached 333.2 mg, only about 6.0% lower than the structure without a pre-cathode, and approximately 1.96 times that of the complete pre-cathode structure. This indicates that relying solely on perforated partitions, spatial separation, and changes in water flow paths cannot achieve the scale inhibition effect of the complete structure; the electrochemical properties of the pre-cathode 3 are a crucial component in producing the aforementioned effect.

[0093] The simple three-electrode control group retains the additional cathode, but does not make it simultaneously form the boundary between the main channel and the electrolysis chamber as in this embodiment, nor does it form a pre-electrochemical pretreatment space and corresponding controlled mass transfer relationship. Its total scale content is 272.2 mg, which, although lower than the structure without a pre-cathode, is still approximately 1.60 times that of the complete pre-cathode scheme; its additional cathode itself has a scale content of 25.3 mg, which is also significantly higher than the 7.1 mg on pre-cathode 3 in this embodiment. Therefore, simply adding a cathode can only achieve limited improvement; only by combining the electrochemical effect, spatial separation effect, and controlled mass transfer effect of the through-hole according to the structural relationship in this embodiment can a more significant overall scale control effect be obtained.

[0094] Figure 5 The changes in cell voltage with electrolysis time for four different module structures during continuous electrolysis are further illustrated. Among them, the cell voltage of the BDD module without a pre-cathode shows a significant accelerating upward trend with operating time, and its fitting relationship is y = 0.00103x. 2 -0.00373x+8.85; the fitting relationship for the insulated front cathode BDD module is y=0.00071x 2+0.0323x+8.3; the fitting relationship for a simple three-electrode BDD module is approximately y=0.0523x+7.35; the fitting relationship for a complete front-cathode BDD module is approximately y=0.02043x+7.89, where x is the electrolysis time in hours (h) and y is the cell voltage in volts (V). Figure 5 It is evident that during 120 hours of continuous operation, the cell voltage growth rate of the complete front cathode structure was significantly lower than that of the structure without a front cathode and the insulated front cathode structure, indicating that the impedance growth and deterioration of the operating state at the main electrolysis interface were effectively delayed.

[0095] Figure 6 The results show the changes in ozone concentration over electrolysis time for four different module structures. The ozone concentration of the complete front-cathode BDD module gradually decreased from approximately 0.50 mg / L initially, remaining at approximately 0.33 mg / L after 120 hours of operation. The ozone concentration of the module without a front cathode decreased to approximately 0.29 mg / L after 120 hours, while the insulated front-cathode module and the simple three-electrode module both decreased to approximately 0.30 mg / L. Particularly in the later stages of continuous operation, the ozone concentration of the complete front-cathode structure was generally higher than the other three groups, indicating that this embodiment can slow down the long-term decay of ozone generation and output capacity of the BDD module while inhibiting scaling.

[0096] Figure 7 The diagram shows the BDD anode plate and its local surface condition after continuous operation with and without a precathode module. Combined with the scale weighing results, it is clear that scale accumulation is faster in the structure without a precathode, reaching a total scale of 354.6 mg after 120 hours, approximately 2.1 times the 169.6 mg in the complete precathode structure. Further customer experiments revealed that as scale thickens near the cathode and proton exchange membrane, the local clamping state within the membrane electrode stack changes, increasing the mechanical bending stress on the BDD anode and potentially causing cracking of the BDD membrane. Figure 7 The differences in surface condition shown correspond to the aforementioned long-term scaling and structural stress changes.

[0097] Therefore, this embodiment does not extend the module life by simply adding a scale-bearing cathode. Instead, it utilizes a pre-cathode 3, distinct from the main cathode 9, positioned between the main flow channel and the main electrolysis region. This simultaneously forms the pre-electrochemical interface, the separation boundary between the main flow channel and the electrolysis chamber, and the controlled mass transfer interface of the through-hole. Experimental results support a coupling effect among these three effects: the insulating separation structure reduces total scale by only about 6.0%, simply adding a cathode reduces total scale by about 23.2%, while the complete pre-cathode structure reduces total scale by about 52.2%. In the absence of repeatability tests and error ranges, the above experimental results support the significant comprehensive scale-inhibiting effect of the structure in this embodiment, but do not describe it as a single, uniquely verified microscopic mechanism.

[0098] Based on the above structure and operation, those skilled in the art can follow... Figure 1 , Figure 2 The module assembly is completed by showing the component stacking and cavity relationships, and is done according to... Figure 3 The process shown is for continuous BDD electrolytic ozone preparation. Figure 4-7 The control experiment shown further verifies the actual role of the controlled mass transfer relationship of the pre-cathode 3, the pretreatment space and the through hole in reducing scaling of the main cathode 9 and the proton exchange membrane 8, slowing down the rise of the cell voltage and maintaining ozone output.

[0099] Example 2

[0100] Based on the BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure described in Example 1, this embodiment further optimizes the opening ratio of the through holes on the pre-cathode 3 to determine the optimal structural parameters of the pre-cathode 3 while taking into account fluid exchange between the main channel and the electrolysis chamber, the electrochemical effect of the pre-cathode, long-term scaling of the main cathode, and the stability of ozone output.

[0101] In Example 1, the pre-cathode 3 is disposed between the main flow channel and the electrolysis chamber, serving as at least part of the common boundary between them. The pre-cathode 3 has multiple through holes, allowing some of the water to be treated in the main flow channel to enter the pre-electrochemical pretreatment space through these holes. After undergoing electrochemical action at the pre-cathode 3, the water then enters the main electrolysis region where the titanium composite cathode 9 is located. Thus, the through holes on the pre-cathode 3 serve two purposes: firstly, they facilitate fluid exchange between the main flow channel and the electrolysis chamber; secondly, they alter the solid conductive area retained by the pre-cathode 3 itself. Therefore, changes in the porosity not only affect the water flow capacity but also further influence the cathode current distribution between the pre-cathode and the main cathode, as well as the local electrochemical state of the main cathode region.

[0102] In this embodiment, the aperture ratio of the front cathode 3 is defined as the ratio of the sum of the projected areas of all through holes on the front cathode 3 to the total projected area of ​​the front cathode 3 when projected along a direction perpendicular to the surface of the front cathode 3. In other words, this embodiment uses the total projected area of ​​the entire front cathode 3 as a unified calculation benchmark, rather than using the local partition area that actually participates in the separation of the main channel and the electrolysis chamber as the denominator.

[0103] To eliminate the influence of variations in the number of through holes, this embodiment uses a front cathode 3 with identical external contours and installation structures. The number of through holes on the front cathode 3 remains consistent across all test groups. Only the width of a single through hole is changed to alter the total projected area of ​​all through holes, resulting in five groups of front cathodes with open area ratios of 9%, 18%, 26%, 35%, and 43%. Except for the different open area ratios of the front cathodes, all other aspects—module structure, influent water quality, flow rate, power supply method, and operating time—remain identical across groups to ensure comparability. Each BDD electrolytic ozone generator module operates continuously for 120 hours, and the changes in cell voltage, output ozone concentration, and scale mass on the main cathode 9, proton exchange membrane 8, and front cathode 3 are recorded after the test. In customer tests, the same number of holes is used, but the width of each hole is varied to achieve five open area ratio levels of 9%, 18%, 26%, 35%, and 43%.

[0104] In this embodiment, each group of pre-cathodes 3 maintains the spatial position described in Example 1, that is, they are all located between the main channel and the main electrolysis region where the titanium composite cathode 9 is located, and still simultaneously perform the functions of pre-electrochemical treatment, spatial separation between the main channel and the electrolysis chamber, and controlled mass transfer through the through holes. Therefore, the variable changed in this embodiment is only the opening ratio of the pre-cathode 3, and does not change the basic fluid processing path of "main channel - pre-cathode - pre-electrochemical pretreatment space - main electrolysis region" formed in Example 1.

[0105] After 120 hours of continuous operation, the scale on the main cathode 9, proton exchange membrane 8, and pre-cathode 3 of each group was cleaned and weighed, and the following results were obtained:

[0106]

[0107] The experimental results show that as the opening ratio of the pre-cathode 3 increases, the scale buildup in the module does not exhibit a simple monotonic increase or decrease trend. Specifically, the scale buildup in the 35% opening ratio group was 147.6 mg for the main cathode, 21.5 mg for the proton exchange membrane, and 7.3 mg for the pre-cathode, with a total module scale buildup of 176.4 mg. The scale buildup in the main cathode, proton exchange membrane, and total module were the lowest among the five groups.

[0108] Compared to the 9%, 18%, 26%, and 43% open area groups, the total scale content of the modules in the 35% open area group was reduced by approximately 22.9%, 30.2%, 17.7%, and 28.0%, respectively; compared to the 18% open area group, the scale content of the main cathode was reduced by approximately 28.1%, and the scale content of the proton exchange membrane was reduced by approximately 34.3%; compared to the 43% open area group, the scale content of the main cathode was reduced by approximately 23.2%, and the scale content of the proton exchange membrane was reduced by approximately 31.1%.

[0109] The results above show that the porosity of the precathode 3 is not just a common geometric parameter for controlling the flow rate, but also affects both fluid mass transfer and the proportion of the solid region of the precathode 3.

[0110] Specifically, when the opening ratio is small, the solid area retained by the pre-cathode 3 is large, and the flux of hardness ions such as calcium and magnesium ions in the main water entering the electrolysis chamber through the through holes is strongly limited. At the same time, the pre-cathode 3 can maintain a large effective working area. However, an excessively small opening ratio will also limit the exchange between the water in the electrolysis chamber and the main channel, so that the hydroxide ions, bubbles, heat generated near the main cathode 9, as well as the generated ozone water, cannot diffuse or be discharged into the main channel through the through holes in time, which can easily lead to a state of insufficient local water renewal.

[0111] For example, at a 9% porosity, approximately 91% of the projected area of ​​the front cathode 3 remains a non-penetrating area, resulting in relatively weak fluid exchange between the main channel and the electrolysis chamber. Although the total amount of hardness ions entering the main electrolysis region is limited, the fluid renewal inside the electrolysis chamber is also significantly restricted. Consequently, the key interfaces of the main cathode and proton exchange membrane may still be in a state of localized high alkalinity, bubble retention, and insufficient mass transfer. Customer experiments also show that the 9% group is not the group with the highest scaling, but it exhibits the most significant long-term ozone output attenuation.

[0112] When the porosity increased to 18%, the fluid exchange between the main channel and the electrolysis chamber was enhanced. However, the supply of hardness ions such as calcium and magnesium entering the main electrolysis area increased simultaneously, and the solid area retained by the pre-cathode 3 decreased accordingly. At this porosity, the fluid renewal capacity was insufficient to completely offset the adverse effects of the increased supply of hardness ions and the increased reaction load on the main cathode. Therefore, the scale content of the main cathode in the 18% group reached 205.4 mg, the scale content of the proton exchange membrane reached 32.7 mg, and the total scale content of the module reached 252.7 mg, which was the highest value in this experiment. This result further illustrates that there is no direct linear relationship between porosity and scaling: "the larger the porosity, the less scaling."

[0113] When the porosity increases to 26%, the water renewal effect provided by the through holes is further enhanced. Hydroxides, bubbles, heat, and micro-deposited crystal nuclei formed near the main cathode 9 are more easily removed from the critical reaction interface by fluid exchange. As a result, the scale content of the main cathode decreases to 176.5 mg, and the total scale content of the module decreases to 214.3 mg. At this point, the beneficial effects of improved mass transfer begin to be apparent. However, the reduction in the solid area of ​​the front cathode 3 and the change in the current load of the main cathode will still affect the polarization of the critical reaction interface and the cell voltage.

[0114] In this embodiment, a 35% opening ratio was determined to be the optimal implementation point value under the tested conditions.

[0115] With an opening ratio of 35%, the total projected area of ​​the through holes in the front cathode 3 accounts for approximately 35% of the total projected area of ​​the front cathode 3, while the front cathode 3 still retains approximately 65% ​​of the non-through solid projected area. Therefore, this structure neither excessively restricts water exchange between the main channel and the electrolysis chamber due to an excessively small opening area, nor significantly reduces the solid functional area of ​​the front cathode 3 due to an excessively large opening area.

[0116] In this state, the through hole can provide a sufficient material exchange channel between the main channel and the electrolysis chamber, so that the hydroxide ions, bubbles and heat generated near the main cathode 9 can be transferred to the main channel side in a timely manner. At the same time, it is beneficial for the ozone water generated by electrolysis to be output from the electrolysis chamber to the main channel. On the other hand, the front cathode 3 still retains a large solid area, so that it can maintain the pre-electrochemical effect described in Example 1 and avoid the main cathode 9 bearing an excessively high local electrochemical load.

[0117] Therefore, a 35% opening ratio actually creates a better balance between the two opposing processes:

[0118] On the one hand, increasing the size of the through-hole is beneficial for fluid renewal, bubble discharge, heat exchange, ozone water output, and the removal of tiny crystal nuclei from the interface between the main cathode and the proton exchange membrane;

[0119] On the other hand, increasing the size of the through hole will increase the supply of hardness ions such as calcium and magnesium in the main water to the main electrolysis area, while reducing the remaining solid area of ​​the front cathode 3 and changing the cathode current distribution between the front cathode and the main cathode and the local current density of the main cathode.

[0120] Customer test results show that a 35% opening ratio is a better balance between the two types of effects mentioned above, thus achieving the lowest scale content in the main cathode, proton exchange membrane, and module.

[0121] When the porosity was further increased to 43%, although the fluid exchange capacity between the main channel and the electrolysis chamber continued to improve, the pre-cathode 3 retained only about 57% of its non-penetrating solid projection area. Simultaneously, hardness ions such as calcium and magnesium in the main water could more continuously replenish the main electrolysis area, making the local pretreatment state formed by the pre-cathode 3 more susceptible to the influence of the main water flow. The further reduction in the solid area of ​​the pre-cathode 3 also altered the cathode current distribution, increasing the local current load and interfacial polarization of the main cathode 9. Ultimately, the scale content of the main cathode in the 43% group rose to 192.3 mg, the scale content of the proton exchange membrane rose to 31.2 mg, the scale content of the pre-cathode reached 21.6 mg, and the total scale content of the module reached 245.1 mg.

[0122] Furthermore, such as Figure 8 As shown, the cell voltage of the BDD electrolytic ozone generating module with five opening ratios of 9%, 18%, 26%, 35%, and 43% was recorded during continuous operation. Under different opening ratios, the cell voltage changed to varying degrees with increasing operating time, but the rate of change differed significantly.

[0123] according to Figure 8 The cell voltage variation trend shown is approximately on the order of 0.018, 0.024, 0.030, 0.020, and 0.037 after fitting the cell voltage variation of each group.

[0124] This shows that the slope of the tank voltage change does not simply change synchronously with the total mass of scale. For example, although the 9% opening ratio is not the group with the lowest scale, its tank voltage change slope is small because the solid area of ​​the front cathode 3 is large and has a strong influence on the local current load of the main cathode; although the fluid renewal is significantly improved with the 26% opening ratio, the local current density and polarization state of the key interface may still cause the tank voltage to increase rapidly; the 43% opening ratio shows the highest tank voltage change rate.

[0125] The slope of the cell voltage change in the 35% open area group was approximately 0.020, significantly lower than that of the adjacent 26% and 43% open area groups, forming a distinct local trough. This indicates that, with sufficient fluid exchange capacity, the 35% open area ratio can effectively mitigate the deterioration of the impedance and polarization state of key reaction interfaces such as the main cathode 9 and proton exchange membrane 8 over continuous operation.

[0126] like Figure 9 As shown, different opening ratios also have a significant impact on the long-term ozone output stability of the BDD electrolytic ozone generator module.

[0127] The initial ozone concentration of the 9% open area group was about 0.64 mg / L, which dropped to about 0.35 mg / L after about 24 hours of operation, and dropped to about 0.16 mg / L after 120 hours of continuous operation. This indicates that the small open area will significantly limit the exchange of ozone water and fluid in the electrolysis chamber to the main channel, causing the long-term ozone output capacity to decay rapidly.

[0128] The ozone concentration in the 18% open area group was approximately 0.28 mg / L after 120 h of operation; although the initial ozone concentration in the 26% open area group was higher, it decreased to approximately 0.24 mg / L after 120 h.

[0129] The ozone concentration in the 35% open area group showed relatively continuous and stable changes during continuous operation, remaining at approximately 0.32 mg / L after 120 hours. While this group did not exhibit the highest instantaneous ozone concentration at all operating times, its long-term output decay was relatively slow. It also showed the lowest main cathode scale buildup, proton exchange membrane scale buildup, and a lower cell voltage growth rate in this experiment, thus demonstrating good long-term overall operational stability.

[0130] The 43% opening ratio group maintained a high ozone concentration during the initial and middle stages of operation, but experienced a significant and rapid decline between 96 and 120 hours, with the ozone concentration reaching approximately 0.30 mg / L after 120 hours. This result indicates that while an excessively high opening ratio can provide sufficient fluid exchange and ozone output conditions in the initial stages of operation, the cumulative effects of increased hardness ion supply, reduced pre-cathode solid area, and deterioration of the main cathode interface over long-term operation ultimately lead to a decrease in ozone output stability.

[0131] like Figure 10 As shown, by comparing the opening ratio of the front cathode as the horizontal axis and the slope of the cell voltage change obtained during the continuous operation of each group as the vertical axis, the influence of the opening ratio on the long-term electrochemical operation of the module can be seen more intuitively.

[0132] from Figure 10 It can be seen that as the aperture ratio increases from 9% to 26%, the slope of the cell voltage change gradually increases; when the aperture ratio reaches 35%, the slope of the cell voltage change decreases, forming a local trough; when the aperture ratio further increases to 43%, the slope of the cell voltage change increases significantly again. This non-monotonic change further indicates that the aperture ratio of the pre-cathode 3 is simultaneously constrained by multiple factors such as fluid exchange capacity, the solid area of ​​the pre-cathode, hardness ion supply, and the local electrochemical state of the main cathode, and cannot be determined solely by the fluid flow area.

[0133] comprehensive Figure 8 The long-term change in the slot voltage shown Figure 9 The long-term changes in ozone concentration shown Figure 10The slope of the cell voltage change and the scale weighing results after 120 hours show that, under the same operating conditions and the structure of the BDD electrolytic ozone generator module in this embodiment, the opening ratio of the pre-cathode 3 is set to 35%, which provides the best overall performance. The customer's original experiment also clearly showed that the main cathode, proton exchange membrane, and total scale in the 35% relative opening area group were the lowest among the five groups, while the cell voltage change rate was low, and the ozone concentration remained relatively stable during 120 hours of continuous operation.

[0134] Therefore, in this embodiment, a front cathode 3 with an opening ratio of 35% is preferably used. That is, when projected along a direction perpendicular to the surface of the front cathode 3, the sum of the projected areas of all through holes accounts for 35% of the total projected area of ​​the front cathode 3. With the number of through holes remaining constant, the required total projected area of ​​through holes can be calculated based on the total projected area of ​​the front cathode 3. Then, the size of each through hole is determined according to the number of through holes, and the actual total opening area is made to reach the above ratio by adjusting the width of each through hole. Thus, those skilled in the art can prepare a structure with a corresponding 35% opening ratio based on the actual size of the front cathode 3.

[0135] With the aforementioned 35% open area structure, the pre-cathode 3 still retains approximately 65% ​​of its non-penetrating solid projection area. This provides sufficient but not excessive fluid exchange channels between the main channel and the electrolysis chamber while maintaining the pre-electrochemical effect. This results in a better match between the supply of hardness ions to the main electrolysis region, the cathode current distribution between the pre-cathode and main cathode, the local current density of the main cathode, hydroxide diffusion, bubble removal, heat exchange, and ozone water output. Experiments showed that under the 35% open area condition, the scale buildup at the main cathode was 147.6 mg, the proton exchange membrane scale was 21.5 mg, the pre-cathode scale was 7.3 mg, and the total scale buildup of the module was 176.4 mg. Furthermore, it maintained an ozone concentration of approximately 0.32 mg / L after 120 hours of continuous operation. Therefore, based on the complete pre-electrochemical pretreatment structure of Example 1, it further reduces the scaling degree at key electrolysis interfaces, slows down the increase in cell voltage over operating time, and improves the long-term ozone output stability of the BDD electrolytic ozone generation module.

[0136] Example 3

[0137] This embodiment, based on the BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure described in Embodiment 1, provides another spatial arrangement of the main flow channel and the main electrolysis unit. By changing the relative arrangement of the flow reaction chamber and the main electrolysis unit, this pre-electrochemical pretreatment structure can be adapted to module structures where the main flow channel surrounds or multiple sets of electrolysis units are arranged along the main flow channel.

[0138] like Figure 11 and Figure 12As shown, the BDD electrolytic ozone generating module of this embodiment includes a flow reaction chamber a, a pre-cathode b, an electrolytic cathode c, a proton exchange membrane d, an electrolytic anode e, and a sealed base plate f. The electrolytic cathode c constitutes the main cathode in the main electrolysis unit, the electrolytic anode e is the BDD anode used to generate ozone, and the proton exchange membrane d is disposed between the electrolytic cathode c and the electrolytic anode e.

[0139] The flow reaction chamber a is a cavity structure with a continuous fluid channel inside, extending along the flow direction of the water to be treated, with an inlet side and an outlet side at both ends. After the water to be treated enters the flow reaction chamber a, the main body of water can flow continuously towards the outlet side along the fluid channel inside the flow reaction chamber a, without requiring all the water to be treated to pass through the main electrolysis unit.

[0140] A localized area for mounting electrolysis components is provided in the flow reaction chamber a. A pre-cathode b is positioned between the flow reaction chamber a and the main electrolysis unit, and at least partially constitutes the interface separating the flow reaction chamber a and the main electrolysis area. For example... Figure 11 As shown, the precathode b has a side structure extending toward the electrolytic cathode c, which allows the precathode b to cooperate with the adjacent structure of the flow reaction chamber a to define the space for the pre-electrochemical pretreatment.

[0141] The pre-cathode b has multiple through holes, which form a fluid exchange channel between the flow reaction chamber a and the pre-electrochemical pretreatment space. The non-through areas of the pre-cathode b, excluding the through holes, spatially separate the flow reaction chamber a from the main electrolysis region. Therefore, as the water to be treated flows along the flow reaction chamber a, a portion of the water continues downstream along the flow reaction chamber a, while the other portion enters the pre-electrochemical pretreatment space through the through holes on the pre-cathode b.

[0142] Along the direction away from the flow reaction chamber a, the pre-cathode b, electrolytic cathode c, proton exchange membrane d, and electrolytic anode e are arranged sequentially. The enclosed base plate f is located on the side of the electrolytic anode e away from the proton exchange membrane d, and cooperates with the corresponding structure of the flow reaction chamber a to form a locally enclosed space for accommodating the pre-cathode b and the main electrolysis unit. This separates the main electrolysis unit from the flow reaction chamber a, while maintaining necessary fluid exchange through the through-hole on the pre-cathode b.

[0143] During electrolysis, the pre-cathode b is in cathode working state and performs pre-electrochemical action on the water to be treated that enters the pre-electrochemical pretreatment space through the through hole. After the pre-electrochemical action, the water further reaches the main electrolysis area composed of the electrolysis cathode c, proton exchange membrane d, and electrolysis anode e, where the main electrolysis unit performs the BDD electrolysis ozone reaction.

[0144] During the above process, the main water in the flow reaction chamber a does not entirely enter the main electrolysis zone, but remains continuously flowing along the flow reaction chamber a. The ozone and / or ozone-containing water generated in the main electrolysis zone can be exchanged and mixed with the main water in the flow reaction chamber a again through the through-hole on the pre-cathode b, and then output towards the outlet side with the water flow in the flow reaction chamber a. Thus, while ensuring the main electrolysis zone has the necessary water renewal and ozone output channels, it avoids the continuous and large-scale direct entry of main water into the area where the electrolysis cathode c is located.

[0145] Compared to the specific structure in Embodiment 1 where the main channel is located on one side of the electrolysis chamber, this embodiment utilizes the flow reaction chamber a to form a continuous main water flow path, and places the electrolysis assembly, consisting of the pre-cathode b, electrolysis cathode c, proton exchange membrane d, and electrolysis anode e, at a local periphery of the flow reaction chamber a. Therefore, the flow reaction chamber a can extend along at least a portion of the periphery of the electrolysis assembly according to the module's spatial shape, without requiring the main channel to maintain a fixed vertical position relative to the main electrolysis area.

[0146] Furthermore, in one specific embodiment, two sets of pre-electrochemical pretreatment and main electrolysis components can be arranged along the flow path of the water to be treated in the flow reaction chamber a. Both sets of electrolysis components adopt the above-mentioned combination structure of pre-cathode b, electrolysis cathode c, proton exchange membrane d, and electrolysis anode e, and respectively cooperate with the flow reaction chamber a through corresponding closed base plates f to form locally enclosed electrolysis areas.

[0147] Specifically, the two sets of electrolysis units can be respectively arranged on opposite sides of the flow reaction chamber a, for example, on the upper and lower sides of the flow reaction chamber a, and staggered along the flow direction of the water to be treated. After the ozone and / or ozone-containing water generated by the first set of electrolysis units is returned to the flow reaction chamber a, it continues to flow downstream with the main water and further passes through the fluid exchange area corresponding to the second set of electrolysis units, thereby forming a series connection between the first set of electrolysis units and the second set of electrolysis units along the fluid treatment path of the water to be treated.

[0148] It should be noted that the "series connection" of the two electrolysis components in this embodiment refers to the two electrolysis components sequentially performing their treatment functions along the fluid treatment path of the water to be treated, and does not necessarily limit the two electrolysis components to being connected in series in the power supply circuit. The specific power supply connection method of the two electrolysis components can be set according to the power supply structure of the module, as long as the pre-cathode b in each group can perform pre-electrochemical function, and the electrolysis anode e, electrolysis cathode c, and proton exchange membrane d can complete the BDD electrolysis ozone reaction.

[0149] With the above structure, regardless of whether a single set of electrolysis components is used or two or more sets of electrolysis components are used along the flow reaction chamber a, the fluid treatment relationship of "the main body of water flows continuously along the flow reaction chamber—part of the water enters the pre-electrochemical pretreatment space through the pre-cathode—enters the main electrolysis area for BDD electrolysis—ozone and / or ozone-containing water re-enters the main water flow" can be maintained. Therefore, this embodiment enables the structure to adapt to different flow reaction chamber shapes and multi-electrolysis component arrangements without changing the basic working mechanism of the pre-cathode.

[0150] Example 4

[0151] Example 1 involves allowing a portion of the water to be treated in the main flow channel to enter the pre-electrochemical pretreatment space through a through-hole on the pre-cathode. After being subjected to the electrochemical action of the pre-cathode, it then enters the main electrolysis region composed of the BDD anode, proton exchange membrane, and main cathode. This reduces the continuous and excessive replenishment of calcium and magnesium ions from the main influent to the local high-pH region where the main cathode is located, and maintains necessary water exchange between the main flow channel and the main electrolysis region through the through-hole. This structure effectively alleviates the scaling problem when a single main electrolysis region continuously treats hard water. Existing embodiments have shown that the through-hole of the pre-cathode not only affects water exchange but also simultaneously affects the conductive physical region retained by the pre-cathode and the cathode current distribution between the pre-cathode and the main cathode. Therefore, the fluid exchange state and the electrochemical load are not two independent factors.

[0152] However, when the above structure is further applied to the dual-group series structure described in Example 3, the first and second electrolysis components are not under completely identical inlet water boundary conditions. After the main water passes through the fluid exchange region corresponding to the first pre-cathode b, some of the water has already undergone pre-electrochemical action and BDD main electrolysis. The ozone-containing water formed in the first main electrolysis region returns to the flow reaction chamber a and mixes with the main water. Therefore, the water continuing to flow to the second electrolysis component may differ from the water initially entering the flow reaction chamber a in terms of hardness ion concentration, local reaction state, and fluid exchange conditions.

[0153] If the first and second groups still use the exact same pre-cathode opening structure and electrolytic load, the amount of calcium and magnesium hardness ion replenishment received per unit area by the two groups of electrolytic cathodes c may differ. Simultaneously, due to differences in fluid renewal rates, the local alkaline environment formed by the cathode reactions in the two groups of electrolytic cathodes c may also differ. Therefore, even if the two electrolytic components are structurally identical, their actual scaling rates may still differ. When any one group of electrolytic cathodes c and its adjacent proton exchange membrane d first form a thicker deposition layer, the impedance within that group of cells, localized heating, and mass transfer resistance will increase first, further limiting the continuous operating time of the entire series module.

[0154] Therefore, the technical problem further solved by this embodiment is: when two sets of pre-electrochemical pretreatment and BDD main electrolysis components are connected in series along the main water flow direction, how to correlate the actual hardness ion supply state obtained by each set of main electrolysis areas with the local electrochemical load of the main cathode, and determine the parameter combination suitable for the current influent and operating conditions accordingly, so that the scaling-driven load of the first and second sets of main cathodes tends to be coordinated, and one set of main electrolysis units is prevented from entering the rapid scaling state in advance.

[0155] The application method of this embodiment includes steps S1-S7.

[0156] S1. The water to be treated, containing calcium ions and / or magnesium ions, is introduced into the flow reaction chamber a of the BDD electrolytic ozone generating module, so that the water to be treated flows continuously from the inlet side to the outlet side along the flow reaction chamber a.

[0157] S2. When the water to be treated reaches the fluid exchange area corresponding to the first set of pre-cathodes b, the first part of the water to be treated continues to flow downstream along the flow reaction chamber a, and the second part of the water to be treated enters the pre-electrochemical pretreatment space defined by the first set of pre-cathodes b and the adjacent enclosing structure through the through hole on the first set of pre-cathodes b.

[0158] S3. Put the first group of pre-cathodes b into the cathode working state and apply electrochemical action to the second part of the water to be treated that enters the corresponding pre-electrochemical pretreatment space; so that the water to be treated after the pre-electrochemical action continues to reach the first group of main electrolysis areas composed of electrolytic cathode c, proton membrane d and electrolytic anode e, and performs BDD electrolysis ozone reaction on the side of electrolytic anode e to generate ozone.

[0159] S4. At least a portion of the ozone and / or ozone-containing water formed in the first group of main electrolysis zones is re-entered into the flow reaction chamber a through the through hole on the first group of front cathodes b, and exchanged and mixed with the main water that continues to flow along the flow reaction chamber a, so that the mixed water continues to be transported to the location of the second group of electrolysis components.

[0160] S5. When the mixed water reaches the fluid exchange area corresponding to the second set of pre-cathodes b, some of the water is again allowed to enter the corresponding pre-electrochemical pretreatment space through the through hole on the second set of pre-cathodes b. After the electrochemical action of the second set of pre-cathodes b, it enters the second set of main electrolysis areas composed of the corresponding electrolytic cathode c, proton membrane d and electrolytic anode e to carry out the BDD electrolysis ozone reaction.

[0161] S6. The ozone and / or ozone-containing water formed in the second group of main electrolysis zones are reintroduced into the flow reaction chamber a and mixed with the main water, and then output from the module outlet side. During the above process, the first and second group of pre-cathodes b maintain cathode working state with the corresponding electrolysis cathodes c, and maintain controlled fluid exchange between the flow reaction chamber a and the corresponding main electrolysis zone through their respective through holes.

[0162] S7. To address the issue of uneven scaling load that may result from the different influent conditions of the first and second main electrolysis zones, a correlation evaluation is conducted on the hardness ion replenishment status and local alkalization status of the two electrolysis components, and the target operating status of the dual-series modules is determined based on the evaluation results; step S7 includes steps S71-S73.

[0163] S71. Obtain the water hardness ion concentration at the corresponding position of the first and second group of pre-cathodes b, the exchange flow rate entering the corresponding pre-electrochemical pretreatment space through the through hole, and the effective reaction area of ​​the corresponding electrolytic cathode c. Based on the above parameters, establish the relative hardness ion supply relationship X received per unit effective area of ​​each group of main cathodes, which is used to characterize the strength of the continuous supply of calcium and magnesium ions from the main water to the corresponding main electrolysis area.

[0164] S72. Obtain the exchange flow rate of the first and second groups entering the corresponding pre-electrochemical pretreatment space through the through hole, the effective reaction area of ​​the corresponding electrolytic cathode c, the total projected area of ​​the through hole of the corresponding pre-cathode b, and the cathode current undertaken by the corresponding electrolytic cathode c under normal electrolysis working conditions. Based on the above parameters, establish the local alkalization relationship Y of each group of cathodes to characterize the relative relationship between the hydroxide generation capacity of the electrolytic cathode c and the water renewal capacity of its area.

[0165] S73. Couple the hardness ion supply relationship X obtained in step S71 with the cathode local alkalization relationship Y obtained in step S72 to form the scaling drive state of the first group and the second group of main electrolysis regions respectively. With the goal of reducing the higher scaling drive state in the two groups, determine the target operating parameter set of the dual-group series module from the preset candidate operating states so that the scaling development of the first group and the second group of main electrolysis regions tends to be coordinated.

[0166] In step S71, the first and second groups of electrolysis components are numbered as Group 1 and Group 2, respectively. For the i-th group of electrolysis components, the molar concentrations of calcium and magnesium ions in the water when entering the fluid exchange zone corresponding to the pre-cathode b of that group are obtained, and the sum of the two is taken as the molar concentration C of the hardness ions in that group. H,i The unit is mol / m 3 .

[0167] Further obtain the exchange flow rate Q of the i-th group of pre-cathode b entering the corresponding pre-electrochemical pretreatment space per unit time. i The unit is m 3 / s, and the effective area A of the electrolytic cathodes c directly participating in the main cathode reaction. c,i The unit is m 2 .

[0168] For the first group of electrolysis components, C H,1 This corresponds to the main water inlet state entering the first group of fluid exchange zones; for the second group of electrolysis components, C H,2 This corresponds to the state of the water after it has passed through the first set of electrolysis components, returned to the flow reaction chamber a, and been remixed before reaching the second set of fluid exchange zones. Therefore, it is no longer assumed that the two sets of electrolysis components have the same hardness ion input conditions.

[0169] The molar concentration C of hardness ions was determined when the module was in a stable operating phase in Example 1. H,0 Pre-electrochemical pretreatment space exchange flow rate Q0 and main cathode effective area A c,0 As a baseline state, the relative hardness ion supply relationship X of the i-th main electrolysis region is... i Determined according to the following formula:

[0170]

[0171] In the formula, C H,i Q i C represents the molar amount of calcium and magnesium hardness ions entering the i-th pre-electrochemical pretreatment space per unit time. H,i Q i / A c,i X represents the hardness ion supply flux allocated to a unit effective area of ​​the electrolytic cathode c; i It is a dimensionless parameter.

[0172] Therefore, X i The calculation incorporates the water hardness concentration, the actual exchange rate entering the main electrolysis zone through the through-holes, and the effective area of ​​the main cathode. If the water hardness concentration at the second set of pre-cathodes (b) changes, or if the exchange flow rates formed by the two sets of through-holes differ, even if both sets of electrolysis cathodes (c) use the same material and area, different X values ​​will be obtained. i .

[0173] Step S72 further evaluates the ability of each group of electrolytic cathodes c to form a localized high-alkaline environment.

[0174] According to the working mechanism described in Example 1, during the cathode reaction at electrolytic cathode c, the number of hydroxide ions formed per unit time is related to the charge borne by the cathode. Simultaneously, the through-holes on the pre-cathode b continuously allow water from the flow reaction chamber a to enter the main electrolysis region and facilitate water exchange within the main electrolysis region. Therefore, the degree of local alkalization at the main cathode cannot be determined solely by the cathode current; it is also influenced by the water renewal capacity of the through-holes.

[0175] For the i-th electrolysis assembly, obtain the cathode current I carried by its electrolytic cathode c during normal operation. i The unit is A, which is the total projected area A of all through holes on the front cathode b. o,i The unit is m 2 And continue using the exchange flow Q from step S71 i and the effective area A of the electrolytic cathode c c,i .

[0176] Among them, I i / (FA c,i This is used to characterize the theoretical molar flux of hydroxide ions generated per unit area of ​​the electrolytic cathode, where F is the Faraday constant; Qi / A o,i This is used to characterize the average exchange rate of water as it enters the corresponding pre-electrochemical pretreatment space through the through-hole of the pre-cathode b. The ratio of these two values ​​describes the relative relationship between cathode hydroxide generation and local water regeneration.

[0177] Using the cathode current I0 and the total projected area A of the through hole during the stable operation phase of Example 1 as examples... o,0 The effective area of ​​the main cathode, A c,0 Using the exchange flow rate Q0 as a reference, the relative cathode local alkalization relationship Y of the i-th group is... i Determined according to the following formula:

[0178]

[0179] It should be noted that Y i This term describes the relative trend of localized alkalization in different main electrolysis regions under the same evaluation scale, and is not directly equivalent to the actual measured pH value. Its physical meaning is that when the cathode current per unit effective area of ​​the electrolysis cathode c increases, and the water renewal achieved through the through-hole of the pre-cathode b is insufficient, hydroxide ions generated by the cathode reaction are more likely to accumulate in localized areas. Conversely, when water exchange is enhanced, under the same cathode current conditions, localized reaction products are more likely to migrate outwards with water renewal.

[0180] In particular, this step, together with step S71, uses the exchange flow Q. i and the effective area A of the electrolytic cathode c c,i However, both introduce hardness ion concentration C.H,i and cathode current I i Total projected area A of the through hole o,i Therefore, the same fluid exchange state can simultaneously affect the supply of hardness ions to the main cathode and the local alkalization process at the cathode, and the directions of the effects on the two are not entirely the same.

[0181] Step S73 considers that the formation of inorganic deposits requires at least two conditions simultaneously: on the one hand, calcium and magnesium ions can continuously enter the main electrolysis region; on the other hand, local alkaline reaction conditions favorable to the formation of sparingly soluble deposits are maintained near the electrolysis cathode c. Therefore, in this embodiment, X i Y i This refers to the relative scaling-driven state of the i-th main electrolysis region.

[0182] When determining the operating parameters of the dual-unit series modules, multiple candidate operating states that meet the normal BDD ozone generation requirements are established. Each candidate operating state corresponds to the determined main water flow conditions and module power supply conditions, and the X values ​​corresponding to the first and second units under that state are obtained respectively. i and Y i .

[0183] For configurable modules with different through-hole structures, the total projected area of ​​the different through-holes of the first and second groups of front cathodes b can be combined into the candidate parameter set during the assembly stage; for modules with a fixed front cathode b structure, the total projected area of ​​the through-holes remains unchanged, and evaluation is only conducted for different water inflow rates and normal power supply operation.

[0184] Let the set of candidate parameters be Ω, and exclude operating states that cannot meet the predetermined effluent flow rate or the predetermined ozone output requirement, then the set of target parameters Θ is... ∗ Determined according to the following formula:

[0185]

[0186] In the formula, Ω is the set of candidate operating parameter combinations that meet the normal operating conditions of the BDD electrolytic ozone generator module; Θ is any candidate operating parameter combination in the candidate operating parameter set Ω, which includes at least the main water flow conditions and the module power supply conditions, and, in the case of using a replaceable front cathode b, also includes the total projected area of ​​the through hole corresponding to the front cathode b; Θ ∗The target operating parameter combination is determined according to the above optimization relationship; X1(Θ) and X2(Θ) are the relative hardness ion supply relationships of the first and second main electrolysis regions under the candidate operating parameter combination Θ, respectively; Y1(Θ) and Y2(Θ) are the relative cathode local alkalization relationships of the first and second main electrolysis regions under the candidate operating parameter combination Θ, respectively; X1(Θ)Y1(Θ) and X2(Θ)Y2(Θ) represent the relative scaling drive states of the first and second main electrolysis regions under the candidate operating parameter combination Θ, respectively; max{⋅} represents taking the larger value among the first and second relative scaling drive states; arg min represents selecting the candidate operating parameter combination from the candidate operating parameter set Ω that minimizes the larger value.

[0187] The above relationship uses the larger scaling-driven state in the two main electrolysis regions as the optimization target. This is because if only minimizing the difference between the two scaling-driven states is used as the optimization objective, it's possible that both groups are in a high scaling-driven state, but their values ​​are very close, which doesn't truly delay module scaling. Therefore, this embodiment directly reduces the higher value of the two groups. Under the premise that the total module flow rate and ozone output meet the usage requirements, when a certain group becomes the first scaling unit limiting the continuous service life of the entire module due to a large hardness ion supply or a high degree of local alkalization, the corresponding X value for that group... i Y i This will become the maximum value mentioned above, thus causing the parameter selection process to preferentially suppress the fouling-driven state of this group.

[0188] Since the first and second groups are connected in series along the water flow direction in the flow reaction chamber a, the actual effect of the first group on the water body will further affect the C of the second group. H,2 Therefore, when determining the candidate operating state, the second set of calculation parameters is obtained again according to the actual water state after the first set of treatment, instead of directly replacing the second set of parameters with the first set of parameters.

[0189] For example, when the influent hardness increases while the main water flow rate remains constant, X1 corresponding to the first group may increase first; when the water treated by the first group continues to enter the area where the second group is located, C of the second group... H,2 The corresponding exchange state will then form an X2 different from the first group. Meanwhile, if the second group experiences a relatively increased electrochemical load per unit electrolytic cathode c due to weaker water renewal, Y2 may rise. In this case, the final optimization process will not mechanically apply identical operating parameters to both groups, but will prioritize reducing the currently higher X2. i Y i This ensures that the overall service life of the series module is no longer determined by the rapid scaling in one of the main electrolysis zones.

[0190] In a specific implementation process, the operating state that has achieved relatively stable scaling, tank voltage, and ozone output performance through long-term operation tests can be used as the baseline state to determine C. H,0 Q0, A c,0 I0 and A o,0 .

[0191] After obtaining the target parameter set according to step S73, the BDD electrolytic ozone generating module is continuously operated according to the water inlet and power supply status corresponding to the target parameter set. If the operating conditions or the hardness of the inlet water changes, steps S71-S73 can be re-executed to redetermine the target operating status based on the actual hardness ion replenishment status of the first and second groups and the local alkalization status of the cathode.

[0192] Therefore, this embodiment, based on the relationship established in Embodiment 1, further addresses the inter-stage load differences generated after multiple main electrolysis zones are connected in series along the water flow path. Step S71 uses the hardness ion concentration, exchange flow rate, and effective area of ​​the main cathode to determine the hardness ion replenishment state per unit area of ​​the main cathode; Step S72 further uses the exchange flow rate and effective area of ​​the main cathode, which are common to S71, and combines them with the total projected area of ​​the through-hole and the cathode current to determine the local alkalization state; Step S73 then couples the two physical states and determines the operating parameters by reducing the highest scaling-driven state in the series system.

Claims

1. A BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure, characterized in that: It includes a main channel, a main electrolysis unit, a front cathode that is separate from the main cathode, and an enclosing structure; the main electrolysis unit includes a BDD anode, a proton exchange membrane, and a main cathode, wherein the BDD anode and the main cathode are respectively disposed on both sides of the proton exchange membrane, and the area where the main electrolysis unit is located constitutes the main electrolysis region; The main channel extends continuously from the inlet end to the outlet end, so that at least a portion of the water to be treated entering the module can flow along the main channel to the outlet end without entering the main electrolysis area. The enclosure structure is disposed around at least a portion of the outer periphery of the main electrolysis unit, and together with the front cathode, it separates the main electrolysis region from the main flow channel. The precathode is positioned before the main electrolysis unit along the fluid treatment path from the main channel into the main electrolysis region of the water to be treated, and at least partially constitutes the separation interface between the main channel and the pre-electrochemical pretreatment space. The precathode and the enclosure structure together define the pre-electrochemical pretreatment space located between the main channel and the main electrolysis region. The pre-cathode is provided with multiple through holes, which form a fluid exchange channel between the main flow channel and the pre-electrochemical pretreatment space. The enclosure structure and the non-through area of ​​the pre-cathode together define the fluid passage from the main flow channel into the main electrolysis region, so that the water to be treated entering the main electrolysis region enters the pre-electrochemical pretreatment space through the through holes, and reaches the main electrolysis region after being subjected to the electrochemical action of the pre-cathode. The main electrolysis zone exchanges fluid with the main channel through the through hole, so that at least part of the ozone and / or ozone-containing water generated by the main electrolysis unit enters the main channel through the through hole, mixes with the water to be treated that continues to flow along the main channel, and is then output from the outlet.

2. The BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure according to claim 1, characterized in that, The module also includes a housing; The enclosure structure is formed by at least a portion of the wall of the outer shell, or by an insulating enclosure component disposed independently of the outer shell, or by at least a portion of the wall of the outer shell and the insulating enclosure component together; The enclosing structure and the pre-cathode together enclose the pre-electrochemical pretreatment space and the main electrolysis region, and restrict the flow of the water to be treated entering the main electrolysis region from the main flow channel by the pre-cathode and its through holes.

3. The BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure according to claim 2, characterized in that, The front cathode simultaneously constitutes: An electrochemical action component for applying electrochemical action to the water to be treated that enters the pre-electrochemical pretreatment space from the main channel through the through hole; A spatial separation component that, together with the non-penetrating area of ​​the front cathode and the enclosing structure, spatially separates the main channel and the main electrolysis area; as well as A fluid exchange component that forms a bidirectional fluid exchange channel between the main flow channel and the pre-electrochemical pretreatment space through the plurality of through holes.

4. A BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure according to claim 3, characterized in that, The main channel is located above the main electrolysis region, and the enclosing structure has an opening facing the main channel; The precathode is disposed at the opening and at least partially spans the opening to form at least a partial cover plate of the pre-electrochemical pretreatment space facing the main channel. The main electrolysis unit is located on the side of the front cathode away from the main flow channel.

5. A BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure according to claim 4, characterized in that, The front cathode is an auxiliary cathode (3); The BDD anode is a composite diamond film anode (7). The proton membrane is a proton membrane (8); The main cathode is a titanium composite cathode (9). The module also includes an anode conductive sheet (6), which is configured in conjunction with the composite diamond film anode (7) to perform planar clamping of the composite diamond film anode (7) and to supply power to the composite diamond film anode (7); The composite diamond film anode (7), proton exchange membrane (8) and titanium composite cathode (9) are stacked together, with the proton exchange membrane (8) located between the composite diamond film anode (7) and the titanium composite cathode (9).

6. A BDD electrolytic ozone generator module with a pre-electrochemical pretreatment structure according to claim 5, characterized in that, The front cathode and the main cathode maintain their cathode polarity during normal electrolysis operation of the BDD ozone generation module and are electrically connected to the same cathode power supply side, forming a parallel cathode branch relative to the BDD anode, so that the cathode current input to the module is distributed between the front cathode and the main cathode.

7. A BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure according to claim 6, characterized in that, Multiple through holes are spaced apart from each other on the front cathode, and at least some of the through holes are located within the effective coverage area of ​​the front cathode covering and separating the main electrolysis region facing the main channel. A non-through conductive region is retained between adjacent through holes and is electrically connected to the main body of the precautionary cathode, so that the precautionary cathode retains a conductive physical region for pre-electrochemical action and cathode current distribution while performing fluid exchange through the through holes. The shape, size, and / or arrangement of the multiple through holes can be the same or different.

8. A BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure according to claim 6, characterized in that, The pre-cathode includes an effective covering portion for forming the separation interface and a conductive extension portion electrically connected to the effective covering portion, with at least a portion of the through holes disposed in the effective covering portion; the overall aperture ratio of the pre-cathode is the ratio of the sum of the projected areas of all through holes on the pre-cathode to the projected area of ​​the overall outer contour of the pre-cathode when projected along a direction perpendicular to the surface of the pre-cathode body plate; by setting the overall aperture ratio, the fluid exchange capacity between the main channel and the pre-electrochemical pretreatment space and the non-through conductive area retained by the pre-cathode are adjusted.

9. An application method for a BDD electrolytic ozone generator module with a pre-electrochemical pretreatment structure, characterized in that, The method, applied to the BDD electrolytic ozone generating module with a pre-electrochemical pretreatment structure as described in any one of claims 1 to 8, comprises: S1. The water to be treated is introduced into the main channel of the BDD electrolytic ozone generating module, so that the water to be treated flows from the inlet end to the outlet end along the main channel. S2. The water to be treated flowing along the main channel is divided into at least two parts, wherein the first part of the water to be treated is kept in the main channel and continues to flow toward the outlet end, and the second part of the water to be treated enters the pre-electrochemical pretreatment space defined by the pre-cathode and the enclosure structure through the through hole on the pre-cathode. S3. Put the pre-cathode into cathode working state and apply an electrochemical action to the second part of the water to be treated that enters the pre-electrochemical pretreatment space. S4. The second part of the water to be treated, which has passed through the pre-electrochemical pretreatment space, continues to enter the main electrolysis area where the main electrolysis unit, which is composed of BDD anode, proton membrane and main cathode, is located. The main electrolysis unit performs an electrolysis reaction and generates ozone. S5. At least a portion of the ozone and / or ozone-containing water formed in the main electrolysis area enters the main channel through the through hole on the front cathode, mixes with the first portion of the water to be treated that is held in the main channel and continues to flow toward the outlet, and is output from the outlet of the module.

10. The application method of a BDD electrolytic ozone generator module with a pre-electrochemical pretreatment structure according to claim 8, characterized in that, The water to be treated is water containing calcium ions and / or magnesium ions; the precautionary cathode and the main cathode maintain cathode polarity during normal electrolysis and are electrically connected to the same cathode power supply side to form a cathode branch in parallel with the BDD anode. By setting the area relationship between the sum of the projected areas of all through holes on the front cathode and the projected area of ​​the overall outer contour of the front cathode, the fluid exchange between the main channel and the pre-electrochemical pretreatment space, as well as the cathode current distribution between the front cathode and the main cathode, can be adjusted to reduce the continuous contact and replenishment of calcium and / or magnesium ions in the main feed water during continuous operation.

Images