An ONOOH-rich aqueous solution preparation device and control method
Patent Information
- Application Number
- CN202611011233.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-08
- Publication Date
- 2026-09-15
Smart Images
Figure CN122745818A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of plasma-activated water preparation, specifically relating to an apparatus and control method for preparing ONOOH-rich aqueous solutions. Background Technology
[0002] Plasma-activated water is a novel biological agent rich in reactive oxygen species (RONS). With its remarkable bactericidal, anti-inflammatory, and anticancer effects, it has become a research hotspot in the biomedical field. As a highly promising adjunctive clinical treatment, plasma-activated water shows broad application prospects in the treatment of infections, inflammation, and tumors. Traditional chemical disinfectants such as alcohol and sodium hypochlorite are highly irritating and corrosive, easily causing severe pain, redness, and even tissue necrosis of biological mucous membranes. In contrast, plasma-activated water offers a safer and more effective in vivo disinfection solution. In oral care, mouthwash based on activated water can effectively inhibit pathogenic bacteria such as Streptococcus mutans; in studies on the treatment of abdominal sepsis, injection of activated water significantly reduced bacterial load and inflammatory response, improving animal survival rates. More importantly, multiple safety studies have confirmed that plasma-activated water exhibits excellent biocompatibility, with no significant toxicity or irritation, whether administered orally, topically, or by injection, providing a solid safety foundation for its clinical translation.
[0003] Among the various active species in plasma-activated water, peroxynitrite (ONOOH) is the core component for achieving strong oxidation and efficient sterilization. However, current preparation technologies still face bottlenecks such as low ONOOH yield and insufficient sterilization effect, making it difficult to meet the needs of large-scale disinfection. Summary of the Invention
[0004] (a) Purpose of the invention The purpose of this invention is to provide an ONOOH-rich aqueous solution preparation device and control method. By setting up a dual-path active gas preparation and microbubble injection structure, efficient mass transfer of active gas and liquid-phase reaction are achieved, improving the generation efficiency and concentration of ONOOH. Combined with a circulating storage module and detection unit, physicochemical parameters are monitored in real time, and the control module automatically switches between generation and storage modes to achieve closed-loop control of the preparation process. This improves the stability, consistency, and preparation efficiency of the ONOOH-rich aqueous solution, and solves the problems of limited ONOOH yield, difficulty in controlling the optimal balance point of ONOOH generation and decomposition in acidic environments, and easy decay of active ingredients and short storage time in traditional plasma-activated water preparation processes.
[0005] (II) Technical Solution To address the above problems, the present invention provides an ONOOH-rich aqueous solution preparation device, comprising: an active gas preparation module, a microbubble injection module, a circulating liquid storage module, and a control module; The active gas preparation module, the microbubble injection module, and the circulating liquid storage module are connected in sequence, and both the active gas preparation module and the circulating liquid storage module are connected to the control module. The active gas preparation module is used to generate a first active gas stream rich in ozone and a second active gas stream rich in low-valence nitrogen oxides. The microbubble injection module includes a first microbubble injection structure and a second microbubble injection structure, and the circulating liquid storage module includes a mixing and activation unit and a detection unit. The first microbubble injection structure and the hybrid activation unit form a first circulating water path, and the second microbubble injection structure and the hybrid activation unit form a second circulating water path; The first microbubble injection structure is used to inject the first active gas flow into the first circulating water path in the form of microbubbles, and the second microbubble injection structure is used to inject the second active gas flow into the second circulating water path in the form of microbubbles; The hybrid activation unit is used to collect the activation liquids from the first microbubble injection structure and the second microbubble injection structure to generate an ONOOH solution. The detection unit is used to detect the physicochemical parameters of the ONOOH solution in the hybrid activation unit. The control module adjusts the working mode of the active gas preparation module according to the physicochemical parameters. The working mode includes a generation mode and a storage mode.
[0006] In another aspect of the present invention, preferably, the active gas preparation module includes a first active gas preparation unit and a second active gas preparation unit, wherein the first active gas preparation unit is used to generate a first active gas flow and the second active gas preparation unit is used to generate a second active gas flow. The first active gas preparation unit is connected to the gas path of the first microbubble injection structure, and the second active gas preparation unit is connected to the gas path of the second microbubble injection structure.
[0007] In another aspect of the present invention, preferably, the first microbubble injection structure includes a first venturi tube and a first rectifier structure, wherein the first venturi tube and the first rectifier structure are connected. The first venturi tube includes a first air inlet, a first liquid inlet, and a first outlet. The first air inlet is connected to the first active gas preparation unit, the first liquid inlet is connected to the mixing and activation unit, and the first outlet is connected to the first rectifier structure. The first venturi tube is used to break the first active gas flow into a micron-sized bubble group, and the first rectification structure is used to reduce the turbulence intensity of the micron-sized bubble group at the first outlet. The second microbubble injection structure includes a second venturi tube and a second rectifier structure, which are connected together. The second venturi tube includes a second air inlet, a second liquid inlet, and a second outlet. The second air inlet is connected to the second active gas preparation unit, the second liquid inlet is connected to the mixing and activation unit, and the second outlet is connected to the second rectifier structure. The second venturi tube is used to break the second active gas flow into a micron-sized bubble cluster, and the second rectifying structure is used to reduce the turbulence intensity of the micron-sized bubble cluster at the second outlet.
[0008] In another aspect of the present invention, preferably, the mixing and activation unit includes a mixing chamber and an activation pool, and the detection unit includes a pH sensor and a NO2 sensor. - sensor; The mixing chamber is connected to the first microbubble injection structure and the second microbubble injection structure, and the mixing chamber is used to collect the activated liquid output from the first microbubble injection structure and the second microbubble injection structure; The mixing chamber is connected to the activation tank, which is used to carry out an activation reaction to generate and store an ONOOH solution. The pH sensor and NO2 - The sensor is installed inside the activation tank. The pH sensor is used to detect the pH value of the ONOOH solution in the activation tank. - The sensor is used to detect NO2 in the ONOOH solution in the activation tank. - concentration.
[0009] In another aspect of the present invention, preferably, the circulating liquid storage module further includes a first liquid pump and a second liquid pump. The first liquid pump is installed in the first circulating water circuit. One end of the first liquid pump is connected to the activation tank, and the other end of the first liquid pump is connected to the first liquid inlet. The second liquid pump is installed in the second circulating water circuit. One end of the second liquid pump is connected to the activation tank, and the other end of the second liquid pump is connected to the second liquid inlet.
[0010] In another aspect of the present invention, preferably, The first active gas preparation unit includes a first plasma generator, a first gas source, a first gas flow controller, and a first discharge control power supply unit. The first gas source, the first gas flow controller, and the first plasma generator are connected in sequence. The first discharge control power supply unit is connected to the first plasma generator. The first plasma generator is a dielectric barrier discharge reactor or a corona discharge reactor. The first gas source is one of oxygen, air, or oxygen-enriched air. The second active gas preparation unit includes a second plasma generator, a second gas source, a second gas flow controller, and a second discharge control power supply unit. The second gas source, the second gas flow controller, and the second plasma generator are connected in sequence. The second discharge control power supply unit is connected to the second plasma generator. The second plasma generator is a sliding arc discharge reactor or a microwave discharge reactor. The second gas source is either air or nitrogen-enriched air.
[0011] In another aspect of the present invention, preferably, a control method for an ONOOH-rich aqueous solution preparation apparatus, the control method being applicable to the ONOOH-rich aqueous solution preparation apparatus as described above, the control method comprising: The working modes of the active gas preparation module are defined, including a generation mode and a storage mode. The operating mode of the active gas preparation module is determined to be the generation mode; The detection unit is used to collect the physicochemical parameters of the ONOOH solution in the activation tank, including pH value and NO2. - concentration; When the pH value reaches the preset pH prediction value, real-time NO2 is obtained. - concentration; Based on the real-time NO2 - The concentration is used to predict the subsequent acidification trend of the ONOOH solution, and the preset pH switching value is corrected to obtain the corrected pH switching value. Using the pH value and the corrected pH switching value, the operating mode of the active gas preparation module is adjusted to storage mode.
[0012] In another aspect of the present invention, preferably, the generation mode includes: the first active airflow is continuously introduced, and the second active airflow is intermittently introduced; The storage mode includes: the second active airflow is stopped, and the first active airflow is continuously, intermittently, or stopped at 30% to 50% of the generation mode flow rate.
[0013] In another aspect of the present invention, preferably, the real-time NO2-based - The concentration predicts the subsequent acidification trend of the ONOOH solution, and corrects the preset pH switching value to obtain the corrected pH switching value, including: According to the real-time NO2 - The concentration and the preset conversion algorithm are used to calculate the increase in hydrogen ion concentration; Based on the hydrogen ion concentration increment and the preset prediction correction algorithm, the preset pH switching value is corrected to obtain the corrected pH switching value.
[0014] In another aspect of the present invention, preferably, the preset conversion algorithm is expressed using the following formula: in, Indicates real-time NO2 - concentration, This indicates the conversion factor for acid production. Indicates the increase in hydrogen ion concentration; The preset prediction correction algorithm is expressed by the following formula: in, This indicates the preset pH switching value. This indicates the increase in hydrogen ion concentration. This indicates the corrected pH switching value.
[0015] (III) Beneficial Effects The above-described technical solution of the present invention has the following beneficial technical effects: This invention, by setting up an active gas preparation module, allows the first and second active gas streams to be injected into corresponding circulating water paths through independent first and second microbubble injection structures, respectively. This achieves a direct synergistic reaction of the two active gases in the liquid phase, avoiding premature reaction or mutual quenching of different active components in the gas phase, improving the utilization rate of active species after entering the liquid phase, and providing stable reaction conditions for the generation of ONOOH. The microbubble injection method introduces the active gas into the liquid. Micron-sized bubbles have a large specific surface area and a long residence time in the liquid phase, which can significantly improve the gas-liquid contact area and mass transfer efficiency, promote the full dissolution of active components such as ozone and nitrogen oxides into the liquid phase, and improve the generation efficiency of free radicals and intermediate active species, thereby increasing the generation rate and final concentration of ONOOH. By setting up a detection unit to monitor the physicochemical parameters of the ONOOH solution in the mixing and activation unit in real time, and by having the control module automatically adjust the working mode of the active gas preparation module based on the detection results, closed-loop control of the active gas generation process is achieved. This allows the active gas output to be dynamically adjusted according to the reaction state, which not only improves the ONOOH generation efficiency, but also helps to get closer to the target range near the peak ONOOH content after entering the storage mode. This ensures a high yield of ONOOH while slowing down its further decay and extending the effective storage time of the ONOOH-rich aqueous solution. Attached Figure Description
[0016] Figure 1 This is a schematic diagram of the overall structure of one embodiment of the present invention; Figure 2 This is a schematic diagram of the overall process of one embodiment of the present invention; Figure 3This is a schematic diagram comparing the ONOOH content of solutions obtained under different mixing methods and their killing effect on Staphylococcus aureus. Figure 4 This is a comparison chart showing the change in the relative concentration of ONOOH after a certain period of time following the activation of the storage mode in one embodiment of the present invention; Figure 5 This is a comparison chart of the disinfection effect on Staphylococcus aureus after a certain period of time following the activation of the storage mode in one embodiment of the present invention; Figure label: 100. Active gas preparation module; 111. First gas source; 112. Second gas source; 121. First gas flow controller; 122. Second gas flow controller; 131. First plasma generator; 132. Second plasma generator; 141. First discharge control power supply unit; 142. Second discharge control power supply unit; 200. Microbubble injection module; 211. First Venturi tube; 212. Second Venturi tube; 221. First rectifier structure; 222. Second rectifier structure; 300. Circulating liquid storage module; 310. Mixing chamber; 320. Activation tank; 330. pH sensor; 340. NO2 - Sensor; 351, First liquid pump; 352, Second liquid pump; 361, First circulating water circuit; 362, Second circulating water circuit; 400. Control module. Detailed Implementation
[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments and the accompanying drawings. It should be understood that these descriptions are merely exemplary and not intended to limit the scope of the invention. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concept of the invention.
[0018] The accompanying drawings show structural schematic diagrams according to embodiments of the present invention. These drawings are not drawn to scale, and some details have been enlarged for clarity, and some details may have been omitted. The shapes of the various regions and layers shown in the drawings, as well as their relative sizes and positional relationships, are merely exemplary and may deviate from reality due to manufacturing tolerances or technical limitations. Furthermore, those skilled in the art can design regions / layers with different shapes, sizes, and relative positions as needed.
[0019] Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.
[0020] In the description of this invention, it should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.
[0021] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0022] The invention will now be described in more detail with reference to the accompanying drawings. In the various drawings, the same elements are indicated by similar reference numerals. For clarity, the various parts in the drawings are not drawn to scale.
[0023] Example 1 An apparatus for preparing ONOOH-rich aqueous solutions, Figure 1 A schematic diagram of the overall structure of an embodiment of the present invention is shown, as follows. Figure 1 As shown, it includes: an active gas preparation module 100, a microbubble injection module 200, a circulating liquid storage module 300, and a control module 400; The active gas preparation module 100, the microbubble injection module 200, and the circulating liquid storage module 300 are connected in sequence, and both the active gas preparation module 100 and the circulating liquid storage module 300 are connected to the control module 400. The active gas preparation module 100 is used to generate two different active gas streams that participate in the ONOOH generation reaction. Specifically, the active gas preparation module 100 includes a first active gas preparation unit and a second active gas preparation unit. The first active gas preparation unit is used to generate a first active gas stream, and the second active gas preparation unit is used to generate a second active gas stream. The first active gas stream is rich in ozone, and the second active gas is rich in low-valence nitrogen oxides, including NO and NO2. The first and second active gas preparation units are set up independently and electrically connected to the control module 400 respectively, so as to realize independent regulation and coordinated control of the different active gas generation processes. The first active gas preparation unit includes a first plasma generator 131, a first gas source 111, a first gas flow controller 121, and a first discharge control power supply unit 141. The first gas source 111, the first gas flow controller 121, and the first plasma generator 131 are connected in sequence. The first discharge control power supply unit 141 is connected to the first plasma generator 131. The first plasma generator 131 is a dielectric barrier discharge reactor or a corona discharge reactor. Under the action of a high-voltage AC or pulsed electric field, oxygen molecules undergo partial ionization and dissociation reactions to form ozone. The first gas source 111 is one of oxygen, air, or oxygen-enriched air. The first gas flow controller 121 controls the flow rate of the first gas source 111, and the first discharge control power supply unit 141 controls the discharge parameters of the first plasma generator 131. The discharge parameters may include the discharge voltage amplitude, frequency, and duty cycle, realizing dynamic control of ozone generation efficiency and by-products, thereby obtaining a stable concentration of ozone-type first active gas flow.
[0024] The second active gas preparation unit includes a second plasma generator 132, a second gas source 112, a second gas flow controller 122, and a second discharge control power supply unit 142. The second gas source 112, the second gas flow controller 122, and the second plasma generator 132 are connected in sequence. The second discharge control power supply unit 142 is connected to the second plasma generator 132. The second plasma generator 132 is a sliding arc discharge reactor or a microwave discharge reactor. The second gas source 112 is either air or nitrogen-rich air. The second gas flow controller 122 controls the flow rate of the second gas source 112, and the second discharge control power supply unit 142 controls the discharge parameters of the second plasma generator 132. In this embodiment, the first gas flow controller 121 controls the flow rate of the first gas source 111 to be 0.5~2.0 L / min, and the second gas flow controller 122 controls the flow rate of the second gas source 112 to be 1.0~4.0 L / min, so as to ensure the stable generation of ozone-mode active gas flow and low-valent nitrogen oxide-mode active gas flow, respectively. Under the bombardment of high-energy electrons, the second plasma generator 132 causes nitrogen and oxygen to undergo excitation, dissociation, and recombination reactions, generating low-valence nitrogen oxide components such as NO and NO2. At the same time, by controlling the ratio of discharge power density to gas flow rate, the conversion to the high-valence state NO3 is suppressed. - The excessive conversion of related substances stably yields a second active gas stream primarily composed of NO and NO2. The first and second active gas preparation units employ independent structural designs and are electrically connected to the control module 400, ensuring physical isolation and coordinated control of the two active gas generation processes. The control module 400 can adjust the flow ratio, timing sequence, and synchronous / intermittent mode of the first and second active gas streams according to the reaction system requirements, thereby achieving spatial or temporal control of ozone and low-valent nitrogen oxides.
[0025] The microbubble injection module 200 includes a first microbubble injection structure and a second microbubble injection structure, and the circulating liquid storage module 300 includes a mixing and activation unit and a detection unit. The first active gas preparation unit is connected to the first microbubble injection structure via a gas path, and the two can be connected via a gas guide pipe. The second active gas preparation unit is connected to the second microbubble injection structure via a gas path, and the two can be connected via a gas guide pipe. The independent gas path can simultaneously inject two different active gases. The first microbubble injection structure and the mixing and activation unit form a first circulating water path 361, and the second microbubble injection structure and the mixing and activation unit form a second circulating water path 362. The first microbubble injection structure is used to inject the first active gas flow into the first circulating water path 361 in the form of microbubbles, and the second microbubble injection structure is used to inject the second active gas flow into the second circulating water path 362 in the form of microbubbles. The mixing and activation unit serves as a centralized liquid processing center, and its outlet is branched to the inlets of the first microbubble injection structure and the second microbubble injection structure, respectively. The outlets of the first and second microbubble injection structures rejoin the mixing and activation unit, ensuring that the liquid passes through the microbubble injection area multiple times during circulation, continuously accumulating the concentration of active substances. The specific content of the first and second microbubble injection structures is not limited here; they can be the same or different structures. The microbubble injection module 200 can be a structure based on the Venturi principle, utilizing the negative pressure generated by the high-speed liquid flow to draw in active gas. At the throat, a huge shear force pulverizes the gas into micron- or nano-sized bubbles. The microbubble injection module 200 can also be a microporous aeration structure. A ceramic microporous membrane or a sintered stainless steel core can be installed within the injection structure, allowing gas to enter the high-speed flowing liquid through the micropores, directly forming high-density microbubbles. Microbubbles have a large specific surface area and a long residence time in water, significantly improving the dissolution efficiency and physicochemical reactivity of active gases in liquids.
[0026] Furthermore, in this embodiment, the first microbubble injection structure includes a first venturi tube 211 and a first rectifier structure 221, and the first venturi tube 211 and the first rectifier structure 221 are connected. The first Venturi tube 211 includes a first air inlet, a first liquid inlet, and a first outlet. The first air inlet is connected to the first active gas preparation unit, the first liquid inlet is connected to the mixing and activation unit, and the first outlet is connected to the first rectifying structure 221. The first Venturi tube 211 is used to break the first active gas flow into a micron-sized bubble group. Specifically, the first Venturi tube 211 includes a contraction section, a throat section, and a diffusion section. The first liquid inlet is connected to the contraction section. After the liquid flow enters, the cross-sectional area gradually decreases. According to Bernoulli's principle, the flow velocity increases sharply, and static pressure energy is converted into kinetic energy. The first air inlet is located in the throat section or the region immediately adjacent to the throat section. When the high-speed liquid flow passes through the throat, a strong jet negative pressure is generated, which automatically draws in the active gas flow generated by the first active gas preparation unit. At the throat, the gas phase collides violently with the extremely high-velocity liquid phase. The strong shear force and turbulent pressure pulsation of the liquid flow shear the continuous gas flow into discrete bubble groups with diameters in the micron range. The bubble crushing process relies on the Reynolds number and flow velocity design at the throat to ensure that the bubbles have a large specific surface area. The gas-liquid mixture flowing out of the Venturi diffuser section is usually in a highly turbulent state, which is not conducive to bubble stability. The first rectifying structure 221 is used to reduce the turbulence intensity of the micron-sized bubble group at the first outlet. The first rectifying structure 221 is located downstream of the first Venturi tube 211, and its interior can use a honeycomb grid, a porous parallel plate, or a straight pipe section of a specific length to divide the large-scale turbulent vortex into several small-scale laminar or quasi-laminar units. In this embodiment, the first rectifying structure 221 includes a buffer chamber and a rectifying net, which transforms the turbulent flow at the Venturi tube outlet into a highly uniform and stable quasi-laminar microbubble group, thereby improving the reaction yield of ONOOH. The fluid coming out of the diffuser section has radial and tangential velocity components, which are disordered. The rectifying structure physically constrains the flow direction of the fluid, transforming it into axial flow. This not only reduces the impact vibration of the fluid on the pipe wall but also lowers the turbulent kinetic energy dissipation rate within the fluid. In highly turbulent environments, the collision frequency between micron-sized bubbles is extremely high, making them prone to merging into larger bubbles and thus losing the advantages of microbubbles. The first rectifying structure 221 reduces the turbulence intensity, allowing the micron-sized bubble group to be uniformly distributed in a stable flow field, reducing bubble merging caused by collisions, thereby maintaining the micron-sized particle size characteristics. The rectified fluid enters the subsequent circulating water path in a more stable state, extending the residence time of microbubbles in the water, allowing the first active gas flow sufficient time to migrate into the liquid through the gas-liquid interface, significantly increasing the activity concentration of the liquid in the mixing and activation unit. The first rectifying structure 221 also acts as a pressure buffer, preventing pressure surges at the Venturi tube outlet from interfering with the flow field inside the detection unit or mixing and activation unit, ensuring the operational stability of the entire circulation system.
[0027] The second microbubble injection structure can be the same as or different from the first microbubble injection structure. In this embodiment, the second microbubble injection structure is the same as the first microbubble injection structure, and includes a second venturi tube 212 and a second rectifier structure 222, which are connected. The second venturi tube 212 includes a second air inlet, a second liquid inlet, and a second outlet. The second air inlet is connected to the second active gas preparation unit, the second liquid inlet is connected to the mixing and activation unit, and the second outlet is connected to the second rectifier structure 222. The second venturi tube 212 is used to break the second active gas flow into a micron-sized bubble group, and the second rectifier structure 222 is used to reduce the turbulence intensity of the micron-sized bubble group at the second outlet. In this embodiment, the second rectifier structure 222 is the same as the first rectifier structure 221.
[0028] The mixing and activation unit is used to collect the liquids from the first microbubble injection structure and the second microbubble injection structure to generate an ONOOH solution. When the first microbubble injection structure introduces oxygen-containing active microbubbles into the first circulating water path 361, and the second microbubble injection structure introduces nitrogen-containing active microbubbles into the second circulating water path 362, the two liquids rich in active components merge in the mixing chamber 310. Dissolved oxygen / ozone and nitrogen oxides in the liquid undergo a redox reaction in the aqueous phase. Specifically, the mixing and activation unit includes a mixing chamber 310 and an activation tank 320. The mixing chamber 310 is connected to the first and second microbubble injection structures and is used to collect the liquids from the first and second microbubble injection structures. The mixing chamber 310 is located at the confluence of the two circulating water paths and has sufficient mixing space inside to allow the liquid flows from the first and second circulating water paths 361 to fully contact each other. The liquid flow rich in ozone, singlet oxygen, hydroxyl radicals, and other oxygen-active species formed by the first microbubble injection structure, and the liquid flow rich in nitric oxide, nitrogen dioxide, and other nitrogen-active species formed by the second microbubble injection structure, undergo high-speed mixing within the mixing chamber 310. Since both liquid flows carry a large number of micron-sized or even submicron-sized bubbles, the microbubbles continuously contract, dissolve, and rupture during the mixing process, further promoting gas-liquid mass transfer and improving the dissolution efficiency of the active components in the liquid phase. The mixing chamber 310 can be designed as a cylindrical, spherical, conical, or flow-guiding container. Inside, it can be equipped with guide plates, baffles, spiral guide vanes, or static mixers to create swirling, shearing, or turbulent flow states between the two liquid flows, further improving mixing uniformity and preventing excessive local concentration differences that could lead to increased side reactions. The effective volume of the mixing chamber 310 can be designed according to the system's processing flow rate to ensure sufficient residence time for the liquid within the mixing chamber 310, guaranteeing adequate contact between the oxygen-active and nitrogen-active components. The mixing chamber 310 is connected to the activation tank 320, which is used for activation reactions to generate and store ONOOH solution. The activation tank 320 primarily continues the redox reactions in the liquid phase and the ONOOH generation reaction, while also serving as a reaction solution storage function. Upon entering the activation tank 320, due to the presence of incompletely dissolved microbubbles and a large number of dissolved reactive species in the liquid, ozone and other reactive oxygen species continue to react with NO, NO2, and their hydration products, gradually forming peroxynitrite (ONOOH) and related intermediate products. Under suitable acidic conditions, ONOOH can remain relatively stable, thus achieving the continuous generation of ONOOH-rich aqueous solutions. The activation tank 320 can be designed with different volumes according to the system's production volume, and its internal structure can maintain slight circulation to avoid excessively high local reactant concentrations or sedimentation, improving the overall reaction uniformity.
[0029] The detection unit is used to detect the physicochemical parameters of the ONOOH solution in the mixed activation unit, providing feedback data to the control module 400 for control. The detection unit includes a pH sensor 330 and an NO2- sensor 340. The pH sensor 330 and NO2- sensor 340 are located within the activation tank 320. The pH sensor 330 detects the pH value of the ONOOH solution in the activation tank 320, and the NO2- sensor 340 detects the NO2 content of the ONOOH solution in the activation tank 320. - Concentration. The control module 400 adjusts the operating mode of the active gas preparation module 100 based on physicochemical parameters. The operating modes include a generation mode and a storage mode. The pH sensor 330 continuously monitors the acidity and alkalinity of the reaction solution, and the control module 400 determines whether the current system has reached the optimal acidity range based on the detection results. When the pH value is detected to gradually decrease to the preset control range, NO2 can be combined. - The concentration further determines the reaction progress, and the working modes of the first and second active gas preparation units are automatically adjusted according to the control strategy. This not only improves the ONOOH generation efficiency, but also helps to get closer to the target range near the peak ONOOH content after entering the storage mode. This ensures a high yield of ONOOH while slowing down its further decay and extending the effective storage time of the ONOOH-rich aqueous solution.
[0030] The control module 400 includes a main controller, which is connected to the gas flow control unit, discharge control unit, pH sensor 330, NO2- sensor 340, first liquid pump 351, and second liquid pump 352 in the active gas preparation module 100. The main controller switches modes based on the liquid pH value and utilizes NO2-... - The concentration is converted into the subsequent acid production to correct the pH threshold and control the switching between production and storage modes.
[0031] The circulating liquid storage module 300 also includes a first liquid pump 351 and a second liquid pump 352, which respectively drive the first circulating water path 361 and the second circulating water path 362 to form independent circulation. The first liquid pump 351 is set in the first circulating water path 361. One end of the first liquid pump 351 is connected to the activation tank 320, and the other end of the first liquid pump 351 is connected to the first liquid inlet. The liquid is transported from the activation tank 320 to the first Venturi tube 211 under the drive of the first liquid pump 351. The second liquid pump 352 is set in the second circulating water path 362. One end of the second liquid pump 352 is connected to the activation tank 320, and the other end of the second liquid pump 352 is connected to the second liquid inlet. The liquid is transported from the activation tank 320 to the second Venturi tube 212 under the drive of the second liquid pump 352. Two circulating water paths independently enrich oxygen- and nitrogen-based reactive species, which then converge in the mixing chamber 310. This avoids direct contact between the two types of reactive gases before injection, preventing ineffective consumption and improving the utilization rate of reactive species and the ONOOH generation efficiency. Both the first liquid pump 351 and the second liquid pump 352 are corrosion-resistant magnetic circulation pumps or diaphragm circulation pumps, and their flow rate and head can be adjusted by the control module 400.
[0032] Example 2 A control method for an ONOOH-rich aqueous solution preparation apparatus, applicable to the aforementioned ONOOH-rich aqueous solution preparation apparatus. Figure 2 An overall flowchart of one embodiment of the present invention is shown, as follows: Figure 2 As shown, the control methods include: The active gas preparation module 100 is configured with the following operating modes: a generation mode and a storage mode. The generation mode includes: a first active gas stream is continuously introduced to continuously obtain an oxidizing precursor, mainly ozone, in the liquid phase; a second active gas stream is intermittently introduced; the intermittent introduction duty cycle can be 20%~80%, and further can be 30%~70%. The storage mode includes: the second active gas stream is stopped, and the first active gas stream is continuously introduced, intermittently introduced, or stopped at 30%~50% of the generation mode flow rate.
[0033] The working mode of the active gas preparation module 100 is determined to be the generation mode; the first active gas flow is continuously introduced to continuously obtain oxidizing precursors, mainly ozone, in the liquid phase; the second active gas flow is intermittently introduced; the intermittent introduction duty cycle is 55%, and the time period is 30s.
[0034] The physicochemical parameters of the ONOOH solution in activation tank 320 were collected using a detection unit. These parameters included pH value and NO2. - The concentration is used to track the liquid acidification process and the accumulation state of low-valent nitrogen oxides in the liquid phase. The intermittent introduction time can be 2s~90s, and further can be 10s~40s.
[0035] Real-time NO2 is obtained when the pH value reaches a preset pH prediction value. - Concentration; the specific value of the preset pH prediction value is not limited here, and optionally it can be 2.4; when the pH value reaches 2.4, real-time NO2 is obtained. - Concentration. Real-time NO2 - Concentration calculations show that it continues to be converted into NO3 in subsequent reactions. - The corresponding theoretical acid production is used to predict the degree of further acidification that the liquid may undergo in subsequent stages.
[0036] Based on the real-time NO2 - The concentration predicts the subsequent acidification trend of the ONOOH solution, and corrects the preset pH switching value to obtain the corrected pH switching value. The specific value of the preset pH switching value is not limited here; it can specifically be 2.2, including: According to real-time NO2 - The concentration and a preset conversion algorithm are used to calculate the increase in hydrogen ion concentration; the preset conversion algorithm is expressed by the following formula: in, Indicates real-time NO2 - concentration, This indicates the conversion factor for acid production. This represents the increase in hydrogen ion concentration; the acid production conversion factor can be 0.7~1.5, and further can be 0.9~1.2. The acid production conversion factor can be determined based on the stoichiometric relationship of the reaction and calibration experiments.
[0037] Based on the increase in hydrogen ion concentration and the preset prediction correction algorithm, the preset pH switching value is corrected to obtain the corrected pH switching value.
[0038] The preset correction algorithm is expressed using the following formula: in, This indicates the preset pH switching value. This indicates the increase in hydrogen ion concentration. This indicates the corrected pH switching value.
[0039] Using the pH value and a corrected pH switching value, the operating mode of the active gas preparation module 100 is adjusted to storage mode. When the pH value drops to the corrected pH switching value, it is determined that the ONOOH content in the liquid phase has approached its peak and begun to decline, thus switching from generation mode to storage mode. Through this method, the remaining NO2 in the liquid phase can be used as a basis for determining the optimal operating mode. -To mitigate the potential for further acidification caused by continued oxidation, the timing of the switch from the formation mode to the storage mode is adjusted to be earlier or later, ensuring that the liquid approaches the target range near the peak ONOOH content after entering the storage mode. In storage mode, the second active gas flow is stopped to reduce further disturbance to the liquid phase system caused by continued input of low-valent nitrogen oxides. Simultaneously, the first active gas flow is adjusted to operate in one of the following ways: continuous flow at 30%–50% of the formation mode flow rate, intermittent flow, or complete cessation of flow. This aims to maintain the stability of the target active component in the liquid phase as much as possible while suppressing further ONOOH decay, thereby extending the effective storage time of the ONOOH-rich aqueous solution.
[0040] In this embodiment, liquid NO2 - Concentration is no longer used as a direct determinant for switching between generation and storage modes; instead, it serves as a correction factor for pH switching. Specifically, when the pH reaches the preset threshold of 2.4, the current NO2 concentration is read first. - Concentration, and then based on NO2 - The concentration calculation is based on the increase in hydrogen ion concentration corresponding to subsequent transformations, and this increase in hydrogen ion concentration is used to correct the preset switching pH threshold. Therefore, this embodiment achieves mode switching based on pH value and utilizes NO2... - The control strategy of adjusting the pH switching value by converting the concentration into the subsequent acid production rate improves the accuracy of the mode switching timing.
[0041] Figure 3 The results show the comparison of the ONOOH content of aqueous solutions obtained under different mixing methods and their disinfection and sterilization effects on Staphylococcus aureus, such as... Figure 3 As shown, the generation mode of this embodiment is superior to other methods in both increasing the ONOOH generation content and enhancing the actual bactericidal performance. This embodiment sets up four groups for comparison: a control group, a traditional gas-phase mixing mode group, a conventional liquid-phase mixing mode group, and the generation mode group of this embodiment. The control group was a deionized water group; the traditional gas-phase mixing mode group was an aqueous solution obtained by mixing the first and second active gas streams in the gas phase before introducing them into water; the conventional liquid-phase mixing mode group was an aqueous solution obtained by separately introducing the first and second active gas streams into water before mixing them, without using the control method of this invention; the generation mode group of this embodiment was an ONOOH-rich aqueous solution prepared using the generation mode of this embodiment, wherein the first active gas stream was continuously introduced, and the second active gas stream was intermittently introduced. The traditional gas-phase mixing mode group, the conventional liquid-phase mixing mode group, and the generation mode group of this embodiment all compared the actual results after treating 500 mL of deionized water for 5 minutes.
[0042] In the detection of ONOOH content, coumarin borate pinacol ester (CBA) was used as a fluorescent probe with an excitation wavelength of 332 nm and an emission wavelength of 470 nm. Its fluorescence intensity was proportional to the concentration of the reactant species. Figure 3 The left vertical axis represents the ONOOH content, with the unit being fluorescence intensity (au). In the sterilization experiment, 500 μL of a Staphylococcus aureus suspension with an OD600 of approximately 3 was coated onto the surface of a polypropylene plastic sheet and treated with this device for 5 minutes. The number of surviving bacteria was then counted after treatment. Figure 3 The vertical axis on the right represents the number of bacteria, in CFU.
[0043] like Figure 3 As shown, the control group had the lowest ONOOH content and the highest bacterial count, indicating that deionized water alone has virtually no effective ONOOH generation capacity and a weak bactericidal effect against Staphylococcus aureus. Compared with the control group, the ONOOH content of both the traditional gas-phase mixing mode group and the conventional liquid-phase mixing mode group was significantly increased, while the bacterial count was significantly decreased. This indicates that whether gas-phase premixing is used before introducing the water or liquid-phase post-mixing is used, both methods can promote ONOOH generation and improve the bactericidal effect to a certain extent.
[0044] Furthermore, compared with the conventional gas-phase mixing mode group, the ONOOH content of the conventional liquid-phase mixing mode group was further increased and the bacterial count was further reduced, indicating that introducing the two active gas streams into the liquid phase system separately before mixing is more conducive to the contact reaction of active precursors and the formation and accumulation of ONOOH in the liquid phase. Furthermore, compared with the conventional liquid-phase mixing mode group, the generation mode group of this embodiment exhibited the highest ONOOH content and the lowest bacterial count, indicating that the generation mode of continuously introducing the first active gas stream and intermittently introducing the second active gas stream in this embodiment can further optimize the synergistic activation process of ozone and low-valent nitrogen oxides in the liquid phase, thereby significantly improving the generation effect of ONOOH-rich aqueous solution and effectively enhancing the disinfection and sterilization effect against Staphylococcus aureus.
[0045] Figure 4 This diagram illustrates a comparison of the relative concentration changes of ONOOH after a certain period of time following the activation of the storage mode according to an embodiment of the present invention. Figure 4As shown, this embodiment introduces a storage mode after the generation mode to examine its effect on the ability to maintain the relative concentration of ONOOH in the ONOOH-rich aqueous solution. This embodiment compares a group where the storage mode is not activated after the generation mode and a group where the storage mode is activated after the generation mode, using deionized water as a control group. Specifically, the group where the storage mode is not activated after the generation mode means that storage mode control is not performed after the ONOOH-rich aqueous solution preparation is completed; the group where the storage mode is activated after the generation mode is completed means that the storage mode is switched according to the control method of this embodiment after the generation mode is completed, i.e., the second active gas flow is stopped, and the first active gas flow is continuously, intermittently, or stopped at 30%~50% of the generation mode flow rate, in order to reduce the degree of continued acidification of the liquid phase system and the excessively rapid decay of ONOOH.
[0046] Furthermore, in this embodiment, samples from each group were tested at storage times of 0 min, 5 min, 10 min, and 15 min, where 0 min represents the initial detection time after the generation mode ended, to compare the changes in the relative concentration of ONOOH over time under different storage conditions. The ONOOH content was characterized using coumarin borate pinacol ester (CBA) as a fluorescent probe, with an excitation wavelength of 332 nm and an emission wavelength of 470 nm. Its fluorescence intensity was positively correlated with the concentration of the target reactive species in the liquid phase. Therefore, under the same detection conditions, the relative ONOOH content in each group of samples can be reflected by changes in fluorescence intensity.
[0047] Furthermore, such as Figure 4 As shown, at the three storage time points of 5 min, 10 min, and 15 min, the relative concentration of ONOOH in the group with storage mode enabled was higher than that in the group without storage mode enabled. This indicates that introducing storage mode after the generation mode ends can effectively slow down the decay process of ONOOH and improve the activity retention capacity of ONOOH-rich aqueous solution during storage. With the extension of storage time, the relative concentration of ONOOH in both groups of samples showed a decreasing trend, but the group with storage mode enabled consistently maintained a higher relative concentration of ONOOH, indicating that this storage mode can extend the effective retention time of ONOOH within a certain time range.
[0048] Furthermore, the results of this embodiment demonstrate that this embodiment not only increases the initial amount of ONOOH generated through the generation mode, but also reduces the decay rate of the active component through the storage mode after the generation mode, enabling the ONOOH-rich aqueous solution to maintain a high activity level after preparation. Therefore, the storage mode of this embodiment can provide a longer effective window for the subsequent use of the ONOOH-rich aqueous solution, thereby improving its usability and stability in practical applications such as disinfection and sterilization.
[0049] Figure 5The diagram illustrates a comparison of the disinfection effects on Staphylococcus aureus after a certain period of time following the activation of the storage mode according to an embodiment of the present invention. Figure 5 As shown, this embodiment illustrates the impact of introducing a storage mode after the generation mode on the retention of the actual bactericidal effect of ONOOH-rich aqueous solutions. The grouping method in this embodiment is similar to... Figure 4 The embodiments are consistent, including a group where the storage mode is not activated after the generation mode, a group where the storage mode is activated after the generation mode, and a deionized water control group. The group where the storage mode is not activated after the generation mode is used to evaluate the bactericidal effect of the ONOOH-rich aqueous solution after natural storage, while the group where the storage mode is activated after the generation mode is used to evaluate the bactericidal effect of the ONOOH-rich aqueous solution regulated by the storage mode of this invention after different storage times.
[0050] In this embodiment, *Staphylococcus aureus* was used as the indicator strain. Specifically, a 500 μL suspension of *Staphylococcus aureus* with an OD600 of approximately 3 was uniformly coated onto the surface of a polypropylene plastic sheet. Then, aqueous solution samples with different storage times were used to treat the sheet for 5 minutes. After treatment, the number of surviving colonies on the polypropylene plastic sheet surface was counted to evaluate the bactericidal performance of different samples after storage. This experiment verifies the correlation between the retention capacity of active components in ONOOH-rich aqueous solutions and the actual bactericidal effect.
[0051] like Figure 5 As shown, at 0 min, the number of surviving bacteria in the storage mode group and the non-storage mode group were basically similar. With the storage time extended to 5 min, 10 min, and 15 min, the number of surviving bacteria in the storage mode group after generation was lower than that in the non-storage mode group, indicating that the ONOOH-rich aqueous solution treated with the storage mode still maintained strong bactericidal ability after storage. As the storage time increased from 5 min to 10 min and 15 min, the bactericidal effect of both groups decreased to some extent, but the storage mode group consistently showed a lower number of surviving bacteria, indicating that the storage mode can mitigate the trend of decreasing bactericidal efficacy with prolonged storage time.
[0052] Furthermore, according to Figure 4 The results of the relative concentration change of ONOOH show that after activating the storage mode, the relative concentration of ONOOH in the ONOOH-rich aqueous solution remains at a higher level, and the corresponding number of surviving Staphylococcus aureus is lower, indicating that there is consistency between the maintenance of ONOOH activity and the actual bactericidal effect. This embodiment further demonstrates that by introducing a storage mode after the generation mode, it is possible to simultaneously improve the retention of active components and the maintenance of bactericidal effect, thereby verifying the effectiveness of the storage mode in extending the use time of ONOOH-rich aqueous solutions and enhancing the actual disinfection and sterilization application effect.
[0053] It should be understood that the specific embodiments described above are merely illustrative or explanatory of the principles of the invention and do not constitute a limitation thereof. Therefore, any modifications, equivalent substitutions, improvements, etc., made without departing from the spirit and scope of the invention should be included within the protection scope of the invention. Furthermore, the appended claims are intended to cover all variations and modifications falling within the scope and boundaries of the appended claims, or equivalent forms of such scope and boundaries.
[0054] The above description does not provide detailed explanations of the technical aspects of each layer's patterning and etching. However, those skilled in the art should understand that various methods existing in the prior art can be used to form layers and regions of the desired shape. Furthermore, to form the same structure, those skilled in the art can also design methods that are not entirely identical to those described above.
[0055] The present invention has been described above with reference to embodiments thereof. However, these embodiments are merely illustrative and not intended to limit the scope of the invention. The scope of the invention is defined by the appended claims and their equivalents. Various substitutions and modifications can be made by those skilled in the art without departing from the scope of the invention, and all such substitutions and modifications should fall within the scope of the invention.
[0056] Although embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and modifications can be made to the embodiments of the present invention without departing from the spirit and scope of the invention.
[0057] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. An apparatus for preparing an ONOOH-rich aqueous solution, characterized in that, include: The system includes an active gas preparation module, a microbubble injection module, a circulating liquid storage module, and a control module. The active gas preparation module, the microbubble injection module, and the circulating liquid storage module are connected in sequence, and both the active gas preparation module and the circulating liquid storage module are connected to the control module. The active gas preparation module is used to generate a first active gas stream rich in ozone and a second active gas stream rich in low-valence nitrogen oxides. The microbubble injection module includes a first microbubble injection structure and a second microbubble injection structure, and the circulating liquid storage module includes a mixing and activation unit and a detection unit. The first microbubble injection structure and the hybrid activation unit form a first circulating water path, and the second microbubble injection structure and the hybrid activation unit form a second circulating water path; The first microbubble injection structure is used to inject the first active gas flow into the first circulating water path in the form of microbubbles, and the second microbubble injection structure is used to inject the second active gas flow into the second circulating water path in the form of microbubbles; The hybrid activation unit is used to collect the activation liquids from the first microbubble injection structure and the second microbubble injection structure to generate an ONOOH solution. The detection unit is used to detect the physicochemical parameters of the ONOOH solution in the hybrid activation unit. The control module adjusts the working mode of the active gas preparation module according to the physicochemical parameters. The working mode includes a generation mode and a storage mode.
2. The apparatus for preparing ONOOH-rich aqueous solution according to claim 1, characterized in that, The active gas preparation module includes a first active gas preparation unit and a second active gas preparation unit. The first active gas preparation unit is used to generate a first active gas flow, and the second active gas preparation unit is used to generate a second active gas flow. The first active gas preparation unit is connected to the gas path of the first microbubble injection structure, and the second active gas preparation unit is connected to the gas path of the second microbubble injection structure.
3. The apparatus for preparing ONOOH-rich aqueous solution according to claim 2, characterized in that, The first microbubble injection structure includes a first venturi tube and a first rectifier structure, and the first venturi tube and the first rectifier structure are connected. The first venturi tube includes a first air inlet, a first liquid inlet, and a first outlet. The first air inlet is connected to the first active gas preparation unit, the first liquid inlet is connected to the mixing and activation unit, and the first outlet is connected to the first rectifier structure. The first venturi tube is used to break the first active gas flow into a micron-sized bubble group, and the first rectification structure is used to reduce the turbulence intensity of the micron-sized bubble group at the first outlet. The second microbubble injection structure includes a second venturi tube and a second rectifier structure, which are connected together. The second venturi tube includes a second air inlet, a second liquid inlet, and a second outlet. The second air inlet is connected to the second active gas preparation unit, the second liquid inlet is connected to the mixing and activation unit, and the second outlet is connected to the second rectifier structure. The second venturi tube is used to break the second active gas flow into a micron-sized bubble cluster, and the second rectifying structure is used to reduce the turbulence intensity of the micron-sized bubble cluster at the second outlet.
4. The apparatus for preparing ONOOH-rich aqueous solution according to claim 3, characterized in that, The mixed activation unit comprises a mixing cavity and an activation pool, and the detection unit comprises a pH sensor and a NO2 - sensor The mixing chamber is connected to the first microbubble injection structure and the second microbubble injection structure, and the mixing chamber is used to collect the activated liquid output from the first microbubble injection structure and the second microbubble injection structure; The mixing chamber is connected to the activation tank, which is used to carry out an activation reaction to generate and store an ONOOH solution. The pH sensor and NO2 - A sensor is arranged in the activation tank for detecting the pH value of the ONOOH solution in the activation tank, and a NO2 - sensor is arranged in the activation tank for detecting the NO2 - concentration of the ONOOH solution in the activation tank.
5. The apparatus for preparing ONOOH-rich aqueous solution according to claim 4, characterized in that, The circulating liquid storage module also includes a first liquid pump and a second liquid pump. The first liquid pump is installed in the first circulating water circuit. One end of the first liquid pump is connected to the activation tank, and the other end of the first liquid pump is connected to the first liquid inlet. The second liquid pump is installed in the second circulating water circuit. One end of the second liquid pump is connected to the activation tank, and the other end of the second liquid pump is connected to the second liquid inlet.
6. The apparatus for preparing ONOOH-rich aqueous solution according to claim 1, characterized in that, The first active gas preparation unit includes a first plasma generator, a first gas source, a first gas flow controller, and a first discharge control power supply unit. The first gas source, the first gas flow controller, and the first plasma generator are connected in sequence. The first discharge control power supply unit is connected to the first plasma generator. The first plasma generator is a dielectric barrier discharge reactor or a corona discharge reactor. The first gas source is one of oxygen, air, or oxygen-enriched air. The second active gas preparation unit includes a second plasma generator, a second gas source, a second gas flow controller, and a second discharge control power supply unit. The second gas source, the second gas flow controller, and the second plasma generator are connected in sequence. The second discharge control power supply unit is connected to the second plasma generator. The second plasma generator is a sliding arc discharge reactor or a microwave discharge reactor. The second gas source is either air or nitrogen-enriched air.
7. A control method for an ONOOH-rich aqueous solution preparation apparatus, characterized in that, The control method is applicable to the ONOOH-rich aqueous solution preparation apparatus as described in claims 1-6, and the control method includes: The working modes of the active gas preparation module are defined, including a generation mode and a storage mode. The operating mode of the active gas preparation module is determined to be the generation mode; The detection unit is used to collect the physicochemical parameters of the ONOOH solution in the activation tank, including pH value and NO2. - concentration; When the pH value reaches the preset pH prediction value, real-time NO2 is obtained. - concentration; Based on the real-time NO2 - The concentration is used to predict the subsequent acidification trend of the ONOOH solution, and the preset pH switching value is corrected to obtain the corrected pH switching value. Using the pH value and the corrected pH switching value, the operating mode of the active gas preparation module is adjusted to storage mode.
8. The control method according to claim 7, characterized in that, The generation mode includes: the first active airflow is continuously introduced, and the second active airflow is intermittently introduced; The storage mode includes: the second active airflow is stopped, and the first active airflow is continuously, intermittently, or stopped at 30% to 50% of the generation mode flow rate.
9. The control method according to claim 7, characterized in that, The basis of the real-time NO2 - The concentration predicts the subsequent acidification trend of the ONOOH solution, and corrects the preset pH switching value to obtain the corrected pH switching value, including: According to the real-time NO2 - The concentration and the preset conversion algorithm are used to calculate the increase in hydrogen ion concentration; Based on the hydrogen ion concentration increment and the preset prediction correction algorithm, the preset pH switching value is corrected to obtain the corrected pH switching value.
10. The control method according to claim 9, characterized in that, The preset conversion algorithm is expressed using the following formula: in, Indicates real-time NO2 - concentration, This indicates the conversion factor for acid production. Indicates the increase in hydrogen ion concentration; The preset prediction correction algorithm is expressed by the following formula: in, This indicates the preset pH switching value. This indicates the increase in hydrogen ion concentration. This indicates the corrected pH switching value.