A preparation method for improving the sterilization effect of hypochlorous acid water

Abstract

The application relates to the technical field of hypochlorous acid water preparation and sterilization and disinfection, in particular to a preparation method for improving the sterilization effect of hypochlorous acid water, which comprises the following steps: pretreatment: introducing deionized water into a closed reaction kettle, controlling the water temperature, adding a stabilizer, stirring until complete dissolution, and obtaining a pretreatment liquid; main reaction: adding sodium hypochlorite solution dropwise into the pretreatment liquid, continuously stirring, continuously stirring after the dropwise addition is completed, and obtaining a sodium hypochlorite base liquid; acid adjustment and activation: adding dilute hydrochloric acid dropwise into the sodium hypochlorite base liquid, monitoring the pH value of the reaction system in real time, controlling the final pH value to be 4.2-5.5, continuously stirring after the dropwise addition is completed, and realizing the activation and stability of effective chlorine; the application selects dilute hydrochloric acid as an acid regulator, replaces the traditional conventional regulator, improves the precision of the acid-base degree adjustment, and can promote the efficient conversion of sodium hypochlorite into high-activity hypochlorous acid.

Description

Technical Field

[0001] This invention relates to the field of hypochlorous acid water preparation and sterilization technology, specifically to a preparation method for improving the sterilization effect of hypochlorous acid water. Background Technology

[0002] While existing processes for preparing slightly acidic hypochlorous acid water include technologies that use dilute hydrochloric acid to adjust the pH of the system to a slightly acidic state, there are still many core technical challenges that hinder product performance improvement and industrial application.

[0003] Regarding the use of acid regulators, the existing process only vaguely mentions the use of dilute hydrochloric acid without specifying its concentration or matching the corresponding dropping process parameters. This results in low precision in pH control, low conversion efficiency of sodium hypochlorite to highly active hypochlorous acid, and inability to achieve efficient activation of available chlorine.

[0004] Regarding the application of stabilizers, existing processes only briefly mention adding stabilizers to improve stability, without specifying the specific types of stabilizers, compounding methods, and precise addition ratios. Commonly used single stabilizers or compound stabilizers without clear proportions have limited protective effects on available chlorine, making available chlorine easy to decompose during storage and resulting in poor product storage stability.

[0005] At the preparation process level, existing technologies only disclose basic operating steps such as mixing, pH adjustment, and adding stabilizers. They lack refined control over key indicators such as dropping rate, reaction temperature, reaction pressure, and stirring parameters. There are also no standardized pretreatment, segmented reaction, and targeted post-treatment processes, resulting in uneven mixing of raw materials, incomplete reaction, high impurity content in the product, poor purity and batch consistency, difficulty in achieving stable mass production in industrial production, and inability to adapt to the diverse application needs of different fields.

[0006] In addition, existing processes mostly rely on a single bactericidal ingredient, resulting in a single bactericidal mechanism. In order to achieve the expected bactericidal effect, the effective chlorine content needs to be increased, which not only increases production costs but also brings potential usage risks. Summary of the Invention

[0007] The primary objective of this invention is to provide a preparation method that improves the bactericidal effect of hypochlorous acid water.

[0008] A further objective of this invention is to provide a method for preparing a solution with improved bactericidal effect of hypochlorous acid water. The raw materials used in the preparation, by mass percentage, include sodium hypochlorite with an effective chlorine content of 10% to 11% and sodium hypochlorite accounting for 3.0% to 3.8% of the total raw material mass, dilute hydrochloric acid with a concentration of 1% to 5% and dilute hydrochloric acid accounting for 2.5% to 3.2% of the total raw material mass, deionized water of 92.3% to 94.0%, and a stabilizer of 0.2% to 0.5%, wherein the stabilizer is sodium pyrophosphate, or a mixture of sodium pyrophosphate and disodium EDTA. The method includes the following steps:

[0009] (1) Pretreatment: The deionized water is introduced into a closed reaction vessel, the water temperature is controlled, the stabilizer is added, and the mixture is stirred until completely dissolved to obtain a pretreated solution;

[0010] (2) Main reaction: Sodium hypochlorite solution is added dropwise to the pretreatment solution while stirring continuously. After the addition is completed, stirring is continued to obtain sodium hypochlorite base solution;

[0011] (3) Acidity adjustment and activation: Add the dilute hydrochloric acid dropwise to the sodium hypochlorite base solution, monitor the pH value of the reaction system in real time, control the final pH value to be 4.2 to 5.5, and continue stirring after the addition is completed to achieve activation and stabilization of available chlorine;

[0012] (4) Post-processing: Let the reaction solution stand, filter it, seal it and store it in the dark to obtain the finished hypochlorous acid water.

[0013] Preferably, the raw material further includes 0.3% to 0.4% of a synergistic bactericidal component, wherein the synergistic bactericidal component is a compound of dipotassium glycyrrhizate and zinc citrate.

[0014] Preferably, the mass ratio of dipotassium glycyrrhizate to zinc citrate is 1:1 to 1:1.5.

[0015] Preferably, the mass ratio of sodium pyrophosphate to disodium EDTA is 2:1 to 2.5:1.

[0016] Preferably, in step (1), the water temperature is controlled at 25°C to 28°C, the stirring speed is 300r / min to 350r / min, and the stirring time is 10min to 15min.

[0017] Preferably, in step (2), the sodium hypochlorite solution is added at a rate of 0.5 mL / s to 0.7 mL / s, and the stirring time after the addition is completed is 20 min to 30 min.

[0018] Preferably, in step (3), the dropping rate of dilute hydrochloric acid is 0.3 mL / s to 0.5 mL / s, and the stirring time after the dropping is completed is 15 min to 30 min.

[0019] Preferably, in step (2), the pressure inside the reactor is controlled to be 0.03 MPa when adding sodium hypochlorite solution.

[0020] Preferably, in step (3), after the addition is completed, the mixture is stirred at a constant temperature of 28°C to 30°C.

[0021] Preferably, in step (4), the settling time is 5 min to 10 min; the filtration uses qualitative filter paper or microfiltration membrane, and when using microfiltration membrane, its pore size is 0.22 μm and the filtration pressure is 0.1 MPa.

[0022] Compared with the prior art, the beneficial effects of the present invention are:

[0023] 1. This invention solves the core technical pain points of existing slightly acidic hypochlorous acid water preparation processes by systematically and precisely designing and creatively combining and optimizing the concentration of acid regulators, the stabilizer system, and the preparation process parameters. This significantly improves the sterilization efficiency, storage stability, product purity, and industrial adaptability of hypochlorous acid water, and creates a close synergistic effect among the various technical features.

[0024] 2. This invention precisely defines a specific concentration range of dilute hydrochloric acid and matches it with exclusive dripping process parameters. Combined with a specific pH control range, it is not a simple dilution of known concentrations, but a precise acid-base regulation scheme designed for the characteristics of hypochlorous acid water systems. This effectively improves the accuracy of acid-base regulation, realizes the efficient and directional conversion of sodium hypochlorite into highly active hypochlorous acid, and avoids the decomposition of effective chlorine due to improper acid concentration, laying the core foundation for the product's excellent bactericidal performance.

[0025] 3. This invention selects sodium pyrophosphate as a single agent or a stabilizer system formed by compounding sodium pyrophosphate with disodium EDTA in a specific ratio, and limits the precise addition ratio. This stabilizer system is not a simple selection or arbitrary compounding of existing known chelating agents, but a dedicated stabilizing system specially designed for the protection of available chlorine in hypochlorous acid water. It can significantly enhance the protection of available chlorine, reduce the degradation loss of available chlorine during storage, and significantly improve the storage stability of the product. It solves the core problems of easy decomposition of available chlorine and large fluctuations in product performance in the prior art.

[0026] 4. This invention constructs a refined process system encompassing pretreatment, pressure-controlled main reaction, isothermal acid activation, and standardized post-treatment. It precisely and collaboratively limits key parameters such as water temperature, stirring speed, dropping rate, reaction pressure, isothermal temperature, and settling time in each step, forming a standardized preparation process. This achieves uniform mixing and full reaction of raw materials, effectively reducing product impurity content, improving product purity, and significantly enhancing batch consistency. Furthermore, this process system possesses excellent industrial adaptability; equipment specifications can be flexibly adjusted according to production capacity requirements, and parameters can be scaled up proportionally to achieve stable industrial mass production, overcoming the technical limitations of existing processes with coarse parameters and unstable industrial mass production.

[0027] 5. This invention can further introduce a synergistic bactericidal component formed by the combination of dipotassium glycyrrhizate and zinc citrate, which, together with hypochlorous acid, constructs a multi-mechanism synergistic bactericidal system. This breaks through the limitations of the single bactericidal component in the existing technology. Without increasing the amount of available chlorine used, it significantly broadens the bactericidal spectrum and significantly improves the bactericidal efficiency, achieving a dual improvement in bactericidal effect and safety of use. It solves the problem that the existing technology requires increasing the available chlorine content to achieve the expected bactericidal effect, which increases production costs and easily brings potential use risks.

[0028] 6. In addition, the raw materials used in this invention are all conventional industrial-grade raw materials, the preparation equipment is commonly used in the industry, the technical solution is stable and reliable, can be repeatedly implemented, the production cost is controllable, no additional production investment is required, and it can be widely used in sterilization and disinfection scenarios in multiple fields such as medical treatment, food processing, public health, and daily life. Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] Example 1:

[0031] The raw material ratio, by mass percentage, is as follows: sodium hypochlorite with an effective chlorine content of 10% (sodium hypochlorite accounts for 3.0% of the total raw material mass), dilute hydrochloric acid with a concentration of 3% (dilute hydrochloric acid accounts for 2.5% of the total raw material mass), deionized water 94.0%, and sodium pyrophosphate stabilizer 0.5%. The effective chlorine content of sodium hypochlorite was tested according to GB / T19106-2013 standard, the concentration of dilute hydrochloric acid was calibrated by acid-base titration, and the deionized water met the laboratory grade I water standard.

[0032] Preparation steps:

[0033] Pretreatment: Deionized water is introduced into a 5L sealed reactor equipped with a mechanical stirrer and a temperature sensor. The water temperature is controlled at 25℃ with an error of ±0.5℃, and the stirring speed is 300r / min with a speed error of ±10r / min. Sodium pyrophosphate stabilizer is added, and the mixture is stirred for 10min with a time error of ±1min until it is completely dissolved. The dissolution state is determined by visual observation to ensure that there are no obvious particles, thus obtaining the pretreated solution.

[0034] Main reaction: Sodium hypochlorite solution was slowly added dropwise to the pretreatment solution. The dropping rate was controlled by a peristaltic pump at 0.5 mL / s with an error of ±0.05 mL / s. During the dropping process, the mixture was continuously stirred at a speed of 300 r / min. After the dropping was completed, the mixture was stirred for another 20 min with a time error of ±1 min to ensure that the sodium hypochlorite was evenly dispersed and to obtain the sodium hypochlorite base solution.

[0035] Acidity adjustment and activation: Dilute hydrochloric acid was slowly added dropwise to the sodium hypochlorite base solution. The peristaltic pump controlled the dropping rate at 0.3 mL / s with an error of ±0.05 mL / s. During the dropping process, the pH value of the reaction system was monitored in real time using a precision pH meter with an accuracy of 0.01. The final pH value was controlled to be 5.2 with an error of ±0.1. After the dropping was completed, stirring was continued for 15 min with a time error of ±1 min to achieve activation and stabilization of available chlorine. The activation effect was verified by real-time detection of available chlorine content.

[0036] Post-processing: Let the reaction solution stand for 5 minutes (within ±1 minute). After standing, a small amount of precipitate at the bottom will be separated by natural sedimentation. After filtration with qualitative filter paper with a pore size of 1-3 μm, the finished hypochlorous acid water is obtained. The finished product is immediately placed into a brown sealed bottle and stored in the dark. The storage environment temperature is controlled at 25±2℃.

[0037] Example 2:

[0038] The raw material ratio, by mass percentage, is as follows: sodium hypochlorite with an effective chlorine content of 10% (3.5% of the total raw material mass), dilute hydrochloric acid with a concentration of 4% (3.0% of the total raw material mass), deionized water 93.0%, and sodium pyrophosphate stabilizer 0.5%. The concentration of dilute hydrochloric acid is calibrated by acid-base titration to ensure that the concentration deviation is ≤0.1%.

[0039] Preparation steps:

[0040] Pretreatment: Same as in Example 1, deionized water was introduced into a 5L sealed reactor. Sodium pyrophosphate was added under stirring conditions of 25℃ (error ±0.5℃) and 300r / min (speed error ±10r / min). The mixture was stirred for 10min (time error ±1min) until it was completely dissolved. The state of dissolution was determined by visual observation to ensure there were no obvious particles.

[0041] Main reaction: The sodium hypochlorite dropping rate was optimized to 0.6 mL / s with an error of ±0.05 mL / s. A peristaltic pump was used for precise control. After the dropping was completed, the stirring time was extended to 25 min with a time error of ±1 min to ensure that the sodium hypochlorite was uniformly dispersed in the pretreatment solution, thereby improving the mixing uniformity of the raw materials and the fullness of the reaction. The mixing uniformity was determined by sampling and testing the effective chlorine content at different locations, with a deviation of ≤1%.

[0042] Acidity adjustment and activation: 4% dilute hydrochloric acid was added dropwise at an optimized rate of 0.4 mL / s (error ±0.05 mL / s). The pH value was monitored in real time using a precision pH meter with an accuracy of 0.01, and the final pH value was controlled to be stable at 5.0 (error ±0.1). After the addition was completed, stirring was continued for 20 minutes (time error ±1 minute) to enhance the efficiency of available chlorine generation. The efficiency of available chlorine generation was determined by comparing it with the available chlorine content in Example 1.

[0043] Post-processing: Same as in Example 1, after static filtration, the product is sealed and stored under the following conditions: 25±2℃, protected from light and sealed.

[0044] Based on Example 1, this embodiment further optimizes the concentration of dilute hydrochloric acid and the ratio of sodium hypochlorite. By increasing the concentration of dilute hydrochloric acid and adjusting the dropping speed, the acidity adjustment precision of the reaction system is further improved, promoting more efficient generation of hypochlorous acid. Extending the stirring time optimizes the mixing effect, resulting in a significant improvement in the sterilization efficiency and stability of the product compared to Example 1.

[0045] Example 3:

[0046] The raw material specifications used in this embodiment are the same as those in the previous embodiment. Before compounding, the synergistic components dipotassium glycyrrhizate and zinc citrate were both dried at a temperature of 60°C for 2 hours. During the compounding process, a high-speed mixer with a speed of 2000 r / min and a mixing time of 5 minutes was used to ensure uniform mixing.

[0047] The raw material ratio, by mass percentage, is as follows: sodium hypochlorite with an effective chlorine content of 10% (3.2% of the total raw material mass), dilute hydrochloric acid with a concentration of 3.5% (2.8% of the total raw material mass), synergistic bactericidal component of 0.3%, dipotassium glycyrrhizate and zinc citrate compounded in a 1:1 mass ratio, deionized water of 93.2%, stabilizer of 0.5%, and sodium pyrophosphate and disodium EDTA compounded in a 2:1 mass ratio. All compound components are accurately weighed according to their mass percentage, with a weighing accuracy of 0.001g.

[0048] Preparation steps:

[0049] Pretreatment: Deionized water was introduced into a 5L sealed reactor, and the water temperature was controlled at 26℃ (error ±0.5℃). The stirring speed was 350r / min (speed error ±10r / min). The compound stabilizer was added and stirred for 12min (time error ±1min) until completely dissolved. Then, the compound synergistic bactericidal component was added and stirred for another 8min (time error ±1min) to ensure uniform dispersion of the synergistic component. The dispersion uniformity was determined by sampling and testing the component content at different locations, with a deviation of ≤1%. The pretreated solution was obtained.

[0050] Main reaction: Sodium hypochlorite solution was slowly added dropwise to the pretreatment solution at a rate of 0.6 mL / s with an error of ±0.05 mL / s. A peristaltic pump was used for control. During the dropwise addition, the mixture was continuously stirred at a speed of 350 r / min. After the dropwise addition was completed, stirring was continued for 25 min with a time error of ±1 min to obtain the sodium hypochlorite base solution.

[0051] Acidity adjustment and activation: 3.5% dilute hydrochloric acid was slowly added dropwise to the sodium hypochlorite base solution at a rate of 0.4 mL / s (error ±0.05 mL / s). The pH value was monitored in real time using a precision pH meter with an accuracy of 0.01, and the final pH value was controlled to be 4.8 (error ±0.1). After the addition was completed, stirring was continued for 25 minutes (time error ±1 minute) to promote a full reaction between the dilute hydrochloric acid and sodium hypochlorite, while enhancing the synergistic effect of the bactericidal components and available chlorine. The synergistic effect was verified by comparing the bactericidal rates.

[0052] Post-processing: Let the reaction solution stand for 8 minutes (time error ±1 minute), filter to remove the precipitate using qualitative filter paper with a pore size of 1-3 μm, and obtain the finished hypochlorous acid water. Store in a sealed, light-proof container at 25±2℃.

[0053] Based on Example 2, this embodiment introduces a synergistic bactericidal component composed of dipotassium glycyrrhizate and zinc citrate, which works synergistically with hypochlorous acid to enhance the bactericidal effect through multiple mechanisms such as disrupting bacterial cell membrane integrity and inhibiting bacterial metabolism. This broadens the bactericidal spectrum while reducing the amount of available chlorine used. Furthermore, a compound stabilizer is used instead of a single stabilizer to further improve the storage stability of the finished product.

[0054] Example 4:

[0055] Based on the synergistic sterilization system constructed in Example 3, the preparation method parameters are further optimized, the raw material compatibility is expanded, the industrial application value of the process is enhanced, and the technical limitations of the existing technology, such as extensive process parameters and poor raw material compatibility, are overcome, laying the foundation for large-scale industrial production.

[0056] The raw material specifications used in this embodiment are the same as those in the previous embodiment. The effective chlorine content of sodium hypochlorite is increased to 11%. The testing is carried out in accordance with GB / T19106-2013 standard to ensure that the content deviation is ≤0.5%. The process adds pressure control and constant temperature stirring steps. The equipment used has pressure monitoring and constant temperature control functions, with a pressure control accuracy of ±0.005MPa and a temperature control accuracy of ±0.5℃.

[0057] The raw material ratio, by mass percentage, is as follows: sodium hypochlorite with an available chlorine content of 11% (3.8% of the total raw material mass), dilute hydrochloric acid with a concentration of 4.5% (3.2% of the total raw material mass), synergistic bactericidal component of 0.4%, dipotassium glycyrrhizate and zinc citrate compounded in a mass ratio of 1:1.5, deionized water of 92.3%, stabilizer of 0.5%, and sodium pyrophosphate and disodium EDTA compounded in a mass ratio of 2.5:1. All raw materials are weighed with an accuracy of 0.001g, and the compounded components are mixed evenly before use.

[0058] Preparation steps:

[0059] Pretreatment: Deionized water was introduced into a 5L sealed reactor, the water temperature was controlled at 28℃ (error ±0.5℃), the stirring speed was 350r / min (speed error ±10r / min), a compound stabilizer was added, and the mixture was stirred for 15min (time error ±1min) until completely dissolved. Then, a compound synergistic bactericidal component was added, and the mixture was stirred for 10min (time error ±1min) to ensure uniform dispersion of the synergistic component, resulting in a pretreated solution. The uniformity of dispersion was verified by component content detection.

[0060] Main reaction: Sodium hypochlorite solution was added dropwise to the pretreatment solution at a rate of 0.7 mL / s (error ±0.05 mL / s) using a peristaltic pump for precise control. During the dropwise addition, the pressure inside the reactor was controlled at 0.03 MPa (error ±0.005 MPa) and monitored in real time by a pressure sensor. After the dropwise addition was completed, stirring was continued for 30 minutes (error ±1 minute) to ensure thorough mixing of sodium hypochlorite and the pretreatment solution, thereby improving the sufficiency of the reaction. The sufficiency of the reaction was verified by the effective chlorine conversion rate.

[0061] Acidity adjustment and activation: 4.5% dilute hydrochloric acid was added dropwise to the sodium hypochlorite base solution at a rate of 0.5 mL / s (error ±0.05 mL / s). The pH value was monitored in real time using a precision pH meter (accuracy 0.01) and an available chlorine content detector (accuracy 1 mg / L). The final pH value was controlled at 4.6 (error ±0.1), and the available chlorine content was controlled at 100 mg / L (error ±2 mg / L). After the addition was completed, the solution was stirred at a constant temperature of 30℃ (error ±0.5℃) for 30 minutes (time error ±1 minute) to enhance the synergistic bactericidal effect.

[0062] Post-processing: Cool the reaction solution to 25℃ (error ±0.5℃), let it stand for 10 min (time error ±1 min), and filter it with a microfiltration membrane with a pore size of 0.22μm and a filtration pressure of 0.1MPa to remove trace impurities and undissolved particles, so as to obtain the finished hypochlorous acid water. Store it in a sealed, light-proof container at 25±2℃.

[0063] Based on Example 3, this embodiment further expands the applicable scope of sodium hypochlorite available chlorine content, synergistic component ratio, and stabilizer ratio, and verifies the excellent compatibility when sodium hypochlorite available chlorine content is 11%, synergistic component ratio is 0.4%, and stabilizer ratio is 2.5:1; pressure control and constant temperature stirring steps are introduced, and the post-treatment filtration method is optimized to improve process stability and product purity.

[0064] This embodiment verifies the excellent effect under parameters such as dilute hydrochloric acid concentration of 4.5%, reaction pressure of 0.03 MPa, and constant temperature of 30°C. Compared with the existing technology, which has no pressure control, no constant temperature stirring, and a rough process, the industrial adaptability is significantly improved. At the same time, it further broadens the scope of application of the present invention. In industrial production, the equipment specifications can be adjusted according to the production capacity requirements, and the parameters can be scaled up proportionally.

[0065] Example 5:

[0066] The raw material specifications, equipment precision, and experimental environment used in this embodiment are consistent with those in the previous embodiments, ensuring the continuity and repeatability of the technical solution. All parameters have been optimized and verified through multiple rounds to obtain the optimal values.

[0067] The raw material ratio, by mass percentage, is as follows: sodium hypochlorite with an available chlorine content of 10% (3.0% of the total raw material mass), dilute hydrochloric acid with a concentration of 2.5% (3% of the total raw material mass), synergistic bactericidal component of 0.3%, dipotassium glycyrrhizate and zinc citrate compounded in a mass ratio of 1:1.2, deionized water of 94.0%, stabilizer of 0.2%, and sodium pyrophosphate and disodium EDTA compounded in a mass ratio of 2.2:1. All raw materials are weighed with an accuracy of 0.001g. The compounded components are thoroughly mixed before use to ensure batch-to-batch consistency.

[0068] Preparation steps:

[0069] Pretreatment: Deionized water was introduced into a closed reactor, and the water temperature was controlled at 25℃ with an error of ±0.5℃. The stirring speed was 350r / min with a speed error of ±10r / min. The compound stabilizer was added and stirred for 12min with a time error of ±1min until it was completely dissolved. Then the compound synergistic bactericidal component was added and stirred for 8min with a time error of ±1min to obtain the pretreated solution. The dissolution and dispersion effects were verified by both visualization and component detection.

[0070] Main reaction: Sodium hypochlorite solution was added dropwise to the pretreatment solution at a rate of 0.6 mL / s (error ±0.05 mL / s) and a reaction pressure of 0.03 MPa (error ±0.005 MPa). After the addition was completed, the mixture was stirred for 25 min (time error ±1 min) to obtain a sodium hypochlorite base solution, ensuring that the raw materials were fully mixed and reacted.

[0071] Acidity adjustment and activation: 3% dilute hydrochloric acid was added dropwise to the sodium hypochlorite base solution at a rate of 0.4 mL / s (error ±0.05 mL / s). The pH value was monitored in real time with an accuracy of 0.01 and the available chlorine content with an accuracy of 1 mg / L. The final pH value was controlled to be 4.7 (error ±0.1) and the available chlorine content to be 100 mg / L (error ±2 mg / L). After the addition was completed, the solution was stirred at a constant temperature of 28℃ (error ±0.5℃) for 25 min (time error ±1 min) to achieve full synergy between available chlorine and synergistic components.

[0072] Post-processing: Cool the reaction solution to 25℃ (error ±0.5℃), let it stand for 8 minutes (error ±1 minute), and filter it through a microfiltration membrane with a pore size of 0.22μm at a filtration pressure of 0.1MPa to obtain the finished hypochlorous acid water. Store it in a sealed, light-proof container at 25±2℃.

[0073] Comparative Example 1:

[0074] The raw material ratio, by mass percentage, is as follows: sodium hypochlorite with an effective chlorine content of 10% (3.0% of the total raw material mass), citric acid with a concentration of 3% (2.5% of the total raw material mass), deionized water 94.0%, and sodium pyrophosphate stabilizer 0.5%. The raw material specifications are consistent with those in Example 1. The citric acid concentration was calibrated by acid-base titration to ensure that the concentration deviation is ≤0.1%.

[0075] Preparation steps: Except for replacing dilute hydrochloric acid with citric acid, which is commonly used in the prior art as an acid regulator, the other steps are completely the same as in Example 1. The final pH value is controlled to be 5.2 with an error of ±0.1. The preparation environment, equipment parameters, and storage conditions are the same as in Example 1 to ensure the fairness and accuracy of the comparison.

[0076] This comparative example simulates a typical technical solution in the prior art that uses traditional citric acid as an acidity regulator, and is used to compare and verify the technical advantages of the present invention using dilute hydrochloric acid as an acidity regulator compared to the prior art. Through comparative testing, the significant role of dilute hydrochloric acid in improving effective chlorine generation efficiency, product stability, and bactericidal effect is clearly demonstrated. This proves that the selection of dilute hydrochloric acid in the present invention is not a conventional replacement of the prior art, but a reasonable technical choice based on raw material characteristics and technical requirements. The results of three parallel experiments all show that the performance of the scheme in this embodiment is better than that of Comparative Example 1, with statistically significant differences (deviation > 2%).

[0077] Comparative Example 2:

[0078] The raw material ratio, by mass percentage, is as follows: sodium hypochlorite with an effective chlorine content of 10% (3.0% of the total raw material mass), dilute hydrochloric acid with a concentration of 8% (2.5% of the total raw material mass), deionized water 94.0%, and sodium pyrophosphate stabilizer 0.5%. The raw material specifications are consistent with those in Example 1. The concentration of dilute hydrochloric acid was calibrated by acid-base titration, with a concentration deviation ≤0.1%.

[0079] Preparation steps: Except for the use of 8% dilute hydrochloric acid, the other steps are completely consistent with those in Example 1. The final pH value is controlled to be 4.3 with an error of ±0.1. The preparation environment, equipment parameters, and storage conditions are the same as those in Example 1 to ensure the reliability of the comparative data.

[0080] This comparative example simulates a conventional technique in existing technologies that uses dilute hydrochloric acid as a regulator but fails to properly control its concentration. This technique represents a standard application of dilute hydrochloric acid in existing technologies. By comparing with Examples 1 and 2, the rationality of the dilute hydrochloric acid concentration range defined in this invention is verified, along with its technical advantages over the crude concentration control schemes in existing technologies. The analysis clarifies the crucial role of concentration optimization in improving product stability and usability. Test results show that the effective chlorine retention rate of the finished product in Comparative Example 2 after 14 days of storage is only 78.3%, far lower than 91.3% in Example 1 and 92.4% in Example 2. This demonstrates that the optimization of dilute hydrochloric acid concentration in this invention is not a routine parameter adjustment, but rather a targeted technical improvement to address performance fluctuations caused by crude concentration control in existing technologies.

[0081] Comparative Example 3:

[0082] The raw material ratio, by mass percentage, is as follows: sodium hypochlorite with an effective chlorine content of 10% (3.2% of the total raw material mass), dilute hydrochloric acid with a concentration of 3.5% (2.8% of the total raw material mass), deionized water 93.5%, stabilizer 0.5%, and sodium pyrophosphate and disodium EDTA compounded in a mass ratio of 2:1. The raw material specifications are consistent with those in Example 3, and all raw materials are accurately weighed with a weighing accuracy of 0.001g.

[0083] Preparation steps: Except for the absence of synergistic bactericidal components, the other steps are completely consistent with those in Example 3. The final pH value is controlled to be 4.8 with an error of ±0.1. The preparation environment, equipment parameters, and storage conditions are the same as those in Example 3 to ensure the validity of the comparison.

[0084] Key Explanation: This comparative example simulates a typical technical solution in the prior art that relies solely on hypochlorite as a single bactericidal component, while also incorporating the conventional application of compound stabilizers, representing a common combination in existing technologies. By comparing with Example 3, the technical advantages of this invention's synergistic bactericidal system, which introduces synergistic bactericidal components, are verified compared to existing technologies and related combinations. The significant role of the synergistic components in broadening the bactericidal spectrum, improving bactericidal efficiency, and reducing the amount of available chlorine used is clearly demonstrated. Test results show that Comparative Example 3 achieved a 99.97% bactericidal rate against Candida albicans within 1 minute, lower than the 99.999% of Example 3, and its storage stability was also significantly inferior to Example 3. This proves that the synergistic system constructed in this invention is not a simple superposition of existing technologies, but rather a rational technical optimization based on multiple bactericidal mechanisms.

[0085] Comparative Example 4:

[0086] The raw material ratio, by mass percentage, is: sodium hypochlorite with an available chlorine content of 10% (sodium hypochlorite accounts for 3.0% of the total raw material mass), and deionized water 97.0%. The raw material specifications are the same as in Example 1, with no other additives.

[0087] Preparation steps: Sodium hypochlorite and deionized water were directly mixed and stirred for 10 minutes at a stirring speed of 300 r / min. No acidity adjustment, stabilizer addition, or synergistic component introduction was performed. The natural pH value was 9.3, resulting in conventional hypochlorous acid water. The storage conditions were 25±2℃, protected from light, and sealed. The preparation environment was the same as that of other examples and comparative examples.

[0088] This comparative example simulates the most traditional method for preparing hypochlorous acid water in the prior art, serving as the basic solution for existing technologies. Through a comprehensive comparison with Examples 1 to 5, the technical advantages of the overall technical solution of this invention compared to existing traditional processes are verified. It is clear that this invention, through a combination of techniques such as dilute hydrochloric acid adjustment, introduction of synergistic components, addition of stabilizers, and optimization of process parameters, achieves a significant improvement in the overall performance of the product. Test results show that all performance indicators of Comparative Example 4 are significantly inferior to the series of products in the embodiments of this invention, proving that the overall technical solution of this invention is not a simple improvement or combination of existing technologies, but rather a technical solution with significant technological advancements.

[0089] Performance testing and results analysis:

[0090] Test sample:

[0091] The test samples were hypochlorous acid water prepared in Examples 1 to 5 and Comparative Examples 1 to 4. All samples underwent initial performance testing within 24 hours after preparation. The performance changes of the samples were also tested after 7 days and 14 days of storage. The storage conditions were sealed, protected from light, and room temperature of 25°C with an error of ±2°C. Three parallel test samples were set for each sample, and the test results were averaged to ensure the authenticity, comparability, and reliability of the test results, and to provide reliable experimental data support for the rationality verification of the technical solution.

[0092] Test items and methods:

[0093] (1) Test of available chlorine content: The iodometric method was used to determine the content according to the standard GB / T19106-2013. Each sample was tested three times and the average value was taken as the final test result. The test accuracy was 1 mg / L and the blank test deviation was ≤0.5 mg / L.

[0094] (2) Bactericidal effect test: Escherichia coli ATCC25922, Staphylococcus aureus ATCC6538, and Candida albicans ATCC10231 were selected as test strains. The activation and culture of the strains were carried out in accordance with GB4789.2-2016 standard. The quantitative bactericidal test of suspension was conducted in accordance with GB14930.2-2016 standard. The concentration of bacterial suspension was 1×10⁻⁶. 6 ~5×10 6 The sterilization rate of the sample after contacting the bacterial suspension with the bacterial suspension for 1 min, 5 min, and 10 min was tested at CFU / mL. Each sample was tested three times and the average value was taken. A sterilization rate of 99.99% or higher was considered qualified, and a sterilization rate of 99.999% or higher was considered excellent.

[0095] (3) Stability test: Test the available chlorine content of the sample after 7 days and 14 days of storage, and calculate the available chlorine retention rate. The available chlorine retention rate is equal to the available chlorine content after storage divided by the initial available chlorine content and then multiplied by 100%. Among them, a retention rate of 90% or above is considered stable, a retention rate of 85% or above is considered basically stable, and a retention rate of less than 85% is considered unstable.

[0096] (4) pH stability test: Test the initial pH value of the sample and the pH value after 14 days of storage, calculate the pH value change. The test uses a precision pH meter with an accuracy of 0.01, which is used after calibration. The pH value change is determined to be stable if it does not exceed 0.5, and unstable if it exceeds 0.5.

[0097] Table 1 Test Results

[0098]

[0099] Based on the above test results, a comprehensive analysis from four dimensions—selection of acid regulator, concentration optimization, construction of synergistic system, and overall technical solution—verifies the significant technical advantages and improved application value of this invention compared to existing technologies and related technology combinations. Furthermore, all test data are derived from the average of three parallel experiments, demonstrating high data reliability and fully supporting the rationality and feasibility of the technical solution of this invention.

[0100] (1) In terms of the selection of acid regulator, compared with Comparative Example 1, it can be seen that Example 1 uses dilute hydrochloric acid as acid regulator, and the initial effective chlorine content reaches 92 mg / L, which is 8.2% higher than the 85 mg / L of citric acid used in Comparative Example 1; the effective chlorine retention rate after 14 days of storage is 91.3%, which is 7.8% higher than the 84.7% of Comparative Example 1, and the pH change is only 0.3, which is much lower than the 0.6 of Comparative Example 1. This shows that dilute hydrochloric acid is significantly better than traditional citric acid regulator in terms of regulation accuracy, effective chlorine generation efficiency and product stability. This selection is not a routine replacement by those skilled in the art, but a reasonable optimization selection based on raw material characteristics and technical requirements.

[0101] (2) From the perspective of optimizing the concentration of dilute hydrochloric acid, the comparison between Example 1, Example 2 and Comparative Example 2 shows that Comparative Example 2 uses 8% high-concentration dilute hydrochloric acid. Although the initial effective chlorine content reaches 120 mg / L, the effective chlorine retention rate after 14 days of storage is only 78.3%, and the pH change is as high as 0.9. The product stability is extremely poor and cannot meet the actual application requirements. In contrast, Example 1 and Example 2 use 3% and 4% dilute hydrochloric acid, respectively. The effective chlorine retention rate after 14 days of storage is over 91%, and the pH change is ≤0.3. The stability is excellent, which proves that the concentration range of 1% to 5% dilute hydrochloric acid specified in this invention is reasonable and scientific. The concentration optimization is not a conventional parameter adjustment, but a key technical improvement to solve the performance fluctuation caused by the crude concentration of the existing technology. From the perspective of constructing a synergistic bactericidal system, comparing Example 3 with Comparative Example 3, it can be seen that after introducing the synergistic bactericidal components of dipotassium glycyrrhizate and zinc citrate, Example 3 achieved an effective chlorine retention rate of 93.1% after 14 days of storage, which is 5.2% higher than the 88.5% in Comparative Example 3 without synergistic components. The 1-minute bactericidal rate against Candida albicans reached 99.999%, which is significantly higher than the 99.97% in Comparative Example 3. This achieves the dual effect of broadening the bactericidal spectrum and improving the bactericidal efficiency. The construction of this synergistic system is not a simple superposition of existing technologies, but a reasonable optimization based on multiple bactericidal mechanisms, which can improve the bactericidal effect while reducing the amount of effective chlorine used.

[0102] (3) From the perspective of the overall technical solution, the advantages of Examples 1 to 5 compared with the traditional extensive process of Comparative Example 4 are more significant. The initial effective chlorine content of Comparative Example 4 is only 75 mg / L, the effective chlorine retention rate after 14 days of storage is only 72.0%, and the 1-minute sterilization rate of the three test strains is less than 99.5%, with extremely poor overall performance. In contrast, the initial effective chlorine content of the series of products in the present invention is all above 92 mg / L, the effective chlorine retention rate after 14 days of storage is all above 91.3%, and the 1-minute sterilization rate of Examples 3 to 5 of the three test strains reaches 99.999%, and the pH stability is excellent. At the same time, Examples 4 and 5 introduce processes such as pressure control, constant temperature stirring, and microfiltration post-treatment, which further improves the purity and industrial adaptability of the products, proving that the present invention has achieved a significant improvement in the overall performance of the products through the integration and optimization of multiple technical means. Furthermore, there is a clear technical progression between Examples 1 to 5, with continuous optimization of performance indicators. Example 5 integrates the advantages of various aspects, and all performance indicators reach the optimal level, proving that the technical solution of the present invention has good scalability and stability, and is not a technical effect obtained by chance. At the same time, each example verifies the wide applicability of the core raw material ratio and process parameters, providing a solid experimental basis for the promotion and application of the technical solution.

[0103] (4) The preparation method for improving the bactericidal effect of hypochlorous acid water provided by the present invention uses dilute hydrochloric acid as an acid regulator. By optimizing the raw material ratio, introducing compound synergistic bactericidal components and compound stabilizers, and improving the preparation method, the bactericidal efficiency, storage stability and applicability of hypochlorous acid water are significantly improved. All raw materials used are conventional industrial-grade raw materials, and the preparation equipment is also commonly used in the industry. The experimental process and parameters of each embodiment and comparative example are disclosed in detail. After multiple parallel experiments, the technical solution is stable, reliable and repeatable. It can be widely used in sterilization and disinfection scenarios in the fields of medical treatment, food processing, daily life and public health. It has positive significance for solving the core pain points of existing hypochlorous acid water preparation technology and promoting the technological upgrading and industrial development of the sterilization and disinfection field.

[0104] (5) The technical advantages of this invention compared to existing technologies and related combinations are specifically reflected in four core aspects: the rational application and optimization of dilute hydrochloric acid, the scientific construction of the synergistic bactericidal system, the systematic optimization of the preparation method, and the rational expansion of the applicable scope. Regarding the application and optimization of dilute hydrochloric acid, this invention addresses the shortcomings of existing technologies in selecting regulators by rationally using dilute hydrochloric acid as both an acidic regulator and a chlorine source auxiliary component. It optimizes and determines the concentration range of 1% to 5% and the precise dripping method, achieving precise pH control from 4.2 to 5.5, thus solving the problems of low precision and easy decomposition of effective chlorine in traditional regulators. Regarding the construction of the synergistic bactericidal system, addressing the limitations of single bactericidal components, it introduces a compound of dipotassium glycyrrhizate and zinc citrate to form a multi-mechanism synergistic bactericidal effect, broadening the bactericidal spectrum and reducing the amount of effective chlorine used, thereby achieving synergistic enhancement.

[0105] In terms of optimizing the preparation method, systematic steps such as pretreatment, segmented and controlled-rate dripping, and pressure control are adopted to improve the uniformity of raw material mixing and the sufficiency of reaction, enhance product purity and stability, and improve industrial adaptability.

[0106] In terms of expanding the scope of application, through extensive experimental verification, the applicable range of core raw material ratios and process parameters has been reasonably expanded to ensure excellent results can be achieved in a wide range and to guarantee the practicality of the technical solution.

[0107] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention.

Claims

1. A method for preparing hypochlorous acid water to improve its bactericidal effect, characterized in that, The raw materials used in the preparation consist of the following components by mass percentage: 3.0% to 3.8% sodium hypochlorite with an available chlorine content of 10% to 11%, 2.5% to 3.2% dilute hydrochloric acid with a concentration of 1% to 5%, 92.3% to 94.0% deionized water, and 0.2% to 0.5% stabilizer, wherein the stabilizer is sodium pyrophosphate, or a compound formed by mixing sodium pyrophosphate and disodium EDTA in a mass ratio of 2:1 to 2.5:1; the method is carried out in a closed reaction vessel equipped with a temperature sensor, a pressure sensor, and a mechanical stirring device, and specifically includes the following steps: (1) Pretreatment: The deionized water is introduced into a closed reaction vessel, the water temperature inside the vessel is controlled at 25°C to 28°C, the stabilizer is added, and the mixture is stirred at a stirring speed of 300r / min to 350r / min for 10min to 15min until it is completely dissolved to obtain a pretreated solution; (2) Main reaction: Sodium hypochlorite is added dropwise to the pretreatment solution at a rate of 0.5 mL / s to 0.7 mL / s. During the dropwise addition, the mixture is continuously stirred and the pressure inside the reactor is controlled at 0.03 MPa. After the dropwise addition is completed, the mixture is stirred at the same speed for 20 min to 30 min to obtain the sodium hypochlorite base solution. (3) Acidity adjustment and activation: The dilute hydrochloric acid was added dropwise to the sodium hypochlorite base solution at a rate of 0.3 mL / s to 0.5 mL / s. During the dropwise addition, the pH value of the reaction system was monitored in real time by a precision pH meter with an accuracy of 0.

01. The final pH value was controlled to be 4.2 to 5.

5. After the dropwise addition was completed, the temperature inside the reactor was adjusted to 28°C to 30°C and stirred at a constant temperature for 15 min to 30 min to achieve activation and stabilization of available chlorine. (4) Post-treatment: Let the acid-adjusted and activated reaction solution stand for 5 to 10 minutes, filter it with qualitative filter paper or microfiltration membrane with a pore size of 0.22 μm. When using microfiltration membrane, the filtration pressure is controlled at 0.1 MPa. After filtration, seal and store in the dark to obtain the finished hypochlorous acid water. The raw materials also include 0.3% to 0.4% of a synergistic bactericidal component, which is a compound of dipotassium glycyrrhizate and zinc citrate.

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