A method and apparatus for electrolysis of slightly acidic hypochlorous acid

Abstract

The application provides a slightly acidic hypochlorous acid electrolysis method and device, a method for improving the stability of electrolytic hypochlorous acid water, and a purification electrolysis method for improving the pH value of existing electrolytic acidic oxidized water to be slightly acidic. The electrolysis method and device adopt an existing two-layer electrode sheet electrolytic cell, and the hydrochloric acid is separated from the acid water between the electrodes to be the original acid water on the upper end of the panel between the positive electrode and the panel, and the outlet of the alkali water is slightly lower than the outlet of the electrolytic unit. The acid water conduit is connected to a plurality of units to form a combined parallel electrolytic cell. The interval surface (bottom) plate is the panel of the next layer unit and the bottom plate of the previous layer unit. The flow switches are arranged in the outlet pipes of the hypochlorous acid flow guide original acid water, the new hydrochloric acid outlet and the original alkali water outlet, and the flow ratio between them is adjusted to indirectly adjust the pH value of the electrolytic oxidized water. The slow electrolysis in series with the laminated electrolytic cell can improve the yield and stability. The degradation rate of the hypochlorous acid at room temperature is less than 10% in 3-6 months, and the stability agent is added to extend to 12 months.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of chlorine-containing disinfectants and the technical category of electrolysis of hypochlorous acid, and specifically relates to a slightly acidic hypochlorous acid purification electrolysis method and an electrolysis device aiming to improve the stability of hypochlorous acid. BACKGROUND

[0002] General traditional disinfectants are toxic to sterilization, and people give these toxic compounds the definition or name of disinfectants, which has certain health hazards and causes artificial secondary environmental pollution. A kind of oxide substance of immune invading microorganisms naturally produced by human white blood cells: hypochlorous acid, is harmless to human body by nature; in recent years, especially after "new crown", the bactericidal power is listed as the second strongest by WHO, and the hypochlorous acid is harmless to life safety, which is fired up, and the environment-friendly hypochlorous acid like a natural real disinfectant is gradually becoming a new industry of chlorine-containing disinfectants known by the public.

[0003] Hypochlorous acid was discovered early, in 1843, by French chemist Antoine Jerome Balard, who added a dilute suspension of mercuric oxide in water to a bottle of chlorine gas, and he named the acid and its salts. The anti-infective properties of hypochlorous acid were known before the use of hypochlorite solutions as antiseptics for war wounds during World War I. More recent studies have increased, such as in the 1940s, London hospitals began to use aerosol solutions containing hypochlorous acid to prevent the spread of pathogens in the air. In 1948, Knox et al. of the Department of Medicine of Columbia University in the United States first proposed that hypochlorous acid is a sulfhydryl inhibitor, and that the inhibition of glucose oxidation is the main factor of the bactericidal properties of chlorine solution. In 1976, American biologist Harrison, J. E. proved the existence of hypochlorous acid in the oxidative burst of white blood cells, and proved that hypochlorous acid has obvious bactericidal effect. French Corinne Le Dantec found that the killing effect of HClO on E. coli is 50 times that of hypochlorite anion, and HClO is hydrolyzed to ClO- above pH>6, published in "Applied and Environment Microbiology" 2002:68(3);1025-1032; Japanese Fukuzaki 2006 published in "Biocontrol Science" The bactericidal principle of hypochlorous acid, hypochlorous acid (HClO) is a small uncharged molecule that can instantly penetrate the membrane wall of the pathogen and enter the interior of the pathogen to cause an oxidation reaction, and the bactericidal force is 80-100 times that of sodium hypochlorite. The principle of its super-strong bactericidal force promotes the popularization and application of hypochlorous acid, and the natural safety of hypochlorous acid disinfection spreads from Japan to Europe and the United States. In 2002, the Japanese Ministry of Health, Labour and Welfare recognized hypochlorous acid as a food additive; Based on various experimental results, the Japanese Ministry of Agriculture, Forestry and Fisheries defined hypochlorous acid water as a specific pesticide (specific control agent, obviously no risk to humans, animals, aquatic products and agricultural products, etc.). In October of the same year, the United States CDC recognized weakly acidic hypochlorous acid as a high-level disinfectant. China's Ministry of Health included the application of acidic electrolyzed oxidizing water in the "Disinfection Technical Specifications" to guide the disinfection of endoscopes, hand disinfection, skin and mucous membrane and environmental object surface disinfection, etc.

[0004] In 2016, the U.S. Food and Drug Administration (FDA) has approved the product with the main active ingredient hypochlorous acid for the treatment of wounds and various infections. On December 27, the National Health and Family Planning Commission issued WS 310.2-2016, which clearly states the application index and method of acid electrolyzed oxidizing water (main component hypochlorous acid) in Part II: Cleaning, Disinfection and Sterilization Technical Operation Specification Appendix C. Hypochlorous acid has been recognized by the following authoritative agencies: World Health Organization Center for Disease Control, Australian Therapeutic Products Administration, U.S. Environmental Protection Agency, Japanese Ministry of Health, European Chemical Agency, and British National Health Service. China's development in the hypochlorous acid industry is relatively late. In April 2019, the People's Republic of China National Standard “Hygienic Standard for Chlorine-containing Disinfectants” GB / T 36758-2018 was implemented. The “New Coronavirus Pneumonia Diagnosis and Treatment Scheme (Trial Fourth Edition)” issued by the National Health Commission states that the virus is sensitive to ultraviolet light and heat, and can be effectively inactivated by 56°C for 30 minutes, diethyl ether, 75% ethanol, chlorine-containing disinfectants, and chloroform lipid solvents.

[0005] In addition to its strong bactericidal properties, hypochlorous acid is also safe. Humans have discovered that hypochlorous acid can be naturally produced by our neutrophils or white blood cells to resist microbial infection and inflammation. This makes hypochlorous acid a natural and friendly disinfectant. In detail, hypochlorous acid naturally exists in activated human neutrophils and other tissue phagocytes. This is due to the oxidative thrust of myeloperoxidase (MPO) on peroxidase and cytoplasm, which is catalyzed by the activation of phagocytes. Hypochlorous acid only acts on organic matter such as bacteria and viruses. When it enters human or animal cells, it is broken down by taurine on the cell surface and consumed by excess organic matter, without affecting the proteins and enzymes below the cell surface layer, so it is harmless to humans and animals. Hypochlorous acid kills bacteria such as Salmonella, Aspergillus niger, hand-foot-mouth disease virus, Norovirus, influenza B virus, poliovirus type I, H1N1 influenza virus, COVID-19 novel coronavirus, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Candida albicans, Shigella, mold, Bacillus subtilis black spore, etc. Hypochlorous acid disinfectant is suitable for general object surfaces in medical and health institutions, public places and households, medical equipment, medical supplies, food and drink, fabrics, fruits and vegetables, and water disinfection. It is also suitable for the treatment of various pollutants in epidemic sources, as well as for the safe disinfection of indoor air, secondary water supply equipment and facilities surfaces, hands and skin mucosa.

[0006] Currently, hypochlorous acid is mainly prepared by electrolysis and non-electrolysis: ① Polarization separation by electrolysis of brine to prepare, brine (lower than physiological salt concentration) is transported into electrolytic cell (or pool) for electrolysis, chloride ions tend to the positive electrode and react with water to generate acidic electrolytic water containing hypochlorous acid (pH 2-3), through ion permeable membrane, sodium ions tend to the negative electrode to form alkaline water (pH ~ 12) and hydrogen gas. ② Electrolysis of dilute hydrochloric acid and brine to prepare, a certain proportion of hydrochloric acid and brine are added to water and transported into the electrolytic cell for mixed electrolysis to generate chlorine gas dissolved in water to obtain acidic hypochlorous acid water and alkaline water, which is basically the same as electrolysis of brine. ③ Electrolysis of hydrochloric acid and pure water into proton membrane electrolytic cell respectively, chlorine ions cannot pass through the proton membrane and tend to the positive electrode to generate chlorine gas which is then dissolved in water to form acidic chlorine-containing water, and hydrogen protons pass through the proton permeable membrane to generate hydrogen gas at the negative electrode. ④ Non-electrolytic chemical method: sodium hypochlorite + hydrochloric acid neutralization reaction, multiple dosing devices are used to add sodium hypochlorite and hydrochloric acid into the water pipeline, and the two are mixed and reacted to generate hypochlorous acid water, by controlling the dosing ratio, micro-acidic hypochlorous acid (pH 6-6.5) mixed water is obtained; the two ions are not electrolyzed but only mixed with acid and base to show near neutrality on the surface, and the non-ionic hypochlorous acid content is not high; non-electrolytic hypochlorous acid uses low concentration (generally ≤80ppm), otherwise it contains too many acid and base electrolytes and cannot be used for food disinfection, and non-electrolytic method is not within the scope of this patent technology.

[0007] The hypochlorous acid electrolysis device mainly polarizes the flowing brine between two ruthenium / iridium electrodes (4-5mm apart) under the action of low voltage (6-15 volt) direct current power supply, the concentration of brine (0.1g%-1g%) is proportional to the electrolysis current (about 8-30 amperes), and chloride ions tend to the positive electrode to form hypochlorous acid water (130-1000ppm). Among them, the hypochlorous acid electrolytic cell is a titanium electrode coated with ruthenium / or titanium electrode coated with iridium / or titanium electrode coated with ruthenium and iridium (high-temperature sintered ceramic surface), which is a long rectangular outer packaging PE plastic sealed shell (see attached Figure 1 ) or a spiral outer packaging circular plastic shell with multiple layers of parallel-plate electrode sheets separated by a spacer membrane, one layer of positive electrode and one layer of negative electrode, multiple positive electrode layers are liquid-guided to one side, and all negative electrode liquids are concentrated and guided to the other side outlet; two water inlets and two water outlets on the front, or combined into one pipe for one inlet or one outlet. There are many commercial products of parallel-plate electrolytic cell at present 〔3-5〕 , but the parallel-plate electrolytic cell can only produce acidic water and alkaline water, and there are few research literatures on the preparation of acidic and alkaline electrolytic water parallel-plate electrolytic cell, and most of the patents for the preparation of acidic and alkaline electrolytic water parallel-plate electrolytic cell belong to improvement, and the development of electrolytic device for micro-acidic hypochlorous acid and the purification electrolytic cell for separating hydrochloric acid and hypochlorous acid in acidic water become demand-oriented 〔6-7〕 .

[0008] Hypochlorous acid is not stable like many oxidants, hypochlorous acid molecules only exist in pH 4-7 aqueous solution, mixed with hydrochloric acid and chlorine at pH 2-3, below pH 1.0 only dissolved chlorine and hydrochloric acid. Greater than pH 7 with hypochlorite salt, sodium hypochlorite disinfection release of hypochlorous acid content is very low, pH 10.0 release hypochlorous acid content is only 0.26%, the higher the alkalinity release content is lower, such as to achieve the same disinfection effect, the need for high concentration of large dose of sodium hypochlorite, resulting in chemical residues, irritability and corrosive. To the reducing molecules, viruses, bacteria surface molecules only need hypochlorous acid millionth PPM concentration can be oxidized to kill, generally air, surface and hand disinfection 200 PPM, food environment disinfection 80 PPM, kill bacterial spores only 30 PPM. And the human body surface rich in negative electron organic matter, low concentration of PPM hypochlorous acid seconds to be consumed light (than the sun luo off a layer of epidermis less than a small layer of molecules to stop), this is also the deep mechanism of hypochlorous acid on the human body safety. Electrolytic hypochlorous acid for acid electrolytic water is not stable because of containing hydrochloric acid, at room temperature about 2-5% per day rate of spontaneous degradation. Stability is also affected by the production of water, process flow and packaging materials, storage temperature, light, even volume, concentration, hypochlorous acid in solution occurs in three forms of decomposition, they are independent of each other, called parallel reaction, namely:

[0009] 2HClO→2HCl+O2↑

[0010] HClO+HCl→H2O+Cl2↑

[0011] 3HClO→2HCl+HClO3

[0012] Under the direct action of sunlight, according to the first form of decomposition; in the presence of dehydrated material (such as CaCl2), according to the second form of decomposition; the chlorine produced by the molecular form of dissolution in water makes the hypochlorous acid water yellow. Heating is particularly prone to third form of decomposition (quote baidu baike).

[0013] In view of the poor room temperature stability of acidic electrolytic water, most electrolytic hypochlorous acid is currently produced on-site, but modern users are reluctant to engage in excessive "professional" operations, and stable on-site hypochlorous acid disinfectant water is exactly what is needed in today's fast-paced society. The instability of acidic electrolytic water is due to the presence of hydrochloric acid, and the degradation of hypochlorous acid by light and heat also produces hydrochloric acid, which further promotes degradation and enters a vicious cycle. The present invention "a method and device for electrolyzing slightly acidic hypochlorous acid" solves the problem of producing a mixture of hydrochloric acid and hypochlorous acid in existing electrolytic hypochlorous acid technology, and purifies and removes the contained hydrochloric acid. The electrolytic device is provided with a hydrochloric acid and hypochlorous acid separation outlet, and the electrolytic cell is innovated to have three water outlet pipes, i.e., a hydrochloric acid and hypochlorous acid outlet separation two water pipes and an alkali water outlet pipe. The electrolytic oxidation of acidic water is basically solved, and the purified slightly acidic hypochlorous acid with a pH of 4-6 after removing hydrochloric acid improves its stability to less than 10% degradation at room temperature for 1-3 months; combined with a 5-11 layer production type electrolytic cell, it is improved to less than 10% degradation in 3-6 months according to the national standard; and with a stabilizer, the stable hypochlorous acid disinfectant solution has less than 10% degradation at room temperature for 12 months or more.

[0014] References:

[0015] (1) Corinne Le Datec, Applied and Environment Microbiology 2002; vol. 68(3): 1025-1032.

[0016] (2) Fukuzaki S et al., Biocontrol Science 2006, vol. 11(4), 147-57.

[0017] (3) Zheng Jizhou et al., Electrolytic cell structure of an electrolytic device, Chinese patent CN201280022422.8.

[0018] (4) Zheng Yu, A laminated mixed electrolytic cell, Chinese patent CN202020040351.6. (5) Zheng Yu, A laminated electrolytic cell for generating acid and alkali electrolytic water, Chinese patent CN202020035460.9.

[0019] (6) Chen Xin Hong, A pure hypochlorous acid electrolytic device with adjustable pH, Chinese patent CN20210630956.X.

[0020] (7) Sun Zhichao, A production method for improving the stability of hypochlorous acid solution, Chinese patent CN20191337543.1. SUMMARY

[0021] "Micro-acidic hypochlorous acid electrolysis method and device", characterized by: a micro-acidic hypochlorous acid electrolysis method for improving the stability of existing electrolytic acidic water and increasing its pH from 2.7 to 4-5.5, the electrolysis method and device are to remove hydrochloric acid in the electrolytic mixed acidic water to prolong the storage stability of hypochlorous acid water, and the acidity between the positive and negative electrodes is reduced after the most acidic water near the positive electrode is guided away. The two-layer electrode stack electrolytic cell with an electrode spacing of 4-9 mm is changed to a purified electrolytic cell that separates hydrochloric acid and hypochlorous acid, the most acidic water next to the positive electrode is guided to a point slightly below the original acid water and alkali water outlet between the positive electrode and the panel, and a new hydrochloric acid outlet is opened at the opposite electrode frame position, the micro-acidic hypochlorous acid between the positive and negative electrodes is guided to a corner of the original acid water outlet, and the negative electrode surface alkaline water is still guided to the opposite corner of the original alkaline water outlet, the three outlet pipes of the hydrochloric acid and hypochlorous acid separation outlet and the alkali water outlet are provided with flow switches and their flow ratio is adjusted to indirectly adjust the pH value of the hypochlorous acid water; the two-layer purified electrolytic cell is used as a basic unit, a common hydrochloric acid conduit is connected to 2-3 or even 4-5 units to form a combined purified electrolytic cell, which can be used as a mass production electrolysis device, every two-layer electrode unit is separated by a panel (bottom), the second to fifth electrolytic cell unit panel is the panel of the next layer and the bottom of the previous layer, and the newly opened hydrochloric acid outlet conduit on the panel penetrates through all the stacked layers of the combined electrolytic cell like the original acid water outlet and alkali water outlet; the device of the two-layer electrode electrolytic cell / or combined purified electrolytic cell is assembled into an instrument and a slow electrolysis method as follows:

[0022] 1) Electrolysis device power supply, electrolytic cell is separately equipped with a stable voltage of 10-24V but allows a maximum of 36-50A direct current power supply, water pump power supply selects a stable voltage of 12-24V and a maximum of 15-30A direct current power supply according to the flow power;

[0023] 2) The device water pump selects a variable flow of 0.2-2L per minute of large torque motor frequency conversion micro water pump, the water pump can share a power supply with other accessories and control single board machine in the device, and the salt water is pumped at a slow speed of less than 1L per minute;

[0024] 3) On-line industrial pH meter for real-time monitoring of hypochlorous acid outlet pH value, and digital ammeter for indicating relative effective chlorine content estimate, as well as other accessory indicator lights, switches, and control single board machine, PE water pipes and wires are used to connect the electrolytic cell and related accessories in a machine box / cabinet to form an electrolysis device;

[0025] 4) Salt water 0.1g%-1.0g% -1.0L / minute flow rate pumped into electrolysis to improve salt water electrolysis efficiency 30%, different concentrations of salt water under the action of >1.25V / mm stabilized ruthenium / iridium electrode current to produce about 100-1000ppm hypochlorous acid water, outlet alkali water by 10%-20% proportion through a shunt water pipe and switch after direct return to the raw material inlet to improve the electrolysis efficiency 30%, electrolytic acid water mixed with part of hydrochloric acid to reduce its pH value, purified electrolytic tank to separate hydrochloric acid and hypochlorous acid and set switch to adjust the hydrochloric acid outlet flow, hypochlorous acid water after separation of hydrochloric acid, its pH value increases to pH4-pH5.5 slightly acidic, hypochlorous acid stability from the lack of half a month of acidic electrolytic water to room temperature 1-3 months degradation less than 10%.

[0026] According to the micro-acidic hypochlorous acid electrolysis method and device, the two-layer electrode purification electrolytic tank is a two-layer electrode purification electrolytic tank with enlarged electrode spacing, the standard electrode spacing of 4mm is enlarged to 6-9mm, a layer of 2-5mm thick positive electrode frame is added between the two-layer laminates of the original positive and negative electrode frames, but the electrode sheets and separators therebetween are not included / removed, the original acid water flow channel on the empty frame negative side is retained, and the positive side / surface thereof is increased with an arc-shaped flow guide for directing the outlet of the acid water as the outlet of the hypochlorous acid, a hydrochloric acid outlet is additionally opened on the surface plate between the positive electrode and the surface plate, and the hydrochloric acid outlet is slightly below the middle of the original acid water and alkali water outlets on the surface plate but still corresponds to the position of the electrode frame, a stabilized 20-24V maximum 36-50A direct current power supply is used as the power supply; the two-layer electrode purification electrolytic tank is used as a basic unit, 2-3 units are stacked in parallel to form a combined purification electrolytic tank to improve the yield, a surface (bottom) plate is added between every two-layer electrode units, a hydrochloric acid outlet is additionally opened on the surface plate slightly below the middle of the two corners on the upper end of the surface plate but still corresponds to the position of the frame, and a left-right symmetrical arc-shaped flow guide is newly engraved between the position of the electrolytic cavity of the surface plate and the hydrochloric acid outlet, the surface plate of the second and third electrolytic tanks is the surface plate of the next layer tank and the bottom plate of the previous layer tank, and the newly opened hydrochloric acid outlet, like the original acid water and alkali water outlets, penetrates all the laminate layers of the combined electrolytic tank, a stabilized 20-24V maximum 36-50A direct current power supply is used as the power supply; the purification electrolytic tank is used in combination with the existing conventional 5-11-layer stacked electrolytic tank, the conventional 5-11-layer stacked electrolytic tank is first used to electrolytically produce sufficient mixed acid water, and the first alkali water 10%-20% is returned to the raw material inlet, the mixed acid water is connected to the inlet of the two-layer electrode purification electrolytic tank or the multi-combined purification electrolytic tank for secondary electrolysis and separation and purification of hypochlorous acid, the number of layers of the two-layer to multi-combined purification electrolytic tank and the stacked electrolytic tank to be matched is determined according to actual requirements; the power supply of the conventional stacked electrolytic tank and the power supply of the purification electrolytic tank are respectively selected from two separate stabilized 8-15V and 20-24V maximum 36-50A direct current power supplies, which can be suitable for some application sites to be made and produced on site.

[0027] According to the micro-acid hypochlorous acid electrolysis method and device, characterized in that: the purification electrolytic cell is combined with 9-11 stacked electrolytic cells and 7-9 stacked electrolytic cells in series, and the salt water is pumped into the conventional 9-11 stacked electrolytic cell at a rate of 0.5L per minute for the first electrolysis, and 10%-20% of the outlet alkali water is taken through a shunt pipe and a switch and is returned to the raw material inlet, the first alkali water outlet switch is also closed a little to force the 10-20% of the electrolytic cell alkali water to the acid water outlet, thereby improving the efficiency of the second electrolysis, and the remaining alkali water is discarded or used; the mixed water of hydrochloric acid and hypochlorous acid from the first electrolysis is input into the conventional 7-9 stacked electrolytic cell for the second electrolysis, thereby increasing the electrolysis efficiency by 60%, and the forced alkali water increases the electrolysis efficiency by 30%, most of the salt is converted into hypochlorous acid molecules, and the alkali water is discarded or used; the secondary acid water is input into the purification electrolytic cell for the third electrolysis and purification of hypochlorous acid, and the hydrochloric acid and alkali water are used separately; the repeated electrolysis improves the electrolysis efficiency by more than 1 times or even more than 1.5 times, and the stability of the hypochlorous acid is improved to less than 10% degradation in 3-6 months at room temperature.

[0028] According to the micro-acid hypochlorous acid electrolysis method and device, characterized in that: the micro-acid hypochlorous acid produced by the comprehensive electrolysis method is added with a step of removing residual sodium chloride, the stability of the hypochlorous acid is improved to less than 10% degradation in 6 months or more at room temperature; the micro-acid hypochlorous acid is stored in a cool place for more than 12 months after adding the self-made weak alkaline stabilizer (1000x liquid), the effective chlorine reduction rate is less than 10%, and the degradation is accelerated to be less than 10% after being placed in a 54C incubator for 14 days.

[0029] According to the micro-acid hypochlorous acid electrolysis method and device, characterized in that: the purification electrolytic cell and various stacked electrolytic cells and accessories are assembled into an instrument, the two-layer electrode electrolytic cell / or combined purification electrolytic cell and existing stacked electrolytic cell, the pH meter online monitoring the hypochlorous acid outlet, the digital ammeter monitoring the electrolysis current as the effective chlorine content estimation, and other accessories such as indicator lights, switches, and control single board, and the PE water pipe and wire are used to connect the electrolytic cell and related accessories in a machine case / or cabinet into an electrolysis instrument.

[0030] WHO listed hypochlorous acid (HCIO) as the second super-strong chlorine-containing disinfectant after chlorine dioxide, which has 5 times the germicidal ability of HCIO. However, chlorine dioxide degrades in water in just 20 minutes, and solid effervescent tablets are generally used. The germicidal ability of HCIO is about 100 times that of the same amount of hypochlorite (CIO-), and low-concentration HCIO is super-friendly and safe because it is consumed by excessive organic matter in a matter of seconds. Therefore, undiluted HCIO is a superior and preferred safe and efficient disinfectant over sodium hypochlorite (84 liquid) and calcium hypochlorite bleaching powder, but the pain point is that electrolytic acidic HCIO water contains hydrochloric acid, increasing its corrosiveness and instability. Freshly prepared electrolytic HCIO water can only be stored for a few days to a few weeks before it becomes inactive, provided that the stability of HCIO products is addressed to extend the shelf life of HCIO water (degradation of less than 10%) for more than a year.

[0031] To verify whether hydrochloric acid is the main reason for the instability of HCIO and other factors affecting stability, find ways to improve the shelf stability of HCIO water and reagents. First, we need to establish a basic HCIO electrolysis device and test the improved effect of the electrolytic tank on separating hydrochloric acid / HCIO, the detection method and instrument of the effective chlorine content of HCIO water, and the efficient test of the stability of HCIO and other influencing factors, and research the final solution or system of the shelf stability of HCIO water. According to the national standard "Hygienic Requirements for Chlorine-containing Disinfectants" GB / T36758-2018 and "Hygienic Requirements for Acidic Electrolyzed Water Generators" GB28234-2020, and referring to the technical requirements, the following self-made electrolysis device and electrolytic tank improvement, electrolysis test and chlorine content monitoring, HCIO stability test and stability extension are gradually completed to establish a micro-acidic HCIO electrolysis combined device that can be stable at room temperature for 3-6 months.

[0032] I. HCIO electrolysis device and electrolytic tank improvement:

[0033] The core of the HCIO electrolysis device is the electrolytic tank, which is composed of titanium metal positive and negative electrode plates with ruthenium / iridium metal plated on the surface, with a narrow gap between them. The electrolytic cavity is 4-5 mm apart between the 1 mm thick positive and negative electrode plates. An isolation membrane can be inserted between the positive and negative electrodes. The outer package is a PE plastic shell and screw seal. A certain concentration of sodium chloride / potassium chloride brine is polarized in the electrolytic cavity, and the chloride ions tend to form HCIO water and hydrochloric acid and chlorine gas mixed acidic water at the positive electrode, while the sodium ions tend to the negative electrode (crossing the cation membrane or "paper" diaphragm) and the negative electrode water molecules OH - Alkaline water and protons H +Electron after the formation of hydrogen. In order to continuously produce hypochlorous acid electrolytic water, set up the continuous flow of salt water through the electrolytic cavity, from the lower end of the inlet pump salt water, outlet is placed in the upper end is convenient for chlorine, hydrogen gas to go up and not easy to be gas blocked water flow, anode layer of acidic water by the cavity flow to the side of the electrolytic cell outlet, negative electrode layer of alkaline water is preset to flow to the other side of the electrolytic cell outlet. Two pieces of electrode electrolysis hypochlorous acid production tends to be limited, increase the electrode area is not only inconvenient operation but also due to two pieces of large electrode is not parallel and easy to close short circuit or only "short circuit" place electrolysis, multiple stacked sheet parallel type electrolytic cell to solve the various specifications of production demand, a general standard of high 12 × 7 cm wide electrode sheet layer of anode stacked layer of negative electrode interval electrolytic cavity and 13 × 7.6 cm diaphragm, separated by multiple anode layer liquid cleverly be concentrated to one side of the communication port, separated by all the negative electrode liquid is directed to the opposite side of the common outlet; the corresponding lower end of the two side inlet and outlet diagonal symmetry, the outer shell of the front lower end of one side of the inlet tube in the cavity connected to the upper end of the diagonal side of the outlet (and are located in the diaphragm the same side); also two into one or two out of one out of the common pipe, standard electrolytic cell internal structure see standard picture (attached Figure 1 ) Can be set to 3, 5, 7, 9 and 11 layers of sheet (electrode sheet number) parallel specifications, anode than negative electrode set a layer is because the negative electrode alkaline water production than the anode acidic water and balance.

[0034] Electrode sheet embedded in high 20 cm × 10 cm wide thick 5 mm hard PE plastic frame, connecting electrode wire from the plastic frame side or lower part of the lead, multiple stacked sheet (such as attached Figure 1) After that, cover the front with a plastic panel of the same size as the frame and a stainless steel bottom plate lined with a silica gel film, and fasten it with stainless steel screws to form an electrolytic cell. Under the action of a low-voltage (6-15V) direct current power supply, the present 1-2L / min flow pump into the salt water between the two ruthenium / iridium electrodes (4mm apart) polarization, the salt water concentration (0.1g%-1g%) and electrolytic current (about 8-30A amperes) are proportional, chloride ions tend to positive electrode to generate hypochlorous acid water (150-1000ppm). But the electrolysis of salt water is very incomplete, according to sodium chloride 0.1g / 100ml (0.1g÷58.44)÷0.1L=0.017M, and according to 150ppm hypochlorous acid (0.15÷52.46)÷1L=0.00286M, because the volume of hypochlorous acid after electrolysis is half of the raw salt water, the calculation molecular ratio is 0.017M÷(0.00286÷2)=11.9, electrolytic hypochlorous acid accounts for only one tenth of the original material molecules, plus hydrochloric acid and chlorine molecules, more than 20% of the raw material sodium chloride is electrolyzed. The test and results of this patent prefer a multi-layered electrolytic cell, Guangdong Dongguan Zhongrui Electrode Industrial Technology Co., Ltd., and Guangdong Foshan Haishi Kelai Technology Co., Ltd. electrolytic cell. Homemade electrolysis instrument: power supply selection of 12V and maximum current 36-50A DC power supply, micro water pump selection of adjustable flow 0.2-2L per minute large torque motor, slow rotation micro pump, and industrial online 1-14pH meter and direct current current indicator.

[0035] Selection of electrode spacing film: like water electrolysis of hydrogen proton permeable membrane or hydrogen fuel cell proton membrane, the main types are perfluorosulfonic acid membrane, fluorine ion and phosphoric acid-based polymer, mica proton membrane and ceramic nanometer diaphragm, etc. Hydrochloric acid water electrolysis selects proton permeable membrane, pumps hydrochloric acid into the side of the diaphragm connected to the positive electrode, and pure water into the other side of the diaphragm connected to the negative electrode, respectively double into the proton membrane electrolytic cell for electrolysis, chlorine ions cannot pass through the proton membrane, on one side of the positive electrode to generate chlorine gas and acid containing chlorine water, hydrogen protons pass through the proton permeable membrane to generate hydrogen gas at the negative electrode; or no diaphragm electrolysis positive electrode generates chlorine gas and acid containing chlorine water, hydrogen protons at the negative electrode are more likely to form hydrochloric acid. Salt water electrolysis selects ion permeable membrane or inorganic material paper membrane, and sends salt water (lower than physiological salt concentration) into the electrolytic cell (or pool) for electrolysis, chloride ions tend to the positive electrode to react with water to generate hypochlorous acid and hydrochloric acid and chlorine gas acidic electrolytic water (pH 2-3), sodium ions tend to the negative electrode to form alkaline water (pH ~ 12) and hydrogen gas; saturated salt water (2-3g%) electrolysis can be without diaphragm and mainly form chlorine gas.

[0036] Electrolytic cell improvement: the existing multi-layer electrolytic cell increases production or yield, but the concentrated positive acid water is guided to one side outlet, which limits its further separation and purification. According to its design idea, at most it can achieve two-way outlet of acid water and alkali water separation, and the hydrochloric acid and slightly acidic hypochlorous acid in the acidic electrolytic water are not separated. The improvement idea is to separate the hydrochloric acid and hypochlorous acid and then discharge them through different outlets of the electrolytic cell, plus the alkali water outlet, a total of three water outlets. The electrolytic cell can only increase one positive hydrochloric acid outlet on the basis of a two-layer electrolytic cell. After selecting a commercial three-layer electrolytic cell, remove one layer of positive electrode sheet including its 5mm thick frame from the bottom layer, and increase a layer of plastic (positive) frame between the original two layers of positive and negative electrode sheets including the frame. However, the thickness of the frame is 2-5mm, and the electrode sheet and the diaphragm between them are not included (removed), the arc-shaped flow guide channel on the negative alkali water side of the empty frame is retained, but the positive side / surface is increased with an arc-shaped flow guide (attached Figure 2 ) engraved on the original acid water outlet. A hydrochloric acid outlet is added on the upper surface of the panel between the upper end of the positive electrode sheet and the panel (lower than the original acid and alkali water outlets, and the three outlets form an inverted triangle), and the improvement is shown in the picture (attached Figure 3 ). The two two-way two-outlet PE pipes on the original plastic panel can be replaced by a larger three-way PE pipe, and the new hydrochloric acid outlet is a small two-way pipe. The flow switch is used to adjust the shunt ratio of hydrochloric acid and hypochlorous acid, and then indirectly adjust the pH value of the hypochlorous acid outlet. The pH value of the hypochlorous acid is monitored online to adjust it to pH 4-pH 5.5. The production of purified slightly acidic hypochlorous acid without corrosive hydrochloric acid can improve the stability from room temperature 3-14 days to room temperature 1-3 months with less than 10% degradation; after being used with the existing 5-11 layer mass production type electrolytic cell, it is further improved to room temperature 3-6 months with less than 10% degradation; the product hypochlorous acid is stable at room temperature for 6-12 months and above with less than 10% degradation after adding a self-made weak alkaline stabilizer to the slightly acidic hypochlorous acid with pH 5-6.5.

[0037] II. Detection of effective chlorine content in hypochlorous acid water

[0038] Chlorine-containing disinfectants refer to disinfectants that can generate hypochlorous acid in water, which mainly rely on the hypochlorous acid molecules released by hydrolysis to achieve the purpose of sterilization and disinfection. The concentration of hypochlorous acid molecules in the solution is extremely difficult to detect, and it is generally calculated by detecting the concentration of effective chlorine to calculate the content of hypochlorous acid. Effective chlorine refers to the oxidizing state chlorine contained in chlorine-containing compounds. Oxidizing state chlorine can release its oxidizing property in oxidation-reduction reactions and be reduced to a reduced state chlorine

natural stable state

[0039] So the following tests and results are used to calculate the hypochlorous acid content by detecting the effective chlorine concentration of acidic electrolytic water and hypochlorous acid. When the effective chlorine content is in the range of 10-500 ppm, use Changchun Jilin University Small Swan Instrument Company GDYS-104SM effective chlorine detector. The results are accurate (highly consistent with the national standard GB / T36758-2018 Appendix A effective chlorine iodine method detection results). When the effective chlorine content exceeds 600 ppm, dilute it with pure water by 1-2 times immediately before detection (the final content x 2-4); when the effective chlorine content is in the range of 100-2000 ppm, use Shanghai Sanais Reagent Co., Ltd. Chlorine test paper. The depth of the brown color is proportional to the concentration. The test paper is relatively fast and simple, but it can only estimate the content in a rough range (100 ppm interval).

[0040] III. Degradation test of the intrinsic cause of hypochlorous acid stability:

[0041] The national standard GB / T36758-2018 stipulates that within the product validity period, the effective chlorine decline rate shall not exceed 10%, the effective chlorine content of liquid chlorine-containing disinfectant shall not be lower than the lower limit of the marked value, and the product validity period shall not be less than 6 months. In addition to the possible intrinsic main factors of hydrochloric acid, the storage temperature, the volume of the sub-packaging body and the packaging material (packaging material) also affect the stability of hypochlorous acid. Generally, electrolytic hypochlorous acid is stored at 4 0 C refrigerator refrigeration degrades at a rate of about 2% per day, and storage at room temperature degrades at a rate of about 5% per day, and accelerated degradation at elevated temperature. For example, storage at 37 0 C for 3 months degrades ≤10%, which is equivalent to a validity period of two years, and storage at 54 0 C for 14 days degrades ≤10%, which is equivalent to a validity period of one year (Disinfection Technical Specification 2002 Edition), and storage at 54 0 C can accelerate the "degradation test" process.

[0042] The degradation rate of hypochlorous acid is much smaller than 1% or even 0.1% after being frozen into ice blocks at zero, and only after being melted into water does it degrade at a rate of 1-2%.

[0043] Electrolytic hypochlorous acid is easy to accumulate on the surface of the liquid when it is packed in large volumes (20 kg or more) and high chlorine content, and the degradation rate is also accelerated when the volume of the bottle is reduced. When 1.0 ml of hypochlorous acid is packed in a 1.5 EP plastic tube, the degradation rate is increased by about 5-10 times. Hypochlorous acid (1.0 ml) is added to the corresponding dose of different reagents, and the chlorine content can be quickly evaluated within a few days (using chlorine test paper). Different packaging materials also significantly affect the stability. The degradation is the least when using 1# polyester plastic bottles with dense and smooth surfaces. The 2-7# plastic bottles are easy to oxidize with hypochlorous acid and consume hypochlorous acid. Even stainless steel is also oxidized by hypochlorous acid.

[0044] 1. Hypochlorous acid destruction test by different concentrations of hydrochloric acid:

[0045] The pH of the electrolytic acid hypochlorous acid in 0.1 g% concentration of brine is about pH 2.7, and the pH of the saturated concentration of brine electrolytic acid water is less than or equal to pH 2. In order to test the effect of different concentrations of pure hydrochloric acid on hypochlorous acid, fresh hypochlorous acid was diluted to different concentrations of 10mN, 1mM, 0.4mM, 0.2mM, 0.1mM, 0.05mM, 0.02mM, 0.01mM concentration gradient, and 1ml was taken into 1.5EP plastic tube at room temperature. The test paper was used to test the available chlorine content of hypochlorous acid every day. The hypochlorous acid containing hydrochloric acid more than 0.1mM was completely degraded in 1-3 days without chlorine content (the test paper was white), and the hypochlorous acid containing hydrochloric acid less than 0.1mM and the control group of hypochlorous acid without hydrochloric acid were degraded in about 4 days without chlorine content (the test paper was white).

[0046] The pH of the pure water diluted 10mM, 1mM, 0.1mM, 0.01mM, 0.01mM pure hydrochloric acid is pH 2.0, pH 3.0, pH 4.0, pH 5.0, pH 6.0 respectively, which is consistent with the report of encyclopedia and textbook. According to the theoretical calculation, the acid hypochlorous acid with pH about 2.7 should contain about 2.6mM of hydrochloric acid, and the molecular quantity is about equal to 150ppm of hypochlorous acid 2.86mM content. The hydrochloric acid and pure hypochlorous acid account for half of the yield of acid electrolytic water, or half of the acid electrolytic water is hydrochloric acid. According to the above destruction test of hydrochloric acid on hypochlorous acid, the destruction dose of 0.1mM, the hydrochloric acid in acid electrolytic water is 26 times and above of the destruction dose, and the hydrochloric acid seriously causes the degradation of hypochlorous acid and initiates the degradation vicious cycle. The electrolytic hypochlorous acid water can basically curb the degradation caused by hydrochloric acid as long as the pH value is greater than pH 4.0.

[0047] 2. The destruction test of other substances on hypochlorous acid:

[0048] The pure water was added with fresh hypochlorous acid by the same dilution method, and 1ml of dilution gradient was taken at room temperature every day to measure chlorine. The results showed that the hypochlorous acid containing >2% pure water was degraded successively in 3 days, and the hypochlorous acid containing ≤1% pure water was degraded in 4-5 days without increasing the original degradation rate. Therefore, the hypochlorous acid can only be used as a disinfectant, and the hypochlorous acid cannot be diluted for use, even if the pure water is used to dilute the hypochlorous acid, the stability of the hypochlorous acid is destroyed, and the disinfection effect is lost soon after dilution. Similarly, tap water test, hypochlorous acid containing ≥1‰ tap water (even one ten thousandth) is degraded soon. The electrolysis of brine cannot be prepared with tap water and crude salt, and pure water must be used to prepare pure salt reagent.

[0049] Sodium chloride is added to fresh hypochlorous acid by equal dilution, and 1 ml of each dilution gradient is taken to measure chlorine at room temperature every day. The results show that hypochlorous acid containing more than > ~ 1 mM sodium chloride accelerates degradation, and salt is also a factor that destroys the stability of hypochlorous acid. Saline (0.1% = 17 mM) still contains 17 x 70% = 12 mM sodium chloride after 30% electrolysis, and it is still necessary to greatly improve the efficiency of electrolysis (salt conversion to hypochlorous acid) and remove 90% of sodium chloride, which is also a prerequisite for stable electrolysis of hypochlorous acid. Similarly, the effect of sodium hydroxide is more complex. Over-concentration (> 20 mM) not only does not significantly increase stability, but also promotes the conversion to hypochlorite salt. The effective chlorine content of sodium hypochlorite is very low, and the disinfection capacity is proportional to the decrease. Precise 1-2 mM sodium hydroxide improves the stability of electrolytic hypochlorous acid. Any trace of organic matter, including polymers, also accelerates the degradation of hypochlorous acid, so even if hypochlorous acid is accidentally drunk / or taken orally, it will be instantly degraded by the excessive organic matter and high concentration of gastric acid in the stomach.

[0050] 3. Hypochlorous acid electrolysis efficiency test:

[0051] The electrolysis efficiency of saline water with different substances, 5 mM hydrochloric acid can produce ~ 140 ppm hypochlorous acid, and its yield is 2-3 times higher than 0.1 g% sodium chloride (pump speed 2 L / min flow rate) to produce 100 ppm. The saline water with added hydrochloric acid only adds the two, and the synergistic effect is not great; adding oxygen and carbon dioxide has no effect, adding sodium carbonate and sodium acetate slightly promotes electrolysis, and saline water containing a large amount of bubbles has a certain effect on promoting electrolysis (bubbles delay the flow rate of saline water, and the yield is 150 ppm at a pump speed of 1 L / min); different concentrations of sodium hydroxide have different effects on promoting electrolysis, and a final concentration of < 1 mM has no effect. Adding ≥ 2-3 mM base + 0.1 g% salt electrolysis yield is 180 ppm, an increase of more than 30%-50%; raw saline water + 10%-20% electrolytic alkali water can also increase the yield of hypochlorous acid by 30%.

[0052] Repeated electrolysis helps to improve efficiency, and repeated electrolysis is to input the electrolyzed acid water into the electrolytic cell as raw material for electrolysis again. The concentration of 0.1 g% sodium chloride is 100 ppm of hypochlorous acid at a pump speed of 2 L / min flow rate, and the second electrolysis yield is 145 ppm, the third electrolysis yield is 180 ppm, the fourth electrolysis yield is 200 ppm, the fifth electrolysis yield is 215 ppm, and the sixth electrolysis yield is 221 ppm. It no longer increases. The efficiency increases the fastest when the electrolysis is repeated twice, and the third, fourth and fifth times are basically close to the peak yield. In theory, hypochlorous acid does not conduct electricity, and the current of repeated electrolysis should change as the salt concentration decreases and the hypochlorous acid increases, but the electrolysis current only decreases by 10% after the fourth and fifth repeated electrolysis. It can be seen that hydrochloric acid plays a significant role.

[0053] Four, electrolysis of slightly acidic hypochlorous acid and combined method:

[0054] Purification electrolytic tank electrolysis micro-acid hypochlorous acid: the two-layer electrode purification electrolytic tank (attached Figure 2 , 3 ), a layer of the same size 2-5mm thick empty frame can be added between the frame containing the positive and negative electrode sheet (pull the electrode spacing), the negative side of the frame is not changed but its positive side / surface increases the arc-shaped flow guide engraved with the original acid water outlet, increased to 6-9mm spacing between the positive and negative electrodes electrolytic cavity flow to the original acid water outlet is hypochlorous acid outlet; on the positive electrode sheet on the top and the panel between the panel on the top of the hydrochloric acid single outlet (next to the positive water is the most acid acid water), the flow switch is used to adjust the flow ratio of hydrochloric acid and hypochlorous acid outlet and then indirectly adjust the pH value of the hypochlorous acid outlet, the online monitoring pH meter adjusts the pH value of the hypochlorous acid to pH4-pH5.5, the DC power supply with stable voltage 20-24V and maximum current 36-50A is selected, and the flow-adjustable micro water pump. The yield of two-layer electrode electrolysis is not high, and two to three or even four to five basic purification tanks can be stacked in parallel to form a combined tank, and the hypochlorous acid water and alkali water are still guided to the left and right oval holes and penetrate to the left and right outlets on the first tank panel; in order to have a common hydrochloric acid outlet for the stacked basic purification tank units, the hydrochloric acid outlet must be opened on the panel and opposite the frame position to connect two to three purification tanks, the second and third tank panels are both the bottom plate of the previous tank and the panel of the next tank, and the hydrochloric acid flows from the panel to the middle or slightly lower of the hypochlorous acid water and alkali water outlet, and a common hydrochloric acid outlet and built-in conduit (see attached Figure 4 ) are opened through all the stacked layers of frames of the basic purification tank.

[0055] Conventional electrolytic cell and purification electrolytic cell in series: purification electrolytic cell solves the main problem of removing hydrochloric acid, but single use does not fully utilize the efficiency advantages of slow flow rate electrolysis, repeated electrolysis, and alkaline brine electrolysis, and there is no efficiency to remove the influence of residual sodium chloride electrolysis. The combination of purification electrolytic cell and existing 5-11 layer production type electrolytic cell has complementary advantages. The conventional 5-11 layer laminated electrolytic cell first electrolyzes a sufficient amount of acid water, and the acid water is directly input into the purification electrolytic cell for secondary electrolysis and purification of hypochlorous acid; the power supply of the conventional laminated electrolytic cell is selected as 12V DC, while the power supply of the purification electrolytic cell is selected as 12-24V two separate maximum 36-50A DC power supply, and the water pump is selected as 0.2-2L / minute flow rate large torque motor micro pump, with a slow flow rate of <1.0L / minute and a 10% backfeed of alkaline water to improve the yield, and a weak acidic hypochlorous acid with a stability of 1 month. Secondary repeated electrolysis + primary purification electrolysis: the acid water electrolyzed by the conventional 9-11 layer laminated electrolytic cell is input into the 7-9 layer laminated electrolytic cell for secondary electrolysis with high efficiency, and the acid water is input into the purification electrolytic cell for third electrolysis and purification of hypochlorous acid; the power supply of the two laminated electrolytic cells is respectively selected as 12V DC, while the power supply of the purification electrolytic cell is selected as 24V DC power supply, and the water pump is selected as an adjustable flow rate micro pump, with a flow rate of 0.5-1.0L / minute and a 10% backfeed of the first alkaline water; repeated electrolysis can remove sodium ions as much as possible. The production of 200-500ppm micro-acidic hypochlorous acid without corrosive hydrochloric acid can improve the stability from 3-14 days at room temperature to less than 10% degradation at room temperature for 3 months according to the national standard; after adding one step to remove residual sodium chloride, it can be increased to room temperature for 6 months with less than 10% degradation; the product hypochlorous acid after adding self-made weak alkaline stabilizer (1000x concentrated solution) has a pH of 5-6.5 and a micro-acidic hypochlorous acid with a stability of 12 months or more at room temperature and a degradation of less than 10%.

[0056] The repeated electrolysis combination device can be scaled up or down, the standard 12x7cm electrode sheet and the area of the device can be enlarged by 30% to more than 1 times, and the yield is correspondingly increased, but the enlarged area increases the current between the electrodes (limited by the rated power of the power supply) and cannot electrolyze high concentration brine, only 200ppm hypochlorous acid can be produced; for the same reason, the electrolytic electrode sheet and the device can also be scaled down, but the electrolytic flow of the electrode sheet cannot be too short, otherwise the brine electrolysis is not sufficient and there is too much residual salt. The scaled-down but slightly longer number of laminated electrolytic cell purification electrolytic cell combination or integrated device is suitable for manufacturing micro desktop hypochlorous acid generator. BRIEF DESCRIPTION OF DRAWINGS

[0057] Figure 1. Conventional stacked electrolytic cell internal configuration, like "reading" from the electrode sheet between the electrolytic cavity open, divided into two parts, 1. The left gray rectangle electrode sheet embedded in the plastic frame and connected to the power from the frame top (left upper protruding stud), frame / arc-shaped flow connection to a corner oval common out / inlet; 2. The right side of the white rectangular isolation film cover the back of the rectangular electrode sheet and connected to the power from the frame lower (right lower protruding part), the back of the flow connection to another corner oval port; generally left electrode sheet and frame top connected to the habit of positive, right electrode sheet and frame lower connected to the habit of negative, a positive stack a negative …, plus the panel, the bottom plate and a circle of bolts fixed after the multi-layer stacked electrolytic cell. Figure 2 . Two-layer purification electrolytic cell internal configuration, 1. The left side is still embedded in the plastic frame of the gray rectangular positive electrode sheet, 2. The right is the original 2-5 mm thick empty frame added between the original positive and negative electrode sheets (without or remove the electrode and diaphragm), the empty frame negative side flow to the original acid water port but its positive side arc-shaped flow to the original acid water port is engraved, the electrolytic cavity flow to the original acid water port between the positive and negative electrodes with a spacing of 6-9 mm is the hypochlorous acid outlet; (on the positive electrode sheet on the end and the panel between the panel on the top of the hydrochloric acid alone outlet), plus the panel and the bottom plate and a circle of bolts fixed after the two-layer purification electrolytic cell.

[0058] Figure 3 . Purification electrolytic cell panel and positive open picture, right 2. For the positive and stacked frame, embedded in the white isolation film cover the back of the electrode sheet and connected to the power from the frame side; left 1. The panel and its four corners round hole inlet and outlet (closed after communication) stacked frame four corners oval port (the inner side of the frame around a circle of bolt fixing hole), the panel on the top of the two corners outlet middle / middle lower open a hydrochloric acid outlet, the hydrochloric acid outlet and the original two corners outlet form a reverse triangle.

[0059] Figure 4 . Multi-unit combination purification tank panel hydrochloric acid outlet diagram, right 2. For the positive and back of the multi-unit diagram covered by the diaphragm, left 1. The panel inside the top of the two corners outlet middle lower (mapping the frame position) open a hydrochloric acid outlet, the panel mapping the electrolytic cavity to the hydrochloric acid outlet between the left and right symmetric arc-shaped flow; the second and fifth unit panel is both the bottom plate of the previous unit and the panel of the next unit, and the acid water flow direction is upward from the panel to the middle lower pre-opened acid water common outlet and conduit in the middle of the hypochlorous acid water and alkali water port. DETAILED DESCRIPTION

[0060] Example one, twice repeated electrolysis + one purification electrolysis:

[0061] Electrolytic acid water contains hydrochloric acid equivalent to hypochlorous acid, and hydrochloric acid is the main component of hypochlorous acid degradation and the fundamental reason for initiating vicious cycle, but hydrochloric acid is also a good raw material more than twice the efficiency of salt water electrolysis, but the limited public security control and the high price of purified hydrochloric acid make it impossible to become a regular electrolysis raw material; Limited salt water electrolysis efficiency is only one-third of salt conversion and one-tenth of hypochlorous acid, and the salt content in electrolytic acid water is still more than six times that of hypochlorous acid, and the excess salt covers the hypochlorous acid and also affects its stability. In order to make full use of hydrochloric acid in acid electrolytic water and effectively produce pure hypochlorous acid water, it is necessary to remove hydrochloric acid from the purification electrolytic cell, and it is also necessary to combine electrolysis methods and devices with slow electrolysis, repeated electrolysis, first-time alkali salt water electrolysis, and electrolytic acid water containing hydrochloric acid secondary electrolysis to improve efficiency.

[0062] Secondary repeated electrolysis + primary purification electrolysis: salt water passes through two repeated electrolysis of two stacked electrolytic cells in series and three electrolysis of a purification electrolytic cell in series, and the power of two conventional stacked electrolytic cells is respectively selected from two separate 12V DC power supplies, and the purification electrolytic cell (attached Figure 2 、 3)Power single use a 24V but the maximum 50A DC power supply, water pump selection adjustable flow 0.2-2L / per minute of large torque motor micro pump, online pH meter and digital ammeter indicate chlorine value. Salt water 0.1g% -0.4g% with 0.5L / per minute flow rate pump, electrolysis of the first choice of conventional 9-11 laminated sheet type electrolytic cell electrolysis, the first electrolysis outlet lye take 10% -20% proportion (through a shunt pipe and switch) back to the first electrolytic cell raw material inlet, raw salt water +10% -20% fresh lye can improve the efficiency of salt water electrolysis 30%; First electrolysis outlet lye switch is also small (small 10-20%) to force electrolytic cell lye 10-20% acid water outlet, improve the efficiency of subsequent acid water secondary electrolysis; The remaining lye discarded or it is used. The first electrolysis of mixed acid water immediately directly into the conventional 7-9 laminated sheet type electrolytic cell for the second electrolysis, the first mixed acid water hypochlorous acid molecule is not ionized, new generation of hydrochloric acid efficient electrolysis, the remaining salt also increased 30% electrolysis of the second two times a total of 60% electrolysis; Plus the lye also increased 30% electrolysis efficiency, the remaining un electrolytic salt is less than the hypochlorous acid molecule; The second electrolysis outlet acid water hypochlorous acid increased 1 times and reduced sodium chloride and hydrochloric acid, lye discarded or it is used. The secondary acid water again immediately input purification electrolytic cell third electrolysis and purification of hypochlorous acid, hydrochloric acid, lye respectively for it is used; Repeat electrolysis comprehensive measures to improve the efficiency of electrolysis 1 times more than 1.5 times. Adjust the purification electrolytic cell hydrochloric acid outlet flow (hydrochloric acid flow less and hypochlorous acid is mixed with part of the hydrochloric acid to reduce the pH value, otherwise the pH value of hypochlorous acid is increased) and indirectly adjust the pH of the hypochlorous acid 4-5, digital ammeter real-time measurement of electrolysis current value and conversion into effective chlorine content (chlorine content is difficult to detect) display relative content value, production of 200ppm-500ppm stable hypochlorous acid without corrosive hydrochloric acid.

[0063] Micro acidic hypochlorous acid is packed in 250-500ml dense light surface No. 1 polyester plastic bottle (PET) and wrapped in opaque plastic film, or packed in 50-100ml dense light surface No. 1 polyester PET spray bottle and packed in opaque white plastic film. Generally can reach room temperature storage 3 months stable, its effective chlorine content is not less than the lower limit of the indicated value or degradation less than 10%, add a step to remove residual sodium chloride step (dialysis method) to improve to room temperature ~ 6 months degradation less than 10%; Add homemade weak alkaline stabilizer (1000x liquid) after storage in cool place can reach 12 months effective chlorine decline rate less than 10%, speed up the degradation and placed 54 0 C incubator 14 days after the instrument measurement effective chlorine drop ≤10%. When the light bleaching chlorine smell indicates that the disinfectant shelf effective!

[0064] Micro acidic hypochlorous acid again do hydrochloric acid, salt water damage test:

[0065] Freshly made micro-acidic hypochlorous acid was diluted by equal ratio to 10mN, 1mM, 0.4mM, 0.2mM, 0.1mM, 0.05mM, 0.02mM, 0.01mM concentration gradient, respectively, 1ml was taken into 1.5EP plastic tube at room temperature, and the effective chlorine content of hypochlorous acid was tested every day using test paper. Hypochlorous acid containing hydrochloric acid ≥0.1mM still degraded without chlorine content (test paper white) in 1-3 days, and hypochlorous acid containing hydrochloric acid below 0.1mM and the control group of hypochlorous acid without hydrochloric acid degraded without chlorine content after ~14 days, proving that the presence of trace amounts of hydrochloric acid destroys hypochlorous acid. Sodium chloride was added to freshly micro-acidic hypochlorous acid by equal ratio dilution, and 1ml of each dilution gradient was taken at room temperature every day to measure the chlorine. The results showed that hypochlorous acid containing more than ~1mM sodium chloride degraded quickly (test paper white) in 2-4 days, and hypochlorous acid containing 1mM and below sodium chloride degraded without chlorine content after ~14 days, proving that the presence of sodium chloride in the product is an important factor in destroying the stability of hypochlorous acid. Micro-acidic hypochlorous acid without hydrochloric acid was used for skin and mucous membrane injury spray disinfection, and it was found that it oxidized the epidermis, causing temporary anesthesia of the surface layer and forming an oxidized film. The surface oxidized film can protect the skin and promote wound healing and repair.

[0066] Advantages of using hypochlorous acid: The World Health Organization (WHO) lists hypochlorous acid (HClO) as the second super-strong chlorine-containing disinfectant after chlorine dioxide, which has 5 times the germicidal ability of hypochlorous acid, but the liquid concentration is only active for 20-30 minutes; hypochlorous acid has 80-100 times the germicidal ability of sodium hypochlorite, and sodium hypochlorite does not release effective chlorine for disinfection and has not been listed as a chlorine-containing disinfectant; sodium hypochlorite is a strong bleaching water suitable for decontamination and cleaning. Chlorine dioxide has a too short stable period and is harmless, making it difficult to bear the heavy responsibility of frontline disinfectants, and it is only suitable for drinking water disinfection. Hypochlorous acid has rapid and short-term oxidation that is non-toxic, and hypochlorous acid is widely recognized as safe for use in the food industry, and less than 200ppm of hypochlorous acid and its residues will not harm the general population, especially children and infants (U.S. Environmental Protection Agency (EPA) Regulation 2022-19799). Shelf-stable hypochlorous acid is most suitable for multi-purpose disinfection in food processing plants and home kitchens, and there is no need to worry about the hidden dangers of residual or secondary poisoning caused by accidental operation; it is especially suitable for personal / individual all-round health and disinfection. Hypochlorous acid has strong oxidation power and can rust metal, and is not suitable for general disinfection of electrical appliances and surgical instruments (appliance use of jieerming professional disinfection).

[0067] Hypochlorous acid is simple to use but still has some disinfection professional characteristics that need attention:

[0068] 1) Hypochlorous acid disinfectant water can only kill surface bacteria and is not effective enough for deep bacteria that have grown into a lump. It is most effective for killing small bacterial spots and viruses that are not visible to the naked eye. Therefore, it is not effective for disinfecting visibly dirty areas, and the effect of disinfection after cleaning is not good. Disinfection after cleaning can maximize the disinfection effect of hypochlorous acid.

[0069] 2) Fruits and vegetables remove pests and diseases, acidic electrolytic water contains equal amount of hydrochloric acid to harm plants, only slightly acidic hypochlorous acid and no excess sodium chloride electrolyte can be used for plant diseases caused by bacteria and viruses, and cannot kill multicellular pests. Potassium salt electrolytic water can be used in combination / alternation with pesticides to reduce the amount of pesticides used. Hypochlorous acid spraying before listing helps to eliminate pesticide residues.

[0070] Fruits and vegetables are preserved by soaking fruits in 500ppm disinfectant water and spraying vegetables with 200ppm hypochlorous acid water to kill bacteria and viruses that cause rotting. Large visible mold spots cannot be killed and need to be detected and discarded. Hypochlorous acid can effectively oxidize plant hormones ethylene to delay the ripening time, but it cannot fundamentally make life "immortal". Leafy vegetables only have a short lifespan, and preservation relies solely on sterilization.

[0071] Prepared food must first disinfect the environment, air, table and tools. Large food materials are soaked and sprayed with disinfectant before being cut and processed. Cutting first and then disinfecting wastes hypochlorous acid and does not work well. Cold chain transportation can use 100ppm hypochlorous acid to make ice cubes. Micro-acidic hypochlorous acid ice blocks have antibacterial and fresh-keeping properties, can remove odors and prevent the spread of infectious bacteria and viruses in the cold chain.

[0072] 3) Disinfection and odor removal in farms. Disinfection cannot replace the cleaning of livestock and sheds, especially stains containing excrement, which contain too much organic matter and are the enemy of hypochlorous acid. The excrement must be cleaned before hypochlorous acid can be sprayed for effective disinfection. To remove odors in the air, a higher concentration of 500ppm hypochlorous acid must be used. Conventional electrolytic acidic water only remains stable for a few days and only maintains deodorization for a few tens of minutes after spraying. Micro-acidic hypochlorous acid has improved stability and can maintain deodorization for several hours after spraying. Spraying 1-2 times a day is sufficient for deodorization. However, excrement cannot be deodorized and must be treated in a separate septic tank.

[0073] Livestock breeding density is too high, and a large amount of antibiotics is commonly used, otherwise it is easy to cause mass illness and death. Hypochlorous acid disinfection does not cause bacteria to develop drug resistance, replacing the daily use of antibiotics in the breeding industry and reducing natural bacterial drug resistance so that humans can have antibiotics when they get sick. Farms lack professional veterinarians and can use hypochlorous acid to treat a large part of livestock diseases.

[0074] 4) Disinfection and medical treatment for pets. The number of pets and pet hospitals has increased significantly with urbanization. Pet hospitals have poor medical facilities and are not as good as veterinarians. Special drugs are also extremely rare. A large part of pet diseases are caused by bacterial and viral infections and wound infections and inflammation. Hypochlorous acid has strong sterilization ability and is non-toxic and safe. It is also compatible with wounds and has no sensation, unlike the strong irritation of chemical drugs. It has no resistance to pets and seems to be a panacea for everything. Immediate disinfection of hypochlorous acid for wounds caused by pet bites helps to prevent the risk of rabies and tetanus infection. It is also effective in removing pet odors.

[0075] 5) Air disinfection in human flow dense places. After great technological progress, human beings have greatly enhanced their resistance to infectious diseases, but the respiratory tract and lung mucosa are still powerless against respiratory diseases. Places such as airports, stations, and peak subways are prone to respiratory infectious diseases such as influenza and new crown. It is also difficult to track the route of the epidemic. Air spraying of hypochlorous acid 1-2 times a day is the most effective and inexpensive control method. The faint bleach chlorine smell during disinfection indicates that it is not out of date. Chlorine smell can effectively kill viruses and aerosol glue. There is no need to measure the effective chlorine content every time.

[0076] Old and young people have low resistance. Places such as kindergartens, primary and secondary schools, and nursing homes are high-risk areas for respiratory diseases. Hand spraying disinfection and indoor spraying disinfection 1-2 times a day are the most effective and inexpensive measures for epidemic prevention. Hypochlorous acid can also remove old odors. Hypochlorous acid wet wipes can be used for immediate body cleaning, which helps to recover skin and mucosal damage and heal bedsores and inflammation.

[0077] 6) Daily disinfection in dental clinics and community clinics. Generally, concentrated chlorine-containing chemicals such as chlorhexidine (also known as chlorhexidine) mouthwash are used for disinfection and medical disinfection. It is a surfactant with weak bactericidal effect. Chemical reagents are not suitable for routine use. Micro-acidic hypochlorous acid is a strong oxidizing mucosa that forms a surface protective film and has a surface anesthetic effect. As a daily disinfection, it is not only effective and safe, but also promotes healing and protects the mucosa. Tooth loss is mainly caused by continuous infection of caries and periodontitis. Regular mouthwash with hypochlorous acid without hydrochloric acid can fundamentally prevent and treat it. For treatment, chlorine dioxide is used. It can easily penetrate the lesion and completely kill bacteria and viruses.

[0078] 7) Skin, mucosa disinfection: Human skin, mucosa is the first line of defense of the body, bacteria invade is also from the skin, mucosa into especially damaged (trauma or disease such as diabetic lesions) infection. And dermatological diseases are not taken seriously, hospital dermatology is the "least favored" department of hospital, the development of medicine for skin, mucosa disease is also limited compared to backward. Dermatological diseases are mainly by close contact infection so a major category of natural belong to sexually transmitted diseases, people obscure in the privacy of sexually transmitted diseases and private medical treatment of medicine become "social leather fresh" chronic disease, hypochlorous acid is not only stronger than chlorhexidine, potassium permanganate disinfection also promote the rapid healing of wounds. Some movie heroes use charcoal fire high temperature coagulation wound and promote healing when injured, the super strong oxidation characteristics of hypochlorous acid can also make the surface layer of the wound molecules coagulation form micro protective film, and stop at the surface without a bit of irritation (the body surface is rich in organic matter with negative electron makes hypochlorous acid instantaneously be consumed light), but the formation of hypochlorous acid surface coagulation film on the internal role of limited bulk lesions. Therefore, chlorine dioxide (effervescent tablets) water penetration is good and used for killing (treatment) of lesions bacteria, hypochlorous acid water affinity, protection of wound is used for daily disinfection and promote wound healing, especially long-term protection, repair of skin micro trauma; skin aging is mainly due to the skin micro trauma repeated infection after bacterial enzymes destroy skin collagen polysaccharide (second is the radiation, free radical oxidation), hypochlorous acid than (plus) skin care products more help to skin anti-aging, beauty whitening.

Claims

1. A micro-acidic hypochlorous acid electrolysis method, characterized by: An improved electrolysis method for increasing the stability of existing acidic water and raising its acidic pH to a micro-acidic pH; The electrolysis method is realized by a micro-acidic hypochlorous acid electrolysis device, which includes a two-layer purified electrolytic cell. The two-layer purified electrolytic cell includes a hydrochloric acid outlet, a micro-acidic hypochlorous acid outlet, and an alkali water outlet. The hydrochloric acid outlet leads out the most acidic acid water hydrochloric acid. The micro-acidic hypochlorous acid outlet leads out the micro-acidic hypochlorous acid. The alkali water outlet leads out the alkali water. The two-layer purified electrolytic cell is formed by adding the hydrochloric acid outlet to the faceplate side of the existing two-layer electrode sheet electrolytic cell at the positive electrode. The micro-acidic hypochlorous acid outlet is the original acid water outlet at one corner of the existing two-layer electrode sheet electrolytic cell. The alkali water outlet is the original alkali water outlet at the opposite corner of the existing two-layer electrode sheet electrolytic cell. The hydrochloric acid outlet is set between the micro-acidic hypochlorous acid outlet and the alkali water outlet or slightly below the middle of the hydrochloric acid outlet on the faceplate between the positive electrode and the faceplate. The hydrochloric acid outlet is connected to the most acidic acid water outlet pipe. One to five two-layer purified electrolytic cells are used for electrolysis in series or parallel. Multiple two-layer purified electrolytic cells are combined in parallel. A hydrochloric acid conduit that only opens between the positive electrode and the faceplate is connected to each two-layer purified electrolytic cell and stacked into a combined electrolytic cell. The outlet pipes of the micro-acidic hypochlorous acid outlet, the hydrochloric acid outlet, and the alkali water outlet are equipped with flow switches to adjust the flow ratio between them and indirectly adjust the pH of the electrolytic oxidized water. It can be connected in series with existing multi-layer stacked electrolytic cells to improve the yield and stability of hypochlorous acid. The core component of the micro-acidic hypochlorous acid electrolysis device is a purified electrolytic cell that separates hydrochloric acid and hypochlorous acid from a standard two-layer electrode sheet electrolytic cell. During electrolysis, the most acidic acid water next to the positive electrode is directed to the hydrochloric acid outlet. The micro-acidic hypochlorous acid between the positive and negative electrodes is directed to the micro-acidic hypochlorous acid outlet. The alkali water on the surface of the negative electrode is directed to the alkali water outlet. The two-layer purified electrolytic cell is the basic unit. Two to five basic units are connected in parallel to form a combined purified electrolytic cell as a mass production device. Each two-layer electrode unit is separated by a faceplate or a bottom plate. The faceplate of the second to fifth electrolytic cell unit is both the faceplate of the next layer unit and the bottom plate of the previous layer unit. The newly added hydrochloric acid outlet on the faceplate has a conduit that passes through all the stacked sheet frames. The conduit only opens between each positive electrode and the faceplate to continuously flow the hydrochloric acid. The most acidic water on the positive electrode cavity side is directed to the positive electrode and the faceplate through the positive electrode plate hole. The micro-acidic hypochlorous acid with reduced acidity in the positive and negative electrode cavities is directed to the micro-acidic hypochlorous acid outlet. The two-layer purified electrolytic cell and the combined basic unit of the purified electrolytic cell are assembled into an electrolysis device with power supply, water pump, online pH meter, digital ammeter, indicator light, switch, and control single board computer accessories. The operation of the micro-acidic hypochlorous acid electrolysis device is as follows: 0.1g%-1.0g% of brine is pumped into the micro-acidic hypochlorous acid electrolytic device at a speed of 0.2L-2.0L per minute to improve the electrolysis efficiency. Different concentrations of brine produce 100-1000ppm of hypochlorous acid under the action of a direct current of ≥1.25V / mm stabilized ruthenium / iridium electrode. The first alkaline water is directly returned to the raw material inlet at a ratio of 10%-20% through a shunt pipe and a switch to further improve the electrolysis efficiency by 30%. The purification electrolytic tank separates hydrochloric acid and hypochlorous acid and adjusts the flow rate of hydrochloric acid outlet with a switch. The pH of the conventional electrolytic acid water is increased from <3.0 to 4-5.5 micro-acidic. The stability of hypochlorous acid water is improved from less than half a month to less than 10% degradation at room temperature for 1-3 months.

2. A micro-acidic hypochlorous acid electrolysis device, characterized by: The micro-acidic hypochlorous acid electrolytic device is used to realize a micro-acidic hypochlorous acid electrolysis method as claimed in claim 1. The micro-acidic hypochlorous acid electrolytic device is assembled into an instrument by a purification electrolytic tank and various stacked electrolytic tanks and accessories. The purification electrolytic tank is a two-layer purification electrolytic tank or a multi-combination purification electrolytic tank combined with the two-layer purification electrolytic tank. The two-layer purification electrolytic tank or the multi-combination purification electrolytic tank and the existing stacked electrolytic tank are separately matched with a stabilized 10-24V but allowed maximum 36-50A direct current power supply. The water pump selects a variable frequency micro water pump with adjustable flow of 0.2-2L per minute and a large torque motor with a stabilized 12-24V maximum 15-30A direct current power supply. An online industrial pH meter is selected to monitor the pH value of the hypochlorous acid outlet in real time. A digital ammeter indicates the relative effective chlorine content estimate. Other accessories include indicator lights, switches, and control single board computers. PE water pipes and wires are used to connect the electrolytic tank and related accessories in a case / cabinet to make an electrolysis instrument.

3. The micro-acidic hypochlorous acid electrolytic device of claim 2, wherein: The purification electrolytic cell is the two-layer purification electrolytic cell, the two-layer purification electrolytic cell is a two-layer electrode purification electrolytic cell with a large electrode spacing, the standard electrode spacing of 4 mm is enlarged to 6-9 mm, the two-layer purification electrolytic cell comprises a hydrochloric acid outlet, a slightly acidic hypochlorous acid outlet and an alkali water outlet, the hydrochloric acid outlet discharges the most acidic acid water hydrochloric acid, the slightly acidic hypochlorous acid outlet discharges slightly acidic hypochlorous acid, and the alkali water outlet discharges alkali water, the two-layer purification electrolytic cell is formed by adding the hydrochloric acid outlet to the face plate side of the positive electrode of the existing two-layer electrode sheet electrolytic cell, the slightly acidic hypochlorous acid outlet is the original acid water outlet at one corner of the existing two-layer electrode sheet electrolytic cell, and the alkali water outlet is the original alkali water outlet at the opposite corner of the existing two-layer electrode sheet electrolytic cell, a layer of 2-5 mm thick positive electrode frame is added between the original positive and negative electrode sheets including the frame, but the electrode sheets and the diaphragm therebetween are not included / removed, the original acid water flow channel on the empty frame negative side is retained, and an arc-shaped flow guide for the original acid water outlet is added to the positive side / surface of the frame as the slightly acidic hypochlorous acid outlet, the hydrochloric acid outlet is arranged on the face plate between the positive electrode and the face plate, and is arranged at a position intermediate or slightly below the slightly acidic hypochlorous acid outlet and the alkali water outlet; a stabilized 20-24V maximum 36-50A direct current power supply is used as the power supply, and the two-layer electrode electrolytic cell with a large spacing is generally used as the purification electrolytic cell and is connected in series with the outlet of the multi-layer stacked electrolytic cell for repeated electrolysis.

4. The slightly acidic hypochlorous acid electrolytic device according to claim 2, characterized in that: The purification electrolytic cell is the two-layer purification electrolytic cell, the two-layer purification electrolytic cell is a two-layer electrode purification electrolytic cell with a large electrode spacing, the standard electrode spacing of 4 mm is enlarged to 6-9 mm, the two-layer purification electrolytic cell comprises a hydrochloric acid outlet, a slightly acidic hypochlorous acid outlet and an alkali water outlet, the hydrochloric acid outlet discharges the most acidic acid water hydrochloric acid, the slightly acidic hypochlorous acid outlet discharges slightly acidic hypochlorous acid, and the alkali water outlet discharges alkali water, the two-layer purification electrolytic cell is formed by adding the hydrochloric acid outlet to the face plate side of the positive electrode of the existing two-layer electrode sheet electrolytic cell, the slightly acidic hypochlorous acid outlet is the original acid water outlet at one corner of the existing two-layer electrode sheet electrolytic cell, and the alkali water outlet is the original alkali water outlet at the opposite corner of the existing two-layer electrode sheet electrolytic cell, a layer of 2-5 mm thick positive electrode frame is added between the original positive and negative electrode sheets including the frame, but the electrode sheets and the diaphragm therebetween are not included / removed, the original acid water flow channel on the empty frame negative side is retained, and an arc-shaped flow guide for the original acid water outlet is added to the positive side / surface of the frame as the slightly acidic hypochlorous acid outlet, the hydrochloric acid outlet is arranged on the face plate between the positive electrode and the face plate, and is arranged at a position intermediate or slightly below the slightly acidic hypochlorous acid outlet and the alkali water outlet; a stabilized 20-24V maximum 36-50A direct current power supply is used as the power supply, and the two-layer electrode electrolytic cell with a large spacing is generally used as the purification electrolytic cell and is connected in series with the outlet of the multi-layer stacked electrolytic cell for repeated electrolysis.

5. A slightly acidic hypochlorous acid electrolytic device according to claim 3 or 4, characterized in that: The said laminated electrolytic cell is a conventional 5-11 layer laminated electrolytic cell, the said purification electrolytic cell is used with the said conventional 5-11 layer laminated electrolytic cell, the conventional 5-11 layer laminated electrolytic cell first electrolyzes to produce enough mixed acid water and 10%-20% first alkaline water back feeding into the raw material inlet, the mixed acid water is connected to the inlet of the two layer purification electrolytic cell or the multi-combination purification electrolytic cell for secondary electrolysis and separation and purification of hypochlorous acid, the power supply of the said laminated electrolytic cell and the power supply of the said purification electrolytic cell are respectively selected as two separate stabilized 8-15V and 20-24V maximum 36-50A direct current power sources, which can be suitable for some application sites for independent operation and self-production of micro-acidic hypochlorous acid for current use.

6. A slightly acidic hypochlorous acid electrolytic device according to claim 3 or 4, characterized in that: The said laminated electrolytic cell includes 9-11 layer laminated electrolytic cell and 7-9 layer laminated electrolytic cell, the said purification electrolytic cell is used with the said 9-11 layer laminated electrolytic cell and the said 7-9 layer laminated electrolytic cell in series repeated electrolysis, the brine is pumped into the conventional 9-11 layer laminated electrolytic cell at 0.5-1L per minute for first electrolysis, 10%-20% of the outlet alkaline water is taken through a shunt pipe and a switch and is back fed into the raw material inlet, the switch of the first alkaline water outlet is also closed a little smaller to force the 10-20% alkaline water of the electrolytic cell to the acid water outlet, to improve the efficiency of the subsequent secondary electrolysis, and the remaining alkaline water is discarded or used; the mixed water of hydrochloric acid and hypochlorous acid from the first electrolysis is input into the conventional 7-9 layer laminated electrolytic cell for second electrolysis, which increases the electrolysis efficiency by 60%, and the forced alkaline water increases the electrolysis efficiency by 30%, most of the salt can be converted into hypochlorous acid molecules, and the alkaline water is discarded or used; the secondary acid water is input into the purification electrolytic cell for third electrolysis and purification of hypochlorous acid, and the hydrochloric acid and alkaline water are respectively reserved; The repeated electrolysis improves the electrolysis efficiency by more than 1 times or even more than 1.5 times, and the stability of the hypochlorous acid water is improved to less than 10% degradation in 3-6 months at room temperature.

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