CN113180056B - Hypochlorous acid disinfectant - Google Patents
Hypochlorous acid disinfectant Download PDFInfo
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- CN113180056B CN113180056B CN202110485349.9A CN202110485349A CN113180056B CN 113180056 B CN113180056 B CN 113180056B CN 202110485349 A CN202110485349 A CN 202110485349A CN 113180056 B CN113180056 B CN 113180056B
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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Abstract
A hypochlorous acid disinfectant able to be stored stably contains iodate, and one or more of sulfate, carbonate, dibasic phosphate, monobasic phosphate and bicarbonate.
Description
Technical Field
The invention relates to a hypochlorous acid disinfectant which can be stably stored.
Background
The 84 disinfectant is a product widely used for killing bacteria and viruses, preventing diseases and inhibiting transmission, is mainly used for disinfecting the surfaces of objects, the environment and the like, and is widely used for sanitary disinfection of hotels, travels, hospitals, food processing industries, families and the like. 84 disinfectant has ideal disinfection effect, low price, convenient use, broad spectrum and high-efficiency sterilization characteristics, but has certain irritation and corrosiveness. Gloves are worn for use because of skin irritation. The 84 sterilizing liquid is generally chlorine (Cl)2) Is prepared by the reaction of the raw materials and sodium hydroxide (NaOH),
Cl2+2NaOH＝NaClO+H2O+NaCl
sodium hypochlorite in the reaction product is the main component of the disinfection solution. Can be obtained by or from the action of bleaching powder and sodium carbonate, and by electrolyzing a dilute NaCl solution and stirring and mixing chlorine gas generated at the anode and NaOH generated at the cathode. The 84 disinfectant is a chlorine-containing disinfectant with sodium hypochlorite as a main component, is colorless or light yellow liquid, has pungent smell, generally has the pH value of 12-13, and has the effective chlorine content of 5.5-6.5%.
Sodium hypochlorite is a strong electrolyte, firstly generates hypochlorite ions (ClO-) through ionization in water, and hypochlorite ions can generate hypochlorous acid if hydrolyzed and further decompose to generate nascent oxygen [ O ] (a substance directly formed by oxygen atoms), so that the hypochlorite ions are very active in chemical property, have extremely strong oxidizing power and play a great role in the disinfection process. 84 the disinfection principle of the disinfectant is that hypochlorite can crack germs through the oxidation reduction effect of hypochlorite with bacterial cell walls and virus shells; because the unstable decomposition generates nascent oxygen, the strong oxidizability of the nascent oxygen causes the protein denaturation of thalli and viruses, thereby causing the death of pathogenic microorganisms; chloride ions can significantly change the osmotic pressure of bacteria and virosomes, leading to their loss of activity and death; in addition, the small amount of hypochlorous acid generated due to instability also has the function of partially killing pathogenic microorganisms.
There are now available technical apparatuses such as AQUACIDO NDX-250KMS available from OSG, Desktop Fineox FO-1000S2 available from First Ocean (First Ocean), LWas series or Was series-anode-HClO generator or Denmark DCW hypochlorous acid generator for producing hypochlorous acid oxidation potential water by electrolysis to produce hypochlorous acid disinfectant.
According to the requirements for sanitation of acidic electrolyzed water generators (GB28234-2020), acidic electrolyzed water, also called strongly acidic electrolyzed water, is an acidic aqueous solution with a high oxidation-reduction potential and a low concentration of effective chlorine generated at an anode by electrolysis in a diaphragm electrolytic cell by adding demineralized water to a low concentration sodium chloride solution, and has a pH of 2-3 and an oxidation-reduction potential of 1100mV or more. Chlorine, oxygen and H are generally produced at the anode in electrolysis+，H+Dissolved in water to exhibit acidity, and OH is generated at the cathode-。
The slightly acidic electrolyzed water, also called slightly acidic electrolyzed oxidizing water, is obviously different from 84 disinfectant in preparation, components and properties, and is also greatly different from acidic electrolyzed oxidizing water. The slightly acidic electrolyzed oxidizing water is generally produced by adding demineralized water to a solution of hydrochloric acid and/or sodium chloride and by electrolysis in an electrolytic cell with or without a diaphragm. Wherein chlorine and H are generally generated at the anode+，H+Dissolved in water and showing weak acidity, chlorine reacts with water to produce hydrochloric acid and hypochlorous acid, and the cathode produces hydrogen. The pH value of the slightly acidic oxidation potential water is less than 7, generally 5-6.5, and the main sterilization component of the slightly acidic oxidation potential water is hypochlorous acid.
The oxidation potential water contains more complicated components and has a larger mutual influence with the pH value. Briefly, between pH4-6, water-soluble chlorine (Cl)2) Nearly zero, while the hypochlorous acid content is highest; water soluble Cl below pH32The content of hypochlorous acid is sharply increased, but the content of hypochlorous acid is sharply reduced; at about pH 8, the hypochlorous acid content sharply decreases to about 20% and continues to sharply decrease as the pH increases, while hypochlorite (OCl)-) But rises sharply. Therefore, the difference of pH causes the large component difference among the 84 disinfectant, the electrolyzed oxidizing water and the slightly acidic electrolyzed oxidizing water.
Hypochlorite (ClO)-) And hypochlorous acid (HCIO) are effective chlorine, but their sterilization principleCompletely different. The cell membrane surface is negatively charged, so hypochlorite (ClO)-And also has negative charge) cannot easily enter the cell interior, while hypochlorous acid (HClO) is a neutral small molecule and can penetrate through a cell membrane to enter the cell interior, and can generate oxidation reaction with bacterial (virus) body protein, nucleic acid, enzyme and the like or destroy the phosphate dehydrogenase of the bacterial (virus) body protein, nucleic acid, enzyme and the like to cause sugar metabolism disorder and cause cell death, thereby killing pathogenic microorganisms. In biological systems, hypochlorous acid (HClO) is generated by oxidation of chloride ions by the action of peroxidase, a source of neutrophils, and hydrogen peroxide. The results of the quantitative analysis showed that 10 ten thousand activated neutrophils could produce about 2X 10 cells within 2h of incubation time-7mol hypochlorous acid. Hypochlorous acid has better virus inactivation effect. Research shows that 250mg/L hypochlorous acid acts on poliovirus prepared according to disinfection technical specification for 10min, and can effectively inactivate the poliovirus. In addition, tests show that hypochlorous acid can effectively kill viruses under the conditions of flushing and gasification. In some experiments, human influenza A virus was selected as a test object, and the virus was treated with 3.5mg/L hypochlorous acid at room temperature for 30 seconds, and the test results showed that the human influenza A virus had an inactivation effect of 3.2 virus (H7N1) in terms of log kill, and the hypochlorous acid reduced the virus titer in the form of direct spraying or indirect spraying under the condition of no organic matter.
According to the existing literature, the bactericidal effect of hypochlorous acid (40ppm) is obviously better than that of sodium hypochlorite (1000ppm) against gram-positive bacteria and fungi. On the premise of the same initial effective chlorine concentration, even if the dilution factor is 2-4 times of that of the strongly acidic electrolyzed water, the slightly acidic electrolyzed water has better disinfection and sterilization capability compared with the strongly acidic electrolyzed water.
The hypochlorous acid subacid electrolyzed oxidizing water used as a disinfectant has higher safety. However, in reality, hypochlorous acid slightly acidic electrolyzed water has complex components and unstable properties, and although some methods for enhancing stability are reported, such as CN107439588B of Rehm treatment company, the stability experiment requirements cannot be met, or the method is not simple and high in cost, and considering the long-term requirements and the current epidemic situation, a hypochlorous acid disinfectant which can be stably stored and can effectively inactivate bacteria and viruses is urgently needed.
Disclosure of Invention
According to one aspect of the invention, a hypochlorous acid disinfectant which is a slightly acidic electrolyzed oxidizing water and contains a halide salt and one or more of dibasic phosphate, monobasic phosphate, sulfate, carbonate and bicarbonate is provided, and can be stably stored. .
According to still another aspect of the present invention, there is provided a hypochlorous acid disinfectant which can be stably preserved, wherein the halide salt is iodate.
According to still another aspect of the present invention, there is provided a hypochlorous acid disinfectant which can be stably preserved, wherein the iodate is potassium iodate or sodium iodate.
According to still another aspect of the present invention, there is provided a storable hypochlorous acid disinfectant, wherein the sulfate, carbonate, dibasic phosphate, monobasic phosphate, and hydrogencarbonate are sodium salts or potassium salts of each.
According to still another aspect of the present invention, there is provided a hypochlorous acid disinfectant which can be stably preserved, wherein the content of the halide salt is 5 to 500 ppm.
According to still another aspect of the present invention, there is provided a hypochlorous acid disinfectant which can be stably preserved, wherein the content of the halide salt is 50 to 200 ppm.
According to still another aspect of the present invention, there is provided a hypochlorous acid disinfectant which can be stably preserved, wherein the amounts of disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium hydrogen carbonate, sodium carbonate, and sodium sulfate are 50 to 400ppm, respectively.
According to still another aspect of the present invention, there is provided a hypochlorous acid disinfectant which can be stably preserved, wherein the effective chlorine concentration of the hypochlorous acid disinfectant is 70 to 600 ppm.
According to still another aspect of the present invention, a hypochlorous acid disinfectant capable of being stably preserved is provided, wherein the effective chlorine concentration of the hypochlorous acid disinfectant is 250-550 ppm.
According to another aspect of the present invention, there is provided a hypochlorous acid disinfectant which can be stably stored, wherein the slightly acidic electrolyzed oxidizing water has a pH of 4.5 to 6.8, an oxidation-reduction potential of not higher than 900mV, and an effective chlorine concentration of 70 to 600 ppm.
According to still another aspect of the present invention, there is provided a hypochlorous acid disinfectant which is slightly acidic electrolyzed oxidizing water containing iodate and one or more of dibasic phosphate, monobasic phosphate, carbonate, sulfate and bicarbonate, and has an effective chlorine decrease of not more than 5% within 12 months of storage at room temperature.
According to still another aspect of the present invention, there is provided a method for producing hypochlorous acid disinfectant, comprising:
(1) adding iodate into subacid oxidation potential water;
(2) standing for 1-8 hours; and
(3) adding one or more of sulfate, carbonate, dibasic phosphate, monobasic phosphate and bicarbonate.
According to still another aspect of the present invention, there is provided a method for producing a hypochlorous acid disinfectant, wherein the slightly acidic electrolyzed oxidizing water has an oxidation-reduction potential of not more than 900mV, a pH of between 4.5 and 6.8, and an effective chlorine concentration of between 70 and 600 ppm.
According to still another aspect of the present invention, there is provided a method for producing hypochlorous acid disinfectant, which comprises producing electrolyzed oxidizing water with low acidity by using common salt as a raw material, controlling the consumption of common salt to about 5 to 13 g/g (in terms of available chlorine) and the consumption of energy to about 5 to 25 w.h/g (in terms of available chlorine).
According to still another aspect of the present invention, there is provided a method for producing hypochlorous acid disinfectant, which comprises controlling the electrolyzed oxidizing water production amount to 500-.
According to another aspect of the present invention, there is provided a hypochlorous acid disinfectant which is slightly acidic electrolyzed oxidizing water and contains iodate, dibasic phosphate and/or monobasic phosphate, and one or more of carbonate, sulfate and bicarbonate.
These and other aspects of the invention will be apparent from and elucidated with reference to the embodiments described hereinafter.
Drawings
The invention will now be described, by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic diagram of the process of the invention. In the figure, hypochlorous acid solution is slightly acidic oxidation potential water.
Detailed Description
The hypochlorous acid disinfectant is obviously different from 84 disinfectant in preparation, components and properties and is also greatly different from acid oxidation potential water. The production process of the hypochlorous acid disinfectant is designed as a quick shallow precipitation electrolysis process. The production apparatus may be a diaphragm electrolyzer.
The electrolytic solution is inorganic salt solution, slightly acidic solution or the mixture of the inorganic salt solution and the slightly acidic solution. For example, in a diaphragm electrolysis cell, the chlorine salt, typically sodium chloride, is present in an amount of about 1 to 15%, and the softened water is mixed with concentrated brine, e.g., saturated brine, and pumped in, typically with a sodium chloride consumption of 1 to 20g/L (anolyte). The anode of the electrolytic cell mainly generates chlorine evolution reaction, little oxygen evolution occurs, and subacid oxidation potential water with hypochlorous acid as a main component is produced; the cathode is subjected to a hydrogen evolution reaction to produce alkaline reduction potential water having a pH of about 12 to 13, and the cathode typically produces less than 0.5%, preferably less than 0.1%, and more preferably less than 0.08% sodium hydroxide. In addition, the content of sodium ions in the slightly acidic oxidation potential water generated by the anode is low (preferably less than 0.9%), and the main effective chlorine component of the slightly acidic oxidation potential water is hypochlorous acid; the slightly acidic electrolyzed water generally contains about 70-650ppm of available chlorine, preferably 100-610ppm of available chlorine, more preferably 105-600ppm, and more preferably 110-570ppm of available chlorine, wherein the main component of the available chlorine is hypochlorous acid. The oxidation-reduction potential of the anode effluent is not more than 1000mV, preferably not more than 900mV, preferably 600-900mV, more preferably 700-850 mV; the pH thereof is controlled to 4 to 7, preferably 4.5 to 6.8, more preferably 5 to 6.5.
There are technical equipments such as AQUACIDO NDX-250KMS available from OSG, Fineox FO-1000S2 available from first ocean corporation, LWas series or Was series-anode-HClO generator, DCW hypochlorous acid generator from Denmark, etc. for producing hypochlorous acid oxidation potential water by electrolyzing saline solution.
The oxidation potential water yield can be controlled at 500-1500L/h, the current value is generally between 90-400A, preferably not less than 100A, the salt consumption is about 2-15 g/g available chlorine, preferably 5-13 g/g available chlorine, the energy consumption is 1-30 W.hr/g available chlorine, preferably 5-25 W.hr/g available chlorine, and about 50-80% of the chloride ions are converted.
The produced slightly acidic electrolyzed water may be left to stand for a period of time, for example, 0.5, 1, 2, 3, 6, 8, 10, 12, 20, 24, 36, 48, 60, 72 hours, preferably 0.5 to 24 hours, more preferably 1 to 8 hours.
The stabilizer is generally an organic or inorganic salt, for example, one or more mixtures of alkali metal or alkaline earth metal water-soluble salts of formate or acetate or phosphate or silicate or halate or hypochlorite or chlorite or perchlorate bromate or carbonate or bicarbonate or acetate or sulfamate or citrate, preferably an inorganic salt, in particular potassium or sodium salts thereof, more preferably a halate, in particular iodate, and one or more mixtures of sulfate, carbonate, hydrogen phosphate, dihydrogen phosphate and hydrogen carbonate, in particular potassium or sodium salts thereof.
Halate refers to oxyacid salts of halogen elements having a valence of +5, such as chlorate, bromate, iodate, preferably their sodium or potassium salts, more preferably iodate, such as NaIO3、KIO3And the like.
The total amount of stabilizers added is generally not more than 0.5% by weight, preferably not more than 0.1%. The components (including halide salts, organic salts and inorganic salts) are generally added in amounts of 0.0005% to 0.05% (i.e. 5 to 500ppm), preferably 0.005% to 0.04% (i.e. 50 to 400ppm), more preferably 0.015% to 0.03%, for example 100, 120, 150, 170, 200, 220, 250, 270, 300, 350, 400, 500ppm, respectively.
The order of addition of the stabilizers is generally to add the halide salt, e.g., iodate, to the slightly acidic electrolyzed water produced and then to add the other stabilizers after a period of standing.
Typically the final product contains about 70-600ppm available chlorine, preferably 100-580ppm, more preferably 160-570ppm, more preferably 250-550ppm available chlorine, in which the main component of available chlorine is hypochlorous acid, typically greater than 80%, preferably greater than 90%, such as 90-92%, more preferably greater than 95%.
The softened water can be tap water softened or purified water produced by pure water production equipment, and has total hardness of less than 25mg/L (as CaCO)3Meter).
FIG. 1 is a schematic process flow diagram of the present invention. The raw water is subjected to activated carbon adsorption filtration, ultrafiltration and reverse osmosis filtration to obtain purified water. Purified water is pumped into the electrolysis cell under the control of a constant pressure valve. Meanwhile, high-concentration chloride solution (the concentration is more than 15 percent), such as saturated salt solution, is pumped into a water inlet pipeline in front of the electrolytic bath by a special pump. The pumping amount of the chlorine salt and the current applied to the electrolytic cell are varied depending on the effective chlorine concentration of the hypochlorous acid solution at the outlet of the electrolytic cell. The production process of the invention is a rapid shallow-evolution electrolysis process, the current is controlled to be 100-350A (according to different product specifications), and the oxidation-reduction potential is controlled to be below 900 mV. The softened water content is controlled at 900-1800L/h, and the chlorine salt content in the electrolytic bath is estimated to be about 1-15%, preferably 2-10%. Purified water is pumped into the electrolysis cell under the control of a constant pressure valve. The subacid oxidation potential water is anode effluent, and the amount of the subacid oxidation potential water accounts for 60-70% of the total effluent; the cathode mainly produces sodium hydroxide solution, and the yield of the sodium hydroxide solution is about 30-40% of the total water yield.
The subacid oxidation potential hypochlorous acid disinfectant has good disinfection effect and high stability by controlling raw materials and production process flow. According to the stability acceleration experiment of the disinfection technical specification (2002 edition) and after being stored for 14 days at 54 ℃, the reduction rate of the sterilization effective components is less than or equal to 10 percent, and the storage period can be determined as 1 year. The effective chlorine of the disinfectant is determined to be reduced by no more than 5 percent, which is far better than the requirement of 10 percent in the technical Specification for disinfection, so that the subacid oxidation potential hypochlorous acid disinfectant can be stably stored for a long time, for example, at least 12 months, 18 months or 24 months. Particularly, the hypochlorous acid electrolyzed water disinfectant with high concentration, which is difficult to be preserved for a long time, particularly the hypochlorous acid electrolyzed water disinfectant with the effective chlorine content of more than 250ppm, for example, the specification of 250-550ppm, can achieve the stable preservation effect.
Example 1
The saturated salt water is pumped into a purified water inflow pipeline before the electrolytic bath from a dosing tank, the water pressure of the purified water is controlled to be 1-1.5bar, the current is controlled to be 120A, the water outlet flow of anodic oxidation potential water is kept at 1200L/h, the pH is controlled to be 5.5-6.7, the effective chlorine concentration is 95-125 ppm, and the oxidation-reduction potential is 800 mV. The resulting hypochlorous acid electrolyzed water was added with 50ppm of potassium iodate, allowed to stand for 8 hours, and then 200ppm each of sodium dihydrogen phosphate, sodium sulfate and sodium hydrogen carbonate was added.
The pH and the concentration of available chlorine were measured, and the content of available chlorine was measured to be 105ppm according to the Disinfection Specification (2002 edition by Ministry of health).
The pH meter YQC-034 detects the environmental temperature of 22 ℃ and the relative humidity of 47% according to the disinfection technical Specification (2002 edition of Ministry of health), determines the pH (25 ℃) to be 6.31 and 6.31, and takes the average value to be 6.31.
Example 2
The saturated salt water is pumped into a purified water inflow pipeline before the electrolytic bath from a dosing tank, the water pressure of the purified water is controlled to be 1-2bar, the current is controlled to be 220A, the water outlet flow of anodic oxidation potential water is kept at 600-280L/h, the pH value is 5.5-6.7, the effective chlorine concentration is 250-280 ppm, and the oxidation-reduction potential is 750-900 mV. The obtained hypochlorous acid electrolyzed water was added with 160ppm of potassium iodate, allowed to stand for 10 hours, and then 200ppm each of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium sulfate, and sodium carbonate was added.
The pH and the concentration of available chlorine were measured, and the content of available chlorine was 262ppm, as measured by the available chlorine measurement in accordance with the Disinfection Specification (2002 edition, Ministry of health).
The pH meter YQC-034 detects the environmental temperature of 22 ℃ and the relative humidity of 47% according to the disinfection technical Specification (2002 edition of Ministry of health), and the pH value (25 ℃) is measured to be 6.29 and 6.29, and the average value is 6.29.
Example 3
The saturated salt water is pumped into a purified water inflow pipeline before the electrolytic bath from a dosing tank, the water pressure is controlled to be 1.5-2bar, the current is 230A-276A, the water outlet flow of anode potential water is 1200L/h, the pH value is 4.5-6.0, the effective chlorine concentration is 540-610 ppm, the oxidation-reduction potential is 700-850mV, the salt consumption per liter of anode electrolytic water is about 5-7 g, and the energy consumption is about 12 W.hr (watt hour). The obtained hypochlorous acid electrolyzed water was added with potassium iodate at 200ppm, allowed to stand for 8 hours, and then added with sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium sulfate, sodium carbonate and sodium hydrogen carbonate at 150ppm each.
The pH and the concentration of available chlorine are detected, and the content of the available chlorine is detected to be 598ppm according to the disinfection technical specification (2002 edition of Ministry of health).
The pH meter YQC-034 detects the environmental temperature of 20 ℃ and the relative humidity of 48% according to the disinfection technical Specification (2002 edition of Ministry of health), and the pH value (25 ℃) is obtained by measurement, wherein the two serial numbers are 4.75 and 4.75, and the average value is 4.75.
Example 4
The hypochlorous acid disinfectant obtained in example 1 was subjected to a stability test. The test is carried out according to the disinfection technical Specification (2002 edition of Ministry of health), and the storage conditions are as follows: the mixture was placed in an incubator at 54 ℃ for 14 days. Detecting the ambient temperature: 22 ℃ and a relative humidity of 47%.
Example 5
The hypochlorous acid disinfectant obtained in example 2 was subjected to a stability test. The test is carried out according to the disinfection technical Specification (2002 edition of Ministry of health), and the storage conditions are as follows: the mixture was placed in an incubator at 54 ℃ for 14 days. Detecting the ambient temperature: 22 ℃ and a relative humidity of 47%.
Example 6
The hypochlorous acid disinfectant obtained in example 3 was subjected to a stability test. The test is carried out according to the disinfection technical Specification (2002 edition of Ministry of health), and the storage conditions are as follows: the mixture was placed in an incubator at 54 ℃ for 14 days. Detecting the ambient temperature: 20 ℃ and 48% relative humidity.
Example 7
Quantitative bacteria killing experiment of hypochlorous acid disinfectant obtained in example 1
Test strain name:
escherichia coli, strain number: 8099, strain generation number: a fifth generation;
staphylococcus aureus, strain number: ATCC6538, strain passage number: a fifth generation;
pseudomonas aeruginosa, strain number: ATCC15442, strain passage number: the third generation;
candida albicans, strain number: ATCC10231, strain passage number: fifth generation
The strain source is as follows: ATCC (American type culture Collection)
Instrumentation and equipment: a biological safety cabinet YQF-057, a biochemical incubator YQF-058 and a biochemical incubator YQF-159.
Basis of examination：
1. Disinfection technical code, ministry of health 2002;
2. the quantitative determination test of the neutralizer suspension is carried out according to the disinfection technical specification, 2002 by Ministry of health; and
3. detecting the ambient temperature: 23 ℃ and a relative humidity of 45%.
And (4) detection conclusion:
1. the neutralizing agent meets the test requirements.
2. The action time is 0.5 minute, 1 minute and 1.5 minutes, the test is repeated for 3 times, the killing log values of the bacillus coli (8099), the staphylococcus aureus (ATCC6538) and the pseudomonas aeruginosa (ATCC15442) are all more than 5.00, and the tested strain is qualified for disinfection.
3. The action time is 0.5 minute, the test is repeated for three times, the killing logarithm of the candida albicans is less than 4.00, and the average logarithm value is 3.81; the action time is 1 minute and 1.5 minutes, the test is repeated for 3 times, the killing logarithm is more than 4.00, and the tested strain is qualified for disinfection.
Example 8
Virus inactivation experiment was performed on hypochlorous acid disinfectant obtained in example 1
Virus name and host:
poliovirus-I type vaccine strain and Vero cell
Instrumentation and equipment: a carbon dioxide incubator (QFM-B-B004), a low-temperature constant-temperature bath DKB-1915(QFM-B-P014), a biological safety cabinet (QFM-B-B031) and an inverted microscope (QFM-B-B012).
Basis of examination：
1. Disinfection technical code, ministry of health 2002;
2. detecting the ambient temperature: 23.2 ℃ and relative humidity 51%.
Inspection method
The action time is 0.5 minute, 5 groups are divided, and the identification test of the physical removal method of the residual disinfectant is carried out;
the action time is 0.5 min, 1 min and 1.5 min, and the action time is repeated for 3 times, and the test temperature is 20 +/-1 ℃.
And (3) detection results:
1. the test result shows that the physical drug-removing method is qualified.
2.0.5 minute experiment, the average inactivation log value is 3.07, and the virus inactivation rate is 99.91%;
1 minute experiment, the average inactivation log value is 4.08, and the virus inactivation rate is 99.99%;
the test is carried out for 1.5 minutes, the average inactivation log value is more than 4.10, and the virus inactivation rate is more than 99.99%.
Example 9
Hard object surface disinfecting test was performed using hypochlorous acid disinfectant obtained in example 1
Equipment
Neutralizing agent: 0.1% sodium thiosulfate PBS;
diluent agent: 0.1% Tween 80 in PBS (0.03mol/L)
Aseptic cotton swab
Test samples: wooden table top
Method
The detection basis is as follows: "Disinfection technical Specification" 2002 edition
The disinfection method comprises the following steps: taking a proper amount of sample, spraying the sample on the surface of the wood, and disinfecting for 15 minutes
Detecting the environment: the temperature is 21 ℃ and the humidity is 46%
The test was repeated 3 times, with 30 tests each.
Test results: the results of 3 times of average control values for killing natural bacteria on the wooden surface are as follows:>1.73，>1.84，>1.77, so average>1.78, the disinfection is qualified.
Example 10
Experiment for quantitative killing of bacteria with hypochlorous acid disinfectant obtained in example 2
Test strain name:
escherichia coli, strain number: 8099, strain generation number: the sixth generation;
staphylococcus aureus, strain number: ATCC6538, strain passage number: the sixth generation;
pseudomonas aeruginosa, strain number: ATCC15442, strain passage number: the third generation;
candida albicans, strain number: ATCC10231, strain passage number: sixth generation
The strain source is as follows: ATCC (American type culture Collection)
Instrumentation and equipment: a biological safety cabinet YQF-057 and a biochemical incubator YQF-159.
Basis of examination：
1. Disinfection technical code, ministry of health 2002;
2. a neutralizer suspension quantitative determination test; and
3. detecting the ambient temperature: 23 ℃ and relative humidity 46%.
And (4) detection conclusion:
1. the neutralizing agent meets the test requirements.
2. The acting concentration of the sample is 50%, the acting time is 0.5 min, 1 min and 1.5 min, the test is repeated for 3 times, the killing log values of the sample to escherichia coli (8099), staphylococcus aureus (ATCC6538) and pseudomonas aeruginosa (ATCC15442) are all more than 5.00, and the tested strain is qualified for disinfection.
3. The acting concentration of the sample is 50%, the acting time is 0.5 min, the test is repeated for three times, the killing logarithm of the candida albicans is less than 4.00, the average logarithm value is 3.87, and the sterilization rate is average 99.98%; the action time is 1 minute and 1.5 minutes, the test is repeated for 3 times, the killing logarithm is more than 4.00, and the tested strain is qualified for disinfection.
Example 11
Example 2 hypochlorous acid disinfectant solution obtained for virus inactivation experiment
Virus name and host:
poliovirus-I type vaccine strain and Vero cell
Instrumentation and equipment: a carbon dioxide incubator (QFM-B-B004), a low-temperature constant-temperature bath DKB-1915(QFM-B-P014), a biological safety cabinet (QFM-B-B031) and an inverted microscope (QFM-B-B012).
Basis of examination：
1. Disinfection technical code, ministry of health 2002;
2. detecting the ambient temperature: 23.2 ℃ and relative humidity 51%.
Inspection method
Sample action concentration 1: 1, acting for 0.5 minute, dividing into 5 groups, and performing an identification test of a physical removal method of the residual disinfectant;
sample action concentration 1: 1, the action time is 0.5 minute, 1 minute and 1.5 minutes, and the action time is repeated for 3 times, and the test temperature is 20 +/-1 ℃.
And (3) detection results:
1. the test result shows that the physical drug-removing method is qualified.
2.0.5 minute experiment, average inactivation logarithm value is 2.04, and virus inactivation rate is 99.06%;
1 minute experiment, average inactivation log value is more than 4.37, and virus inactivation rate is more than 99.99%;
the test of 1.5 minutes shows that the average inactivation log value is more than 4.21 and the virus inactivation rate is more than 99.99 percent.
Example 12
Quantitative bacteria killing experiment of hypochlorous acid disinfectant obtained in example 3
Test strain name:
escherichia coli, strain number: 8099, strain generation number: a fourth generation;
staphylococcus aureus, strain number: ATCC6538, strain passage number: a fourth generation;
pseudomonas aeruginosa, strain number: ATCC15442, strain passage number: a fourth generation;
candida albicans, strain number: ATCC10231, strain passage number: fourth generation
Bacillus subtilis var niger, strain number: ATCC9372, strain passage number: fifth generation
The strain source is as follows: ATCC (American type culture Collection)
Instrumentation and equipment: a biological safety cabinet YQF-057 and a biochemical incubator YQF-159.
Inspection method：
1. Disinfection technical code, ministry of health 2002;
2. the quantitative determination test of the neutralizer suspension is carried out according to the disinfection technical specification, 2002 by Ministry of health; and
3. detecting the ambient temperature: 20 ℃ and 42% relative humidity.
4. Sample preparation: a sample of 200ml is measured and is made into 1000ml with hard water for standby.
And (4) detection conclusion:
1. the neutralizing agent meets the test requirements.
2. The acting concentration of the sample is 20 percent, the acting time is 0.5 minute, 1 minute and 1.5 minutes, the test is repeated for 3 times, the killing log values of the sample to escherichia coli (8099), staphylococcus aureus (ATCC6538) and pseudomonas aeruginosa (ATCC15442) are all more than 5.00, and the tested strain is qualified for disinfection.
3. The acting concentration of the sample is 20%, the acting time is 0.5 min, 1 min and 1.5 min, the test is repeated for three times, the killing logarithm of the candida albicans is greater than 4.00, the sterilization rate is greater than 99.99%, and the tested strain is qualified for sterilization.
4. The original concentration of the sample, the acting time of 20 minutes, 40 minutes and 60 minutes, the test is repeated three times, the killing logarithm of the black variant spore of the bacillus subtilis is more than 5.00, the average sterilization rate is more than 99.999 percent, and the tested strain is qualified for disinfection.
Example 13
Virus inactivation experiment was performed on the hypochlorous acid disinfectant obtained in example 3
Virus name and host:
poliovirus-I type vaccine strain and Vero cell
Instrumentation and equipment: a carbon dioxide incubator (QFM-B-B045) at 37 ℃, a low-temperature thermostatic bath DKB-1915(QFM-B-P014), a biological safety cabinet (QFM-B-B031) and an inverted microscope (QFM-B-B012).
Basis of examination：
1. Disinfection technical code, ministry of health 2002;
2. detecting the ambient temperature: 20.5 ℃ and 52% relative humidity.
Inspection method
The sample has the action concentration of 20 percent and the action time of 1 minute, and is divided into 5 groups, the test temperature is 20 +/-1 ℃, and the identification test of the physical removal method of the residual disinfectant is carried out;
the action concentration of the sample is 20 percent, the action time is 1 minute, the action is repeated for 3 times, and the test temperature is 20 +/-1 ℃.
And (3) detection results:
1. the test result shows that the physical drug-removing method is qualified.
2.1 min experiment, the average inactivation log value is 4.01, and the virus inactivation rate is 99.99%.
Besides the tests, other microbial index tests, lead, arsenic and mercury index measurement tests, metal corrosion tests, domestic drinking water disinfection field tests, hard surface disinfection tests, air disinfection simulation field tests, hand disinfection tests, forearm skin disinfection tests, artificial bacteria-staining ceramic disc disinfection tests and cucumber surface sterilization tests are all qualified; the results of inhalation toxicity test, damaged skin irritation test, acute oral toxicity test, acute eye irritation test, vaginal mucosa irritation test, mouse bone marrow erythrocyte micronucleus test and the like prove that the product of the invention has no toxicity, no irritation and no damage to chromosomes in vivo.
In the present invention, "plural" means at least two.
Although claims have been formulated in this application to particular combinations of features and some embodiments have been shown and described, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles of the invention, the scope of which is defined in the claims. It will be understood by those skilled in the art that modifications (additions and/or deletions) may be made to the components, ingredients, systems described herein without departing from the full scope and spirit of the invention, which encompass such modifications and any and all equivalents thereof.
Claims (9)
1. A hypochlorous acid disinfectant which can be stably stored is subacid oxidation potential water and contains 500ppm of iodate, and also contains one or more of dibasic phosphate, monobasic phosphate, sulfate, carbonate and bicarbonate with the dosage of 50-400ppm respectively, wherein the effective chlorine concentration is 250-600 ppm.
2. The hypochlorous acid disinfectant of claim 1, wherein the iodate is potassium iodate or sodium iodate.
3. The hypochlorous acid disinfectant of claim 1, wherein the sulfate, carbonate, dibasic phosphate, monobasic phosphate, and bicarbonate salts are each sodium or potassium salts.
4. The hypochlorous acid disinfectant of claim 1, wherein the effective chlorine concentration of the hypochlorous acid disinfectant is 250-550 ppm.
5. The hypochlorous acid disinfectant of claim 1, wherein the slightly acidic electrolyzed oxidizing water has a pH of 4.5 to 6.8 and an oxidation-reduction potential of not more than 900 mV.
6. The hypochlorous acid disinfectant of claim 1, which is slightly acidic electrolyzed oxidizing water containing iodate and one or more of dibasic phosphate, monobasic phosphate, carbonate, sulfate, and bicarbonate, and which has an effective chlorine decrease of no more than 5% within 12 months of storage at ambient temperature.
7. A method of producing the hypochlorous acid disinfectant of claim 1, comprising:
(1) adding iodate into subacid oxidation potential water;
(2) standing for 1-8 hours; and
(3) adding one or more of sulfate, carbonate, dibasic phosphate, monobasic phosphate and bicarbonate.
8. The method of claim 7 wherein the slightly acidic oxidative potential water has an oxidation-reduction potential of no more than 900mV and a pH of between 4.5 and 6.8.
9. The method of claim 7, wherein common salt is used as a raw material in the production of the slightly acidic electrolyzed oxidizing water, and common salt consumption is controlled to be 5 to 13 g/g of available chlorine, and energy consumption is controlled to be 5 to 25W-h/g of available chlorine.
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