CN112544630A - Hypochlorous acid solution stabilizer and application thereof - Google Patents
Hypochlorous acid solution stabilizer and application thereof Download PDFInfo
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- CN112544630A CN112544630A CN202011359410.7A CN202011359410A CN112544630A CN 112544630 A CN112544630 A CN 112544630A CN 202011359410 A CN202011359410 A CN 202011359410A CN 112544630 A CN112544630 A CN 112544630A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
Abstract
The invention discloses a hypochlorous acid solution stabilizer which is any one or more of chitosan, cyclodextrin, polyalcohol, a surfactant and sulfamate. The invention also discloses application of the hypochlorous acid solution stabilizer in improving the stability of the hypochlorous acid solution. The invention also discloses a method for promoting the stability of the hypochlorous acid solution to be improved, which comprises the following steps: 1) preparing a hypochlorous acid initial solution; 2) a hypochlorous acid solution stabilizer is added to the hypochlorous acid initial solution. The invention also discloses a hypochlorous acid solution. The product prepared by the invention has 68mg/L +/-15% of available chlorine content, the pH value of 5.0-7.5 and the reduction rate of the available chlorine as low as 10%, and has industrial production and practical application values.
Description
Technical Field
The invention belongs to the technical field of hypochlorous acid solution production, and relates to a hypochlorous acid solution stabilizer and application thereof.
Background
The conventional methods for producing hypochlorous acid water include a pH adjustment method and an electrolysis method, wherein the pH adjustment method is formed by diluting hypochlorite with citric acid or hydrochloric acid, and the produced hypochlorous acid solution has low content of hypochlorous acid molecules and high content of hypochlorite radicals, so that the sterilizing effect is inferior to that of the hypochlorous acid solution prepared by the electrolysis method.
The electrolysis method is to electrolyze chloride or hydrochloric acid or a mixture solution of hydrochloric acid and chloride. The hypochlorous acid solutions produced by these two methods have poor stability and cannot be stored for a long time. In the prior art, a stabilizing agent is added into a hypochlorous acid solution prepared by an electrolytic method in patent CN110952108 to improve the stability of the hypochlorous acid solution, so that the hypochlorous acid solution can be placed in a constant-temperature and constant-humidity oven at 54 ℃ for 14 days, the reduction rate of available chlorine is less than or equal to 10 percent, and the effective period of the product reaches more than one year. But in the research of the hypochlorous acid solution products on the market, a laboratory stability experiment method is adopted, the samples are placed in a constant-temperature constant-humidity oven at 54 ℃ for 14 days, and the reduction rate of the effective chlorine does not reach the sanitary requirement of the GB-T36758-2018 chlorine-containing disinfectant. Therefore, how to improve the stability and safety and sanitation requirements of sodium hypochlorite solution is a problem to be solved in the field.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
It is a further object of the present invention to provide a secondary chlorate solution stabilizer.
It is another object of the present invention to provide the use of a hypochlorous acid solution stabilizer for improving the stability of a hypochlorous acid solution.
It is another object of the present invention to provide a method for promoting the improvement of the stability of hypochlorous acid solution.
It is yet another object of the present invention to provide a hypochlorous acid solution.
Therefore, the technical scheme provided by the invention is as follows:
the hypochlorous acid solution stabilizer is any one or more of chitosan, cyclodextrin, polyalcohol, surfactant and sulfamate.
Preferably, the hypochlorous acid solution stabilizer is added in an amount of at least 0.01% by mass concentration.
The hypochlorous acid solution stabilizer is applied to improving the stability of the hypochlorous acid solution.
A method of promoting the stability of a hypochlorous acid solution, comprising the steps of:
1) preparing a hypochlorous acid initial solution;
2) and adding a hypochlorous acid solution stabilizer into the hypochlorous acid initial solution, wherein the hypochlorous acid solution stabilizer is any one or more of chitosan, cyclodextrin, polyalcohol, surfactant and sulfamate.
Preferably, in the method for promoting the stability improvement of the hypochlorous acid solution, in the step 1), the specific steps of preparing the hypochlorous acid initial solution include:
dilute hydrochloric acid solution with volume concentration of 4-12% and water solution containing 10-50ppm regulator are placed in the electrolytic tank of hypochlorous acid generator to form the described hypochlorous acid initial solution.
Preferably, in the method for promoting the stability improvement of a hypochlorous acid solution, in the step 2), at least 0.01% of the hypochlorous acid solution stabilizer is added to the hypochlorous acid initial solution in a volume concentration.
Preferably, in the method for promoting the stability improvement of the hypochlorous acid solution, the regulator is one or more of carbonate, bicarbonate and chloride.
Preferably, in the method for promoting the stability of the hypochlorous acid solution, domestic water is used as the aqueous solution.
Preferably, in the method for promoting the stability of the hypochlorous acid solution, a plurality of electrode units are arranged in the hypochlorous acid generator electrolytic tank, and each electrode unit comprises:
the electrode device comprises a plurality of electrode parts, a plurality of electrode parts and a plurality of control circuits, wherein each electrode part comprises a first electrode tube, a second electrode tube and a third electrode tube which are sleeved from outside to inside in a concentric ring shape, a first containing space is formed between the inner wall of the first electrode tube and the outer wall of the second electrode tube, a second containing space is formed between the inner wall of the second electrode tube and the outer wall of the third electrode tube, the first electrode tube and the third electrode tube are respectively and electrically connected with a power cathode to form a cathode tube, the second electrode tube is electrically connected with a power anode to form an anode tube, a mixed solution of the dilute hydrochloric acid solution and the aqueous solution is contained in the first containing space and the second containing space, and the electrode parts are connected in parallel;
a cooling part including an annular housing in which the plurality of electrode parts are arranged, the annular housing being in liquid communication with the inside of the plurality of third electrode tubes to form a third accommodation space in which a cooling liquid is accommodated.
A hypochlorous acid solution produced by any of the methods described herein.
The invention at least comprises the following beneficial effects:
firstly, the hypochlorous acid solution stabilizer is prepared and successfully applied to the production process of the hypochlorous acid solution, the prepared hypochlorous acid solution has the effective chlorine content of 68mg/L +/-15 percent, the pH value of 5.0-7.5, the reduction rate of the effective chlorine is as low as 2 percent, the hypochlorous acid solution is not easy to decompose, the quality guarantee period is as long as one year, the hypochlorous acid solution stabilizer is convenient to store, can be sold in the market in a commodity form, and has industrial production and practical application values;
secondly, the stability of the product exceeds that of most chlorine-containing solution supplies on the market, the product completely meets the record standard of the chlorine-containing disinfectant, the product belongs to disinfectant products, and the reduction rate of the available chlorine in the effective period of one year is controlled within 2 percent, so that the disinfection effectiveness of the product is greatly ensured (the reduction rate of the available chlorine of the product on the market in one year is over 15 percent and does not meet the sanitary requirement of GB-T36758-2018 chlorine-containing disinfectant);
the invention explains the stabilization principle and the support of related data in detail, the principle of a stabilization system is clear, reference significance is provided for the industrial production and the practical application of the hypochlorous acid solution, the reaction can be carried out by adding a proper amount of chlorine carriers from the consideration of chain reaction, and the reversible reaction of HClO decomposition:
adding Cl ions to promote the forward reaction, specifically referring to a hypochlorous acid stability diagram in figure 1, and selecting a regulator as a buffer system and regulating the pH (5.0-7.5);
the hypochlorous acid solution prepared by the fourth step has a killing effect on escherichia coli and staphylococcus aureus enzyme;
the hypochlorous acid solution has rich application scenes, is used for disinfection or deodorization scenes required by people or pets, and comprises disinfection of the surface of a common hard object and the air in a room or other closed spaces.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a schematic diagram illustrating the stability of hypochlorous acid in the present invention;
FIG. 2 is a comparison of hypochlorous acid stability tests in one example of the present invention;
fig. 3 is a schematic structural diagram of an electrode unit in one embodiment of the present invention.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The invention provides a hypochlorous acid solution stabilizer, which comprises the following components: the hypochlorous acid solution stabilizer is one or more of chitosan, cyclodextrin, polyalcohol, surfactant and sulfamate.
In some embodiments of the present invention, it is preferable that the hypochlorous acid solution stabilizer is added in an amount of at least 0.01% by mass concentration.
The invention also provides application of the hypochlorous acid solution stabilizer in improving the stability of the hypochlorous acid solution.
The invention also provides a method for promoting the stability improvement of a hypochlorous acid solution, which comprises the following steps:
1) preparing a hypochlorous acid initial solution;
2) and adding a hypochlorous acid solution stabilizer into the hypochlorous acid initial solution, wherein the hypochlorous acid solution stabilizer is any one or more of chitosan, cyclodextrin, polyalcohol, surfactant and sulfamate.
In one embodiment of the present invention, preferably, in the step 1), the specific step of preparing the hypochlorous acid initial solution comprises:
dilute hydrochloric acid solution with volume concentration of 4-12% and water solution containing 10-50ppm regulator are placed in the electrolytic tank of hypochlorous acid generator to form the described hypochlorous acid initial solution.
In one embodiment of the present invention, it is preferable that at least 0.01% of the hypochlorous acid solution stabilizer is added to the hypochlorous acid initial solution in the step 2) in a volume concentration.
In one embodiment of the present invention, preferably, the modifier is any one or more of carbonate, bicarbonate and chloride.
In one embodiment of the present invention, the aqueous solution is preferably domestic water.
In one embodiment of the present invention, it is preferable that the hypochlorous acid generator electrolytic tank is provided therein with a plurality of electrode units, each of which includes:
the electrode device comprises a plurality of electrode parts, a plurality of electrode parts and a plurality of control circuits, wherein each electrode part comprises a first electrode tube, a second electrode tube and a third electrode tube which are sleeved from outside to inside in a concentric ring shape, a first containing space is formed between the inner wall of the first electrode tube and the outer wall of the second electrode tube, a second containing space is formed between the inner wall of the second electrode tube and the outer wall of the third electrode tube, the first electrode tube and the third electrode tube are respectively and electrically connected with a power cathode to form a cathode tube, the second electrode tube is electrically connected with a power anode to form an anode tube, a mixed solution of the dilute hydrochloric acid solution and the aqueous solution is contained in the first containing space and the second containing space, and the electrode parts are connected in parallel;
a cooling part including an annular housing in which the plurality of electrode parts are arranged, the annular housing being in liquid communication with the inside of the plurality of third electrode tubes to form a third accommodation space in which a cooling liquid is accommodated. The electrode unit has high structural utilization rate and small occupied volume, and convex-concave structures and the like can be additionally arranged on the surface of the electrode to further increase the surface area of the electrode unit. Meanwhile, a cooling part is formed between the annular shell and the electrode, so that the space is saved, the produced hypochlorous acid solution is rapidly cooled, the volatilization is reduced, and the stability of the hypochlorous acid solution is improved.
The invention also provides a hypochlorous acid solution prepared by any one of the methods.
In order to make the technical solution of the present invention better understood by those skilled in the art, the following examples are now provided for illustration:
the invention provides a hypochlorous acid solution stabilizer and application thereof, wherein the hypochlorous acid solution stabilizer is applied to a hypochlorous acid solution production process, the prepared hypochlorous acid solution has the effective chlorine content of 68mg/L +/-15 percent, the pH value of 5.0-7.5, the reduction rate of the effective chlorine is as low as 2 percent, and the hypochlorous acid solution stabilizer meets the recorded standard of a chlorine-containing disinfectant.
A hypochlorous acid solution stabilizer is one or more of chitosan, cyclodextrin, polyalcohol, surfactant and sulfamate.
The application of the hypochlorous acid solution stabilizer is used in the stable production method for improving hypochlorous acid solution.
As a preferred scheme, the method for improving the stable production of the hypochlorous acid solution comprises the following specific steps:
adding 10-50ppm of regulator into domestic water, wherein the regulator is one or a mixture of more of carbonate, bicarbonate and chloride;
preparing a dilute hydrochloric acid solution with the volume concentration of 4-12% as an electrolysis raw material of the hypochlorous acid generator;
thirdly, the dilute hydrochloric acid solution and the regulator in the first step enter an electrolytic bath of a hypochlorous acid generator through a pump body, and are mixed and electrolyzed to generate a hypochlorous acid initial solution;
adding the hypochlorous acid solution stabilizer into the hypochlorous acid initial solution to generate hypochlorous acid solution.
Preferably, the hypochlorous acid solution stabilizer is added in an amount of at least 0.01%.
As a preferable scheme, the physical and chemical indexes of the prepared hypochlorous acid solution are as follows: the content of available chlorine is 68mg/L +/-15%, the pH value is 5.0-7.5, and the reduction rate of the available chlorine is as low as 10%.
As a preferable scheme, the prepared hypochlorous acid solution enables the reduction rate of available chlorine to be as low as 2% by the chain reaction principle.
As a preferred scheme, the chain reaction principle: the chlorine salt is oxidized by hypochlorous acid, the generated chlorine gas is not released but interacts with the hypochlorous acid stabilizer to form an intermediate compound, the compound is decomposed to generate hypochlorous acid, and the reaction is circulated, and after the chlorine is released from the hypochlorous acid stabilizer, more chlorine salt molecules are formed to provide a continuous raw material for the circulation.
Preferably, the hypochlorous acid stabilizer acts as a chlorine carrier.
A hypochlorous acid solution, prepared according to any of the above stable manufacturing methods for enhancing hypochlorous acid solution, for use in disinfection or deodorization scenarios for humans or pets, including disinfection of surfaces of generally hard objects and air in rooms or other enclosed spaces, oral products, wound cleaning and disinfection, and the like.
The specific formula of the hypochlorous acid solution is as follows: 99.0 to 100.0 percent of HClO, 0.01 to 0.03 percent of sulfamic acid, 0.005 to 0.03 percent of phosphate and 0.002 to 0.010 percent of chloride.
The specific formula of the hypochlorous acid solution is as follows: 99.0 to 100.0 percent of HClO, 0.01 to 0.03 percent of chitosan, 0.005 to 0.03 percent of phosphate and 0.002 to 0.010 percent of chloride.
Preparation of hypochlorous acid solution
The first scheme is as follows:
adding 20ppm of carbonate into domestic water;
preparing a dilute hydrochloric acid solution with the volume concentration of 4% as an electrolysis raw material of the hypochlorous acid generator;
thirdly, the dilute hydrochloric acid solution and the carbonate with the concentration of 20ppm in the step I enter an electrolytic bath of a hypochlorous acid generator through a pump body, and a hypochlorous acid initial solution is generated through mixing and electrolysis;
fourthly, adding 0.01 percent of hypochlorous acid solution stabilizer sulfamic acid into the hypochlorous acid initial solution to generate hypochlorous acid solution.
The final specific hypochlorous acid solution comprises the following components in percentage by mass: 99.0% of HClO, 0.01% of sulfamic acid, 0.03% of phosphate and 0.96% of chloride.
Scheme II:
the preparation method is the same as the first scheme, and the final specific hypochlorous acid dissolving formula is as follows: 99.5% of HClO, 0.03% of chitosan, 0.03% of phosphate and 0.44% of chloride.
Scheme three
Adding 10ppm of carbonate into domestic water;
preparing a dilute hydrochloric acid solution with the volume concentration of 5% as an electrolysis raw material of the hypochlorous acid generator;
thirdly, the dilute hydrochloric acid solution and the carbonate with the concentration of 10ppm in the step I enter an electrolytic tank of a hypochlorous acid generator through a pump body, and a hypochlorous acid initial solution is generated through mixing and electrolysis;
and fourthly, adding 0.02 percent of hypochlorous acid solution stabilizer cyclodextrin into the hypochlorous acid initial solution to generate hypochlorous acid solution.
The final specific hypochlorous acid solution comprises the following components in percentage by mass: 99.5 percent of HClO, 0.02 percent of cyclodextrin, 0.03 percent of phosphate and 0.010 percent of chloride.
Scheme four
Adding 50ppm of carbonate into domestic water;
preparing a dilute hydrochloric acid solution with the volume concentration of 12% as an electrolysis raw material of the hypochlorous acid generator;
thirdly, the dilute hydrochloric acid solution and the carbonate with the concentration of 50ppm in the step I enter an electrolytic tank of a hypochlorous acid generator through a pump body, and a hypochlorous acid initial solution is generated through mixing and electrolysis;
adding 0.02% of hypochlorous acid solution stabilizer polyhydric alcohol into the hypochlorous acid initial solution to generate hypochlorous acid solution.
The final specific hypochlorous acid solution comprises the following components in percentage by mass: 99.8 percent of HClO, 0.02 percent of polyalcohol, 0.005 percent of phosphate and 0.0020 percent of chlorine salt.
Scheme five
Adding 30ppm of carbonate into domestic water;
preparing a dilute hydrochloric acid solution with the volume concentration of 10 percent as an electrolysis raw material of the hypochlorous acid generator;
thirdly, the dilute hydrochloric acid solution and the carbonate of 30ppm in the step I enter an electrolytic bath of a hypochlorous acid generator through a pump body, and a hypochlorous acid initial solution is generated through mixing and electrolysis;
and fourthly, adding 0.04 percent of hypochlorous acid solution stabilizer surfactant into the hypochlorous acid initial solution to generate hypochlorous acid solution.
The final specific hypochlorous acid solution comprises the following components in percentage by mass: 99.7% of HClO, 0.04% of surfactant, 0.01% of phosphate and 0.008% of chloride.
Scheme six
Adding 40ppm of carbonate into domestic water;
preparing a dilute hydrochloric acid solution with the volume concentration of 8% as an electrolysis raw material of the hypochlorous acid generator;
thirdly, the dilute hydrochloric acid solution and the carbonate of 40ppm in the step I enter an electrolytic bath of a hypochlorous acid generator through a pump body, and a hypochlorous acid initial solution is generated through mixing and electrolysis;
fourthly, adding 0.05 percent of hypochlorous acid solution stabilizer sulfamic acid into the hypochlorous acid initial solution to generate hypochlorous acid solution.
The final specific hypochlorous acid solution comprises the following components in percentage by mass: 98.7 percent of HClO, 0.05 percent of sulfamic acid, 0.03 percent of phosphate and 0.94 percent of chloride.
Scheme seven
Adding 35ppm of carbonate into domestic water;
preparing a dilute hydrochloric acid solution with the volume concentration of 7 percent as an electrolysis raw material of the hypochlorous acid generator;
thirdly, the dilute hydrochloric acid solution and the 35ppm carbonate in the step I enter an electrolytic bath of a hypochlorous acid generator through a pump body, and a hypochlorous acid initial solution is generated through mixing and electrolysis;
adding hypochlorous acid solution stabilizer chitosan 0.01%, cyclodextrin 0.01%, polyol 0.01%, surfactant 0.01% and sulfamate 0.01% into hypochlorous acid initial solution to generate hypochlorous acid solution.
The final specific hypochlorous acid solution comprises the following components in percentage by mass: 99.0% of HClO, 0.01% of chitosan, 0.01% of cyclodextrin, 0.01% of polyalcohol, 0.01% of surfactant, 0.01% of sulfamate, 0.03% of phosphate and 0.95% of chloride.
Scheme eight
Adding 30ppm of carbonate into domestic water;
preparing a dilute hydrochloric acid solution with the volume concentration of 9 percent as an electrolysis raw material of the hypochlorous acid generator;
thirdly, the dilute hydrochloric acid solution and the carbonate of 30ppm in the step I enter an electrolytic bath of a hypochlorous acid generator through a pump body, and a hypochlorous acid initial solution is generated through mixing and electrolysis; be provided with a plurality of electrode units in the hypochlorous acid generator electrolysis trough, every electrode unit all includes: the electrode device comprises a plurality of electrode parts, a plurality of electrode parts and a plurality of control circuits, wherein each electrode part comprises a first electrode tube, a second electrode tube and a third electrode tube which are sleeved from outside to inside in a concentric ring shape, a first containing space is formed between the inner wall of the first electrode tube and the outer wall of the second electrode tube, a second containing space is formed between the inner wall of the second electrode tube and the outer wall of the third electrode tube, the first electrode tube and the third electrode tube are respectively and electrically connected with a power cathode to form a cathode tube, the second electrode tube is electrically connected with a power anode to form an anode tube, a mixed solution of the dilute hydrochloric acid solution and the aqueous solution is contained in the first containing space and the second containing space, and the electrode parts are connected in parallel; a cooling part including an annular housing in which the plurality of electrode parts are arranged, the annular housing being in liquid communication with the inside of the plurality of third electrode tubes to form a third accommodation space in which a cooling liquid is accommodated.
Fourthly, adding 0.02 percent of hypochlorous acid solution stabilizer chitosan, 0.02 percent of polyol and 0.02 percent of sulfamic acid into the hypochlorous acid initial solution to generate hypochlorous acid solution.
The final specific hypochlorous acid solution comprises the following components in percentage by mass: 98.7 percent of HClO, 0.02 percent of chitosan, 0.02 percent of polyol, 0.02 percent of sulfamic acid, 0.05 percent of phosphate, 0.03 percent of chloride.
Control protocol:
the preparation method is the same as the first scheme, but no hypochlorous acid solution stabilizer is added in the prepared hypochlorous acid initial solution, and the final specific hypochlorous acid solution has the following formula: 99.5% of HClO, 0.06% of phosphate and 0.44% of chloride.
A laboratory stability experiment method is adopted, samples of the scheme I, the scheme II and the comparison scheme are placed in a constant-temperature constant-humidity oven 14d at 54 ℃, the reduction rate of effective chlorine is considered, the results are shown in figure 2, the scheme I and the scheme II show that the reduction rate of the effective chlorine of the samples added with the stabilizing agent is maintained within 2 percent, the sanitation requirement of the chlorine-containing disinfectant GB-T36758-2018 is met, the test result of the scheme II is considered as an error and can be ignored, the samples prepared by the scheme I are sent to a third party for detection, the reduction rate of the tested effective chlorine is 1.65 percent, the reduction rate of the effective chlorine in the comparison scheme is as high as 38.21 percent within an error allowable range, and the reduction rate of the effective chlorine after the stabilizing agent is added is obviously reduced.
Technical effects
Hypochlorous acid solution index test
The hypochlorous acid solution prepared according to the present invention (hereinafter referred to as a sample as a small shell cooker) was measured according to the determination of the content of available chlorine in the Disinfection Specification (2002 edition)TMDisinfectant), and the sample number delivered to the detection institution is WP-20079171-JC-01, and the results show that the hypochlorous acid solution prepared in the present invention has an average value of 60.6mg/L of available chlorine before storage and an average value of 59.6mg/L of available chlorine when stored at 54 ℃ for 14 days. The hypochlorous acid solution prepared by the invention has the expiration date of 1 year (sample 'Xiaohulidshi') determined by an accelerated test method for measuring the stability of sterilized products in accordance with the technical Specification for Disinfection (2002 edition) 2.2.3.2.1 Disinfection productTMThe disinfectant is characterized in that after the disinfectant is placed in an environment with the temperature of 54 ℃ for 14 days, the content reduction rate of the available chlorine content is 1.65%, the storage period can be determined as one year, and the main content of the report is described in detail below).
Sample name: small shell small powerTMDisinfectant
First, equipment
1. Test samples: small shell small powerTMDisinfectant
2. Standard solution name: sodium thiosulfate standard titration liquid
Second, method
1. The detection basis is as follows: disinfection technical Specification (2002 edition)
2. Detection conditions are as follows: the ambient temperature was 20.5 ℃ and the humidity was 69% RH. The number of experimental repetitions: 6 times.
Three, result in
After the sample is stored for 14 days at 54 ℃, the effective rate content and the reduction rate result are shown in table 1 and table 2.
TABLE 1 test results of effective content (g/L) of samples after 14 days storage
TABLE 2 stability test results before and after storage of samples
Fourth, conclusion
Sample "XiaohuxiaolishiTMThe disinfectant is placed in an environment with the temperature of 54 ℃ for 14 days, the content reduction rate of the available chlorine content is 1.65%, and the storage period can be determined as one year.
In addition, the average value of the effective chlorine content of the hypochlorous acid solution prepared by the method is 77.9mg/L before storage, the average value of the effective chlorine content is 68.4mg/L when the hypochlorous acid solution is stored for 3 months at 37 ℃, and the reduction rate of the effective chlorine is about 12 percent.
According to the quantitative sterilization test determination method of the bacterial suspension of 2002 edition-2.1.1.7.4 in the disinfection technical Specification, the killing effect of the hypochlorous acid solution on staphylococcus aureus is detected, the sample number sent to a detection mechanism is 2020FM08060R01, the hypochlorous acid solution prepared by the invention shows that the killing log value of the hypochlorous acid solution on staphylococcus aureus (ATCC 6538) is more than 5.00, and the detected strain is qualified for disinfection. The detection conclusion is as follows:
the action time of the sample stock solution is respectively 10min, 20min and 30min, the test is repeated for 3 times, the killing log value of staphylococcus aureus (ATCC 6538) is more than 5.00, the sample stock solution meets the evaluation regulation of 2002 edition-2.1.1.7.4 of disinfection technical specification (the killing log value is more than or equal to 5.00), and the sample is qualified for the disinfection of the tested strain.
According to a disinfection technical specification 2002 edition-2.1.1.5.5 neutralizer suspension quantitative identification test and a disinfection technical specification 2002 edition-2.1.1.7.4 bacteria suspension quantitative sterilization test determination method, the killing effect of the hypochlorous acid solution on escherichia coli is detected, the sample number sent to a detection mechanism is 2020FM08059R01, the result shows that the hypochlorous acid solution prepared by the invention has a killing logarithm value of more than 5.00 on escherichia coli (8099), and the detected strains are disinfected to be qualified. The detection conclusion is as follows:
1. quantitative identification test of neutralizer suspension: korean PBS solution containing 3% Tween-80, 0.5% sodium thiosulfate, 0.5% L-histidine, 0.5% peptone, 0.85% sodium chloride, 1.43% lecithin, and 0.1% cysteine, and can effectively neutralize "Caligus ChachiensisTMDisinfectant ", and neutralizing agent and neutralizing product have no adverse effect on Escherichia coli.
2. Quantitative sterilization test of suspension: the action time of the sample stock solution is respectively 10min, 20min and 30min, the test is repeated for 3 times, the killing logarithm value of the sample stock solution to escherichia coli (8099) is more than 5.00, the sample stock solution meets the evaluation regulation of 2002 edition-2.1.1.7.7 of disinfection technical specification (the killing logarithm value is more than or equal to 5.00), and the sample is qualified for the disinfection of the tested strain.
According to a test method for identifying a hard surface disinfection site in 2002 edition-2.1.2.10, the sample number of the sample sent to a detection mechanism is 2020FM08061R01, and the hypochlorous acid solution prepared by the method can achieve a disinfection effect on the surface of a hard object. The detection conclusion is as follows:
the sample stock solution has the action time of 20min respectively, the average killing logarithm value of the sample stock solution to the natural bacteria on the surface of a working table is more than 1.92, the sample stock solution meets the evaluation regulation of 2002 edition-2.1.2.10.4 of disinfection technical specification (the killing logarithm value is more than or equal to 1), and the sample stock solution is judged to be qualified for disinfection.
According to the on-site test method for air disinfection effect in the 'disinfection technical specification' 2002 edition-2.1.3, the sample number of the sample sent to a detection mechanism is 2020FM19117R01, and the hypochlorous acid solution prepared by the invention is detected to be in line with the on-site air disinfection effect. The detection conclusion is as follows:
nebulization of 200mL samples to 20m with a nebulizer3The experiment is carried out in the experimental cabin for 30min, the experiment is repeated for 3 times, the detection results of the natural bacteria elimination rate in the air are all more than 90, the test result accords with the evaluation regulation of 2002 edition-2.1.3.5 of disinfection technical Specification (the natural bacteria elimination rate is all more than or equal to 90), and the disinfection is qualified.
The number of modules and the processing scale described herein are intended to simplify the description of the invention. Modifications and variations of the hypochlorous acid solution of the present invention, its use, and the like will be apparent to those skilled in the art.
The invention provides a hypochlorous acid solution stabilizer and application thereof, wherein the stabilizer is one or a mixture of more of chitosan, cyclodextrin, polyalcohol, surfactant and sulfamate, the stabilizer is applied to the production of the hypochlorous acid solution, the effective chlorine content of the prepared product is 68mg/L +/-15%, the pH value is 5.0-7.5, the reduction rate of the effective chlorine is as low as 10%, and the industrial production and practical application value are realized.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (10)
1. The hypochlorous acid solution stabilizer is characterized in that the hypochlorous acid solution stabilizer is any one or more of chitosan, cyclodextrin, polyalcohol, surfactant and sulfamate.
2. The hypochlorous acid solution stabilizer according to claim 1, wherein said hypochlorous acid solution stabilizer is added in an amount of at least 0.01% by mass concentration.
3. Use of the hypochlorous acid solution stabilizer of claim 1 for improving the stability of hypochlorous acid solution.
4. A method for promoting the stability improvement of a hypochlorous acid solution is characterized by comprising the following steps:
1) preparing a hypochlorous acid initial solution;
2) and adding a hypochlorous acid solution stabilizer into the hypochlorous acid initial solution, wherein the hypochlorous acid solution stabilizer is any one or more of chitosan, cyclodextrin, polyalcohol, surfactant and sulfamate.
5. The method of promoting the stability improvement of a hypochlorous acid solution of claim 4, wherein the specific steps of preparing the hypochlorous acid initial solution in step 1) comprise:
dilute hydrochloric acid solution with volume concentration of 4-12% and water solution containing 10-50ppm regulator are placed in the electrolytic tank of hypochlorous acid generator to form the described hypochlorous acid initial solution.
6. The method for promoting the stability of hypochlorous acid solution according to claim 4, wherein the hypochlorous acid stabilizer is added to the hypochlorous acid initial solution in a concentration of at least 0.01% by volume in step 2).
7. The method for promoting the stability of a hypochlorous acid solution of claim 5, wherein the modifying agent is any one or more of a carbonate, a bicarbonate, and a chloride salt.
8. The method for promoting the stability of hypochlorous acid solution according to claim 5, wherein said aqueous solution is domestic water.
9. The method of promoting the stability of a hypochlorous acid solution of claim 5, wherein a plurality of electrode units are disposed in the hypochlorous acid generator cell, each electrode unit comprising:
the electrode device comprises a plurality of electrode parts, a plurality of electrode parts and a plurality of control circuits, wherein each electrode part comprises a first electrode tube, a second electrode tube and a third electrode tube which are sleeved from outside to inside in a concentric ring shape, a first containing space is formed between the inner wall of the first electrode tube and the outer wall of the second electrode tube, a second containing space is formed between the inner wall of the second electrode tube and the outer wall of the third electrode tube, the first electrode tube and the third electrode tube are respectively and electrically connected with a power cathode to form a cathode tube, the second electrode tube is electrically connected with a power anode to form an anode tube, a mixed solution of the dilute hydrochloric acid solution and the aqueous solution is contained in the first containing space and the second containing space, and the electrode parts are connected in parallel;
a cooling part including an annular housing in which the plurality of electrode parts are arranged, the annular housing being in liquid communication with the inside of the plurality of third electrode tubes to form a third accommodation space in which a cooling liquid is accommodated.
10. A hypochlorous acid solution produced by the method of any one of claims 4 to 9.
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