CN115152788A - Activation-free chlorine dioxide disinfectant and production process thereof - Google Patents

Activation-free chlorine dioxide disinfectant and production process thereof Download PDF

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CN115152788A
CN115152788A CN202211086867.4A CN202211086867A CN115152788A CN 115152788 A CN115152788 A CN 115152788A CN 202211086867 A CN202211086867 A CN 202211086867A CN 115152788 A CN115152788 A CN 115152788A
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chlorine dioxide
mixed solution
activating agent
sodium
activation
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侯云秀
陈小平
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Shandong Huashi Pharmaceutical Co ltd
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Shandong Huashi Pharmaceutical Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/22Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00Disinfectants; Antimicrobial compounds or mixtures thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00Fungicides

Abstract

The application provides an activation-free chlorine dioxide disinfectant and a production process thereof, relates to the field of disinfectants, and is used for solving the problem of low stability of the disinfectants. Specifically, the application provides an activation-free chlorine dioxide disinfectant, which comprises deionized water, pure chlorine dioxide, an activating agent and a stabilizing agent, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A. And mixing an activating agent in the mixed solution A, and mixing the activating agent with the mixed solution A to obtain a mixed solution B, wherein the activating agent comprises one or more of sodium ammonium sulfate, oxalic acid, citric acid and tartaric acid. And mixing a stabilizer in the mixed solution B to obtain a mixed solution C, wherein the stabilizer comprises one or more of sodium stannate, magnesium silicate, sodium glycinate and sodium carbonate. Wherein, the proportion of the deionized water, the pure chlorine dioxide, the activating agent and the stabilizing agent is (90-98.5): (1-9.5): (0.01-0.03): (0.1-0.4).

Description

Activation-free chlorine dioxide disinfectant and production process thereof
Technical Field
The application relates to the technical field of disinfectants, in particular to an activation-free chlorine dioxide disinfectant and a production process thereof.
Background
Chlorine dioxide is in a V-shaped molecular configuration in terms of its chemical structure. Has unpaired free electron, active chemical property, capacity of oxidizing toxic matter in water, and strong adsorption and killing effect on cell membrane. Chlorine dioxide has a similar pungent odor and is relatively corrosive to chlorine. With the improvement of the life quality of people, the requirements on water quality are more and more strict, so that the requirements on the use specification of the chlorine dioxide disinfectant are more and more strict.
Chlorine dioxide gas is easily volatilized and is difficult to control and store after being obtained, so that the chlorine dioxide gas is limited by the difficulty in control and storage when being used as a gaseous product for sterilization. In view of this, in the prior art, when chlorine dioxide gas is used for air sterilization, chlorine dioxide is basically synthesized through on-site reaction in the reaction bin, so that chlorine dioxide is generated on site and used on site.
The chlorine dioxide product has the safety risks of explosion, corrosion and the like in storage, transportation and use, needs to be activated when in use, is not easy to operate, and limits the application of the chlorine dioxide disinfectant in the aspects of environment, daily disinfection and the like. Although some activation-free chlorine dioxide disinfectant products appear in the market in recent years, the products have low content purity and poor stability, the effective period is only half a year, the maximum period is not more than one year, and the application is not ideal. The market urgently expects an activation-free chlorine dioxide disinfectant with good stability, long effective period, convenience and good effect.
Disclosure of Invention
The embodiment of the application provides an activation-free chlorine dioxide disinfectant and a production process thereof, which are used for solving the problem of low stability of the chlorine dioxide disinfectant.
In order to achieve the above purpose, the embodiment of the present application adopts the following technical solutions:
in a first aspect, the application provides an activation-free chlorine dioxide disinfectant, which comprises deionized water, pure chlorine dioxide, an activating agent and a stabilizing agent, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A. And mixing an activating agent in the mixed solution A, and mixing the activating agent with the mixed solution A to obtain a mixed solution B, wherein the activating agent comprises one or more of sodium ammonium sulfate, oxalic acid, citric acid and tartaric acid. And mixing a stabilizer in the mixed solution B to obtain a mixed solution C, wherein the stabilizer comprises one or more of sodium stannate, magnesium silicate, sodium glycinate and sodium carbonate. Wherein, the proportion of the deionized water, the pure chlorine dioxide, the activating agent and the stabilizing agent is (90-98.5): (1-9.5): (0.01-0.03): (0.1-0.4).
When the disinfectant is used, the activating agent is mixed with the inert chlorine dioxide aqueous solution, namely the activating agent arouses and activates the inert chlorine dioxide aqueous solution in a nonvolatile state, so that the chlorine dioxide in the aqueous solution is volatilized and released. Therefore, the effects of immediately reacting chemical raw materials and uniformly releasing chlorine dioxide gas can be achieved, and the air can be conveniently sterilized and used at any time. Overcomes the defects that the prior art needs to synthesize chlorine dioxide on site, can not store and uniformly release chlorine dioxide gas.
The inert chlorine dioxide aqueous solution is in a non-volatile state and can be obtained by selecting sodium chlorate (NaClO) from the chlorine dioxide aqueous solution 3 ) Sodium chlorite (NaClO) 2 ) Or sodium hydroxide (NaOH) is added, so that the chlorine dioxide in the aqueous solution is kept in a nonvolatile inert state. The activator comprises water-absorbent resin and activator raw material, specifically sodium citrate (C) 6 H 5 O 7 Na 3 ·2H 2 O), sodium dihydrogen phosphate (NaH) 2 PO 2 ) Sodium bicarbonate (NaHCO) 3 ) And a water absorbent resin (SAP). After the water-absorbent resin, the raw materials of the activating agent and the inert chlorine dioxide aqueous solution are mixed, the activating agent awakens and activates the inert chlorine dioxide aqueous solution in a nonvolatile state, so that the regional limitation and the time limitation of the use of the chlorine dioxide disinfectant are overcome, and the sterilizing effect is strong. Also, the addition of stabilizers further promotes the stability of the disinfectant.
In one possible implementation, the activator is sodium ammonium sulfate, and the ratio of the sodium ammonium sulfate is 0.02.
In one possible implementation, the stabilizer is sodium stannate, and the proportion of the sodium stannate is 0.2.
In one possible implementation, the activating agent is citric acid, and the proportion of the citric acid is 0.03.
In one possible implementation, the stabilizer is sodium carbonate, and the proportion of the sodium carbonate is 0.3.
In one possible implementation, the activator is a mixture of oxalic acid and citric acid, the ratio of the activator is 0.02, and the ratio of the oxalic acid to the citric acid is 0.003.
In a possible implementation manner, the stabilizer is a mixture of magnesium silicate and sodium glycinate, the ratio of the stabilizer is 0.3, and the ratio of the magnesium silicate to the sodium glycinate is 0.23.
In a second aspect, the present application provides a process for the production of an activation-free chlorine dioxide disinfectant, comprising:
s1: preparing chlorine dioxide, weighing sodium chlorite and hydrochloric acid, adding the sodium chlorite and the hydrochloric acid into a high-purity chlorine dioxide generator to react to generate a mixture, and separating the mixture to obtain pure chlorine dioxide;
s2: adding the pure chlorine dioxide obtained in the step S1 into deionized water to obtain a mixed solution A;
s3: adding an activating agent into the mixed solution A obtained in the step S2 to obtain a mixed solution B;
s4: and (4) adding a stabilizer into the mixed solution B obtained in the step (S3) to obtain a mixed solution C.
In one possible implementation, the extraction temperature of pure chlorine dioxide in step S1 is between 20 ℃ and 23 ℃.
In one possible implementation, the ratio of the amount of sodium chlorite to the amount of hydrochloric acid is 1:1.
The invention has the beneficial effects that:
when the disinfectant is used, the activating agent is mixed with the inert chlorine dioxide aqueous solution, namely the activating agent awakens and activates the inert chlorine dioxide aqueous solution in a non-volatile state, so that the chlorine dioxide in the aqueous solution is volatilized and released. Therefore, the effects of immediate reaction of chemical raw materials and uniform release of chlorine dioxide gas can be achieved, and the air can be conveniently sterilized and used at any time. The activation-free chlorine dioxide disinfectant overcomes the defects that chlorine dioxide needs to be synthesized on site in the prior art, and chlorine dioxide gas cannot be stored and released uniformly.
Drawings
FIG. 1 is a topographical view of Staphylococcus aureus without activated chlorine dioxide disinfectant as provided in some embodiments herein;
fig. 2 is a topographical view of staphylococcus aureus after 10 min exposure to an activation-free chlorine dioxide disinfectant as provided in some embodiments of the present application.
Detailed Description
In some embodiments, the terms "first," "second," "third," and "fourth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", "third" and "fourth" may explicitly or implicitly include one or more of the features.
In some embodiments, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
It is to be understood that the above-described orientations and positional relationships, as referred to by the terms "inner", "outer", and the like, are based on the orientations and positional relationships shown in the drawings and are only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus are not to be construed as limiting the present invention; the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.
The molecular formula of the chlorine dioxide is ClO 2 Molecular weight is 67.457. Chlorine atom is combined with 2 oxygen atoms by 2 coordinate bonds, an unpaired electron exists on the outer layer of the chlorine atom, the chloride ion has a valence of +4, the oxidation of the chlorine ion is 2.5 times that of the chlorine ion, and Mn can be oxidized 2+ By oxidation to Mn 4+ Of Fe 2+ Is oxidized into Fe 3+ Oxidation of cyanide to CO 2 And N 2 Can rapidly convert S within a certain Ph range 2- Oxidized to sulfate. The chlorine dioxide has strong corrosivity and is extremely unstable, and when the concentration of the chlorine dioxide in the air exceeds 9.5 percent, the chlorine dioxide is extremely easy to explode. The freezing point of the chlorine dioxide is-59 ℃, and orange red crystals are formed when the temperature is reduced to be below the freezing point; the boiling point of the chlorine dioxide is 11 ℃, so the chlorine dioxide exists in a gas form at room temperature, the color of the chlorine dioxide ranges from orange yellow to yellow green, when the concentration of the chlorine dioxide is higher, the color of the chlorine dioxide is orange yellow or yellow red, the smell of the chlorine dioxide is similar to that of the chlorine gas, and the chlorine dioxide has irritation; when the concentration is lower, the tea wine is yellow green or light yellow, and has light sweet taste and fresh grass taste. The chlorine dioxide is very soluble in water, the solubility of the chlorine dioxide in water is 5-8 times that of the chlorine dioxide, and when the water temperature is low, the chlorine dioxide hardly reacts with the water; chlorine dioxide can react with hot water to generate oxygen, hypochlorous acid and chlorine. The chlorine dioxide aqueous solution is easily decomposed under light and is stable in a low-temperature and dark environment, so that the chlorine dioxide aqueous solution should be stored in a low-temperature dark place.
At the molecular level, chlorine dioxide can interact with biological macromolecules in the microorganism body, so that the biological macromolecules lose the original physiological and biochemical functions, and the microorganism is killed. This is an important way to explain the mechanism by which disinfectants kill microorganisms. The protein and amino acid are important components forming the microorganism and are main players of the life activity of the microorganism, and the chlorine dioxide has strong oxidation effect and can oxidize various reductive amino acids, so that the protein or amino acid forming the microorganism is changed, the life activity of the microorganism is influenced, and the microorganism is killed. Cysteine, tyrosine and tryptophan are rapidly oxidized by chlorine dioxide under ex vivo conditions, thereby losing biological activity, and chlorine dioxide inactivates microorganisms. The inactivation of microbial protease by chlorine dioxide is further proved by using 6-phosphoglucose dehydrogenase of saccharomycetes and bovine serum albumin as models. The extremely low concentration of chlorine dioxide can inactivate more than 90% of the glucose-6-phosphate dehydrogenase in a short time, and the oxidation product of the action of chlorine dioxide and glucose-6-phosphate dehydrogenase is analyzed by mass spectrometry, confirming that tryptophan and tyrosine are subjected to covalent oxidation under the action of chlorine dioxide.
The principle that chlorine dioxide inactivates protein at the level of amino acid, chlorine dioxide does not generate chlorination reaction with protein, so that the generation of teratogenic, carcinogenic and mutagenic byproducts such as organic chloride is avoided, and the chlorine dioxide is one of the advantages of using chlorine dioxide as a disinfectant. The DNA molecule is used as a carrier substance of microorganism genetic information and plays an important role in the propagation heredity of microorganisms and the transcription and translation of biomacromolecule substances. Chlorine dioxide can damage the DNA molecules of microorganisms and may damage their genetic material, affecting their growth and reproduction. Chlorine dioxide can destroy conjugated double bonds between purine and pyrimidine in DNA molecules, so that the structure and the form of the DNA molecules are changed, the change of the DNA form structure can possibly obstruct the transcription, translation and expression of the DNA molecules, and finally, the microorganisms cannot produce substances closely related to life activities, such as protein, polysaccharide, lipid and the like, so that the microorganisms die. Chlorine dioxide reacts with 5' -GMP (i.e., guanosine monophosphate) in DNA molecules to generate guanosine radicals, which change the structure of the original nucleic acid molecule and represent another expression of the chlorine dioxide disinfection mechanism.
At the level of individual microorganisms, the mechanism of action of microorganisms on bacteria and of microorganisms on viruses can be elucidated. The disinfection mechanism of chlorine dioxide to bacteria: during the disinfection process, different from other chlorine-containing disinfectants, for example, hypochlorous acid and chlorine gas can obviously destroy the morphological structure of bacteria after acting on the bacteria, and the morphological structure of the bacteria is not obviously damaged after the chlorine dioxide acts on the bacteria. Therefore, the main way of chlorine dioxide sterilization is not by destroying the morphological structure of the bacteria. After the chlorine dioxide is acted on the escherichia coli, the genetic material is found not to leak out, and the cell wall of the escherichia coli is still intact. Chlorine dioxide is used for increasing the permeability of bacterial cell walls, so that sodium ions, potassium ions and other substances in the bacterial cells leak, the osmotic pressure difference between the inside and the outside of the bacterial cell membranes is intensified, the limit of individual bacteria bearing is exceeded, and then the bacterial cells die, and the purpose of sterilization is achieved. Chlorine dioxide is easily adsorbed on the cell wall of bacteria and wraps around the cell wall of the bacteria, so that the utilization of the bacteria to protein is prevented, and a regeneration system of the bacteria cells is damaged, thereby playing a sterilization role. Chlorine dioxide easily penetrates cell membranes of bacteria and destroys protease systems in bacteria, and chlorine dioxide can destroy ATP enzyme of bacteria, and the death rate of bacteria is increased along with the destruction of ATP enzyme.
The disinfection mechanism of chlorine dioxide to virus is as follows: the mechanism of chlorine dioxide for inactivating virus is that chlorine dioxide takes the nucleic acid molecule of virus as a target spot to make the nucleic acid molecule lose function and inactivate. Chlorine dioxide not only degrades viral RNA, but also inhibits viral RNA synthesis. The inactivation mechanism of hepatitis A virus by chlorine dioxide, the hepatitis A virus lacks a section of RNA segment about 600 pb, so that the virus RNA is damaged. Thus, chlorine dioxide acts on nucleic acid molecules, which is one of the major causes of viral inactivation. Secondly, the chlorine dioxide takes the protein capsid of the virus as an action target spot to destroy the capsid function and lead the capsid to be inactivated. After the f2 phage is inactivated by chlorine dioxide, the phage loses the infection ability to the host, but the nucleic acid molecules of the phage still have relative activity, so researchers speculate that chlorine dioxide acts on the protein capsid and causes it to be destroyed, which is the main reason for virus inactivation.
Chlorine dioxide has the following characteristics. Firstly, chlorine dioxide disinfection has broad spectrum; not only can kill most bacteria, fungi and viruses in the nature, but also can inactivate the spores formed by protists, algae and various fungi. Secondly, the chlorine dioxide disinfection has high efficiency; when the content of chlorine dioxide in the water body reaches 0.1mg/L, 99.9% of bacterial propagules in the water body can be killed, when the using concentration reaches 50mg/L, all harmful microorganisms in the nature including bacterial spores, bacteriophage, classical swine fever virus and the like can be killed, and the disinfection effect is 2 times that of hypochlorous acid and 2-5 times that of chlorine and is far higher than that of other chlorine-containing disinfectants. Thirdly, the chlorine dioxide disinfection has higher safety; in the disinfection process, chlorine dioxide mainly performs the oxidation action and does not generate chlorination reaction with organic matters, so that organic chlorine compounds with 'causing' effect (teratogenicity, carcinogenicity and mutation) such as trichloromethane and the like are not generated, and other toxic byproducts are not generated; when the concentration of the chlorine dioxide is lower than 500mg/L, the chlorine dioxide hardly affects human bodies, and because of the high efficiency of the chlorine dioxide, the using concentration of the chlorine dioxide is usually far lower than 500mg/L, the chlorine dioxide does not cause harm to human bodies or animals in the using process; after the chlorine dioxide disinfection, no residue is generated, and no secondary harm is caused to the environment. Fourthly, the disinfection effect of the chlorine dioxide is little influenced by the environment; chlorine dioxide can completely kill microorganisms at a concentration of tens of ppm even in the case of organic interference; the PH application range of the chlorine dioxide is wider, and the chlorine dioxide has higher sterilization effect in the PH range of 2-10; the disinfection effect of chlorine dioxide is little influenced by the change of environmental temperature, and microorganisms can be effectively killed at higher and lower temperatures.
Chlorine dioxide is a high-efficiency, nontoxic and safe green disinfectant, and is widely applied to various fields of human life development. It is used not only as a disinfectant, biocide and preservative but also as bleaching, oxidizing, mildew proofing, air freshening, deodorizing, etc., classified by its use. When used as disinfectant, the chlorine dioxide can be used for water body and air disinfection and public and production places.
When the chlorine dioxide reaches 0.2mg/L in the water body, 100 percent of escherichia coli in the water body can be killed within 30 min; in the air, the concentration of chlorine dioxide reaches 1-3 mg/L, and the killing rate of microorganisms can reach more than 99.9% within a certain time; chlorine dioxide, at concentrations of tens of ppm, completely kills microorganisms in public and production locations. When the chlorine dioxide is used as the preservative, the respiration of vegetables and fruits can be inhibited, the generation amount of ripening agents such as ethylene is reduced, microorganisms causing decay of the vegetables and the fruits are killed, the decay speed of the vegetables and the fruits is delayed, and the preservation time is prolonged; chlorine dioxide with the concentration of 50mg/L has good fresh-keeping effect.
When the chlorine dioxide is used as an air purification freshener and a mildew preventive, the indoor freshness can be kept, the indoor grass fragrance can be achieved, when the chlorine dioxide is slowly released at a low concentration, the chlorine dioxide is harmless to human bodies, but has a disinfection effect on air, the odor and the peculiar smell in the air can be effectively removed, and the mildew occurrence can be reduced; in the processes of packaging, transporting and managing picked fruits, 3-5 ppm of chlorine dioxide is added, compared with the process of adding 100-200 ppm of sodium hypochlorite, the two methods can inactivate salmonella attached to mangos, but the speed of inactivating putrefying bacteria by chlorine dioxide is higher, the use is safe and meets the supervision standard of mango processing, and the adoption of chlorine dioxide as a first-selected disinfectant has higher feasibility; in the production process of potatoes, brown rot or wilt caused by ralstonia solanacearum is a main limiting factor in the production of potatoes, the ralstonia solanacearum can pollute a water channel irrigation system, and chlorine dioxide can disinfect a water channel, the ground and equipment to prevent the brown rot or the wilt from spreading to disease-free areas.
Therefore, the following chlorine dioxide disinfectants have been proposed for the purpose of not improving the stability of chlorine dioxide disinfectants.
The application provides an activation-free chlorine dioxide disinfectant, which comprises deionized water, pure chlorine dioxide, an activating agent and a stabilizing agent, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A. And mixing an activating agent in the mixed solution A, and mixing the activating agent with the mixed solution A to obtain a mixed solution B, wherein the activating agent comprises one or more of sodium ammonium sulfate, oxalic acid, citric acid and tartaric acid. And mixing a stabilizer in the mixed solution B to obtain a mixed solution C, wherein the stabilizer comprises one or more of sodium stannate, magnesium silicate, sodium glycinate and sodium carbonate. Wherein, the proportion of the deionized water, the pure chlorine dioxide, the activating agent and the stabilizing agent is (90-98.5): (1-9.5): (0.01-0.03): (0.1-0.4).
The following examples are given based on the differences in the starting materials of the activator and stabilizer.
Example one
An activation-free chlorine dioxide disinfectant comprises deionized water, pure chlorine dioxide, an activating agent and a stabilizing agent, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A. And mixing an activating agent in the mixed solution A, and mixing the activating agent with the mixed solution A to obtain a mixed solution B, wherein the activating agent is sodium ammonium sulfate. And mixing the stabilizer in the mixed solution B to obtain a mixed solution C, wherein the stabilizer is sodium stannate. Wherein, the proportion of deionized water, pure chlorine dioxide, activating agent and stabilizing agent is 95:4.78:0.02:0.2.
when the disinfectant is used, the activating agent is mixed with the inert chlorine dioxide aqueous solution, namely the activating agent arouses and activates the inert chlorine dioxide aqueous solution in a nonvolatile state, so that the chlorine dioxide in the aqueous solution is volatilized and released. Therefore, the effects of immediately reacting chemical raw materials and uniformly releasing chlorine dioxide gas can be achieved, and the air can be conveniently sterilized and used at any time. Overcomes the defects that the prior art needs to synthesize chlorine dioxide on site, can not store and uniformly release chlorine dioxide gas.
The inert chlorine dioxide aqueous solution is in a non-volatile state and can be obtained by selecting sodium chlorate (NaClO) from the chlorine dioxide aqueous solution 3 ) Sodium chlorite (NaClO) 2 ) Or sodium hydroxide (NaOH) is added, so that the chlorine dioxide in the aqueous solution is kept in a nonvolatile inert state. The activator comprises water-absorbent resin and activator raw material, specifically sodium citrate (C) 6 H 5 O 7 Na 3 ·2H 2 O), sodium dihydrogen phosphate (NaH) 2 PO 2 ) Sodium bicarbonate (NaHCO) 3 ) And a water absorbent resin (SAP). After the water-absorbent resin, the raw material of the activating agent and the inert chlorine dioxide aqueous solution are mixed, the activating agent awakens and activates the inert chlorine dioxide aqueous solution in a non-volatile state, thereby overcoming the regional limitation and the time limitation of the use of the chlorine dioxide disinfectant and having strong disinfection effectAnd (5) sterilization. And, the addition of stabilizers further promotes the stability of the disinfectant.
Example two
An activation-free chlorine dioxide disinfectant comprises deionized water, pure chlorine dioxide, an activating agent and a stabilizing agent, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A. And mixing an activating agent in the mixed solution A, and mixing the activating agent with the mixed solution A to obtain a mixed solution B, wherein the activating agent is citric acid. And mixing the stabilizer in the mixed solution B to obtain a mixed solution C, wherein the stabilizer is sodium carbonate. Wherein, the proportion of the deionized water, the pure chlorine dioxide, the activating agent and the stabilizing agent is 96:3.67:0.03:0.3.
EXAMPLE III
An activation-free chlorine dioxide disinfectant comprises deionized water, pure chlorine dioxide, an activating agent and a stabilizing agent, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A. And mixing an activating agent in the mixed solution A, mixing the activating agent with the mixed solution A to obtain a mixed solution B, wherein the activating agent is a mixture of oxalic acid and citric acid, and the ratio of the oxalic acid to the citric acid is 0.003. And mixing a stabilizer in the mixed solution B, and mixing the stabilizer with the mixed solution B to obtain a mixed solution C, wherein the stabilizer is a mixture of magnesium silicate and sodium glycinate, and the ratio of the magnesium silicate to the sodium glycinate is 0.23. Wherein, the proportion of the deionized water, the pure chlorine dioxide, the activating agent and the stabilizing agent is 96:3.68:0.02:0.3.
example four
An activation-free chlorine dioxide disinfectant comprises deionized water, pure chlorine dioxide, an activating agent and a stabilizing agent, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A. And mixing an activating agent in the mixed solution A, and mixing the activating agent with the mixed solution A to obtain a mixed solution B, wherein the activating agent is a mixture of sodium ammonium sulfate and tartaric acid, and the ratio of the sodium ammonium sulfate to the tartaric acid is 0.002. And mixing a stabilizer in the mixed solution B, mixing the stabilizer with the mixed solution B to obtain a mixed solution C, wherein the stabilizer is a mixture of sodium glycinate and sodium carbonate, and the ratio of the sodium glycinate to the sodium carbonate is 0.13. Wherein, the proportion of deionized water, pure chlorine dioxide, activating agent and stabilizing agent is 97:2.69:0.01:0.3.
EXAMPLE five
An activation-free chlorine dioxide disinfectant comprises deionized water, pure chlorine dioxide, an activating agent and a stabilizing agent, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A. And mixing an activating agent in the mixed solution A, and mixing the activating agent with the mixed solution A to obtain a mixed solution B, wherein the activating agent is citric acid. And mixing the stabilizer in the mixed solution B, and mixing the stabilizer with the mixed solution B to obtain a mixed solution C, wherein the stabilizer is sodium carbonate. Wherein, the proportion of the deionized water, the pure chlorine dioxide, the activating agent and the stabilizing agent is 98.5:9.5:0.03:0.4.
EXAMPLE six
An activation-free chlorine dioxide disinfectant comprises deionized water, pure chlorine dioxide, an activating agent and a stabilizing agent, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A. And mixing an activating agent in the mixed solution A, and mixing the activating agent with the mixed solution A to obtain a mixed solution B, wherein the activating agent is citric acid. And mixing the stabilizer in the mixed solution B, and mixing the stabilizer with the mixed solution B to obtain a mixed solution C, wherein the stabilizer is sodium carbonate. Wherein, the proportion of deionized water, pure chlorine dioxide, activating agent and stabilizing agent is 90:1:0.01:0.1.
EXAMPLE seven
An activation-free chlorine dioxide disinfectant comprises deionized water, pure chlorine dioxide, an activating agent and a stabilizing agent, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A. And mixing an activating agent in the mixed solution A, mixing the activating agent with the mixed solution A to obtain a mixed solution B, wherein the activating agent is a mixture of citric acid and tartaric acid, and the ratio of the citric acid to the tartaric acid is 0.01. And mixing a stabilizer in the mixed solution B, and mixing the stabilizer with the mixed solution B to obtain a mixed solution C, wherein the stabilizer is a mixture of sodium stannate and magnesium silicate, and the ratio of the sodium stannate to the magnesium silicate is 0.2. Wherein, the proportion of deionized water, pure chlorine dioxide, activating agent and stabilizing agent is 95:4.78:0.03:0.4.
after the activation-free chlorine dioxide disinfectant is used, the appearance of the staphylococcus aureus after 10 min of action is shown in figure 1, and it can be seen that the staphylococcus aureus is in a full spherical shape before the action of chlorine dioxide, three and five are gathered into strings, while the staphylococcus aureus after the action of chlorine dioxide becomes dry and shriveled, and loses the original spherical shape as shown in figure 2. The action of the activation-free chlorine dioxide disinfectant enables the content of staphylococcus aureus to leak out, so that bacteria die.
The application provides a production process of an activation-free chlorine dioxide disinfectant, which comprises the following steps:
s1: preparing chlorine dioxide, weighing sodium chlorite and hydrochloric acid, adding into a high-purity chlorine dioxide generator for reaction to generate a mixture, and separating the mixture to obtain pure chlorine dioxide;
s2: adding the pure chlorine dioxide obtained in the step S1 into deionized water to obtain a mixed solution A;
s3: adding an activating agent into the mixed solution A obtained in the step S2 to obtain mixed solution B;
s4: and (4) adding a stabilizer into the mixed solution B obtained in the step (S3) to obtain a mixed solution C.
In some embodiments, the extraction temperature of pure chlorine dioxide in step S1 is between 20 ℃ and 23 ℃.
In some embodiments, the sodium chlorite to hydrochloric acid is used in a ratio of 1:1.
The product has high stability, and the stability is reduced to 2.4 percent at the constant temperature of 54 ℃ for 14 days, which is higher than that of other similar products. (see Table 1)
TABLE 1 chlorine dioxide content measurement results
Figure DEST_PATH_IMAGE001
The disinfectant obtained by the production process is in a nonvolatile inert chlorine dioxide aqueous solution, overcomes the regional limitation and the time limitation of the use of the chlorine dioxide disinfectant, and has strong disinfection and sterilization effects. Also, the addition of stabilizers further promotes the stability of the disinfectant.
The particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.

Claims (10)

1. An activation-free chlorine dioxide disinfectant, comprising:
deionized water;
pure chlorine dioxide, wherein the pure chlorine dioxide is mixed in the deionized water, and the pure chlorine dioxide is mixed with the deionized water to obtain a mixed solution A;
the activating agent is mixed in the mixed solution A and mixed with the mixed solution A to obtain mixed solution B, and the activating agent comprises one or more of sodium ammonium sulfate, oxalic acid, citric acid and tartaric acid;
the stabilizer is mixed in the mixed solution B, the stabilizer is mixed with the mixed solution B to obtain a mixed solution C, and the stabilizer comprises one or more of sodium stannate, magnesium silicate, sodium glycinate and sodium carbonate;
wherein the proportion of the deionized water, the pure chlorine dioxide, the activating agent and the stabilizing agent is
(90-98.5):(1-9.5):(0.01-0.03):(0.1-0.4)。
2. An activation-free chlorine dioxide disinfectant as set forth in claim 1, wherein said activating agent is sodium ammonium sulfate, and the ratio of said sodium ammonium sulfate is 0.02.
3. An activation-free chlorine dioxide disinfectant as claimed in claim 2, wherein the stabilizing agent is sodium stannate, and the ratio of sodium stannate is 0.2.
4. An activation-free chlorine dioxide disinfectant as set forth in claim 1, wherein said activating agent is citric acid, and the ratio of said citric acid is 0.03.
5. The activation-free chlorine dioxide disinfectant as recited in claim 4, wherein said stabilizer is sodium carbonate, and the ratio of said sodium carbonate is 0.3.
6. An activation-free chlorine dioxide disinfectant as set forth in claim 1, wherein said activating agent is a mixture of oxalic acid and citric acid, said ratio of said activating agent is 0.02, and said ratio of oxalic acid to citric acid is 0.003.
7. The activation-free chlorine dioxide as claimed in claim 6, wherein the stabilizer is a mixture of magnesium silicate and sodium glycinate, the ratio of the stabilizer to the magnesium silicate is 0.3, and the ratio of the magnesium silicate to the sodium glycinate is 0.23.
8. A production process of an activation-free chlorine dioxide disinfectant is characterized by comprising the following steps:
s1: preparing chlorine dioxide, weighing sodium chlorite and hydrochloric acid, adding into a high-purity chlorine dioxide generator for reaction to generate a mixture, and separating the mixture to obtain pure chlorine dioxide;
s2: adding the pure chlorine dioxide obtained in the step S1 into deionized water to obtain a mixed solution A;
s3: adding an activating agent into the mixed solution A obtained in the step S2 to obtain mixed solution B;
s4: and (4) adding a stabilizer into the mixed solution B obtained in the step (S3) to obtain a mixed solution C.
9. A process for producing an activation-free chlorine dioxide disinfectant as set forth in claim 8, wherein in step S1, the extraction temperature of said pure chlorine dioxide is between 20 ℃ and 23 ℃.
10. A process for producing an activation-free chlorine dioxide disinfectant as claimed in claim 9, wherein the amount ratio of sodium chlorite to hydrochloric acid is 1:1.
CN202211086867.4A 2022-09-07 2022-09-07 Activation-free chlorine dioxide disinfectant and production process thereof Pending CN115152788A (en)

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CN106879626A (en) * 2017-03-23 2017-06-23 中山市卫乐化工有限公司 A kind of chlorine dioxide disinfection liquid and preparation method thereof
CN111758724A (en) * 2020-07-02 2020-10-13 黄惠良 Chlorine dioxide disinfection spray with fruity flavor and preparation method thereof
CN111972412A (en) * 2020-08-27 2020-11-24 上海辉文生物技术股份有限公司 Chlorine dioxide slow-release composition and production process thereof
US20220153580A1 (en) * 2019-12-04 2022-05-19 Dyc Co., Ltd. Chlorine dioxide composition having excellent long-term stability at room temperature and method for preparing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106879626A (en) * 2017-03-23 2017-06-23 中山市卫乐化工有限公司 A kind of chlorine dioxide disinfection liquid and preparation method thereof
US20220153580A1 (en) * 2019-12-04 2022-05-19 Dyc Co., Ltd. Chlorine dioxide composition having excellent long-term stability at room temperature and method for preparing same
CN111758724A (en) * 2020-07-02 2020-10-13 黄惠良 Chlorine dioxide disinfection spray with fruity flavor and preparation method thereof
CN111972412A (en) * 2020-08-27 2020-11-24 上海辉文生物技术股份有限公司 Chlorine dioxide slow-release composition and production process thereof

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