KR20190115372A - Method and apparatus for producing of pure chlorite solution - Google Patents

Abstract

The present invention relates to a technology for providing pure chlorite (ClO_2^-), which does not include metal ions or metal salts in a chlorite aqueous solution which is used for sterilization, sanitation and water purification in indoor and outdoor places and environments where a sanitation condition is bad, or used as a disinfectant, a sterilizer and a fungistat during a food and water purification process. The technology of the present invention can be applied to a method and an apparatus for preparing a chlorite aqueous solution, which can be used with high efficiency by being supplied in a low cost structure to sterilization, water purification, food, and a field of requiring disinfection, sterilization, antibacterializing processes during various treating processes requiring sanitation by disinfection or sanitation treatment in places or environments where humans or animals live by obtaining a pure chlorite aqueous solution by a simple operation. The method of the present invention comprises: a chlorite dilution step of diluting chlorite in water; a positive ion removing step of removing positive ions by an ion exchange contact method of allowing positive ions of the chlorite diluted in the water to be in contact with a positive ion exchange resin using an underwater pump or powerless or spray gun or manual discharge pump device; and a concentration adjusting step of properly maintaining a concentration of a chlorite (HClO2) aqueous solution removed with the positive ions through processes.

Description

Method for producing pure chlorine dioxide aqueous solution and apparatus for producing the same {Method and apparatus for producing of pure chlorite solution}

The present invention is used when disinfection, hygiene, or purification is required due to a deteriorated environment due to poor indoor or outdoor hygiene, or when a disinfection, sterilization, or sterilization function is required during food storage or water purification. The invention is in the art to provide pure chlorine dioxide (Chlorite, ClO ₂ ) that does not contain metal ions (Metal ions) or metal salts (Metal salts).

More specifically, the chlorine dioxide salt dilution step of diluting the chlorine dioxide salt in water to perform the above task; Cations in chlorine dioxide diluted in water are brought into contact with the cation exchange resin by the means of transport of an underwater pump, a non-powered pump, a spray gun, and a manual discharge pump, to remove the cations by ion exchange means. Cation removal step; Related Art The present invention relates to a method for preparing a pure chlorine dioxide solution comprising a dilution step for appropriately maintaining a concentration of a cation-free chlorine dioxide (ClO ₂ ) aqueous solution and an apparatus for producing a chlorine dioxide solution used therein.

Sterilization or disinfection is a process that completely kills or extinguishes bacteria distributed on or inside a protected object. Sterilization is an operation that makes sterilization possible. By killing pathogens on the surface or inside of the object to remove the propagation or infectivity, it refers to the operation to make a safe state, sterilization is the safest form of disinfection.

Disinfection is an operation that prevents the contamination of microorganisms by killing the hospital microorganisms, or by inhibiting the infectivity to prevent activity even if not necessarily killed. Sterilization refers to an operation that kills all bacteria and makes them aseptic. In general, pathogenic microorganisms are less resistant in the outside world, so they are easier to kill than non-pathogenic microorganisms.

Microorganisms have different resistance to bactericidal action, especially spore-forming bacteria, which are dormant under normal sterilization conditions, but grow again when the conditions are good. When coexisted with proteins such as sputum and feces, it becomes much more resistant than when suspended in saline solution.

However, in general, when a pathogen is transmitted, it usually coexists with a protein, so sterilization conditions should be various sterilization or disinfection methods depending on the object or purpose.

Disinfection is the killing of pathogens to prevent infection or transmission of the disease, not the killing of all microorganisms, especially non-resistant bacterial spores, rather than the sterilization of extreme physical and chemical processes that can kill all kinds of organisms. It is less affected and is being disinfected with sunlight, heat and chemicals.

Chemical disinfection is the most common method for disinfection, and chemical disinfection is a method of killing bacteria by using a disinfectant agent. In this case, liquid and gas are used. Although it may be said to be complete, it may not be possible depending on the object.

Disinfectant conditions should be strong and harmless, simple to handle, easy to produce, inexpensive, and free of odors.

Disinfectants used so far are phenol (C6H5OH), cresol soap solution (cresol, CH ₃ C ₆ H ₄ OH), formaldehyde (HCHO), flushing water (mercury chloride 2, HgCl ₂ ), alcohol, reverse soap solution, Chlorinating agents (chlorine, bleaching powder, sodium chlorine oxide, chlorine inorganic compounds), iodine, quicklime, hydrogen peroxide, medicated soap, mercury chromium liquid, etc. are selectively used according to the object or the kind of infectious disease.

In the case of the phenol, the use concentration is a 3% aqueous solution, the sterilization action depends on the bacterial protein coagulation action, cell lysis action, enzyme action, etc. The defects are effective against skin mucous membranes, numbness, corrosive to metals, viruses, and follicles. Its advantages are that it is safe for sterilization and does not change chemically for a long time. It is known to be suitable for disinfection of clothing, containers, soil, feces and soil.

In the case of cresol soap liquid, it is not soluble in water, so cresol soap liquid is used in the same amount of cresol soap liquid 3 at a ratio of 97. The dissolving power is twice as strong as phenol, and cresol disinfects viruses. Although less effective, it is known to be effective in bactericidal.

The formaldehyde is a gas body made by oxidizing methyl alcohol (methanol), has a strong irritant smell, is well soluble in water, has a strong reducing power, has a sterilizing effect even at low concentrations, and has a simple generator using methyl alcohol, a sealed room I generate it in a specially made box and use it to disinfect things inside it.

Formalin is an aqueous solution containing more than 37% formaldehyde. It acts on proteins at high dilution concentrations, has a strong sterilizing effect that cannot be recovered, and has a strong sterilizing effect against apo. Formalin is used for general disinfection. 1.5% aqueous solution is used and its use is known to be suitable for disinfection of clothing, ceramics, wood products, celluloid, rubber products and the like.

The flood water is a colorless, odorless, toxic and not corrosive to water and corrodes metals, so containers are made of plastic, and chemicals should be distinguished by dyeing with fucin, etc. For skin disinfection, 0.1-0.5% aqueous solution is used. E. coli, Staphylococcus aureus are killed in 5-10 minutes, irritant to mucous membrane, but can not be used for disinfection of rubber products and metal products.

The methyl alcohol is strong sterilization in 70-75% aqueous solution, mainly used for disinfection of resins, skin, instruments, etc., but easy to use alcohol, evaporation is fast and effective for spore-free bacteria, but it is not effective for apopoietic bacteria. Known.

The reverse soap solution is a surfactant having a strong penetration and sterilization power, and is generally used to make an aqueous solution of 0.1-0.5%. It is colorless, odorless, and non-irritating, so it is suitable for disinfection of resins, utensils and containers. It is widely used in cosmetics.

In the case of the chlorine disinfectant, fluorine chlorine, oxo, etc. belong to a halogen element, and chlorine that forms a protein and a halogen complex in living cells and stops cell metabolism and eventually kills the cells has a high sterilizing power in gaseous state. However, due to its strong irritability and corrosiveness, it is not used except for large-scale disinfection such as tap water and sewage poisoning. Bleach powder (chlor lime CaOCl ₂ ) is used to disinfect generator chlorine in water, and it is used to disinfect beverages and swimming pools. It is used at the level of ppm concentration, and sodium chlorine dioxide (NaOCl) is bactericidal by chlorine element generated in solution.

The iodine has strong sterilization like chlorine, but has a low side effect on skin mucous membranes even at dark concentrations, but it uses a 100-fold solution (effective amount of iodine 100 ~ 200 ppm) for disinfection of resins, instruments, etc. This has the disadvantage of roughening and irritating skin.

In the case of quicklime, add about half of the amount of quicklime to make it look like mud or make 5 times (20%) aqueous solution of lime oil, and use powder when disinfecting water or wet place. It is known that it is good to spray it directly, and quicklime is used to disinfect manure, earth and sand, manure cans, waste bins, sewers and water tanks. Defects are not effective against Mycobacterium tuberculosis, spores, etc., and are known to be suitable for widespread disinfection because of their low cost.

In the case of hydrogen peroxide, oxidant disinfectants are drugs that stop cell metabolism by oxidizing Sulfurhydryl (-SH) groups. Hydrogen peroxide (H2O2) is used for disinfection with an aqueous solution of 2.5 to 3.5% (oxypool), and has no color. It is known to oxidize and sterilize pathogens with a clear, odorless but sometimes odorous liquid such as ozone.

In the case of the medicated soap, various disinfectants are added to the soap base, which is used to simultaneously act on the soap disinfecting action and chemical disinfection by the disinfectant.

Mercury chromium solution is commonly referred to as red medicine, Mercury chromium 2% aqueous solution, it is used as it is when wound disinfection, Mercury chromium is a mild fungicide or sometimes irritable without chemically belonging to inorganic mercury compounds Care should be taken, and the suppression of bacterial growth lasts relatively long.

The sterilization targets according to the infectious diseases are as follows.

First typhoid fever. paratyphoid fever. cholera. In the case of dysentery, oral infections are infectious diseases of the digestive system, so manure, earth and sand, residual food, utensils, and toilets are a problem, and the patient's clothing, bedding, filth, waste bins and sewers must be disinfected.

Second, in case of smallpox, scarlet fever, the patient's runny nose, sputum, succulents, contaminants, clothing, bedding, conveying equipment, patient's food equipment, bedroom floor, and caregiver. Disinfect the contact body and clothing.

Third, in the case of large pteria, epidemic meningitis-the patient's runny nose, sputum and their contaminated utensils and utensils, books, toys, bedding, bedding or other items in the room, and the caregiver's clothing and body are disinfected. In case of the fourth folio, disinfection is carried out, but at the outset, diphtheria is used.

In order to reduce the damage caused by the germs, many efforts have been made to prevent and disinfect hygiene pests such as flies and mosquitoes, and to prevent infectious diseases.

Health problems caused by food are caused by oral infectious diseases such as cholera, dysentery, typhoid fever, tuberculosis, anthrax, brucellosis (salmonellosis), avian influenza (AI) Parasitic diseases, food poisoning (bacterial, natural poisons, chemicals, and other factors), and categorizing foodborne diseases according to their causes, the original ingredients of food ingredients are harmful, toxic, endogenous, food-borne endogenous, food production Physical, chemical and biological factors in the manufacture, processing, storage and distribution of exogenous foods that cause harmful or toxic substances to be mixed or contaminated in the process of growth, manufacture, processing, storage, distribution and consumption. It is classified as an inducement to produce toxic substances in food and cause disease.

In addition, infectious diseases require susceptibility of infectious agents, paths of infection, and hosts, and in order to develop diseases, sufficient infectious agents must be present in qualitative and quantitative terms as infectious agents, and there must be sufficient contact opportunities for infectious agents. People must exist.

Most infectious diseases occur and become epidemic when three conditions of infectious agent, infection route, and susceptibility are met. Infectious diseases do not end with a transient like food poisoning, but must be severely treated such as quarantine or contact disinfection. Is different.

Therefore, as a business owner, the most important thing is thorough prevention, and it is important to inspect workers regularly to make sure that there are no carriers, and to habitually disinfect fingers.

Chlorine dioxide (ClO2) was first discovered by Humphrey Davy in 1814. Since it was proposed as a disinfectant for water treatment by Berge in 1900, it has been widely used for sterilizing drinking water, removing odors, and bleaching in the United States and Europe. In particular, since 1972, chlorine dioxide, unlike chlorine, has been found to not react with organic contaminants in water to produce carcinogenic trihalomethanes.

However, domestic law restricts its use for the removal of heavy metals such as iron (Fe) and manganese (Mn) by treating chlorine in parallel with the chlorine (in case of aqueous solutions). : H7 (E. coli O157: H7), Salmonella sp. (Salmonella sp.) To reduce the level of at least one hundred thousand is suggested as a bactericidal criteria, the efficacy of chlorine dioxide is the Food and Drug Administration It satisfies this regulatory standard and has been shown to be more effective at eradicating Listeria bacteria contaminating fruits and vegetables than any other currently available sterilization methods. It's especially harder to get rid of than the pathogenic bacteria in. Because Listeria is a viable organism that can survive in refrigerators and freezers. And it has been known it is difficult to remove its activity.

One of the advantages of the chlorine dioxide sterilization method is that it can be applied at any time before or after harvesting apples and during processing, and in small food processing companies that do not have heat sterilization devices to remove contaminants. It is easy to use, and also has the advantage of avoiding the problem that the taste of the fruit changes with heating.

In addition to the above properties, chlorine dioxide has the advantage of killing bacteria and viruses without high risk in most environmental applications. So far, the solution containing chlorine dioxide is used as food for people. It can be applied to get the effect of sterilization and disinfection by contacting the surface of food material or poor hygiene condition for the disinfection, sanitary treatment, water purification treatment of the place or the object with poor hygiene condition or sanitary condition.

Therefore, in order to maintain the freshness of all foods used as food ingredients for the health of the human body or animals and to provide a healthy living environment in which viruses or bacteria are not present or minimized, the liquid chlorine dioxide source is used to improve the freshness. It is necessary to provide for the presence of steamy chlorine dioxide sources in all spaces that are not in direct contact with food surfaces to maintain or where sanitization requires sterilization or disinfection.

Moreover, in the case of fruit and vegetable, respiration and transpiration are continuously performed during the handling, transportation, storage, and sales process, and in the export countries where long-term transportation is required, claims due to corruption, wilting, aging, and deterioration occur. Advancement of post-harvest life extension technology is still an urgent task, especially given the economic loss rate of 10% to 50% due to corruption during distribution and storage in developing countries and developing countries. It is necessary to develop a simple food storage technology while technology is necessary and meets economic feasibility.

Looking at the prior art to maintain the freshness and disinfection of the food using chlorine dioxide, sanitary treatment, water purification treatment to date as follows.

In Korean Laid-Open Patent Publication No. 10-2017-0103219 A, a tubular shape having a predetermined length from the top of the reaction vessel to a predetermined length is positioned inside the reaction vessel, and mixed with sodium chlorine dioxide and sulfuric acid flowing into the upper end and flowing inward. A device for generating chlorine dioxide by a reaction tube is proposed. The cited invention discloses that when a chlorine dioxide source is applied as a disinfectant for drinking water as a by-product of sodium sulfate is generated while chlorine dioxide is generated by reaction with sodium chlorine dioxide and sulfuric acid. Health problems may occur, and when sprayed with a disinfectant on the surface of the object has a problem that can cause aesthetic problems due to the final bleaching phenomenon.

Korean Patent Publication No. 10-1807966 B1 proposes a chlorine dioxide generation device capable of quantitative chlorine dioxide generation by supplying chlorine dioxide and acid such as citric acid at a set time interval. Chlorine dioxide has the advantage of being able to supply quantitatively at time, but has a similar problem as described in Korean Patent Laid-Open Publication No. 10-2017-0103219 A as sodium citrate is generated as a by-product.

In Korean Laid-Open Patent Publication No. 10-2017-0127271 A, an aqueous solution of sodium chlorine dioxide and an aqueous sulfuric acid solution pass through the reaction tube to produce chlorine dioxide with high production yield and excellent purity, and frequent corrosion problems of the connecting parts due to the high concentration of the reaction tank. In order to provide an improved structure, a chlorine dioxide generator having an improved structure has been proposed. According to the composition of the present invention, sodium sulfate is generated as a by-product, which is described in Korean Patent Publication No. 10-1807966 B1. The same drawback is shown.

Korean Patent Application Publication No. 10-1793957 B1 proposes a chlorine dioxide gas generator that can uniformly and continuously generate a desired low chlorine dioxide gas by means of a technical configuration for supplying sodium chlorine dioxide and hydrochloric acid. As it occurs, the disadvantages presented in Korean Laid-Open Patent Publication No. 10-2017-0103219 A are not solved.

Compared with the prior art as described above, in the application of the present technology, by-ion exchange method using a cation exchange resin does not generate any by-products, and the technical configuration of the present invention is composed of pure chlorine dioxide in water. It can be completely different.

In addition, the present inventors have investigated through domestic and foreign search engines, as a method for providing chlorine dioxide is proposed by the technical configuration by the supply of organic and inorganic acid (Acid) to the aqueous solution containing sodium chlorine mostly It was confirmed that there is no technical configuration of the production method and production apparatus of the chlorine dioxide solution consisting of a technical configuration in which no by-products are generated by the ion exchange method using a cation exchange resin, and pure chlorine dioxide is generated in water.

The present application can prepare an aqueous solution containing pure chlorine dioxide for maintaining the freshness of food, disinfection, sanitary treatment, water purification treatment, while the conventional methods for providing a pure chlorine dioxide solution researched and developed so far by-products necessarily The invention was completed by confirming that it can be caused to adversely affect the health of the human body, and can solve the problem that can be a bad result on the visual plastering effect caused by bleaching with the present technology.

As the present disclosure reveals in the background art, all the methods developed to constitute chlorine dioxide in water so far can cause adverse effects on the human body or the storage object when by-products are generated and the by-products are applied to the food field, and disinfect on the surface of the object. It is an invention started with the problem to find a solution to solve the problem of having a big limitation in compatibility due to the result of the exposure of the visual imperfection by whitening when sprayed for.

The present invention is used for disinfection or sanitary treatment in indoor or outdoor sanitary conditions or places, metal ions or ions in chlorine dioxide solution used as food storage and management, disinfection during sterilization, sterilization and disinfectant. A chlorine dioxide dilution step for diluting chlorine dioxide in water as a means for providing pure chlorine dioxide (Chlorite, ClO ₂ ) in the absence of metal salts; A cation contact cation removal step for removing cations by an ion exchange method by contacting a cation in chlorine dioxide diluted in water with a cation exchange resin; The purpose is to obtain a pure chlorine dioxide solution through a concentration control step to properly maintain the concentration of the cation-free chlorine dioxide (ClO ₂ ) aqueous solution.

The present invention is used for disinfection or sanitary treatment in places and environments with poor sanitary conditions indoors and outdoors, or metal ions or metal salts on chlorine dioxide solutions used as disinfection, sterilization and disinfectant during food and water purification processes. It is a technology to provide pure chlorine dioxide (Chlorite, ClO ₂ ) does not contain metal salts).

The technical idea of the present invention is to provide chlorine dioxide in a method of preparing pure chlorine dioxide (ClO ₂ ) containing no metal ions or metal salts in a chlorine dioxide solution to provide disinfection, sterilization, and bactericidal effects. The chlorine dioxide dilution step for dilution in water, the ion exchange contact step for contacting the cation exchange resin by a transfer means to remove the cations in the dilute chlorine dioxide diluted in water, and the cation is removed through the ion exchange contact step. The present invention was completed by confirming that a pure chlorine dioxide aqueous solution can be obtained through a process including a concentration adjusting step for appropriately maintaining a concentration of pure chlorine dioxide (ClO ₂ ) aqueous solution.

The dilution step of the chlorine dioxide salt may be applied so that the chlorine dioxide salt selected from sodium chlorine dioxide (NaClO ₂ ) or potassium chlorine dioxide (KClO ₂ ) is diluted to a concentration of 0.01 ppm to 35% by weight, the cation exchange resin When the basic polymer matrix of the ion exchange resin is represented by R, a cation exchange resin represented by R-SO ₃ H or R-COOH may be used to adsorb and remove only cations in chlorine dioxide. The chlorine (ClO ₂ ) concentration step may be used to adjust the concentration of pure chlorine dioxide produced by the ion exchange method using a cation exchange resin to a concentration of 0.01 ppm to 5% by weight.

The technical idea of the present invention is a manufacturing apparatus for providing pure chlorine dioxide (ClO ₂ ) containing no metal ions or metal salts in a chlorine dioxide solution to provide disinfection, sterilization and bactericidal effects. The chlorine dioxide dilution tank for diluting the chlorine salt in water and the chlorine dioxide diluted in the dilution tank are contacted with the cation exchange resin by a transport means selected from an underwater pump, a non-powered pump, a spray gun, and an exhaust pump. Through a simple configuration comprising an ion exchange reactor to remove cations by the ion exchange method and a concentration control tank to properly maintain the concentration of the cation-free chlorine dioxide (ClO 2) aqueous solution through the ion exchange reactor. Disclosed is a manufacturing apparatus for obtaining an aqueous chlorine dioxide solution.

As the related art reveals in the background, chlorine dioxide manufacturing means for disinfection, sterilization, and disinfectant has been supplied with organic and inorganic acids (Acid), so that the components contained in the final water are disinfected, sterilized and disinfected. By-products of alkaline salts, which can be harmful to the human body, are created and coexist in chlorine dioxide, which can serve a role, limiting the use of by-products in the food and water purification sectors, as well as by-products contained in water. After spraying on the water, the water evaporates and dries, then bleaching occurs on the surface of the object, providing the effect of solving the problem of providing a poor visual effect.

In addition, the present application provides pure chlorine dioxide (Chlorite, ClO ₂ ) which does not contain metal ions or metal salts in chlorine dioxide in water, thus causing adverse effects on human health without whitening. By providing a pure chlorine dioxide (ClO ₂ ) aqueous solution does not provide the effect that can be widely used in various fields to improve the food and human living environment.

1 is an illustration of an embodiment that is applied to pass a sodium chlorite solution using a power submersible pump to a cation exchange resin to provide a pure chlorite solution provided herein.
Figure 2 is an illustration of an embodiment that is adapted to allow passage of a sodium chlorite solution without a force to a cation exchange resin to provide a pure chlorite solution provided herein.
3 is an illustration of an embodiment applied to allow passage of a sodium chlorite solution using a spray gun type to a cation exchange resin to provide a pure chlorite solution provided herein.
4 is an illustration of an embodiment applied to pass a sodium chlorite solution using a manual discharge pump type to a cation exchange resin to provide a pure chlorite solution provided herein.

Prior to presenting the embodiments of the invention for implementing the technical idea of the present application by showing the drawings, the terms or words used in the specification or claims of the present application should not be interpreted limited to the ordinary or dictionary meanings. The scope of the present application should be construed as meanings and concepts consistent with the technical spirit of the present invention, and the examples described herein are merely exemplary embodiments of the present invention and do not represent all of the technical ideas of the present invention. It is to be understood that there may be various equivalents and variations in place of them at the time of the present application.

BRIEF DESCRIPTION OF THE DRAWINGS The drawings presented herein will be described with reference to the brief drawings applied in the form of embodiments to confirm that the inventors may obtain the desired effects of the invention.

1 is an illustration of an embodiment that is applied to be able to pass and contact the sodium chlorine dioxide solution using a power submersible pump to the cation exchange resin to provide a pure chlorine dioxide solution provided herein, Figure 2 is provided herein Illustrative illustration of an embodiment that is applied to pass and contact a non-powered sodium chlorine dioxide solution through a cation exchange resin to provide a pure chlorine dioxide solution, and FIG. 3 is a spray gun to provide a pure chlorine dioxide solution provided herein. Is an illustration of an embodiment that is applied to pass and contact a sodium chlorine dioxide solution using a cation exchange resin, Figure 4 is a sodium chlorine dioxide using a manual discharge pump type to provide a pure chlorine dioxide solution provided herein Pass the solution through the cation exchange resin An illustration of embodiments is also.

1 is intended to provide a large amount of pure chlorine dioxide solution by the power, the technical configuration of FIG. 1 is to store the diluted chlorine dioxide solution in the sodium chlorine dioxide solution storage unit 600 dissolved in water, The sodium chlorine dioxide (NaClO 2) solution is moved to the cation exchange resin storage unit 500 by the operation of the pump 900, and is ion exchanged by the cation exchange resin stored in the cation exchange resin storage unit 500 as shown in Scheme 1. Sodium in sodium chlorine is combined with the cation exchange resin, and hydrogen ions (H +) discharged from the cation exchange resin are present as hydrogen ions (H +) in the water, and metal ions and salts (Salts) through the chlorine dioxide outlet 200. Pure chlorine dioxide (ClO2) that does not exist) can be applied in a form that is configured to make.

Cation exchange resin-SO ₃ H + NaClO ₂ → Cation exchange resin-SO ₃ Na + ClO ₂ + H ⁺ -<Scheme 1>

Figure 2 illustrates an embodiment that can be applied to obtain a large amount of pure chlorine dioxide solution by powerlessness using the high and low position, the technical configuration of Figure 2 is a chlorine dioxide dissolved in dilute sodium chlorine dioxide solution To store in the sodium solution storage unit 600, and to place the cation exchange resin storage unit 500 in a lower position than the sodium chlorine dioxide solution storage unit 600, the sodium chlorine dioxide solution storage unit 600 by no power Sodium chlorine dioxide solution stored in the chlorine dioxide discharge unit 200 while passing through the cation exchange resin storage unit 500 may be applied in the form configured to make pure chlorine dioxide (ClO ₂ ) by the reaction scheme 1. It is shown.

FIG. 3 shows that a small amount of pure chlorine dioxide solution can be provided by an operation method such as a spray gun 100 when applied to a small scale such as a home. The technical configuration of FIG. When the sodium (chlorine dioxide) solution is stored in the sodium chlorine dioxide solution storage unit 600 dissolved in water, and the gun operation unit 300 is operated by hand before and after, the pump body 400 is driven to cation exchange. The connection line between the resin storage unit 500 and the sodium chlorine dioxide storage unit 600 dissolved in water is subjected to a vacuum so that the sodium chlorine dioxide solution stored in the chlorine dioxide storage unit 600 dissolved in the water is a cation exchange resin storage unit ( It will be shown that it can be applied to obtain and use pure chlorine dioxide (ClO2) by the reaction scheme 1 while moving to the chlorine dioxide discharge unit 200 beyond.

In FIG. 4, a small amount of pure chlorine dioxide solution can be obtained by a manual method such as a manual discharge pump 700 which is usually pressurized with a finger such as a shampoo discharge means. The technical configuration of FIG. The sodium chlorine solution is stored in the sodium chlorine dioxide solution storage unit 600 dissolved in water, and when the push button 800 is operated up and down by hand, the pump body 400 is driven and the cation exchange resin storage unit ( 500) and the connection line between the sodium chlorine dioxide storage unit 600 dissolved in water is subjected to a vacuum so that the sodium chlorine dioxide solution stored in the sodium chlorine dioxide storage unit 600 dissolved in the water inside the cation exchange resin storage unit (500) It will be shown that it can be applied to make pure chlorine dioxide (ClO ₂ ) by the reaction scheme 1 while moving to the chlorine dioxide discharge unit 200 through the). .

Therefore, the present invention is used for disinfection, sanitary treatment, and water purification in places and environments where indoor and outdoor hygiene conditions are poor, or metal ions on chlorine dioxide solution used as disinfection, sterilization, and disinfectant during food and water purification processes. To provide pure chlorine dioxide (Chlorite, ClO ₂ ) that does not contain metal salts (Metal salts), more specifically chlorine dioxide dilution step for diluting chlorine dioxide in water is for example sodium chlorine dioxide After one chlorine dioxide salt of potassium chlorine dioxide is selected, it can be used freely and extensively diluted from low to high concentration according to the use, the dilution concentration thereof is in a wide range of 0.01 ppm to 35% by weight. Pure chlorine dioxide (ClO ₂ ) dissolved in water at a concentration of 0.01 ppm to 35% by weight after dilution, followed by a cation removal step. As a solution can be prepared, a high concentration of chlorine dioxide in which sodium (Na) or potassium (K) is removed by a cation removal step is prepared by diluting with a high concentration of chlorine dioxide in a dilution step of chlorine dioxide. In the dilution step, a pure chlorine dioxide solution dissolved in water at a concentration of 0.01 ppm to 35% by weight may be prepared in a dilution step so as to properly maintain the concentration of chlorine dioxide (ClO ₂ ), which is a later stage.

The cation removal step removes sodium or potassium, which is an alkali metal, from the chlorine dioxide salt combined with sodium (Na) or potassium (K), so that salts combined with alkali metal or alkali metal in water are not present. In order to remove only the cation combined with chlorine dioxide in order to provide a pure chlorine dioxide solution, the cation removal step can be prepared and used by an ion exchange method using a cation exchange resin, a cation and an anion combined with each other Chlorine salts can remove cations, which are alkali metals, by ion exchange methods, and when ion exchanges a substance with an aqueous solution of salts, ions in the substance come into the solution, and ions in the solution Ions in the solution and insoluble resins (ion exchange resins) In the present invention, a substance exhibiting an ion exchange phenomenon is used as an ion exchanger for a reversible exchange reaction of ions having the same positive or negative value, and the cation exchange resin used in the present invention is a sulfonic acid as an exchange group in the basic polymer matrix of the network structure. The combination of the group (-SO ₃ H) and the carboxyl group (-COOH) is called cation exchange resin, and cations such as Na ⁺ and H ⁺ are exchanged. Ionize.

If the basic polymer matrix of the ion exchange resin is represented by R, it can be represented as R-SO ₃ H (sulphonic acid group) or R-COOH (carboxyl group) as cation exchange resin, and is ionized in water as follows.

_{R-SO 3 H R-SO} 3 - + H + + NaClO 2 -> R-SO 3 Na + ClO 2 + H ⁺

^{R-COOH R-COO - +} H + + KClO 2 -> R-SO 3 K + ClO 2 + H ⁺

Accordingly, in the present invention, a cation of sodium or potassium in chlorine salts dissolved in water is ion-exchanged with a cation exchange resin, thereby making it possible to prepare pure water-soluble chlorine dioxide in a wide concentration range.

As such, the pure chlorine dioxide in the water can be changed according to the use or the amount by the ion exchange method using a cation exchange resin. When a large concentration of the chlorine dioxide solution in a wide concentration range is required as shown in FIG. A large amount of pure chlorine dioxide solution can be prepared by applying a sodium chlorine dioxide solution to the cation exchange resin by using a power submersible pump or a non-powered method having a different position as shown in FIG. When pure chlorine dioxide solution is required, a small amount of pure chlorine dioxide solution is prepared by passing the sodium chlorine dioxide solution using a spray gun type as shown in FIG. 3 or a manual discharge pump type as shown in FIG. 4 through a cation exchange resin. can do.

The concentration control step of the chlorine dioxide is not particularly limited, and may be all possible by diluting to a concentration capable of maintaining a constant concentration of chlorine dioxide according to the intended use.

Accordingly, the present invention provides a chlorine dioxide dilution step for diluting chlorine dioxide in water; Cation removal step for removing cations by an ion exchange method configured to contact a cation exchange resin by mobilizing a cation of chlorine dioxide diluted in water to an apparatus of an underwater pump, a non-powered spray gun, or a manual discharge pump. Wow; It is possible to produce pure chlorine dioxide in water according to the use or amount, including a concentration adjusting step to properly maintain the concentration of the cation-free chlorine dioxide (ClO ₂ ) aqueous solution.

Hereinafter, an embodiment to which the technical idea of the present invention is applied will be described, but it is obvious that the technical idea of the present invention is not limited by the embodiment.

Example 1

In order to confirm the possibility of producing a pure chlorine dioxide solution free of cations and salts, 350 g of sodium chlorine dioxide powder purchased from Samjeon Pure Co., Ltd. was weighed in a beaker, and then about 600 ml of distilled water was added and stirred. After completely dissolving the sodium chlorine dioxide, it was transferred to a 1L volumetric flask and filled with distilled water to the graduation line, and stirred to prepare a 35% by weight sodium chlorine dioxide solution.

Prepare 200 ml of 35% by weight sodium chlorine dioxide solution in a 250 ml beaker, supply enough Samyang Corp. cation exchange resin (SK1BH) to it, and stir for 5 minutes to prepare a chlorine dioxide solution. An aliquot was performed for Na analysis.

Example 2

Except for experimenting with potassium chlorite (Potassium chlorite) was carried out in the same manner as in Example 1.

Example 3

The same procedure as in Example 1 was conducted except that a 10% sodium chlorine dioxide solution was prepared.

Example 4

The same procedure as in Example 1 was conducted except that a 1% sodium chloride solution was prepared.

Example 5

After preparing the spray gun, install a trap filled with Samyang Corp. cation exchange resin (SK1BH) in the middle of the inlet line, dilute 25% sodium chlorine dioxide solution purchased from Daemyung Chemical to 0.1% concentration, and then spray gun container. The chlorine dioxide solution produced at the spray gun outlet was collected by filling in the lid, closing the lid, and hand-operated to prepare a sample for Na analysis.

 Example 5

After preparing the spray gun, install a trap filled with Samyang Corp. cation exchange resin (SK1BH) in the middle of the inlet line, dilute 25% sodium chlorine dioxide solution purchased from Daemyung Chemical to 0.1% concentration, and then spray gun container. The chlorine dioxide solution produced at the spray gun outlet was collected by filling in the lid, closing the lid, and hand-operated to prepare a sample for Na analysis.

Example 6

After preparing the discharge pump type container, install a trap filled with Samyang Corp. cation exchange resin (SK1BH) in the middle of the discharge pump inlet line, and dilute the 25% sodium chlorine dioxide solution purchased from Daemyung Chemical to 0.01 ppm concentration. It was then filled in a spray gun container, the lid was closed and a push button was applied by hand to collect the chlorine dioxide solution produced at the discharge pump outlet to make a sample for Na analysis.

Example 7

The prepared glass column was filled with Samyang Corp. cation exchange resin (SK1BH), and 25% sodium chlorine dioxide solution purchased from Daemyung Chemical Co., Ltd. was diluted to 5% concentration through a column to prepare a chlorine dioxide solution. Its solution was used as a sample for Na analysis.

Comparative Example 1-7

As in the conventional method, the chlorine dioxide solution prepared in Examples 1 to 7 was prepared using a sulfuric acid diluted to 1/5 with a weak acid of 5.5 to prepare a chlorine dioxide solution, and as a sample for Na analysis. It was.

Na analysis of Comparative Examples 1 to 7 and Examples 1 to 7 was measured by a Thermo Scientific iCAP 6500 duo Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-AES), and the analysis results thereof are shown in Table 1.

division Analysis item Na K Example 1 N.D. - Example 2 - N.D. Example 3 N.D. - Example 4 N.D. - Example 5 N.D. - Example 6 N.D. - Example 7 N.D. - Comparative Example 1 8.7% - Comparative Example 2 - 8.8 Comparative Example 3 2.5% - Comparative Example 4 0.23% - Comparative Example 5 240 ppm - Comparative Example 6 N.D (estimated: 0.0025 ppm) - Comparative Example 7 1.2% - Note: N.D. means non-detectable, the detection limit of Na and K is 0.01 ppm.

As shown in Table 1, Comparative Examples 1 to 7, which are conventional methods, were found to be contained at concentrations below the detection limit of ICP, and thus could not be detected. Other Comparative Examples 1 to 5 and Comparative Example 7 and As described above, when a chlorine dioxide solution using the conventional method was prepared, a large amount of by-product of sodium was formed. In Comparative Examples 1 to 5 and Comparative Example 7, the sodium was converted into the molecular weight of sodium relative to the molecular weight of sodium chlorine dioxide. As a result of comparing the theoretical value with the actual value, it was confirmed that the concentration of sodium was detected at a concentration similar to the theoretical value. On the other hand, in Examples 1 to 7 of the present invention, since Na is not detected at all, according to the present method, pure chlorine dioxide (Metal ions) or metal salts (Metal salts) are not included in the chlorine dioxide solution. It was confirmed that ClO ₂ ) can be prepared.

Therefore, the present invention can sufficiently solve the problem of chlorine dioxide produced by the conventional method, so that it can be widely used in various fields such as food and hygiene, which does not adversely affect the health of the human body without the occurrence of whitening phenomenon. A big advantage was confirmed.

100: spray gun 200: chlorine dioxide discharge
300: operating part 400: pump body
500: cation exchange resin storage unit 600: chlorine dioxide storage unit dissolved in water
700: manual discharge pump 800: push button
900: power submersible pump

Claims (5)

In the method for producing a pure chlorine dioxide (ClO2) aqueous solution containing no metal ions or metal salts in the chlorine dioxide solution to provide disinfection, sterilization and bactericidal effect,
Chlorine dioxide dilution step for diluting chlorine dioxide in water;
An ion exchange contacting step of contacting the cation exchange resin by a conveying means to remove cations in chlorine dioxide diluted in water;
A concentration adjusting step for appropriately maintaining the concentration of the pure chlorine dioxide (ClO 2) aqueous solution from which the cation is removed through the ion exchange contacting step;
Method for producing a pure chlorine dioxide aqueous solution comprising a. The method of claim 1,
The dilution step of the chlorine dioxide salt is prepared so that the chlorine dioxide salt selected from sodium chlorine dioxide (NaClO 2) or potassium chlorine dioxide (KClO 2) is diluted to a concentration of 0.01 ppm to 35% by weight. Way. The method of claim 1,
The cation exchange resin is used as a process of adsorbing and removing only cations in chlorine dioxide by using a cation exchange resin represented by R-SO3H or R-COOH when the basic polymer matrix portion of the ion exchange resin is represented by R. Method for producing a pure chlorine dioxide aqueous solution characterized in that. The method of claim 1,
The concentration control step of the chlorine dioxide (ClO2) is a method of producing a pure chlorine dioxide aqueous solution characterized in that the pure chlorine dioxide made by the ion exchange method using a cation exchange resin is adjusted to a concentration of 0.01 ppm to 5% by weight. In the manufacturing apparatus for obtaining a pure chlorine dioxide (ClO2) aqueous solution containing no metal ions or metal salts in the chlorine dioxide solution to provide disinfection, sterilization and disinfection effect,
A chlorine dioxide dilution tank to dilute chlorine dioxide in water and
Chlorine dioxide diluted in the dilution tank is contacted with a cation exchange resin by a transport means selected from an underwater pump, a non-powered pump, a spray gun, and an exhaust pump to remove cations by ion exchange. Reactor and
Apparatus for producing a pure chlorine dioxide aqueous solution comprising a concentration control tank for properly maintaining the concentration of the chlorine dioxide (ClO2) aqueous solution from which the cation is removed through the ion exchange reaction tank.

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