KR20210082627A - Method and apparatus for producing of pure chlorite solution - Google Patents

Abstract

The present invention relates to a method for preparing pure aqueous chlorine dioxide (ClO_2) solution free from metal ions or metal salts and used for disinfection, sanitary treatment and water purification in indoor and outdoor places and environments with poor hygiene, or as a disinfectant, sterilizing agent or fungistatic agent during food and water purification processes. The method includes the steps of: a chlorine dioxide salt dilution step of diluting chlorine dioxide salt in water; a cation removing step of removing cations through an ion exchange process that includes contacting the cations of chlorine dioxide salt diluted in water with a cation exchange resin by using an aqueous pump, power-off or spray gun or a manual discharge pump device; and a concentration-controlling step of maintaining the concentration of the aqueous chlorine dioxide (ClO_2) solution from which cations are removed from the above process. The present invention can be applied to a method and apparatus for preparing chlorine dioxide solution in which pure chlorine dioxide is obtained by such a simple method, and the resultant chlorine dioxide solution can be supplied to various fields requiring disinfection, sanitary sterilization treatment and water purification in human or animal living places and environments with poor hygiene, and disinfecting, sterilizing or fungistatic steps during food and water purification processes through a cost-efficient structure and can be used therein with high efficiency.

Description

Method and apparatus for producing pure chlorine dioxide aqueous solution

The present invention is an aqueous solution of chlorine dioxide used when disinfection, sanitation, or purification treatment is required due to an environment degenerated into a place with poor indoor or outdoor hygiene, or when disinfection, sterilization, and sterilization functions are required during food storage or water purification process. It is an invention in the technical field to provide _{pure chlorine dioxide (Chlorite, ClO 2} ) that does not contain metal ions or metal salts.

More specifically, a chlorine dioxide salt dilution step of diluting the chlorine dioxide salt in water to perform the above task; The cation in chlorine dioxide diluted in water is configured to contact the cation exchange resin by mobilizing the moving means of an underwater pump, a non-powered pump, a spray gun, and a manual discharge pump. a cation removal step; A method for producing a pure chlorine dioxide solution comprising a dilution step to properly maintain the concentration of an aqueous solution of _{chlorine dioxide (ClO 2} ) from which cations have been removed, and a chlorine dioxide solution production apparatus used therein.

Sterilization or disinfection process is to completely kill or annihilate the bacteria distributed on or on the surface of the object to be protected. Sterilization is the safest form of sterilization by killing pathogens on the surface or inside of an object to eliminate transmission or infectivity.

Disinfection is used to prevent contamination of microorganisms by killing pathogenic microorganisms or suppressing the infectivity so that they cannot be activated even if they cannot necessarily be killed. Sterilization refers to an operation that completely kills all microorganisms to make them sterile. Generally, pathogenic microorganisms have weak resistance in the outside world, so they can be killed more easily than conditions that kill non-pathogenic microorganisms.

Microorganisms have different resistance to sterilization depending on their type, and in particular, in the case of spore-forming bacteria, they remain dormant under normal sterilization conditions and reproduce again when conditions improve. When it coexists with proteins such as , phlegm, and feces, the resistance becomes much stronger than when it is suspended in physiological saline.

However, in general, when pathogens are transmitted, it is common to coexist with proteins. Therefore, various sterilization or disinfection methods must be used for sterilization conditions depending on the target or purpose.

Disinfection (消毒) is the killing of pathogens to prevent infection or transmission of disease, and does not kill all microorganisms, especially non-resistant bacterial spores, rather than sterilization that undergoes extreme physical/chemical processes that can kill all kinds of organisms. The effect is less, and disinfection is in progress with sunlight, heat, and chemicals.

Chemical disinfection is used as the most common method for disinfection, and in the case of chemical disinfection, it is a method to kill bacteria by using a disinfecting agent. Although it can be said that it is complete, there are cases where it cannot be implemented depending on the object.

The conditions for the disinfectant should be strong sterilization power and harmlessness, the handling method should be simple, the disinfection object should not be damaged, the production should be easy and the price should be low, and it is desirable that there is no smell.

The disinfectants used so far are phenolic acid (C ₆ H ₅ OH), cresol soap solution (cresol, CH ₃ C ₆ H ₄ OH), formaldehyde (HCHO), sulphur (mercuric chloride, HgCl ₂ ), alcohol, Reverse soap solution, chlorine agent (chlorine, bleach powder, sodium hypochlorite, inorganic chlorine compound), iodine, quicklime, hydrogen peroxide, medicinal soap, mercurochrome solution, etc. are selectively used depending on the purpose or type of infectious disease. have.

In the case of the above phenolic acid, the concentration used is a 3% aqueous solution, and the sterilization action depends on the bacterial protein coagulation action, cell lysis action, and the action of the enzyme system. It is known that it is suitable for sterilization of clothes, containers, filth, feces, and vomit because it has a safe sterilization power and does not change chemically even if left for a long time.

In the case of the cresol soap solution, it does not dissolve well in water, so cresol soap solution 3 to 97 water is used to make the same amount of cresol soap solution. Although the effect is small, it is known to be effective in sterilizing bacteria.

The formaldehyde is a gas made by oxidizing methyl alcohol (methanol), has a strong irritating odor, is well soluble in water, has a strong reducing power, has a sterilization effect even at a low concentration, has a simple generator using methyl alcohol, and has a closed room. I generate it in a specially made box and use it to sterilize the things inside.

Formalin is an aqueous solution containing 37% or more of formaldehyde, and it acts on proteins even at high dilution concentrations, has an irreversible sterilization power, and has a strong sterilization effect on spores. 1.5% aqueous solution is used, and its use is known to be suitable for disinfection of clothes, ceramics, wood products, celluloids, rubber products, etc.

The above water is colorless, odorless, highly toxic, and corrosive to metal, so the container uses plastic, and the chemical solution must be distinguished by dyeing it with fuchsin, etc., but the sterilization power is strong, but the higher the chemical solution, the stronger , 0.1-0.5% aqueous solution is used for skin disinfection, and it kills Escherichia coli and staphylococcus in 5-10 minutes. It is highly irritating to the mucous membrane, but cannot be used for disinfection of rubber products and metal products.

The methyl alcohol has strong sterilization power in 70-75% aqueous solution, and is mainly used for disinfection of resins, skin, instruments, etc. It is easy to use, but alcohol evaporates quickly and is effective against spore-free bacteria, but has no effect on spore-forming bacteria. is known

The reverse soap solution is a surfactant with strong penetrating and sterilizing power, and is generally used by making 0.1-0.5% aqueous solution. Because it is colorless, odorless, and non-irritating, it is suitable for sterilizing resins, instruments, and containers, and is widely used in beauty, has little detergency, and is known to be ineffective against Mycobacterium tuberculosis.

In the case of the disinfectant for chlorine, fluorine, chlorine, oxo, etc. are included in the halogen elements. Chlorine, which forms a protein and halogen complex in living cells, stops cellular metabolism and eventually kills cells, has great sterilizing power in the gaseous state. but not obsolete by the non-irritation and large disinfection corrosive strong, such as water, sewer dodok bleaching powder (chlor lime CaOCl ₂₎ plays a sterilization taking the generator chlorine in the water, sseuyimyeo in drinking water or swimming pool disinfection when beverage sterilization 0.2-0.4 Used at the level of ppm concentration, sodium hypochlorite (NaOCl) has a bactericidal action by chlorine element generated in the solution.

The iodine has a strong sterilizing power like chlorine, but has weak side effects on the skin mucous membrane even at a high concentration, but uses an about 100-fold solution (effective iodine content of 100-200 ppm) for disinfection of resins, instruments, etc. It has the disadvantage of corrosive and roughening of sensitive skin.

In the case of the above quicklime, add half of the amount of quicklime to a mud-like state or use a 5-fold (20%) aqueous solution of lime milk. Use powder to disinfect water or damp places. It is known that it is better to spray directly there, and quicklime is used for disinfection of manure, vomit, manure bins, trash bins, sewers, and water tanks. The drawback is that it is ineffective against Mycobacterium tuberculosis and spores, and the advantage is that it is suitable for widespread disinfection because it is cheap.

In the case of the hydrogen peroxide, the oxidizing agent disinfectant is an agent that oxidizes sulfurhydryl (-SH) groups to stop cell metabolism, and hydrogen peroxide (H ₂ O ₂ ) is used for disinfection with 2.5 to 3.5% aqueous solution (oxyfull), A colorless, transparent, odorless, but sometimes ozone-like liquid that is known to sterilize by oxidizing pathogens.

In the case of the medicinal soap, various sterilizing agents are added to the soap base, and it is intended to simultaneously act the washing action of the soap and the chemical disinfection action by the sterilizing agent, and is used for hand skin disinfection.

The Mercurochrome solution is often referred to as a red drug, and it is a 2% aqueous solution of Mercurochrome, which is used as it is when disinfecting wounds. Mercurochrome is a mild disinfectant that chemically belongs to inorganic mercury compounds and is a mild disinfectant, but is sometimes hypersensitive. should be taken care of, and the inhibitory action of bacterial growth lasts for a relatively long time.

The disinfection target according to the type of infectious disease is as follows.

First typhoid. paratyphoid fever. cholera. In the case of dysentery, since it is an oral infection and is an infectious disease of the digestive system, the patient's excrement, vomit, leftover food, tableware, and toilet become a problem, and the patient's clothing, bedding, filth, trash can, and sewer must be disinfected.

Second, in case of smallpox or scarlet fever, the patient's runny nose, sputum, mucus, contaminated equipment, clothing, bedding, transport equipment, the patient's food equipment, the bedroom floor, and the caretaker. Disinfect the contact person's body and clothing.

Third, in the case of daphtheria, the patient's runny nose and sputum and their contaminated instruments, tableware, books, toys, bedding, other objects in the room, and the caregiver's clothing and body are disinfected. Fourth, in case of polio, it is equivalent to the disinfection of dysentery, but it is equivalent to the disinfection of diphtheria at the beginning of the outbreak.

In order to reduce the damage caused by these outbreaks, various methods are used to continuously disinfect and disinfect vulnerable areas, thereby exterminating sanitary pests such as flies and mosquitoes and making great efforts to prevent infectious diseases that are prone to infectious diseases in advance.

Health disorders caused by food include oral infectious diseases such as cholera, dysentery, typhoid, tuberculosis, anthrax, brucellosis (salmonellosis), and common human diseases such as bird flu (AI), roundworms, pinworms, hookworms, pedestomas, and gandistomas. There are parasitic diseases and food poisoning (bacteria, natural poisons, chemical substances, other factors), and if food-borne diseases are classified according to their causes, the original ingredients of food raw materials are harmful and toxic, so endogenous, food production. Physical, chemical, and biological factors in the process of manufacturing, processing, storing and distributing exogenous foods that cause disease due to mixing or contamination of harmful or toxic substances from outside in the process of growth, manufacturing, processing, storage, distribution and consumption It is classified as an inducer that produces toxic substances in food and causes disease.

In addition, in order for an infectious disease to occur, the source of infection, the route of infection, and the susceptibility of the host are required. In order for disease to occur, sufficient pathogens must exist qualitatively and quantitatively as the source of infection. People must exist.

Most infectious diseases occur and become prevalent when three conditions of infection source, infection route, and susceptibility are met. different from

Therefore, the most important thing as a business owner is thorough prevention, regular inspection of workers to make sure there are no carriers, and making a habit of finger disinfection is important.

Chlorine dioxide (ClO ₂ ) was first discovered by Humphrey Davy in 1814, and since its use as a disinfectant for water treatment was proposed by Berge in 1900, it has been widely used for drinking water sterilization, odor removal, and bleaching in the United States and Europe. In particular, since 1972, it has been found that chlorine dioxide, unlike chlorine, does not react with organic pollutants in water to produce trihalomethanes, a carcinogen.

However, domestic law (in the case of aqueous solution) restricts its use to the removal of heavy metals such as iron (Fe) and manganese (Mn) by concurrent (post-treatment) treatment with chlorine, but in the US Food and Drug Administration, Listeria and E. coli O157 :H7 (E. coli O157:H7), Salmonella sp., the efficacy of reducing the level of at least 1 in 100,000 is presented as a disinfectant standard, and the efficacy of chlorine dioxide is It has been confirmed that this method is more effective in eradicating Listeria bacteria that contaminate fruits and vegetables than any other sterilization method currently available. This is because it is particularly difficult to remove these bacteria compared to the pathogenic bacteria of , but Listeria bacteria have a strong enough vitality to survive in the refrigerator or freezer, and it is known that it is difficult to remove the activity.

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

In addition to the above characteristics, chlorine dioxide has the advantage that it can kill bacteria or viruses without high risk in most environmental applications. So far, people have used solutions containing chlorine dioxide as food ingredients. It can be applied to obtain the effect of sterilization and disinfection by contacting the surface of foodstuffs or places with poor hygiene for disinfection, sanitary treatment, or water purification of a place or object with poor freshness or sanitary condition.

Therefore, in order to maintain the freshness of all foods used as ingredients for the beneficial health of the human body or animals, as well as provide a healthy living environment in which viruses or bacteria do not exist or can be minimized, liquid chlorine dioxide source maintains the freshness. It is necessary to provide a vaporized chlorine dioxide source in all spaces required without direct contact with the surface of food to maintain or the place to be sanitized where sterilization or disinfection is required.

Moreover, in the case of fruits and vegetables, respiration and transpiration continue during the handling, transportation, storage, and sales process, resulting in a decrease in freshness. In the case of exporting countries that require long-term transportation, claims due to corruption, wilting, aging, and deterioration occur. Advancement of post-harvest life extension technology is still an urgent task, especially considering that the economic loss rate due to corruption during distribution and storage in developing countries and developing countries has reached a minimum of 10% to a whopping 50%, extending the lifespan to maintain freshness Technology is essential and there is a need to develop convenient food storage technology while satisfying economic feasibility.

The prior art for maintaining the freshness of food and providing disinfection, sanitation, and water purification using chlorine dioxide to date is as follows.

In Korean Patent Laid-Open Publication No. 10-2017-0103219 A, a tubular shape formed with a predetermined length from the top to the bottom of the reactor is located inside the reactor, and sodium chloride and sulfuric acid are introduced at the top and are mixed while flowing inward. A device for generating chlorine dioxide water by a reaction tube is proposed, and the cited invention reacts with sodium chloride and sulfuric acid to generate chlorine dioxide and generates a by-product of sodium sulfate. When the chlorine dioxide source is applied as a disinfectant for drinking water Health problems may occur, and when a disinfectant is sprayed on the surface of an object, it has a problem that may cause aesthetic problems due to the final whitening phenomenon.

Korean Patent Application Laid-Open No. 10-1807966 B1 proposes a chlorine dioxide generating device capable of generating a fixed amount of chlorine dioxide as it can supply an acid such as sodium chloride and citric acid in a fixed amount at a set time interval. Although it has the advantage that chlorine dioxide can be supplied quantitatively over time, as sodium citrate is generated as a by-product, it has a similar problem as described in Korean Patent Application Laid-Open No. 10-2017-0103219 A.

In Korea Patent Laid-Open No. 10-2017-0127271 A, the sodium chloride aqueous solution and the sulfuric acid aqueous solution pass through the reaction tube to generate chlorine dioxide with high production yield and excellent purity, and frequent corrosion problems of 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 is proposed. According to the configuration of the cited invention, sodium sulfate is generated as a by-product, which is described in Korean Patent Application Laid-Open No. 10-1807966 B1. It presents the same disadvantages.

Korean Patent Publication No. 10-1793957 B1 proposes a chlorine dioxide gas generator capable of uniformly and continuously generating a desired low concentration of chlorine dioxide gas by a technical configuration of supplying sodium chloride and hydrochloric acid, but sodium chloride as a by-product As this occurs, the disadvantages presented in Korean Patent Laid-Open No. 10-2017-0103219 A are not resolved.

Compared to the prior art as described above, in the application of the present technology, no by-product is generated by the ion exchange method using a cation exchange resin, and pure chlorine dioxide is generated in water. can be completely different.

In addition, as a result of research conducted by the present inventors through domestic and foreign search engines, most of the methods for providing chlorine dioxide are suggested by the technical construction by supplying organic and inorganic acids to an aqueous solution containing sodium chloride. By the ion exchange method using the cation exchange resin of

While the present application can prepare an aqueous solution containing pure chlorine dioxide for maintaining food freshness, disinfection, sanitation, and water purification, the conventional methods for providing a pure chlorine dioxide solution researched and developed so far are It is possible to solve problems that may adversely affect the health of the human body and give bad results to the visual cosmetic effect due to the whitening phenomenon.

As disclosed in the background art, all methods developed so far to constitute chlorine dioxide in water generate by-products, and when the produced by-products are applied to the food field, they can adversely affect the human body or storage objects, and disinfect the object surface It is an invention that started with the task of finding a way to solve the problem of having a large limitation in compatibility due to the exposure result of visual impurity due to the whitening phenomenon when sprayed for

Metal ions or metal ions in chlorine dioxide solutions used for disinfection or sanitary treatment in environments or places with poor indoor and outdoor sanitary conditions, or used as disinfectants, sterilizers, and sterilizers during food storage and management, and water purification processes A chlorine dioxide dilution step for diluting the chlorine dioxide in water as a means for providing _{pure chlorine dioxide (Chlorite, ClO 2} ) in a state that does not contain metal salts; a cationic cation removal step for removing cations by an ion exchange method by contacting cations in chlorine dioxide diluted in water with a cation exchange resin; It has the purpose of obtaining a pure chlorine dioxide solution through a concentration control step to properly maintain the concentration of an aqueous solution of _{chlorine dioxide (ClO 2} ) from which cations have been removed.

The present invention is used for disinfection or sanitation in places and environments with poor indoor and outdoor hygiene, or metal ions or metal salts (metal ions) or metal salts ( It is a technology to provide pure chlorine dioxide (Chlorite, ClO _{2 ) that does not contain metal salts).}

The technical idea of the present application is to provide disinfection, sterilization, and sterilization effects in a method for producing _{pure chlorine dioxide (ClO 2 ) that does not contain metal ions or metal salts in a chlorine dioxide solution.} Chlorine dioxide dilution step for dilution in water, ion exchange contact step of contacting with cation exchange resin by means of transport to remove cations in chlorine dioxide diluted in water, and ion exchange contact step, the cations are removed This invention was completed by confirming that pure chlorine dioxide (ClO ₂ ) aqueous solution can be obtained through a process including a concentration control step for properly maintaining the concentration of the aqueous solution.

The dilution step of the chlorine _{dioxide salt may be applied so that the chlorine dioxide salt selected from sodium chloride dioxide (NaClO 2} ) or potassium chloride dioxide (KClO ₂ ) is diluted to a concentration of 0.01 ppm to 35% by weight, and the cation exchange resin is 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 is used to adsorb and remove only cations in chlorine dioxide. In the step of controlling the concentration of chlorine (ClO ₂ ), pure chlorine dioxide made by an ion exchange method using a cation exchange resin may be used by adjusting the concentration of 0.01 ppm to 5 wt%.

The technical idea of the present application is a manufacturing device for providing _{pure chlorine dioxide (ClO 2} ) that does not contain metal ions or metal salts in the chlorine dioxide solution in order to provide disinfection, sterilization, and sterilization effects. A chlorine dioxide dilution tank for diluting the flame chlorine in water and the chlorine dioxide diluted in the dilution tank are brought into contact with the cation exchange resin by a transfer means selected from a submersible pump, a non-powered pump, a spray gun, and a discharge pump. Through a simple configuration comprising an ion exchange reaction tank and a concentration control tank to properly maintain the concentration of an aqueous solution of _{chlorine dioxide (ClO 2} ) from which cations have been removed through the ion exchange reaction tank to remove cations by the ion exchange method. Disclosed is a manufacturing apparatus capable of obtaining a pure aqueous chlorine dioxide solution.

As the related technology of the present application reveals in the background, most of the chlorine dioxide production means for disinfection, sterilization, and sterilization have been supplied so far, so organic and inorganic acids (Acid) are supplied. Among the chlorine dioxide that can provide a role, by-products of alkali salts that can be harmful to the human body are created and coexisted, so there is a limit to the use of food or water purification by by-products, as well as by-products contained in water on the surface of the object. It provides an effect to solve the problem of providing a poor visual effect due to the occurrence of whitening on the surface of the object after the water evaporates and dries after being sprayed.

_{In addition, the present application provides pure chlorine dioxide (Chlorite, ClO 2} ) that does not contain metal ions or metal salts in chlorine dioxide in the water, thereby adversely affecting human health without causing whitening. It provides an effect that can be widely used in the food field and various fields to improve the living environment of people by providing a pure chlorine dioxide (ClO _{2 ) aqueous solution.}

1 is an exemplary view of an embodiment applied to allow a sodium chloride solution using a power submersible pump to pass through a cation exchange resin to provide a pure chlorine dioxide solution provided herein.
Figure 2: Illustrative view of an embodiment applied to allow a non-motorized sodium chloride solution to be passed through a cation exchange resin to provide a pure chlorine dioxide solution provided herein.
Figure 3: Illustrative view of an embodiment applied to pass a sodium chloride solution using a spray gun type to a cation exchange resin so as to provide a pure chlorine dioxide solution provided herein.
Figure 4: An exemplary embodiment applied to pass the sodium chloride solution using a manual discharge pump type to the cation exchange resin so as to provide the pure chlorine dioxide solution provided herein.

Prior to describing the embodiments of the invention for implementing the technical idea of the present application by presenting the drawings, the terms or words used in the specification or claims of the present application should not be construed as being limited to conventional or dictionary meanings. , the scope of protection of the present application should be interpreted in meaning and concept consistent with the technical spirit of the present invention, and the examples described in the present specification are only the most preferred embodiment of the present invention and do not represent all of the technical spirit of the present invention. Therefore, it should be understood that there may be various equivalents and modifications that can be substituted for them at the time of filing the present application.

The drawings presented herein will be described with reference to the simplified drawings applied in the form of embodiments in order to confirm whether the inventors can obtain the desired effects of the invention.

1 is an exemplary view of an embodiment applied to pass a sodium chloride solution using a power submersible pump to a cation exchange resin to provide a pure chlorine dioxide solution provided herein, and to contact the cation exchange resin, FIG. 2 is provided herein It is an exemplary view of an embodiment applied so that a sodium chloride solution without power can be passed through and contacted with 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 It is an exemplary view of an embodiment applied so that the sodium chloride solution using the type can pass through and contact the cation exchange resin, and FIG. 4 is sodium chloride using a manual discharge pump type to provide the pure chlorine dioxide solution provided herein. It is an exemplary view of an embodiment applied to allow the solution to pass through and contact the cation exchange resin.

In FIG. 1, the purpose is to provide a large amount of pure chlorine dioxide solution by power, and 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, and the power By driving the pump 900, the sodium chloride (NaClO ₂ ) solution moves to the cation exchange resin storage unit 500, and ion exchange is performed by the cation exchange resin stored in the cation exchange resin storage unit 500 as shown in Scheme 1. as the sodium in the sodium chlorine dioxide combined with a cation exchange resin, hydrogen ions (H ⁺⁾ are released from the cation exchange resin is a metal and the presence of hydrogen ions (H ⁺⁾ state in water through the chlorine dioxide outlet 200 ion and It shows that it can be applied in a form that is configured to make pure chlorine dioxide (ClO _{2 ) without salts.}

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

2 shows an embodiment that can be applied to obtain a large amount of pure chlorine dioxide solution by no power using the high and low positions, and the technical configuration of FIG. 2 is a diluted sodium chloride solution with chlorine dioxide dissolved in water When stored in the sodium solution storage unit 600, and the cation exchange resin storage unit 500 is located at a lower position than the sodium chloride solution storage unit 600, the sodium chloride solution storage unit 600 by non-power The sodium chloride solution stored in the cation exchange resin moves to the chlorine dioxide discharge unit 200 while passing through the storage unit 500, so that pure chlorine dioxide (ClO ₂ ) is produced by Reaction Equation 1. Can be applied in a form is shown.

3 shows that a small amount of pure chlorine dioxide solution can be provided by an operating method such as a spray gun 100 when applied on a small scale such as a household, and the technical configuration of FIG. 3 is diluted chlorine dioxide Sodium (chlorine dioxide salt) solution is stored in the sodium chlorine dioxide solution storage unit 600 dissolved in water, and when the hand gun operation unit 300 is operated forward and backward, the pump body unit 400 is driven and cation exchange A vacuum is applied to the connection line between the resin storage unit 500 and the sodium chlorine dioxide storage unit 600 dissolved in water, so that the sodium chloride solution stored in the chlorine dioxide storage unit 600 dissolved in water is transferred to the cation exchange resin storage unit ( 500) and moving to the chlorine dioxide discharge unit 200, it shows that it can be applied to obtain and use _{pure chlorine dioxide (ClO 2 ) by the above Reaction Equation 1.}

4 shows that a small amount of pure chlorine dioxide solution can be obtained by a manual method such as a manual discharge pump 700 that applies pressure with a finger, such as a shampoo discharge means. When the sodium chloride solution is stored in the sodium chloride solution storage unit 600 dissolved in water, and the push button 800 is operated up and down by hand, the pump body 400 is driven while the cation exchange resin storage unit ( 500) and the sodium chloride solution stored in the sodium chloride storage unit 600 dissolved in the water inside the container is a cation exchange resin storage unit (500) as a vacuum is applied to the connection line of the sodium chloride storage unit 600 dissolved in water. ), while moving to the chlorine dioxide discharge unit 200, by the above Reaction Equation 1, pure chlorine dioxide (ClO ₂ ) It shows that it can be applied to be made.

Therefore, the present application is used for disinfection, sanitary treatment, and water purification in places and environments with poor indoor and outdoor hygiene, or metal ions on chlorine dioxide solutions used as disinfectants, sterilizers, and sterilizers during food and water purification processes. To provide pure chlorine dioxide (Chlorite, ClO ₂ ) that does not contain or metal salts, more specifically, the chlorine dioxide dilution step for diluting the chlorine dioxide in water is, for example, sodium chloride or potassium chloride after one kind of chlorine dioxide is selected, it can be freely used from a low concentration to a high concentration according to the purpose, and it can be widely diluted and used, and its dilution concentration is 0.01 ppm to 35% by weight in a wide range of concentrations _{After dilution, it is possible to prepare a pure chlorine dioxide (ClO 2} ) solution dissolved in water at a concentration of 0.01 ppm to 35% by weight through a cation removal step, which is the next step. In another method, a high concentration of diacid in the dilution step of chlorine dioxide After dilution with pyrochlorite, a high concentration of chlorine dioxide from which sodium (Na) or potassium (K) is removed by the cation removal step is prepared, and then 0.01 ppm in the dilution step to properly maintain the concentration of _{chlorine dioxide (ClO 2 ), which is a later step.} A pure chlorine dioxide solution dissolved in water at a concentration of up to 35% by weight can be prepared.

The cation removal step removes sodium or potassium, which is an alkali metal, from chlorine dioxide combined with sodium (Na) or potassium (K), so that alkali metals or alkali metal-bound salts (Salts) present in water do not exist. In order to provide a pure chlorine dioxide solution, it is intended to remove only cations bound to chlorine dioxide, and the cation removal step can be prepared and used by an ion exchange method using a cation exchange resin, and a diacid in which cations and anions are bonded to each other. The flame retardant can remove cations, which are alkali metals, through the ion exchange method. In ion exchange, when a substance is brought into contact with an aqueous solution of salt, the ions in the substance come out into the solution, and the ions in the solution move into the substance. A substance that exhibits an ion exchange phenomenon is used as an ion exchanger of a reversible exchange reaction of ions having the same charge (positive or negative) between various ions in solution and an insoluble resin (ion exchange resin). The cation exchange resin used in the present invention is a cation exchange resin that combines a sulfonic acid group (-SO ₃ H) and a carboxyl group (-COOH) as an exchange group to a basic polymer matrix having a network structure, and is called a cation exchange resin, such as ^{Na +} , H ⁺ The cations are exchanged, and when this resin is penetrated into water, the part that is an exchanger ionizes like an inorganic acid.

If the basic polymer matrix of the ion exchange resin is represented by R, it can be represented as R-SO ₃ H (sulfonic acid group) or R-COOH (carboxyl group) as a cation exchange resin, and ionizes 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, cations of sodium or potassium in chlorine dioxide dissolved in water are ion-exchanged by a cation exchange resin, and pure water-soluble chlorine dioxide in a wide concentration range can be prepared.

As described above, pure chlorine dioxide in water by the ion exchange method using a cation exchange resin can be prepared differently depending on the use or amount, and when a large amount of chlorine dioxide solution in water with a wide concentration range is required, as shown in FIG. A large amount of pure chlorine dioxide solution in water can be prepared by using a powered submersible pump or by applying the sodium chloride solution to pass through the cation exchange resin by a non-powered method with a different location as shown in FIG. When a pure water chlorine dioxide solution is required, a small amount of pure water chlorine dioxide solution is prepared by applying a spray gun type as shown in FIG. 3 or a sodium chloride solution using a manual discharge pump type as shown in FIG. 4 to pass through the cation exchange resin can do.

The concentration control step of the chlorine dioxide is not particularly limited, and it can be said that it is possible to dilute it to a concentration that can keep the concentration of chlorine dioxide constant according to the intended use and use it.

Accordingly, in the present invention, a chlorine dioxide dilution step for diluting the chlorine dioxide in water; A cation removal step for removing cations by an ion exchange method configured to bring the cations of chlorine dioxide diluted in water into contact with the cation exchange resin by mobilizing a submersible pump or a device of a spray gun or a manual discharge pump. Wow; It is possible to prepare pure chlorine dioxide in water according to the use or amount, including the concentration control step to properly maintain the concentration of the cation-free chlorine dioxide (ClO _{2 ) aqueous solution.}

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

Example 1

In order to check the possibility of preparing a pure chlorine dioxide solution without cations and salts, 350 g of sodium chloride powder purchased from Samjeon Pure Chemical was measured in a beaker, and then about 600 ml of distilled water was added and stirred After completely dissolving sodium chloride, it was transferred to a 1L volumetric flask, filled with distilled water up to the scale line, and stirred to prepare a 35 wt% sodium chloride solution.

200 ml of the prepared 35 wt% sodium chloride solution was aliquoted into a 250 ml beaker, and Samyang cation exchange resin (SK1BH) was sufficiently supplied thereto, followed by stirring for 5 minutes to prepare a chlorine dioxide solution, and then the supernatant stock solution Na analysis was performed by aliquoting.

Example 2

The same procedure as in Example 1 was performed, except that the experiment was conducted with potassium chloride.

Example 3

It was carried out in the same manner as in Example 1, except that a 10% concentration of sodium chloride solution was prepared.

Example 4

It was carried out in the same manner as in Example 1, except that a 1% concentration of sodium chloride solution was prepared.

Example 5

After preparing the spray gun, install a trap filled with Samyang Corporation's cation exchange resin (SK1BH) in the middle of the inlet line, dilute 25% sodium chloride solution purchased from Daemyung Chemical to 0.1% concentration, and then spray gun container. After filling the vial, closing the lid, and applying a hand gesture, the chlorine dioxide solution made from the spray gun outlet was collected and used as a sample for Na analysis.

Example 5

After preparing the spray gun, install a trap filled with Samyang Corporation's cation exchange resin (SK1BH) in the middle of the inlet line, dilute 25% sodium chloride solution purchased from Daemyung Chemical to 0.1% concentration, and then spray gun container. After filling the vial, closing the lid, and applying a hand gesture, the chlorine dioxide solution made from the spray gun outlet was collected and used as a sample for Na analysis.

Example 6

After preparing a discharge pump type container, install a trap filled with Samyang Corporation cation exchange resin (SK1BH) in the middle of the discharge pump inlet line, and dilute 25% sodium chloride solution purchased from Daemyung Chemical to 0.01 ppm concentration. Then, after filling the spray gun container, closing the lid, and applying the push button by hand, the chlorine dioxide solution made from the discharge pump discharge part was collected and used as a sample for Na analysis.

Example 7

Filling the prepared glass column with cation exchange resin (SK1BH) from Samyang, and passing a solution obtained by diluting 25% sodium chloride solution purchased from Daemyung Chemical to 5% concentration through the column to prepare a chlorine dioxide solution, This solution was used as a sample for Na analysis.

Comparative Examples 1 to 7

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

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

As shown in Table 1, looking at Comparative Examples 1 to 7, which is a conventional method, in Comparative Example 6, it was contained at a concentration below the detection limit of ICP and could not be detected. It was confirmed that a large amount of sodium by-product was formed when a chlorine dioxide solution was prepared using the conventional method, and in Comparative Examples 1 to 5 and Comparative Example 7, it was converted into the molecular weight of sodium compared to the molecular weight of sodium chloride. 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 was not detected at all, according to the method of the present application, pure chlorine dioxide (Chlorite, ClO ₂ ) It was confirmed that it 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 sanitation fields that do not adversely affect human health without causing whitening. A great advantage was identified.

100: spray gun 200: chlorine dioxide outlet
300: operation unit 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 _{pure chlorine dioxide (ClO 2} ) that does not contain metal ions or metal salts in chlorine dioxide solution to provide disinfection, sterilization, and sterilization effects,
a chlorine dioxide dilution step for diluting the chlorine dioxide in water;
an ion exchange contacting step of contacting the cation exchange resin with a cation exchange resin by means of a transfer means to remove cations in the chlorine dioxide diluted in water;
Concentration control step for properly maintaining the concentration _{of the pure chlorine dioxide (ClO 2} ) aqueous solution from which cations have been removed through the ion exchange contact step;
A method for producing a pure chlorine dioxide aqueous solution, characterized in that it comprises a. According to claim 1,
The dilution step of the chlorine dioxide salt is sodium chloride (NaClCO ₂ ) or potassium chloride (KClO ₂ ) chlorine dioxide salt selected from 0.01 ppm to 35 wt% pure aqueous solution of chlorine dioxide, characterized in that it is applied to be diluted to a concentration of 0.01 ppm to 35 wt% manufacturing method. According to claim 1,
The cation exchange resin is a process for adsorbing and removing only cations in chlorine dioxide by using a cation exchange resin represented by _{R-SO 3} H or R-COOH when the basic polymer matrix of the ion exchange resin is represented by R Method for producing a pure chlorine dioxide aqueous solution, characterized in that applied. According to claim 1,
The concentration control step of the chlorine dioxide (ClO ₂ ) is pure chlorine dioxide made by an ion exchange method using a cation exchange resin is adjusted to a concentration of 0.01 ppm to 5 wt % Method for producing a pure chlorine dioxide aqueous solution . In a manufacturing apparatus for providing _{pure chlorine dioxide (ClO 2} ) that does not contain metal ions or metal salts in the chlorine dioxide solution to provide disinfection, sterilization, and sterilization effects,
A chlorine dioxide dilution tank for diluting chlorine dioxide in water and
The chlorine dioxide diluted in the dilution tank is brought into contact with a cation exchange resin by a transfer means selected from a submersible pump, a non-powered pump, a spray gun, and a discharge pump to remove cations by an ion exchange method. reaction tank and
The apparatus for producing a pure chlorine dioxide aqueous solution, characterized in that it comprises a concentration control tank for properly maintaining the concentration of the _{chlorine dioxide (ClO 2} ) aqueous solution from which cations have been removed through the ion exchange reaction tank.

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