JPH11157805A - Production kit for aqueous chlorine dioxide, aqueous chlorine dioxide precursor composition and production of aqueous chlorine dioxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production kit for aq. chlorine dioxide with which a small amt. of aq. chlorine dioxide in relatively low concn. can be timely, easily and safely produced on-site in high purity, and to provide an aq. chlorine dioxide precursor compsn. and a producing method for aq. chlorine dioxide. SOLUTION: This production kit for aq. chlorine dioxide contains a chlorite soln., acid and chloride of alkali metals or the like. In the kit, the chlorite soln. is kept in a state of not contacting with the acid during the kit is not used for the production. To produce aq. chlorine dioxide, the chlorite soln. is statically added to the mixture liquid of the acid, alkali metal chloride and water and left to stand for 30 sec to 10 min and then, the two liquids are mixed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a kit for producing chlorine dioxide water and a method for producing the same, and more particularly to a kit for producing chlorine dioxide water in various places in a simple and high yield. , A chlorine dioxide water precursor composition and a method for producing chlorine dioxide water.

[0002]

_2. Description of the Related Art Chlorine dioxide is a substance represented by the chemical formula ClO ₂ , which is a gaseous substance at a normal temperature of a melting point of −59 ° C. and a boiling point of 11 ° C., and has strong oxidizing power and bactericidal properties. Explosive at gas concentration of 10% or more, about 30% against water at normal temperature and normal pressure
It has a solubility of 00ppm (mg / l), sterilization and disinfection,
It is used for a wide range of applications, such as deodorization, decolorization, insect repellent and off-flavor improvement.

Conventionally, chlorine dioxide has been used in large-scale industrial applications such as pulp bleaching to add chlorate to mineral acids alone, or to salts such as salt, hydrogen peroxide, sulfur dioxide, or methanol, or to reduce them. Manufactured by adding substances. For medium-scale use such as sterilization / disinfection of drinking water, improvement of off-flavor taste, deodorization and decolorization of industrial wastewater, etc. In the production, a so-called one-liquid one-gas method in which a chlorite aqueous solution and an acid aqueous solution, a chlorite solution and a chlorine gas (including hypochlorous acid and an acid) are reacted, and a chlorite solution and an acid solution are reacted. So-called two-liquid method, or chlorite solution,
A so-called three-component method of reacting a hypochlorite solution and an acid solution is mainly performed.

On the other hand, methods and kits for easily producing a small amount of chlorine dioxide have been proposed in order to achieve environmental sterilization or sterilization and deodorization of fruit boxes and fish boxes during transportation and storage.
For example, JP-A-5-237365 discloses that an acid aqueous solution is sealed in a silicone rubber tube,
There is disclosed a device in which a chlorite solution is sealed in a frangible tube, in which a silicone rubber tube is bent to break the frangible tube so that an acid solution and chlorite are removed. Reacts with salt solution to generate chlorine dioxide. Also, in Japanese Utility Model Application No. 6-10996,
A device comprising an outer bag containing powder chlorite and an easily breakable inner bag containing citric acid water, crushing and breaking this inner bag, mixing with the contents of the outer bag and reacting to generate chlorine dioxide is disclosed. ing.

[0005]

However, in the chlorine dioxide generating apparatus according to the above-mentioned invention and the invention, there is no danger in handling since a very small amount of temporary but high-concentration chlorine dioxide gas is generated. However, there were human safety issues. In addition, the chlorine dioxide generation reaction between the acid and chlorite in these appliances is represented by the following formula: 5NaClO ₂ + 4HCl = 4ClO ₂ + 5NaCl + 2
It is represented by H ₂ O, the theoretical yield with respect to chlorite is 80%, and the reaction rate is slow unless heated with strong acid, and the actual yield is as low as about 60%. There was a problem that was not the target.

[0006] Incidentally, chlorine dioxide is not widely used because its concentration decreases over time, and the operation of the generator and the handling of high-concentration chlorine dioxide water require specialized knowledge. It is also recommended that the occurrence of the problem be performed at the place of use (on-site) and at the time of use (timely). Under these circumstances, if it is attempted to sterilize chicken eggs or cut vegetables using a specific generator as in the past, 1 to 50 mg / 100 to 400 L of water is required.
It is conceivable that the chlorine dioxide concentration is maintained by adding L chlorine dioxide water and adding concentrated chlorine dioxide water several L per minute.

[0007] However, there is no chlorine dioxide generator capable of producing a small amount of chlorine dioxide water at such a low concentration, and no other method has been proposed which is simple and can withstand practical use. Therefore, the most realistic method is to add a certain amount of chlorine dioxide to the added tap water or hot water to a predetermined concentration and send it to a water tank, but if this is to be realized, , 500-20
There is a need for a method and a kit that can produce a small amount of 00 mg / L chlorine dioxide water on-site in a timely, simple, safe, high-purity manner.

The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to supply a relatively small amount of chlorine dioxide water at a relatively low concentration on-site in a timely manner. Another object of the present invention is to provide a chlorine dioxide water production kit, a chlorine dioxide water precursor composition, and a method for producing chlorine dioxide water that can be produced easily, safely and with high purity.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor statically brought a chlorite solution into contact with a predetermined mixture of chloride, acid and water, It has been found that the above-mentioned object is achieved by, for example, standing still for a while, and the present invention has been completed.

That is, the chlorine dioxide water production kit of the present invention comprises a chlorite solution, an acid, and a chloride of an alkali metal and / or an alkaline earth metal. Is characterized in that the chlorite solution and the acid do not come into contact with each other.

Further, the aqueous chlorine dioxide precursor composition of the present invention is obtained by statically adding a chlorite solution to a mixed solution containing an alkali metal and / or alkaline earth metal chloride, an acid and water. It is characterized by being added.

Further, in the method for producing chlorine dioxide water of the present invention, when producing chlorine dioxide water using a chlorite solution and an acid, an acid and a chloride of an alkali metal and / or an alkaline earth metal are used. And water are statically added to the mixture containing chlorite and left for 30 seconds to 10 minutes, and then the two solutions are mixed.

[0013]

In the present invention, a chlorite solution is gently brought into contact with a mixture of an acid containing a specific chloride and water,
By leaving the solution to stand for a while, and then mixing both solutions, chlorine dioxide water can be obtained in high yield.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention relates to the production of chlorine dioxide water by a so-called two-liquid method. As described above, the chlorine dioxide water production kit of the present invention comprises a chlorite solution, an acid, a predetermined chloride, With water according to.

Here, the chlorite solution means an aqueous solution containing chlorite. As a specific compound of the salt, sodium chlorite is suitably used. An alkali metal or alkaline earth metal chlorite such as calcium chlorite can also be used.

Examples of the acid include organic acids such as citric acid and tartaric acid, and mineral acids such as phosphoric acid, hydrochloric acid and sulfuric acid. Hydrochloric acid is preferred in terms of reaction efficiency. Further, the chloride of the predetermined alkali metal and / or alkaline earth metal is not particularly limited as long as it contains a chloride ion, and sodium chloride, potassium chloride or calcium chloride and any of these may be used. And sodium chloride is particularly preferably used.

Further, the kit of the present invention does not use water as an essential element, because water is usually available locally for producing chlorine dioxide water.
If this is an essential component of the kit, the kit may become bulky or heavy as a whole, making transport inconvenient. The water used for the production of chlorine dioxide water is desirably water without turbidity or coloration, such as tap water or groundwater.

Each component constituting the kit of the present invention, ie,
The chlorite solution, the acid, the chloride and the water if necessary may be separately packed, but in order to avoid unnecessary reactions and to ensure safety, the chlorite solution and It must be packaged so that it does not come into contact with acid.
In the present kit, it is most preferable that the container is divided into a container filled with a chlorite solution and a container filled with a mixed solution of an acid, chloride and water in terms of production of chlorine dioxide water.

Specifically, the kit is divided into a chlorite solution and a mixed solution of acid, chloride and water, wherein sodium chlorite is 0.1 to 30 w / v% and hydrochloric acid is 0.1 to 30%. 20w /
v% and sodium chloride are preferably dissolved in water at a rate of 0.01 to 30 w / v%. Note that [w / v
%] Indicates the number of g of solute contained in 100 ml of the solvent (water in the above case).

The above-mentioned sodium chlorite is 0.1 w / v
If the amount is less than 30%, the yield sharply decreases. If the amount exceeds 30% w / v, there is a danger in handling. Further, hydrochloric acid is commercially available only in the above-mentioned range, and cannot be obtained.

As described above, it is preferable that each component is packaged. Specifically, this packaging can be performed by filling each component into a bag or a container. Examples of the material of such a container include glass, ceramics, and plastic, but plastic is preferable from the viewpoint of transportation, cost, and handling. Further, it is preferable that the container filled with the chlorite solution has a light-shielding property.

When the kit is constructed by filling the chlorite solution, the acid and the water in separate containers, the colors of the containers may be changed so that the two solutions are not mistakenly used,
It is desirable to take measures such as changing the color of the label. In addition, when packaging is performed for each component, it is desirable to make each container have a different color or a different label color. Further, in order to facilitate the production of chlorine dioxide water, the order of addition of the components, the volume of fresh water to be added, and the like may be clearly indicated on all or a part of the above-described container.

It is also possible to add a preparation container for producing chlorine dioxide water by mixing various components to the kit of the present invention.
Examples include a 20 L opaque or colored polyethylene square bottle or a cardboard union container with a special polyethylene bag-like container. The produced chlorine dioxide water is preferably stored in a cool and dark place. Further, if a marking indicating the amount of the solution (component) to be filled is provided on such a preparation container, the production of chlorine dioxide water can be further performed on the container.

Incidentally, in order to suppress the chlorine dioxide concentration in the chlorine dioxide water from being released into the atmosphere and reducing the concentration of chlorine dioxide, a preparation container in which polyethylene is coated with nylon to form a double structure or laminated is used. Good to use. In addition, the kit of the present invention is preferably stored together with the above-described various components and, in some cases, a container or preparation container filled with the components, a box or a case, or the like. , Transportability and storage stability can be improved.

Next, the method for producing chlorine dioxide water of the present invention will be described. As described above, in the production method of the present invention, a chlorite solution is statically added to a mixed solution containing an acid, the chloride and water, and the mixture is allowed to stand for a while, and then the two solutions are mixed. And typically can be performed using the kit of the present invention described above.

Here, static addition means that when the chlorite solution is added to the above mixture, the solution is added gently so that the two solutions are not mixed as much as possible. It is preferable that the chlorite solution is added by using a glass rod, a dropper, a pipette, a funnel, or the like. The chlorine dioxide water precursor composition of the present invention is obtained by such static addition, and a desired chlorine dioxide water can be obtained by subjecting the precursor to the following standing to mixing.

In the production method of the present invention, after the above-mentioned static addition, the mixture is allowed to stand for a while, and the standing time is typically 30 seconds to 10 minutes. If the standing time is less than 30 seconds,
Although the yield is not sufficient and the standing time is preferably longer,
It is enough to stand still for 10 minutes. However, you may leave still for 10 minutes or more. Then, after standing, the two liquids are mixed, but the method of mixing is not particularly limited, and may be gentle stirring or vigorous stirring, or a stirring means such as a blade. Mechanical stirring may be non-mechanical stirring by merging / separation of flow paths, and furthermore,
The container may simply be inverted.

Although chlorine dioxide water is obtained by the static addition, standing and mixing as described above, the chlorine dioxide formation reaction is typically completed within 30 minutes after mixing.

As for the addition of water, it is not necessary to add a predetermined amount at a time to achieve the intended concentration of chlorine dioxide water, but it may be added in a plurality of portions. For example, half of a predetermined amount of water is added to prepare a mixture containing an acid, the above-mentioned chloride and water, and a chlorous acid solution is statically added thereto, and a series of operations are performed to perform a series of operations. After producing the chlorine water, by adding and diluting the remaining half of the water,
An intended concentration of chlorine dioxide water can be obtained. The water can be added in two or more portions,
At the time of the chlorine dioxide generation reaction, the chlorine dioxide concentration is 2,000 to 3,000 p.
It is preferable to add an amount so as to be about pm.

As a specific example of the production method of the present invention, a sodium chlorite solution is used as a chlorite solution, and hydrochloric acid is used as an acid.
The reaction is carried out as a hydrochloric acid excess of 1: 1.4 (molar ratio), and sodium chloride is used as the chloride. When the standing time is about 10 minutes and the mixing is one time of inverting and restoring the container, the concentration is 2000 to 30 with a yield of about 90%.
00 ppm chlorine dioxide water can be obtained in 3 to 30 minutes.

[0031]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1) 5 ml was placed in a 1 L volumetric flask.
Of 5N hydrochloric acid (f = 1.003) was added, and 10 g of sodium chloride was further dissolved and added to 900 ml of ion-exchanged water. Then, 10.0 W / V% sodium chlorite 2
0 ml was gently added to the above-mentioned mixed solution of hydrochloric acid, sodium chloride and water so as not to mix as much as possible, and after measuring up, the mixture was allowed to stand for 2 to 3 minutes. Thereafter, the volumetric flask was inverted and reconstituted for mixing, and the time-dependent change in the chlorine dioxide free concentration was determined by a colorimetric method (manufactured by Tokyo Koden Co., Ltd., trade name ANA-700W 450 mm, 10 mm cell). Table 1 shows the obtained results. Note that the theoretical amount of chlorine dioxide generated is 1193 ppm.

[0033]

[Table 1]

(Comparative Example 1 and Examples 2 to 8) The same operation as in Example 1 was repeated, except that the standing time after raising the scalpel was changed. Here, there is no standing time in Comparative Example 1, the standing time is 1 minute in Example 2, the 2 minutes in Example 3, the 3 minutes in Example 4, the 4 minutes in Example 5, and the 5 minutes in Example 6, 7 minutes is Example 7, and 10 minutes is Example 8. Tables 2 and 3 show the obtained results.

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

As described above, according to the present invention, the chlorite solution is brought into static contact with a predetermined mixture of chloride, acid and water, and is allowed to stand for a while. A chlorine dioxide water production kit, a chlorine dioxide water precursor composition, and a method for producing chlorine dioxide water that can produce a relatively small amount of chlorine dioxide water at a relatively low concentration on-site in a timely, simple, and safe manner with high purity. Can be provided.

Claims (6)

[Claims] A chlorite solution, an acid, and a chloride of an alkali metal and / or an alkaline earth metal, wherein the chlorite solution and the acid are used except during the production of chlorine dioxide water. A chlorine dioxide water production kit, wherein the kit does not come into contact with the water. 2. The chlorine dioxide water production kit according to claim 1, wherein the mixed solution of the acid and the chloride and the chlorite solution are packaged. 3. The packaging according to claim 1, wherein the packaging is performed using a container.
3. The chlorine dioxide water production kit according to claim 2, wherein the procedure for producing the chlorine dioxide water using the kit is described in the container. 4. The alkali metal and / or alkaline earth metal chloride is sodium chloride, and its compounding amount is 0.1%.
0.1 to 30 w / v%, the acid is hydrochloric acid, the compounding amount is 0.1 to 20 w / v%, and the chlorite is sodium chlorite, the compounding amount is 0.1 to 20 w / v%. 30w / v
%, And the chlorine dioxide water production kit according to any one of claims 1 to 3. 5. A chlorine dioxide solution comprising a chlorite solution statically added to a mixed solution containing a chloride of an alkali metal and / or an alkaline earth metal, an acid and water. Precursor composition. 6. In producing chlorine dioxide water using a chlorite solution and an acid, a mixed solution containing an acid, an alkali metal and / or an alkaline earth metal chloride, and water, A method for producing chlorine dioxide water, comprising statically adding a chlorite solution, allowing the solution to stand for 30 seconds to 10 minutes, and then mixing the two solutions.