KR20170117719A - Apparatus to produce gaseous chlorine dioxide with increased productivity and lethal activity - Google Patents

Abstract

The present invention relates to a chlorine dioxide gas generator having improved productivity and bactericidal activity. The present invention can increase the production yield of chlorine dioxide gas by directly reacting acid or chlorite / chloric acid solution fine particles, and can effectively control the production amount and the production time point. In addition, by using the reaction chamber and the particulate state solution capable of directly reacting at a high concentration, the production yield of the chlorine dioxide gas can be further improved, and the relative humidity inside the apparatus can be raised in a short time to sterilize the produced chlorine gas The effect can be remarkably improved.

Description

TECHNICAL FIELD [0001] The present invention relates to a chlorine dioxide gas generator having improved productivity and bactericidal activity,

The present invention relates to a chlorine dioxide gas generator having improved productivity and bactericidal activity.

In general, chlorine dioxide (ClO ₂ ) is known to have strong sterilizing power, oxidizing power, deodorizing power, and sterilizing power about 2.5 times stronger than other chlorinated disinfectants. In addition, the bactericidal power of chlorine dioxide is not greatly affected even in the range of pH 6 to 10, and when reacting with organic substances, trihalomethanes (THMs), haloacetic acid (HAAs ), Haloacetonitrile (HANs), etc., and does not react with ammonia. Therefore, in the food manufacturing process, the water treatment plant, and the sewage treatment plant, (UV), chlorine, ozone, and other disadvantages.

 On the other hand, chlorine dioxide is a powerful oxidizer that accepts electrons and can be easily dissolved in water to produce a pale yellow chlorine dioxide solution. Unlike hydrolyzed chlorine gas, chlorine dioxide exists in the form of dissolved gas in solution, and free radicals react slowly with water in the gaseous state, 7 to 10 million times slower than the hydrolysis of chlorine gas. However, free radicals exist in the gaseous state above 11 ° C-12 ° C, and these properties are important for the storage and injection of chlorine dioxide and affect the efficiency of chlorine dioxide. Particularly, when the concentration of chlorine dioxide gas is 10% or more, not only the explosive property is increased but also the explosive property is high even under a certain pressure, so that it can not be packed in a container and it is difficult to store in a gaseous state. Due to the limitations due to these physical properties, it is inconvenient to use chlorine dioxide as a disinfectant directly in a place where it is needed.

At present, a liquid chlorine dioxide solution is widely used as a chemical disinfectant, but it has a disadvantage that not only the residual risk of the solution but also the careful attention and skillful knowledge are required due to the safety accident in the manufacturing process. Recently, a disinfection method using chlorine dioxide gas, which exhibits excellent penetration and surface disinfecting effect and is less likely to remain on the surface than chlorine dioxide liquid, is attracting attention. Conventionally, as a production method of chlorine gas, there is a method of obtaining chlorine dioxide gas by spontaneous vaporization from a chlorine dioxide solution. However, this method does not have high production yield of gas and it is difficult to control the production time point of chlorine dioxide gas. In addition, the chlorine dioxide gas increases the bactericidal activity when the relative humidity or the water activity of the sample is high. When the chlorine dioxide gas is produced through natural vaporization, it is difficult to increase the relative humidity or the water activity of the sample. There is a disadvantage that it can not be expected.

Under these circumstances, research on a new technology capable of controlling the concentration and rate of chlorine dioxide gas production and increasing the relative humidity or the water activity of the sample has been actively conducted (Korean Patent Laid-Open No. 10-2016-0001155) It is true.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a chlorine dioxide gas generator capable of improving the production yield of chlorine dioxide gas and effectively controlling the production amount and the production time point. .

It is another object of the present invention to provide a chlorine dioxide gas generator capable of enhancing the sterilizing effect of the generated chlorine dioxide gas.

However, the technical problem to be solved by the present invention is not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

According to an aspect of the present invention, there is provided an apparatus for generating chlorine dioxide, comprising: an air compressor; A first solution fine particle containing portion for containing the first solution fine particles produced by colliding with the high pressure gas discharged from the air compressor; A second solution fine particle containing portion which receives the second solution fine particles produced by colliding with the high pressure gas discharged from the air compressor; A reaction part for generating chlorine dioxide gas by the reaction between the first and second fine solution particles; And a connecting portion positioned between the first and second solution fine particle accommodating portions and the reaction portion and moving the first and second solution fine particles to the reaction portion,

Wherein the reaction unit comprises: a reaction chamber in which the reaction between the first and second solution fine particles introduced from the connection part proceeds; And a chlorine dioxide gas accommodation chamber connected to the reaction chamber, the chlorine dioxide gas accommodation chamber containing chlorine dioxide gas.

According to still another aspect of the present invention, the connecting portion of the present invention is a spray nozzle for spraying fine particles contained in first and second solution fine particle containing portions into a reaction portion. A transfer tube for providing a passage through which the injected fine particles can move to the reaction part; And a control valve for controlling the supply amount of the first and second solution fine particles, wherein the control valve is separately connected to the first solution fine particle accommodating portion and the second solution fine particle accommodating portion, respectively.

According to another aspect of the present invention, there is provided a process for producing a chlorine dioxide gas, comprising the steps of: measuring a concentration of chlorine dioxide gas in a decompression portion or a reaction portion formed in one side of the reaction portion to reduce the internal pressure of the reaction portion; A gas generating device is provided.

According to another aspect of the present invention, there is also provided a method of disinfection or sterilization using chlorine dioxide gas produced from the apparatus.

The chlorine dioxide gas generating apparatus according to the present invention can increase the production yield of chlorine dioxide gas by directly reacting the acid or the chlorite / chlorate solution fine particles, and can effectively control the production amount and the production time point. Furthermore, by using a reaction chamber and a solution in a fine particle state which can be directly reacted at a high concentration, the production yield of chlorine dioxide gas can be further improved, and the relative humidity of the inside of the apparatus can be raised within a short time, The sterilizing effect can be remarkably improved.

1 is a perspective view showing a chlorine dioxide gas generating apparatus according to an embodiment of the present invention.
2 is a perspective view illustrating a chlorine dioxide gas generating apparatus equipped with a reaction chamber according to an embodiment of the present invention.
Fig. 3 is a chlorine dioxide gas generator of the present invention manufactured to verify the effects of the present invention.
Fig. 4 is a chlorine dioxide gas generator equipped with a reaction chamber, manufactured to verify the effect of the present invention.
FIG. 5 is a diagram showing a state of use of the chlorine dioxide generating device according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings, in order that those skilled in the art can easily carry out the present invention. In the following detailed description of the preferred embodiments of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In the drawings, like reference numerals are used throughout the drawings.

In addition, in the entire specification, when a part is referred to as being 'connected' to another part, it may be referred to as 'indirectly connected' not only with 'directly connected' . Also, to "include" an element means that it may include other elements, rather than excluding other elements, unless specifically stated otherwise.

FIGS. 1 and 2 are perspective views of a chlorine dioxide gas generating apparatus according to an embodiment of the present invention, and FIGS. 3 and 4 are views showing a chlorine dioxide gas generating apparatus manufactured according to an embodiment of the present invention.

1 and 2, a chlorine dioxide gas generating apparatus 10 according to an embodiment of the present invention includes an air compressor 100, a first solution fine particle accommodating portion 200, a second solution fine particle accommodating portion 200, And a concentration measuring unit 700. The concentration measuring unit 700 may include a reaction unit 400, a reaction unit 400, and a connection unit 500.

By adopting such a configuration, the production yield of chlorine dioxide gas can be increased, the production amount and the production time point can be effectively controlled, and the germicidal effect of the chlorine dioxide gas can be enhanced by increasing the relative humidity inside the apparatus in a short time .

Hereinafter, each component constituting the chlorine dioxide gas generating apparatus 10 according to the instant embodiment of the present invention will be described in detail.

The air compressor 100 is configured to provide a high-pressure gas which collides with the first and second solutions contained in the first and second solution fine particle receiving portions 200 and 300 to generate these fine particles, And generates and discharges gas at a high pressure. 1 and 2, the air compressor for discharging the high-pressure gas is connected to the first and second solution receiving portions 200 and 300 through the gas transfer pipe 110, , And the gas transfer pipe 110 may have a Y-shaped pipe structure. 3 and 4, the air compressor 100 is connected to the decompression unit 600 through a pipe to control the pressure inside the reaction unit by sucking and circulating air inside the reaction unit, And can promote the generation of gas.

The first and second solution fine particle storage parts 200 and 300 are spaces for accommodating the first and second solution fine particles generated by the collision of the high pressure gas discharged from the air compressor 100 into the first and second solutions 1 and 2, the first and second solution fine particle storing units 200 and 300 are supplied with high pressure gas from the air compressor 100 through the gas feed pipe 110, The first and second solution fine particles generated through the first and second fine particle receiving portions 200 and 300 are accommodated in the separated first and second fine particle accommodating portions 200 and 300, respectively. The solution contained in the first solution fine particle storage part 200 may include sodium chlorite (NaClO ₂ ), sodium chlorate (NaClO ₃ ) And a chlorous acid / chloric acid solution such as potassium chloride (KClO ₃ ) solution, and the solution contained in the second solution fine particle storage part 300 may be hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, citric acid, , Lactic acid, tartaric acid, fumaric acid, propionic acid, succinic acid, and adipic acid solutions.

The reaction part 400 is a space for generating the chlorine dioxide solution fine particles through the reaction between the first solution fine particles and the second solution fine particles and for receiving the vaporized chlorine dioxide gas therefrom. Specifically, the reaction part 400 receives the first solution fine particles and the second solution fine particles generated in the first and second solution fine particle receiving parts 200 and 300 through the connection part 500, To produce chlorine dioxide solution fine particles. Thereafter, the chlorine dioxide gas can be obtained through vaporization in accordance with the pressure regulation in the reaction part. As the series of processes proceeds in the reaction part 400, the production yield of the chlorine dioxide gas can be improved.

In one embodiment of the present invention, when the sodium chloride solution is used as the first solution and the hydrochloric acid solution is used as the second solution, the sodium chlorite solution fine particles and the hydrochloric acid solution fine particles are injected into the reaction part. In order to produce the chlorine dioxide solution fine particles , The reaction of the following formula 1 proceeds.

[Formula 1]

_{5NaClO 2 + 4HCl 4ClO 2 + 5NaCl} + 2H 2 O

As shown in FIGS. 1 and 2, the reaction part 400 can be provided in a single chamber form so that the inter-particulate reaction and the chlorine dioxide gas can be integrally formed. In addition, A reaction chamber 410 in which the second solution fine particle reaction proceeds; And a chlorine gas accommodating chamber 420, as shown in FIG.

The reaction chamber 410 has a structure for enhancing the reactivity between the first and second fine particles of the solution to further improve the production yield of the chlorine dioxide gas. In the same manner as described above, the first and second The first and second solution fine particles generated in the solution fine particle storage parts 200 and 300 are introduced and the chlorine dioxide solution fine particles are produced through the chemical reaction. In this manner, by directly reacting the first and second solutions injected in the particulate state at a high concentration, not only the production rate of the chlorine dioxide solution fine particles is increased, but also the vaporization rate to the chlorine dioxide gas is increased. In addition, since the relative humidity of the entire reactor 400 can be rapidly increased by using the moisture contained in the first and second fine solution microparticles injected into the reaction chamber 410, the sterilizing effect of the produced chlorine dioxide gas can be improved Can be significantly improved.

The chlorine gas accommodating chamber 420 is configured to accommodate the chlorine dioxide gas generated by the vaporization of the chlorine dioxide solution fine particles in the reaction chamber 410. If necessary, And an object to be treated with the chlorine dioxide gas may be placed at the lower end. In an embodiment of the present invention, the chlorine dioxide gas receiving chamber 420 is arranged adjacent to the outer circumferential or outer surface of the reaction chamber 410, and the chlorine dioxide gas receiving chamber 420 And the reaction chamber 410 may be connected to each other.

As shown in FIGS. 1 and 2, the connection part 500 includes a connection part 500 and a connection part 500. The connection part 500 connects the first and second solution fine particle storage parts 200 and 300 to the reaction part 400, 1 and the second solution fine particle storage part 200, 300 into the reaction part; And a transfer pipe 520 for providing a path through which the injected fine particles can move to the reaction part 400. [

 The injection nozzle 510 is configured to inject the first and second solution fine particles contained in the receiving portions 200 and 300 to the reaction portion 400. Specifically, the first and second solution fine particle receiving portions 200 , 300) and the transfer pipe (520). As one example, the air compressor 100 and the first and second solution fine particle receiving parts 200 and 300 may be integrated with each other to form a nebulizer.

The transfer pipe 520 is provided to provide a path through which the first and second solution fine particles injected through the injection nozzle 510 can move to the reaction part 400. The first solution fine particle accommodating part 200 and the 2 solution fine particle storage part 300, respectively. In addition, the supply amount of the first and second solution fine particles introduced into the reaction part 400 can be controlled by using the control valve 530 located at one side of the transfer pipe 520, and the production amount of the chlorine dioxide gas And production time can be adjusted.

The chlorine dioxide gas generating apparatus 10 of the present invention may further include a decompression unit 600 for lowering the internal pressure of the reaction unit 400, as shown in FIGS. In one embodiment of the present invention, as shown in FIGS. 3 and 4, the depressurization portion 600 may be connected to the air compressor 100 through a pipe. That is, the air inside the reaction part 400 can be discharged to the outside through the decompression part 600 using the suction of the air compressor 100 as a power source, and the air that has flowed out to the outside can be returned to the air compressor 100 Not only the first and second solution fine particle storage parts 200 and 300 can be used to generate the first and second solution fine particles but also the pressure inside the reaction part 400 can be controlled through the series of processes. .

In addition, the chlorine dioxide gas generator 10 of the present invention may further include a concentration measuring unit 700 capable of measuring the concentration of the generated chlorine dioxide gas.

5 is a diagram showing a state of use of the chlorine dioxide gas generating apparatus 10 according to an embodiment of the present invention. 5, the high-pressure gas discharged by the air compressor 100 is transferred to the first and second solution fine particle storage parts 200 and 300 through the gas transfer pipe 110, 2 solution to produce first and second solution microparticles, respectively. The generated first and second solution fine particles are injected from the first and second solution fine particle storage parts 200 and 300 to the reaction part 400 through the transfer pipe 520 by the injection nozzle 510, The transfer tube 520 is separated from and connected to the first and second solution fine particle storage sections 200 and 300 and is connected to the first and second solution fine particle storage sections 200 and 300 through a control valve 530 disposed in the transfer tube 520. The feed rate can be adjusted individually. The first and second fine particles of the solution introduced into the reaction unit 400 or the reaction chamber 410 are directly reacted to generate fine particles of the chlorine dioxide solution. At this time, the decompression unit 600 formed at one side of the reaction unit, By lowering the pressure, the vaporization of the chlorine dioxide gas is promoted, and the vaporized chlorine dioxide gas can be obtained in the reaction part 400 or the chlorine dioxide gas receiving part 420.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the following examples.

[Example]

Example 1. Comparison of production amount according to the generation method of chlorine dioxide gas

In this embodiment, a change in the production amount according to the generation method of the chlorine dioxide gas was confirmed. A method of spontaneously vaporizing from a chlorine dioxide solution, a method of spraying a sulfuric acid solution and a sodium chlorite solution into the inside of a device, a method of spraying a sulfuric acid solution and a sodium chlorite solution into a reaction chamber inside the device, , And their chlorine dioxide gas production were measured and compared, respectively.

Specifically, the production of chlorine dioxide gas through natural vaporization is carried out by introducing 4 ml of a chlorine dioxide solution (5% sulfuric acid (w / v) and 50,000 g / ml sodium chlorite mixed solution) into a 10 L- 10 minutes and 20 minutes. In the case of spraying into the inside of the apparatus in a fine particle state, 5% sulfuric acid (w / v) and 50,000 g / mL sodium chlorite solution Were sprayed in a particulate form for 5 minutes, 10 minutes, and 20 minutes using a nebulizer in an amount of 2 ml each. Finally, a method of injecting into the reaction chamber in the apparatus in a particulate state is a method of spraying 2 ml of 5% sulfuric acid (w / v) and 50,000 g / ml sodium chlorite solution in a reaction chamber provided inside a 10 L- The chlorine dioxide gas was produced by spraying in a particulate form for 5 minutes, 10 minutes, and 20 minutes using a riser.

As a result, as shown in the following Table 1, in the case of the method through spontaneous vaporization, the concentration of chlorine dioxide gas produced was 70 ppm after 5 minutes, reached 140 ppm or 210 ppm respectively after 10 minutes or 20 minutes , 200 ppm, or 330 ppm, respectively, for 5 minutes, 10 minutes, or 20 minutes after the spraying of the solution into the inside of the device in the state of fine particles. By spraying and reacting each solution in particulate form, The production rate of the gas can be remarkably improved. In addition, the method of injecting the fine particles into the reaction chamber in the apparatus showed 150 ppm, 250 ppm, or 390 ppm, respectively, over 5 minutes, 10 minutes, or 20 minutes, By using the reaction chamber, it was found that the production rate of the chlorine dioxide gas can be further increased.

Example  2. Comparison of Relative Humidity with Generation Method of Chlorine Dioxide Gas

In this embodiment, a change in the relative humidity inside the container or the apparatus according to the generation method of the chlorine dioxide gas was examined. The chlorine dioxide gas was generated in the same manner as in Example 1, and the changes in the relative humidity in the vessel or the apparatus were compared with each other over time.

As a result, as shown in Table 2 below, the initial internal relative humidity was measured as 21% to 24% in all three methods, showing no significant difference. However, the method of spontaneous vaporization of chlorine dioxide solution has a relatively little change in relative humidity of 22%, 21%, and 23% over time, while the method of spraying into the reaction chamber in a device or apparatus in particulate form , It increased rapidly to 90% or 88% in 10 minutes. After 20 minutes, the relative humidity reached 98% or more in both methods, showing a large difference. From the above results, it can be seen that the method of generating chlorine dioxide gas by spraying in the form of particulate rather than the conventional method of spontaneously vaporizing chlorine dioxide solution is easier to control the relative humidity.

Example  3. Comparison of sterilizing power according to the generation method of chlorine dioxide gas

In the present embodiment, a difference in germicidal effect according to the generation method of chlorine dioxide gas was examined. The chlorine dioxide gas was generated in the same manner as in Example 1, and the generated chlorine dioxide gas was treated with almonds and the change in the population of common bacteria present in the almonds after one hour of treatment was compared. Table 3 shows the results of measuring the number of general bacteria present in almonds when treated with different production methods of chlorine dioxide gas for 1 hour.

As a result, as shown in the following Table 3, the number of general bacteria existing in the initial ternal was 3.2 ± 0.1 log CFU / g. After 1 hour from the treatment of the chlorine dioxide gas generated by each method, the method through natural vaporization was 3.0 ± 0.2 log CFU / g, and the decrease of general bacteria was small. In the case of the method of spraying into the inside of the apparatus, the number of general bacteria was reduced to 1.7 ± 0.4 log CFU / g after 1 hour in the absence of the reaction chamber, and further decreased in the case of the reaction chamber, And the population decreased to 0.8 ± 0.1 log CFU / g. From the above results, it was found that the harmful microorganisms can be more effectively sterilized through the chlorine dioxide gas generating apparatus of the present invention.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

10: Chlorine dioxide gas generator
100: Air Compressor
110: gas transfer pipe
200: First solution fine particle accommodating portion
300: second solution fine particle accommodating portion
400: reaction part
410: reaction chamber
420: Chlorine dioxide gas accommodation chamber
500: Connection
510: injection nozzle
520: conveying pipe
530: Regulating valve
600:
700: Concentration measuring unit

Claims (9)

Air compressors;
A first solution fine particle containing portion for containing the first solution fine particles produced by colliding with the high pressure gas discharged from the air compressor;
A second solution fine particle containing portion which receives the second solution fine particles produced by colliding with the high pressure gas discharged from the air compressor;
A reaction part for generating chlorine dioxide gas by the reaction between the first and second fine solution particles; And
And a connecting portion which is located between the first and second solution fine particle containing portions and the reaction portion and moves the first and second solution fine particles to the reaction portion.
The method according to claim 1,
Wherein the reaction unit comprises: a reaction chamber in which the reaction between the first and second solution fine particles introduced from the connection part proceeds; And
And a chlorine dioxide gas accommodation chamber connected to the reaction chamber, the chlorine dioxide gas accommodation chamber containing chlorine dioxide gas.
The method according to claim 1,
Wherein the connection portion injects fine particles contained in the first and second solution fine particle containing portions into the reaction portion; And
And a transfer tube for providing a passage through which the injected fine particles can move to the reaction part.
The method of claim 3,
Wherein the connecting portion further comprises a regulating valve for regulating the supply amount of the first and second solution microparticles.
The method according to claim 1,
Wherein the connecting portion is separately connected to the first solution fine particle accommodating portion and the second solution fine particle accommodating portion, respectively.
The method according to claim 1,
And a decompression unit formed at one side of the reaction unit to decompress the internal pressure of the reaction unit.
The method according to claim 1,
And a concentration measuring unit formed on one side of the reaction unit for measuring the concentration of chlorine dioxide gas in the reaction unit.
The method according to claim 1,
Wherein the first solution is selected from the group consisting of sodium chlorite (NaClO ₂ ), sodium chlorate (NaClO ₃ ) And a solution of potassium chlorate (KClO ₃ ).
The method according to claim 1,
The second solution is any one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, citric acid, acetic acid, malic acid, lactic acid, tartaric acid, fumaric acid, propionic acid, succinic acid, Characterized in that the chlorine dioxide gas generator is a chlorine dioxide gas generator.

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