Chlorine-containing gas generation device and chlorine-containing gas generation method

Abstract

The purpose of the present invention is to simplify, and not complicate, the configuration of a device for generating a chlorine-containing gas. This chlorine-containing gas generation device (100) generates a chlorine-containing gas that contains at least one of chlorine dioxide gas and chlorine gas, the chlorine-containing gas generation device (100) comprising: a storage part (10) that stores calcium hypochlorite powder; a gas supply part (20) that supplies a raw-material gas to the storage part (10); and a chlorine-containing gas supply part (30) that supplies, to the outside of a device body (B), a chlorine-containing gas generated due to the raw-material gas coming into contact with the calcium hypochlorite powder.

Description

Chlorine-containing gas generator and chlorine-containing gas generation method

[0001] The present invention relates to a chlorine-containing gas generator and a chlorine-containing gas generator.

[0002] Conventionally, chlorine-containing gas generators have been developed that generate chlorine-containing gas by contacting hypochlorite crystals with a raw material gas. For example, the chlorine-containing gas generator disclosed in Patent Document 1 comprises a crystal cooling unit and a gas dehumidification cooling unit. In the apparatus of Patent Document 1, the crystal cooling unit holds the hypochlorite crystals in a cooled state. The gas dehumidification cooling unit dehumidifies and cools the raw material gas before contacting the hypochlorite crystals with the raw material gas.

[0003] Furthermore, a conventional method for producing chlorine dioxide is the technology disclosed in Patent Document 2. Patent Document 2 discloses a method for producing chlorine dioxide by reacting sodium chlorate with a reducing agent. In the production method of Patent Document 2, the reaction zone (chlorine dioxide generation tank) is divided into reaction zones A and B, and chlorine dioxide is obtained from reaction zones A and B respectively. Sodium chlorate, methanol, and sulfuric acid are added to reaction zone A, and hydrogen peroxide is added to reaction zone B to the waste liquid from reaction zone A, or hydrogen peroxide and sulfuric acid are added to decompose the remaining sodium chlorate.

[0004] Japanese Unexamined Patent Publication No. 2022-032147 Japanese Unexamined Patent Publication No. 3-115102

[0005] However, the conventional technologies described above have room for improvement in that the configuration of the chlorine-containing gas generator or chlorine dioxide generator is complex.

[0006] In the chlorine-containing gas generator described in Patent Document 1, sodium hypochlorite is used as the hypochlorite crystal. Since sodium hypochlorite is hygroscopic, the chlorine-containing gas generator in Patent Document 1 requires a crystal cooling section and a gas dehumidification cooling section in order to generate chlorine-containing gas stably over a long period of time, and there is room for improvement in terms of the complexity of the device.

[0007] Furthermore, the chlorine dioxide generator described in Patent Document 2 requires a chlorine dioxide generation tank for reacting sodium chlorate with a reducing agent, and equipment for discharging reaction wastewater. The chlorine dioxide generator described in Patent Document 2 also has the problem of the device configuration becoming complicated due to the generation of chlorine dioxide gas.

[0008] One aspect of the present invention aims to realize a chlorine-containing gas generator and a chlorine-containing gas generator method that do not require a complex and simple configuration for generating chlorine-containing gas.

[0009] A chlorine-containing gas generator according to one aspect of the present invention is a chlorine-containing gas generator that generates a chlorine-containing gas containing at least one of chlorine dioxide gas and chlorine gas in order to solve the above problems, and comprises a storage section for storing calcium hypochlorite powder, a gas supply section for supplying raw material gas to the storage section, and a chlorine-containing gas supply section for supplying the chlorine-containing gas generated when the raw material gas comes into contact with the calcium hypochlorite powder to the outside of the main body of the device.

[0010] A method for generating chlorine-containing gas according to one aspect of the present invention is a method for generating a chlorine-containing gas that contains at least one of chlorine dioxide gas and chlorine gas, in order to solve the above-mentioned problems, and includes a raw material gas contact step of generating a chlorine-containing gas by contacting calcium hypochlorite powder with a raw material gas.

[0011] According to one aspect of the present invention, the configuration of the apparatus for generating chlorine-containing gas can be simplified without complicating it.

[0012] Figure 101 is a diagram showing the schematic configuration of a chlorine-containing gas generator according to one embodiment of the present invention, Figure 102 is a diagram showing the schematic configuration of a modified example of the chlorine-containing gas generator shown in Figure 101, and Figure 103 is a diagram showing the schematic configuration of another modified example of the chlorine-containing gas generator shown in Figure 101. Figure 1 is a diagram showing the schematic configuration of a cartridge container as an example of the configuration of a storage section provided in the chlorine-containing gas generator shown in Figure 1. Figure 1 is a diagram showing the schematic configuration of the chlorine-containing gas generator used in the examples. Figure 401 is a graph showing the results of Example 1, showing the relationship between chlorine dioxide gas concentration, chlorine gas concentration and aeration time, Figure 402 is a microscopic image showing the state of bleaching powder before continuous aeration and after 205 days of continuous aeration, and Figure 403 is a graph showing the results of Example 2, showing the relationship between chlorine dioxide gas concentration, chlorine gas concentration and aeration time. Figure 3 is an image showing the results of measuring the number of bacteria in the water of each of the tanks A to I in Example 3.

[0013] [Technical Concept of Embodiments of the Invention] The inventors diligently studied how to simplify the configuration of a chlorine-containing gas generator using hypochlorite. As a result, they discovered that by using calcium hypochlorite powder as the hypochlorite, the calcium hypochlorite powder does not deliquesce under normal temperature and humidity conditions, and chlorine-containing gas can be generated. Based on this discovery, they found that by using calcium hypochlorite powder as the hypochlorite, the configuration of the chlorine-containing gas generator can be simplified, and thus completed the chlorine-containing gas generator and chlorine-containing gas generation method according to this embodiment. Furthermore, they discovered that the chlorine-containing gas generator and chlorine-containing gas generation method according to this embodiment not only simplifies the configuration of the device but also enables the stable generation of chlorine-containing gas for a long period of time.

[0014] Furthermore, upon further investigation of the components of the chlorine-containing gas generated from the chlorine-containing gas generator, it was surprisingly found that the chlorine-containing gas contains chlorine gas (Cl ２ ) and chlorine dioxide gas (ClO ２It was found that ) was included. According to the chlorine-containing gas generator and chlorine-containing gas generation method of this embodiment, chlorine dioxide gas can be generated simply by bringing the raw material gas into contact with calcium hypochlorite, so the configuration of the chlorine dioxide gas generator can be simplified compared to conventional devices.

[0015] [Embodiment 1] Hereinafter, one embodiment of the present invention will be described in detail. Figure 101 is a diagram showing the schematic configuration of the chlorine-containing gas generator 100 according to this embodiment.

[0016] As shown in Figure 1, 101, the chlorine-containing gas generator 100 is a device that generates a chlorine-containing gas containing at least one of chlorine gas and chlorine dioxide gas. This chlorine-containing gas generator 100 generates a chlorine-containing gas by contacting a raw material gas with calcium hypochlorite powder S (sometimes simply referred to as powder S). In the configuration shown in Figure 1, the raw material gas is air.

[0017] The raw material gas is not particularly limited, but examples include nitrogen gas, oxygen gas, carbon dioxide gas, and air. These raw material gases may be used individually or as a mixture of two or more gases. From the viewpoint of ease of obtaining the raw material gas, air is preferred as the raw material gas.

[0018] The chlorine-containing gas generator 100 comprises a storage unit 10, a gas supply unit 20, and a chlorine-containing gas supply unit 30. The storage unit 10 stores calcium hypochlorite powder S. The gas supply unit 20 supplies raw material gas (air) to the storage unit 10. The chlorine-containing gas supply unit 30 supplies chlorine-containing gas, which is generated when the raw material gas (air) comes into contact with the calcium hypochlorite powder S, to the outside.

[0019] For example, the storage section 10 is composed of a container for storing powder S. The storage section 10 has an inlet for introducing air and an outlet for releasing chlorine-containing gas. The storage section 10 may also be a reaction tube capable of storing powder S. The storage section 10 may also include a substance for supporting powder S. Specific examples of such a substance for supporting powder S include powder carriers such as filters. The storage section 10 may also include other powders for mixing with powder S, and powder S may be supported on these other powders.

[0020] The gas supply unit 20 includes an air compressor 21 and an introduction pipe P2. The introduction pipe P2 is a pipe that connects the air compressor 21 and the storage unit 10. The configuration of the introduction pipe P2 is not particularly limited as long as it is a configuration that can connect the air compressor 21 and the storage unit 10. In the chlorine-containing gas generator 100, air from the air compressor 21 is introduced into the storage unit 10 via the introduction pipe P2.

[0021] The chlorine-containing gas supply unit 30 is equipped with a discharge pipe P3. The discharge pipe P3 is connected to the storage unit 10. Chlorine-containing gas passes through the discharge pipe P3. The configuration of the discharge pipe P3 is not particularly limited, as long as it is configured to release chlorine-containing gas from the storage unit 10.

[0022] In the chlorine-containing gas generator 100, air from the air compressor 21 is introduced into the storage unit 10 via the introduction pipe P2. This air then comes into contact with the calcium hypochlorite powder S inside the storage unit 10, generating chlorine-containing gas. The chlorine-containing gas generated inside the storage unit 10 is then released outside the chlorine-containing gas generator 100 through the discharge pipe P3. This chlorine-containing gas contains at least one of chlorine gas and chlorine dioxide gas as gas components.

[0023] Here, the melting point of calcium hypochlorite is 100°C, which is higher than that of sodium hypochlorite pentahydrate (27°C), which is a hypochlorite. Furthermore, calcium hypochlorite has lower hydrophilicity compared to sodium hypochlorite and does not show deliquescence at normal temperature (about 25°C). Therefore, according to the chlorine-containing gas generator 100, it is not necessary to hold the hypochlorite crystals in a cooled state as in the case of using sodium hypochlorite crystals as the hypochlorite, and it is not necessary to dehumidify and cool the air before contacting the hypochlorite crystals. Furthermore, since chlorine dioxide gas can be produced simply by contacting air with the powder S, it is not necessary to complicate the device configuration in the production of chlorine dioxide gas. Therefore, according to the chlorine-containing gas generator 100, the device configuration for generating the chlorine-containing gas can be simplified without being complicated.

[0024] (Modified Example of Chlorine-Containing Gas Generator 100) 102 in FIG. 1 is a diagram showing a schematic configuration of a modified example of the chlorine-containing gas generator 100 shown in 101 of FIG. 1. As shown in 102 of FIG. 1, the chlorine-containing gas generator 100A as the modified example includes another gas supply unit that supplies a raw material gas (air) to the chlorine-containing gas supply unit 30. The other gas supply unit includes an air compressor 31 and an introduction pipe P4. The introduction pipe P4 is a pipe that connects the discharge pipe P3 of the chlorine-containing gas supply unit 30 and the air compressor 31. The configuration of the introduction pipe P4 is not particularly limited as long as it can connect between the air compressor 31 and the discharge pipe P3. In the chlorine-containing gas generator 100A, the air from the air compressor 31 is introduced into the discharge pipe P3 through the introduction pipe P4. Thus, in the chlorine-containing gas generator 100A, air from the air compressor 31 is introduced into the chlorine-containing gas generated in the storage unit 10 according to the concentration of the chlorine gas component or the chlorine dioxide gas component. Thereby, the concentration of the chlorine gas component or the chlorine dioxide gas component supplied by the chlorine-containing gas supply unit 3 can be adjusted.

[0025] Figure 103 shows a schematic configuration of another modified example of the chlorine-containing gas generator 100 shown in Figure 101. As shown in Figure 103, in the modified chlorine-containing gas generator 100B, the gas supply unit 20 is configured to supply raw material gas (air) to the chlorine-containing gas supply unit 30. More specifically, the gas supply unit 20 is configured to include an introduction pipe P4 that connects the air compressor 21 and the discharge pipe P3 of the chlorine-containing gas supply unit 30. In the configuration shown in Figure 103, the configuration of the introduction pipe P4 is not particularly limited as long as it is capable of connecting the air compressor 21 and the discharge pipe P3. In the chlorine-containing gas generator 100B, air from the air compressor 21 is introduced into the discharge pipe P3 via the introduction pipe P4. According to the modified configuration shown in Figure 1, part 103, similar to the modified configuration shown in Figure 1, part 102, the concentration of chlorine gas or chlorine dioxide gas supplied by the chlorine-containing gas supply unit 30 can be adjusted by introducing air from the air compressor 21 to the chlorine-containing gas generated in the storage unit 10 according to the concentration of chlorine gas or chlorine dioxide gas. In the modified configuration shown in Figure 1, part 103, from the viewpoint of more accurately adjusting the concentration of chlorine gas or chlorine dioxide gas, it is preferable that the chlorine-containing gas generator 100B is equipped with a switching unit in the air compressor 21 that switches between introducing air to the introduction pipe P4 and stopping the introduction of air. In a configuration equipped with such a switching unit, the control of the amount of air introduced by the air compressor 21 via the introduction pipe P4 is performed in conjunction with a chlorine gas meter that measures the concentration of chlorine gas in the chlorine-containing gas and a chlorine dioxide gas meter that measures the concentration of chlorine dioxide gas in the chlorine-containing gas.

[0026] In the configuration shown in 101 to 103 of FIG. 1, since the gas supply unit 20 supplies air to the storage unit 10 by the air compressor 21, the inside of the storage unit 10 is in a positive pressure state. However, the gas supply unit 20 only needs to be configured to supply air to the storage unit 10, and is not limited to the configuration in which the inside of the storage unit 10 is made into a positive pressure state by the air compressor 21 as shown in 101 to 103 of FIG. 1. For example, the gas supply unit 20 may be configured to include a negative pressure unit that makes the inside of the storage unit 10 into a negative pressure state. In this configuration, the inside of the storage unit 10 becomes a negative pressure state by the negative pressure unit, and the air outside the storage unit 10 is sucked into the storage unit 10, thereby supplying air to the storage unit 10.

[0027] In the configuration shown in 101 to 103 of FIG. 1, a flow meter A (see FIG. 3) for measuring the flow rate of air from the air compressor 21 may be provided between the air compressor 21 and the storage unit 10. And the gas supply unit 20 may include a raw material gas flow rate adjustment unit that adjusts the flow rate of air based on the measured value data by the flow meter A.

[0028] Also, in the chlorine-containing gas supply unit 30, a flow meter B (see FIG. 3) for measuring the flow rate of the chlorine-containing gas discharged from the storage unit 10 may be provided in the discharge pipe P3. The chlorine-containing gas supply unit 30 may include a chlorine gas meter for measuring the concentration of the chlorine gas component in the chlorine-containing gas, and a chlorine dioxide gas meter for measuring the concentration of the chlorine dioxide gas component in the chlorine-containing gas.

[0029] And in the configuration shown in 101 to 103 of FIG. 1, the raw material gas flow rate adjustment unit may be configured to feedback the measured value data of the three flow meter B, chlorine gas meter and chlorine dioxide gas meter, and adjust the flow rate of air from the air compressor 21 based on the measured value data of the three and the measured value data of the flow meter A.

[0030] Furthermore, in the configuration shown in 102 of Figure 1, a flow meter A for measuring the air flow rate from the air compressor 31 may be provided in the introduction piping P4. In this case, the raw material gas flow rate adjustment unit may be configured to adjust the air flow rate from the air compressor 31 based on the three measurement values ​​from the flow meter B, the chlorine gas meter, and the chlorine dioxide gas meter, and the three measurement values ​​and the measurement value from the flow meter A for measuring the air flow rate from the air compressor 31.

[0031] As described above, calcium hypochlorite does not deliquesce at room temperature (around 25°C). Therefore, even when the chlorine-containing gas generator 100 is installed under high temperature and high humidity conditions in summer, there is no need to provide a cooling unit for cooling the powder S in the storage unit 10. Furthermore, there is no need to provide a dehumidifying and cooling unit for dehumidifying and cooling the raw material gas in the gas supply unit 20. Thus, the chlorine-containing gas generator 100 has a simple configuration that is independent of temperature and humidity from summer to winter. In this respect, the chlorine-containing gas generator 100 according to this embodiment can be said to have a configuration that does not include a cooling unit for cooling the powder S and a dehumidifying and cooling unit for dehumidifying and cooling the raw material gas.

[0032] In the chlorine-containing gas generator 100, the amount of chlorine-containing gas produced can be appropriately set by changing the temperature and absolute humidity of the raw material gas, as well as the space velocity of the raw material gas.

[0033] In the chlorine-containing gas generator 100, the space velocity (SV) of the raw material gas supplied to the calcium hypochlorite powder S is 0.001 h. －１ ~3,000,000h －１ Preferably, 2000h －１ ~1,000,000h －１ It is more preferable that this be the case, and 5,000h －１ ~100,000h －１ It is even more preferable that the following conditions are met. Furthermore, the packing density of the calcium hypochlorite powder S in the storage section 10 is preferably 0.1 g / mL to 2.3 g / mL, more preferably 0.3 g / mL to 1.5 g / mL, and even more preferably 0.5 g / mL to 1 g / mL.

[0034] Here, the space velocity (SV) is the ventilation rate of the raw material gas with respect to the calcium hypochlorite powder S (m ３ / h) / the volume of the packed bed of the calcium hypochlorite powder S in the storage unit 10 (m ３ ), that is, the ventilation rate of the raw material gas with respect to the calcium hypochlorite powder S (m ３ / h) × the bulk density of the calcium hypochlorite powder S in the storage unit 10 (g / m ３ ) / the weight of the calcium hypochlorite powder S (g). The space velocity (SV) can be calculated by measuring the numerical values of each requirement included in the above definition and calculating according to the definition.

[0035] (Calcium hypochlorite powder S) The powder S may be any powder containing calcium hypochlorite, and so-called exposed powder can be mentioned. As the exposed powder, ordinary exposed powder with an available chlorine concentration of 30% to 35% and high-grade exposed powder with 60% to 70% can be mentioned. As the powder S, high-grade exposed powder with 60% to 70% is preferable.

[0036] Also, in the storage unit 10, the powder S may be in a form supported in a porous material, in a form mixed and diluted with other powders, or in a form combining these forms. That is, the storage unit 10 may be configured to accommodate a mixture of the powder S and other powders. Examples of the other powder include inorganic fillers. Examples of the inorganic filler include silica sand, silica gel, zeolite (molecular sieve), glass beads, foamed glass, etc.

[0037] (Configuration example of the storage unit 10) The storage unit 10 is not particularly limited as long as it can accommodate the powder S and allow the raw material gas to flow in and release the chlorine-containing gas. The storage unit 10 may be a replaceable cartridge container. FIG. 2 is a diagram showing a schematic configuration of a cartridge container 10A as a configuration example of the storage unit 10 provided in the chlorine-containing gas generator 100 shown in FIG. 1.

[0038] As shown in Figure 2, the cartridge container 10A comprises a bottomless cylindrical container body 10a and lids 10b and 10c. Lid 10b closes the air inlet opening in the container body 10a. Lid 10c closes the chlorine-containing gas outlet opening in the container body 10a. The powder S is contained within the space formed by the container body 10a and the lids 10b and 10c. Furthermore, to prevent the lids 10b and 10c from detaching from the container body 10a due to the pressure of the incoming air, the container body 10a and the lids 10b and 10c are firmly fixed together, for example, by bolts or screws.

[0039] Furthermore, the lid 10b of the cartridge container 10A is provided with an inlet-side mounting portion 11a. In addition, the lid 10c of the cartridge container 10A is provided with an outlet-side mounting portion 11b. On the airflow side of the cartridge container 10A, the inlet-side mounting portion 11a is detachably connected to, for example, the introduction pipe P2 in the chlorine-containing gas generator 100 shown in Figure 1. On the chlorine-containing gas outlet side of the cartridge container 10A, the outlet-side mounting portion 11b is detachably connected to, for example, the discharge pipe P3 in the chlorine-containing gas generator 100 shown in Figure 1. Since the inlet-side mounting portion 11a and the outlet-side mounting portion 11b are provided in this way, the cartridge container 10A can be removed from the chlorine-containing gas generator.

[0040] Here, as the time elapsed since contact with air, the powder S ceased to generate chlorine-containing gas. In other words, powder S is a consumable item. Therefore, when using powder S for a long period of time, it is necessary to periodically replace the depleted powder S with undepleted powder S. With the above configuration, the depleted powder S can be replaced with undepleted powder S. Note that the cartridge container is not limited to the configuration shown in Figure 2, and any conventionally known configuration can be used as long as it is removable from the chlorine-containing gas generator.

[0041] Furthermore, a retaining plate 12 and a blow-up prevention plate 13 are provided inside the cartridge container 10A. Both the retaining plate 12 and the blow-up prevention plate 13 have multiple through holes. The retaining plate 12 is a member that holds the powder S inside the cartridge container 10A. The blow-up prevention plate 13 is a member that prevents the powder S from blowing up towards the chlorine-containing gas outlet side. The retaining plate 12 is also provided on the air inlet side of the blow-up prevention plate 13. Inside the cartridge container 10A, the retaining plate 12 is provided so as to be spaced apart from the lid 10b. Inside the cartridge container 10A, the blow-up prevention plate 13 is provided so as to be spaced apart from the lid 10c. The multiple through holes provided in the retaining plate 12 are evenly distributed within the surface of the retaining plate 12. In the cartridge container 10A, air passes through the multiple through holes in the retaining plate 12 and comes into contact with the powder S. Therefore, according to the configuration of the cartridge container 10A, the powder S can be brought into contact with air evenly. Furthermore, if the cartridge container 10A contains powder S, or a substance that supports the powder S, or other powders that are mixed with the powder S, a mesh-like member may be installed in the cartridge container 10A to prevent these powders from passing through.

[0042] (Use of the chlorine-containing gas generator according to this embodiment) The applications of the chlorine-containing gas generator according to this embodiment are not particularly limited as long as they are in a technical field that requires chlorine-containing gas, and can be applied to a wide range of applications. Preferably, the chlorine-containing gas generator according to this embodiment can be applied to sterilization applications. In this case, the chlorine-containing gas generator according to this embodiment can sterilize various viruses, bacteria, fungi, etc. in a wide range of industrial fields such as food, medical, housing, public facilities, aquaculture, and livestock farming. Furthermore, the chlorine-containing gas generator according to this embodiment can sterilize objects in various states, regardless of whether they are gases, liquids, or solids, such as sterilizing liquids such as treated water and washing water, or purifying contaminated spaces (space sterilization).

[0043] Furthermore, the chlorine-containing gas has decolorizing and deodorizing effects in addition to sterilization. Therefore, the chlorine-containing gas generator according to this embodiment can be used not only for sterilization but also for decolorization and deodorization purposes.

[0044] (Method for generating chlorine-containing gas according to this embodiment) The method for generating chlorine-containing gas according to this embodiment is a method for generating a chlorine-containing gas containing at least one of chlorine gas and chlorine dioxide gas, and includes a raw material gas contact step in which a raw material gas is brought into contact with calcium hypochlorite powder to generate a chlorine-containing gas. The raw material gas is, for example, air. According to the method for generating chlorine-containing gas according to this embodiment, the apparatus configuration for generating chlorine-containing gas can be simplified without complicating it.

[0045] Furthermore, the raw material gas contact step can employ any process as long as it is possible to contact the calcium hypochlorite powder with the raw material gas. For example, the raw material gas contact step can be carried out using the chlorine-containing gas generator described above.

[0046] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0047] One embodiment of the present invention includes the following [1] to [5].

[0048] [1] A chlorine-containing gas generator that generates a chlorine-containing gas containing at least one of chlorine dioxide gas and chlorine gas, comprising: a storage section for storing calcium hypochlorite powder; a gas supply section for supplying a raw material gas to the storage section; and a chlorine-containing gas supply section for supplying the chlorine-containing gas generated when the raw material gas comes into contact with the calcium hypochlorite powder to the outside of the main body of the device.

[0049] [2] The space velocity (SV) of the raw material gas supplied to the calcium hypochlorite powder is 0.001 h －１ ~3,000,000h －１The chlorine-containing gas generator described in [1].

[0050] [3] A chlorine-containing gas generator according to [1] or [2], wherein the raw material gas is air.

[0051] [4] A chlorine-containing gas generator, any of [1] to [3], comprising another gas supply unit for supplying raw material gas to the chlorine-containing gas supply unit.

[0052] [5] A chlorine-containing gas generator according to any of [1] to [3], wherein the gas supply unit is configured to supply raw material gas to the chlorine-containing gas supply unit.

[0053] [6] The storage unit is a chlorine-containing gas generator according to any of [1] to [5], which is equipped with a replaceable cartridge container.

[0054] [7] A method for generating a chlorine-containing gas that includes at least one of chlorine dioxide gas and chlorine gas, comprising a raw material gas contact step of generating a chlorine-containing gas by contacting a raw material gas with calcium hypochlorite powder.

[0055] The following describes specific examples and comparative examples of the present invention. It should be noted that the present invention is not limited to the following examples and can be implemented with appropriate modifications without altering its essence.

[0056] Figure 3 shows a schematic configuration of the chlorine-containing gas generator used in this embodiment. As shown in Figure 3, the chlorine-containing gas generator used in this embodiment consists of a compressor (air compressor), a reaction tube, and ClO ２ Gas meter, and Cl ２ It is equipped with a gas meter. The reaction tube contains 5g of bleaching powder (high-grade bleaching powder: effective chlorine concentration 70%). The compressor and the reaction tube are connected by piping, so that air from the compressor comes into contact with the bleaching powder in the reaction tube. In addition, a pipe is connected to the reaction tube to release the chlorine-containing gas generated by the contact between the air and the bleaching powder. ClO ２ Gas meter, and Cl ２The gas meters measure the concentrations of chlorine dioxide gas and chlorine gas components in the chlorine-containing gas released from the piping. A flow meter A is installed between the reaction tube and the compressor to measure the air flow rate, and the reaction tube and ClO ２ Gas meter and Cl ２ A flow meter B for measuring the flow rate of chlorine-containing gas is installed between the gas meter and the gas meter.

[0057] In this embodiment, in the chlorine-containing gas generator shown in Figure 3, air is passed through the reaction tube from a compressor at a flow rate of 1.5 L / min, and the concentrations of chlorine dioxide gas component and chlorine gas component in the chlorine-containing gas released from the reaction tube are measured as follows: ClO ２ Gas meter and Cl ２ Measure using a gas meter.

[0058] [Example 1] Using the chlorine-containing gas generator shown in Figure 3, air was continuously supplied from the compressor to the reaction tube at a flow rate of 1.5 L / min for 205 days. Then, ClO ２ Gas meter and Cl ２ A gas meter was used to track and measure the concentrations of chlorine dioxide gas and chlorine gas in the chlorine-containing gas released from the reaction tube. Figure 4 shows the results of Example 1, where 401 is a graph showing the relationship between chlorine dioxide gas concentration, chlorine gas concentration and aeration time, and 402 is a microscopic image showing the state of bleaching powder before continuous aeration and after 205 days of continuous aeration.

[0059] As shown in Figure 4, 401, in continuous aeration, the largest release peaks of chlorine dioxide gas and chlorine gas components appeared immediately after the start of aeration. After that, several small release peaks were observed for both chlorine dioxide gas and chlorine gas components. Overall, the chlorine dioxide gas component was released in greater quantities than the chlorine gas component. The reason why the release amounts of chlorine dioxide gas and chlorine gas components were highest immediately after the start of aeration is thought to be due to the Ca(OCl) in the bleaching powder. ２The chlorine content of the particles is thought to be highest immediately after the start of aeration. Furthermore, the reason why small release peaks of chlorine dioxide gas and chlorine gas components appeared is thought to be as follows: (1) Ca(OCl) ２ The chlorine contained in the particles is ClO ２ , Cl ２ As a result of being released, Ca(OCl) ２ A change occurs in the crystal structure of the particles, Ca(OCl) ２ (2) Ca(OCl) ２ The surface area increases as the particles break, and this allows Ca(OCl) ２ This is because the contact area between the particles and the air has increased.

[0060] Therefore, the state of the bleaching powder before continuous aeration and after 205 days of continuous aeration was observed using a microscope (ECLIPSE Si). As a result, as shown in 402 of Figure 4, Ca(OCl) ２ The particle size was smaller after 205 days of continuous aeration compared to before aeration. From this, Ca(OCl) ２ The particles' molecular bands were disrupted and their crystalline structure collapsed due to the release of chlorine-containing gas, resulting in the formation of Ca(OCl) ２ It is thought that the particle size decreased. In addition, when the weight of the bleaching powder was measured, it was 5.08 g before the start of aeration, while it was 4.51 g after 205 days of continuous aeration. As a result, the weight of the bleaching powder after 205 days of continuous aeration decreased by 0.58 g from the weight before the start of aeration.

[0061] [Example 2] Using the chlorine-containing gas generator shown in Figure 3, air was intermittently supplied from the compressor to the reaction tube at a flow rate of 1.5 L / min for 102 hours. During this intermittent supply, the intervals between supply and supply cessation were as shown in Table 1 below. Then, ClO ２ Gas meter and Cl ２ Using a gas meter, the concentrations of chlorine dioxide gas and chlorine gas components in the chlorine-containing gas released from the reaction tube during intermittent aeration were tracked and measured. Figure 4, section 403, shows the results of Example 2 and is a graph showing the relationship between chlorine dioxide gas concentration, chlorine gas concentration, and aeration time. As shown in Figure 4, section 403, in the case of intermittent ventilation, the release amounts of chlorine dioxide gas and chlorine gas components were highest immediately after the start of ventilation, and a large release peak appeared when ventilation was resumed. The reason for the release peak observed when ventilation was resumed is that Ca(OCl) was released during the ventilation interruption. ２ Chlorine diffuses from the inside to the outside of the particle and remains on the particle surface, Ca(OCl) ２ Because the chlorine concentration on the surface of the particles and inside the reaction tube increases, it is thought that if aeration is resumed in this state, release peaks of chlorine dioxide gas and chlorine gas components will appear. Also, similar to the continuous aeration in Example 1, Ca(OCl) due to aeration ２ The increase in surface area due to particle fracture is also considered to be one of the reasons for the occurrence of the emission peak.

[0062] [Example 3] A chlorine-containing gas produced by the chlorine-containing gas generator shown in Figure 3 was absorbed into ion-exchanged water to prepare a chlorine-containing gas absorption solution (hereinafter simply referred to as absorption solution).

[0063] Using the above absorbent solution, we conducted a water quality improvement test for mysid shrimp farming. The procedure for this test was as follows (1) to (5).

[0064] (1) 5 liters of artificial seawater, prepared three days prior, were added to nine tanks A through I.

[0065] (2) 30 American mysid shrimp were placed in each of the tanks A to I (total: 9 tanks x 30 shrimp = 270 shrimp).

[0066] (3) For tanks A to C, no absorbent solution is added and it is treated as a blank tank. For tanks D to F, the effective chlorine concentration is 0.05 ppm, CIO ２ Concentration 2.5×10 －３ Add absorbent solution to achieve ppm concentration, and for tanks G to I, the effective chlorine concentration is 0.62 ppm, CIO ２ The absorbent solution was added to achieve a concentration of 0.03 ppm.

[0067] (4) After two hours, the number of bacteria in the water of each tank was measured using a biochecker (San-ai Biochecker TTL <manufactured by San-ai Obli Co., Ltd.>).

[0068] (5) After one week, the survival rate of the American mysid shrimp in each tank was checked.

[0069] The survival rate of the American mysid shrimp was calculated according to the following formula. X is the total number of surviving American mysid shrimp (in tails) measured in each tank, and Y is the total number of surviving American mysid shrimp measured in each tank when the absorption solution was added (3 tanks × 30 shrimp / tank = 90 shrimp). Survival rate (%) = X / Y × 100.

[0070] Figure 5 shows the results of measuring the number of bacteria in the water of each tank using the procedure (4) described above. From Figure 5, it can be seen that the number of bacteria in the water decreased as the amount of absorbent solution added increased.

[0071] Furthermore, Table 2 shows the results of measuring the survival rate of American shrimp in procedure (5). Table 2 shows that adding the absorbent solution reduced the number of bacteria in the water, improved water quality, and increased the survival rate of American mysid shrimp.

[0072] In Example 3, a chlorine-containing gas absorbent solution was prepared and added to the water tank. In addition to using a chlorine-containing gas absorbent solution, directly aerating the water tank with chlorine-containing gas produced by the chlorine-containing gas generator shown in Figure 3 is also effective in improving water quality.

[0073] 10 Storage unit 10A Cartridge container 20 Gas supply unit 21 Air compressor 30 Chlorine-containing gas supply unit 100 Chlorine-containing gas generator

Claims

1. A chlorine-containing gas generator that generates a chlorine-containing gas containing at least one of chlorine dioxide gas and chlorine gas, comprising: a storage section for storing calcium hypochlorite powder; a gas supply section for supplying a raw material gas to the storage section; and a chlorine-containing gas supply section for supplying to the outside the chlorine-containing gas generated when the raw material gas comes into contact with the calcium hypochlorite powder.

2. The space velocity (SV) of the raw material gas supplied to the calcium hypochlorite powder is 0.001 h. －１ ~3,000,000h －１ The chlorine-containing gas generator according to claim 1.

3. The chlorine-containing gas generator according to claim 1, wherein the raw material gas is air.

4. The chlorine-containing gas generator according to claim 1, further comprising another gas supply unit for supplying raw material gas to the chlorine-containing gas supply unit.

5. The chlorine-containing gas generator according to claim 1, wherein the gas supply unit is configured to supply raw material gas to the chlorine-containing gas supply unit.

6. The chlorine-containing gas generator according to any one of claims 1 to 5, wherein the storage unit is a replaceable cartridge container.

7. A method for generating a chlorine-containing gas that includes at least one of chlorine dioxide gas and chlorine gas, comprising a raw material gas contact step of contacting a raw material gas with calcium hypochlorite powder to generate a chlorine-containing gas.

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