Chlorine dioxide generator

Abstract

The present invention relates to a chlorine dioxide generator. The object of the present invention is to provide a device that can stably generate chlorine dioxide for a long period of time with a simpler structure than conventional chlorine dioxide generators. The solution to the problem is to provide a novel chlorine dioxide generator that utilizes the reaction of a chlorite aqueous solution and a catalyst.

Description

Technical Field

[0001] The present invention relates to a novel chlorine dioxide generating device. Background Art

[0002] Chlorine dioxide gas is known to be safe for living animals at low concentrations (e.g., below 0.1 ppm). On the other hand, even at such low concentrations, it still has deactivation and deodorization effects on microorganisms such as bacteria, fungi, and viruses.

[0003] Methods for generating chlorine dioxide are known, for example: a method for stably generating chlorine dioxide using a composition containing dissolved chlorine dioxide gas, a chlorite aqueous solution, and a pH adjuster (Patent Document 1); and a method for producing chlorine dioxide by electrolyzing an electrolyte containing chlorite (Patent Document 2).

[0004] Furthermore, in recent years, a device for generating chlorine dioxide by irradiating solid chlorite with visible light has been proposed (Patent Document 3).

[0005] [Prior art literature]

[0006] [Patent Document]

[0007] [Patent Document 1] WO / 2008 / 111357

[0008] [Patent Document 2] WO / 2009 / 154143

[0009] [Patent document 3] WO / 2015 / 098732. Summary of the invention

[0010] [Problems to be solved by the invention]

[0011] An object of the present invention is to provide a device capable of stably generating chlorine dioxide for a long period of time with a simpler structure than conventional chlorine dioxide generating devices.

[0012] [Methods to solve the problem]

[0013] The inventors of the present application have intensively studied and successfully developed a novel chlorine dioxide generator that utilizes the mechanism of generating chlorine dioxide by the reaction of a chlorite aqueous solution with a catalyst, thereby completing the present invention.

[0014] That is, one embodiment of the present invention is a chlorine dioxide generator, which includes a humidifying mechanism and a bubbling mechanism, wherein:

[0015] The device comprises a reaction container, a humidification container and an air introduction device.

[0016] The reaction container contains a chlorite aqueous solution and a catalyst.

[0017] The humidification container contains a humidification solution,

[0018] The humidification container includes a first conduit for introducing air from outside the device.

[0019] The humidification container and the reaction container are connected to each other via a second conduit, or are connected to each other in such a manner that air above the solutions contained in the respective containers can move between the containers.

[0020] The humidification container is substantially sealed.

[0021] The air introduction device is arranged in the flow path of the chlorine dioxide generating device.

[0022] The humidification container is configured in such a manner that "when the air introduction device is in operation, the air provided through the first conduit is bubbled into the humidification solution to humidify the air in the humidification container",

[0023] The reaction container is configured such that “the humidified air in the humidification container is bubbled into the chlorite aqueous solution in the reaction container via the second conduit”.

[0024] One embodiment of the present invention is a chlorine dioxide generator, which includes a humidifying mechanism and a bubbling mechanism, wherein:

[0025] The device comprises a reaction container, a reaction solution storage container, a humidification container and an air introduction device.

[0026] The reaction container contains a catalyst,

[0027] The reaction solution storage container contains a chlorite aqueous solution,

[0028] The humidification container contains a humidification solution,

[0029] The humidification container includes a first conduit for introducing air from outside the device.

[0030] The humidification container and the reaction solution storage container are connected to each other via a second conduit, or are connected to each other in such a manner that air above the solutions contained in the respective containers can move between the containers.

[0031] The reaction solution storage container is connected to the reaction container via a third conduit.

[0032] The humidification container is substantially sealed.

[0033] The reaction solution storage container is substantially airtight.

[0034] The air introduction device is arranged in the flow path of the chlorine dioxide generating device.

[0035] The humidification container is configured in such a manner that “when the air introduction device is in operation, the air provided from the air introduction device via the first conduit is bubbled into the humidification solution, thereby humidifying the air in the humidification container”.

[0036] The reaction liquid storage container is configured such that "when the air introduction device is operated, the humidified air in the humidification container is supplied to the reaction liquid storage container",

[0037] The reaction container is configured such that “when the air introduction device is operated, the chlorite aqueous solution in the reaction solution storage container is supplied to the reaction container via the third conduit, and then the humidified air in the reaction solution storage container is bubbled into the chlorite aqueous solution in the reaction container via the third conduit”.

[0038] The reaction liquid storage container and the reaction container are configured in such a manner that "when the air introduction device is stopped from an operating state, the reaction liquid moved to the reaction container during the operating state by the air introduction device returns to the reaction liquid storage container via the third conduit."

[0039] In one embodiment of the present invention, the reaction container is arranged above the reaction solution storage container.

[0040] One embodiment of the present invention is configured such that "when the air introduction device is operated, the air in the chlorite aqueous solution bubbled into the reaction container comes into contact with the catalyst."

[0041] In one embodiment of the present invention, "the reaction container is at least partially open, and the air containing chlorine dioxide generated in the reaction container is released to the outside of the device."

[0042] According to one embodiment of the present invention, when the air introduction device is in operation, the reaction container only contains the chlorite aqueous solution and the catalyst.

[0043] One embodiment of the present invention does not include an electrolysis mechanism.

[0044] In one embodiment of the present invention, the chlorite aqueous solution is an alkali metal chlorite aqueous solution or an alkaline earth metal chlorite aqueous solution.

[0045] In one embodiment of the present invention, the aqueous solution of alkali metal chlorite salt is an aqueous solution of sodium chlorite, an aqueous solution of potassium chlorite or an aqueous solution of lithium chlorite, and the aqueous solution of alkaline earth metal chlorite salt is an aqueous solution of calcium chlorite, an aqueous solution of magnesium chlorite or an aqueous solution of barium chlorite.

[0046] In one embodiment of the present invention, the concentration of the chlorite aqueous solution is 0.01 to 45 weight %.

[0047] In one embodiment of the present invention, the humidifying solution is water.

[0048] In one embodiment of the present invention, the humidifying solution is tap water.

[0049] In one embodiment of the present invention, the catalyst is a solid catalyst.

[0050] In one embodiment of the present invention, the catalyst is a metal-based catalyst, a mineral-based catalyst, a carbon-based catalyst or a combination thereof.

[0051] In one embodiment of the present invention, the metal-based catalyst is a catalyst comprising platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo) or a compound of platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), and molybdenum (Mo); the mineral-based catalyst is a catalyst comprising silicon (Si) or a silicon-containing compound; and the carbon-based catalyst is a catalyst comprising activated carbon.

[0052] In one embodiment of the present invention, the catalyst is supported on a carrier.

[0053] In one embodiment of the present invention, the carrier is a carrier comprising a material selected from the group consisting of titanium, valve metal, stainless steel, nickel, ceramic, carbon and porous substances.

[0054] In one embodiment of the present invention, the air introduction device is: a device for introducing air into the flow path of the chlorine dioxide generating device from the starting point of the flow path, a device for moving the air in the flow path in one direction in the middle of the flow path of the chlorine dioxide generating device, or a device for sucking the air in the flow path from the end point of the flow path of the chlorine dioxide generating device.

[0055] In one embodiment of the present invention, the air introduction device is an electric air pump.

[0056] In one embodiment of the present invention, "the concentration of chlorine dioxide contained in the air released from the device at the time point when the device is continuously operated for 1 month" can be maintained at least 50% compared with "the concentration of chlorine dioxide contained in the air released from the device at the time point when the device is continuously operated for 1 week".

[0057] The scope of the present invention also includes inventions in which one or more features of the present invention described above are arbitrarily combined.

[0058] [Effects of the Invention]

[0059] Compared with the conventional chlorine dioxide generation method / generation device, the present invention has at least one of the following advantages.

[0060] (1) Improved safety and durability

[0061] The present invention utilizes the generation of chlorine dioxide caused by the reaction of chlorite with a catalyst. This method has almost no risk of generating a large amount of chlorine dioxide due to a rapid reaction, and it has been confirmed that no harmful gases other than chlorine dioxide gas are generated. Therefore, compared with the "method of adding acidic substances to chlorite to generate chlorine dioxide" or "the method of using electrolysis", it is safer (for example, when chlorine dioxide is generated by electrolysis, if the electrolyte deteriorates, chlorine or hydrogen will be generated). In addition, the power of the device of the present invention is only the air introduction device, so the risk of device failure is low, and it is easy to repair in the event of device failure.

[0062] (2) Maintenance-free

[0063] The present invention has a humidifying mechanism that prevents the evaporation of water in the chlorite aqueous solution, so that chlorine dioxide can be stably generated for several months without maintenance. In addition, when the life of the chlorite aqueous solution reaches the end, the device can continue to operate by simply replacing the chlorite aqueous solution.

[0064] (3) Miniaturization and cost reduction

[0065] The present invention has an extremely simple structure compared to, for example, a chlorine dioxide generating device utilizing electrolysis, and thus the device can be miniaturized or the cost can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 Design Example 1 of the present invention is shown.

[0067] Figure 2 Design Example 2 of the present invention (when the reaction is stopped) is shown.

[0068] Figure 3 Design Example 2 (at the time of reaction) of the present invention is shown.

[0069] Figure 4 Design Example 3 of the present invention (when the reaction is stopped) is shown.

[0070] Figure 5 Design Example 4 of the present invention (when the reaction is stopped) is shown.

[0071] Figure 6 Design Example 4 (at the time of reaction) of the present invention is shown.

[0072] Figure 7 Design Example 5 of the present invention (when the reaction is stopped) is shown.

[0073] Figure 8 Design Example 6 of the present invention (when the reaction is stopped) is shown.

[0074] Fig. 9 Shows the design of the apparatus used in Experiment 1.

[0075] Fig.10 The results of Experiment 1 (the amount of chlorine dioxide generated) are shown.

[0076] Fig.11 The results of Experiment 2 (qualitative analysis of generated gas) are shown.

[0077] Fig.12 The results of Experiment 3 (without humidification mechanism) are shown.

[0078] Fig.13 The results of Experiment 3 (with humidification mechanism) are shown.

[0079] Description of Reference Numerals

[0080] 1.11 Air introduction device

[0081] 2, 2', 2", 12, 12' conduit

[0082] 3 Humidification container

[0083] 4 Humidification solution

[0084] 5. Reaction solution storage container

[0085] 5', 9, 13 reaction containers

[0086] 6.14 Chlorite aqueous solution

[0087] 7.15 Catalyst

[0088] 8 Small diameter holes. DETAILED DESCRIPTION

[0089] use Figures 1 to 8 The design examples shown are used to explain the embodiments of the present invention.

[0090] Design Example 1

[0091] Figure 1 The chlorine dioxide generating device of one embodiment of the present invention shown in the figure comprises: a reaction container 5', a humidification container 3 and an air introduction device 1; the reaction container 5' contains a chlorite aqueous solution 6 and a catalyst 7, and the humidification container 3 contains a humidification solution 4. The air introduction device 1 and the humidification container 3 are connected by a first conduit 2, and the humidification container 3 and the reaction container 5' are connected by a second conduit 2'. The humidification container 3 is substantially sealed.

[0092] In the reaction container 5', chlorine dioxide is generated by the reaction of the chlorite aqueous solution 6 and the catalyst 7. If the air introduction device 1 is operated, the air provided through the first conduit 2 will humidify the air in the humidification container 3 by being bubbled into the humidification solution 4;

[0093] The humidified air in the humidification container 3 is bubbled into the chlorite aqueous solution 6 in the reaction container 5' through the second conduit 2'. When the chlorite aqueous solution 6 and the catalyst 7 are stirred by bubbling, the chlorine dioxide generated on the surface of the catalyst 7 is released from the catalyst surface, and chlorine dioxide is generated again on the surface of the catalyst 7. The chlorine dioxide released by bubbling is released to the outside of the device together with the air through the third conduit (gas release pipe) 2" provided at the upper part of the reaction container 5'.

[0094] Figure 1 The chlorine dioxide generator of the present invention shown in the figure is provided with a bubbling mechanism centered around the air introduction device 1, which can promote the reaction between the chlorite aqueous solution 6 and the catalyst 7, and can release the generated chlorine dioxide to the outside of the device. In addition, the chlorine dioxide generator of the present invention is provided with a humidification mechanism centered around the humidification container 3, thereby preventing the evaporation of the chlorite aqueous solution 6 in the reaction container 5', thereby enabling the device to operate for a very long time.

[0095] Design Example 2

[0096] Figure 2 as well as Figure 3 The chlorine dioxide generator of one embodiment of the present invention shown is also a device for generating chlorine dioxide based on the same principle as that of Design Example 1, but in this Design Example, a control mechanism for the reaction between the catalyst and the chlorite aqueous solution is further provided.

[0097] (1) When the reaction stops

[0098] The device shows when the reaction stops. Figure 2. In the device of Design Example 2, in addition to the device of Design Example 1, a reaction liquid storage container 5 is further provided. The reaction liquid storage container 5 contains only the chlorite aqueous solution 6 and does not contain the catalyst 7. On the other hand, the reaction container 9 contains only the catalyst 7 and does not contain the chlorite aqueous solution 6. The reaction container 9 is arranged above the reaction liquid storage container 5, and the reaction container 9 and the reaction liquid storage container 5 are connected by a conduit 2". The conduit 2" is arranged in a manner that "the lower end is immersed in the chlorite aqueous solution 6 in the reaction liquid storage container 5". In this state, since the chlorite aqueous solution 6 does not contact the catalyst 7, chlorine dioxide is not generated.

[0099] (2) Reaction time

[0100] The device during the reaction is shown in Figure 3 . When the air introduction device 1 is in operation, a flow path is formed in the direction of the arrow in the figure, and the chlorite aqueous solution 6 in the reaction liquid storage container 5 is guided into the reaction container 9 via the conduit 2". During the operation of the air introduction device 1, since the reaction liquid storage container 5 becomes a positive pressure, the chlorite aqueous solution 6 can be maintained in the reaction container 9. In addition, the chlorite aqueous solution 6 is bubbled by the air supplied via the isolation conduit 2". In this state, the chlorite aqueous solution 6 comes into contact with the catalyst 7, and since the chlorite aqueous solution 6 and the catalyst 7 are stirred by the bubbling, chlorine dioxide can be generated as efficiently as in the case of Design Example 1. The chlorine dioxide freed by bubbling can be released from the upper part of the reaction container 9 to the outside of the device together with the air.

[0101] (3) When the reaction stops

[0102] If the air introduction device 1 is stopped from the state (2), the positive pressure state of the reaction solution storage container 5 is released, so the chlorite aqueous solution 6 in the reaction container 9 returns to the reaction solution storage container 5 and becomes Figure 2 In this state, the chlorite aqueous solution 6 does not contact the catalyst 7, so no chlorine dioxide is generated.

[0103] As described above, the device of Design Example 2, like the device of Design Example 1, can not only generate chlorine dioxide for an extremely long period of time, but also can control the generation of chlorine dioxide by a simple mechanism such as an air introduction device.

[0104] Design Example 3

[0105] Figure 4The chlorine dioxide generator of one embodiment of the present invention shown is a device having the same control mechanism as that of Design Example 2. Design Example 3 is designed in such a way that "the humidification container 3 and the reaction liquid storage container 5 are integrated, and only the air above the individual containers can move between the containers." By omitting the conduit 2' and integrating the humidification container 3 and the reaction liquid storage container 5, the size of the device can be reduced.

[0106] Design Example 4

[0107] Figure 5 as well as Figure 6 The chlorine dioxide generator of one embodiment of the present invention shown is a device having the same control mechanism as that of Design Example 2. Design Example 4 is set in a manner that "the end of the reaction liquid storage container side of the conduit 2' is immersed in the chlorite aqueous solution" and "the end of the reaction liquid storage container side of the conduit 2' is located below the lower end of the conduit 2". With such a design, bubbling can also be performed in the reaction liquid storage container 5 during the operation of the air introduction device 1.

[0108] If the operation / stop of the device is repeated, the amount of chlorine dioxide dissolved in the chlorite aqueous solution 6 can be increased. If the amount of chlorine dioxide dissolved in the chlorite aqueous solution 6 increases, chlorine dioxide can be released from the chlorite aqueous solution 6 even when the reaction is stopped. In this design example, by bubbling in the reaction solution storage container 5, the dissolved chlorine dioxide can be removed while the chlorite aqueous solution 6 is present in the reaction solution storage container 5, and the release of chlorine dioxide can be prevented when the reaction is stopped. In addition, during the reaction, excessive release of chlorine dioxide due to the influence of dissolved chlorine dioxide can be prevented, and as a result, the generation of chlorine dioxide can be more stably regulated.

[0109] Design Example 5

[0110] Figure 7 The chlorine dioxide generator according to one embodiment of the present invention shown is a device having the same control mechanism as that of Design Example 2. Design Example 5 is different from Design Example 2 in that an air introduction device is provided in the middle of the flow path.

[0111] Design Example 6

[0112] Figure 8 The chlorine dioxide generator of one embodiment of the present invention shown is a device having the same control mechanism as that of Design Example 2. Design Example 6 is different from Design Example 2 in that a suction-type air introduction device is provided at the terminal end of the flow path.

[0113] In the above description, the content of the present invention is explained with reference to the design examples, but the present invention can be specifically presented in various forms and is not to be construed as being limited to the design examples described herein. For example, in one embodiment of the present invention, the size and shape of the device can be optimized by making various changes to the configuration of the container and the conduit constituting the device.

[0114] The chlorite used in the present invention can be exemplified by alkali metal chlorites or alkaline earth metal chlorites. Examples of alkali metal chlorites include sodium chlorite, potassium chlorite, and lithium chlorite, and examples of alkaline earth metal chlorites include calcium chlorite, magnesium chlorite, and barium chlorite. Among them, sodium chlorite and potassium chlorite are more preferred in terms of easy acquisition, and sodium chlorite is most preferred. These chlorine oxyalkalis can be used alone, and two or more can also be used. The proportion of chlorite in the chlorite aqueous solution is more preferably 0.01% by weight to 45% by weight. When it is less than 0.01% by weight, the chlorite required for the production of chlorine dioxide may be exhausted in a short time, and when it exceeds 45% by weight, the problem of chlorite being saturated and easily precipitated may occur. Considering safety and stability, the efficiency of the production of chlorine dioxide, etc., the more preferred range is 0.1% by weight to 25% by weight, the more preferred range is 1% by weight to 20% by weight, and the more preferred range is 2 to 15%.

[0115] The catalyst used in the device of the present invention is not limited as long as it can react with the chlorite aqueous solution to produce chlorine dioxide, but since it needs to be separated from the chlorite aqueous solution when the reaction stops, a solid catalyst (or a heterogeneous catalyst) is more preferably used. Examples of the solid catalyst that can be used in the device of the present invention include metal catalysts (for example, platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), or compounds of platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo)), mineral catalysts (for example, silicon (Si) or silicon-containing compounds), and carbon catalysts (for example, catalysts containing activated carbon).

[0116] The catalyst used in the device of the present invention can be used alone, but in order to improve the reaction efficiency of the chlorite aqueous solution and the catalyst, a catalyst supported on a carrier can be used. The carrier supporting the catalyst is not limited as long as it helps to improve the reaction efficiency of the chlorite aqueous solution and the catalyst, but it is more preferably, for example, a catalyst selected from titanium, valve metal ( valve metal), stainless steel, nickel, ceramics, carbon and porous substances.

[0117] The air introduction device that can be used in the device of the present invention is not limited as long as it can move the air or chlorite aqueous solution in the flow path of the device in one direction, and can be, for example, an electric air pump. The electric air pump can be supplied with power by a power supply device via a cable, or by a battery.

[0118] The air introduction device that can be used in the device of the present invention can be set in various positions as long as it can move the air or chlorite aqueous solution in the flow path of the device in one direction. For example, the air introduction device can be set at the starting point of the flow path to introduce air into the flow path; the air introduction device can also be set in the middle of the flow path to move the air in the flow path in one direction; the air introduction device can also be set at the end of the flow path to suck the air in the flow path to move the air or chlorite aqueous solution in the flow path of the device in one direction.

[0119] In the device of the present invention, the gas introduced into the flow path in the device by the air introduction device is typically air, but an inactivated gas such as nitrogen or argon may also be used.

[0120] The chlorine dioxide generating device of the present invention may further include a blower fan for releasing the chlorine dioxide gas generated in the device to the outside of the device. By including the blower fan, the chlorine dioxide gas generated in the device can be efficiently sent to the outside of the device. In addition, the amount of chlorine dioxide gas sent to the outside of the device can also be adjusted by adjusting the air volume of the fan. For example: when the amount of chlorine dioxide gas generated is large, the chlorine dioxide gas outside the device can be diffused further by increasing the air volume of the blower fan; when the amount of chlorine dioxide gas generated is small, the chlorine dioxide gas outside the device can be prevented from being spread unnecessarily by reducing the air volume of the blower fan, and the concentration of chlorine dioxide gas outside the device can be adjusted within a certain range.

[0121] The terms used in this specification are used to describe specific embodiments and are not intended to limit the invention.

[0122] In addition, the term "comprising" used in this specification is intended to indicate the existence of the recorded matters (components, steps, elements or numbers, etc.), and does not exclude the existence of matters (components, steps, elements or numbers, etc.) other than the recorded matters, except where it is obvious that a different understanding is required in the context of the article.

[0123] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as those widely understood by those skilled in the art. Unless otherwise defined, the terms used herein should be interpreted as having a meaning consistent with the meanings in this specification and the relevant technical field, and should not be interpreted as idealized or overly formalized meanings.

[0124] The embodiments of the present invention may be described with reference to schematic diagrams. However, in the case of schematic diagrams, they may be exaggerated for the purpose of clear description.

[0125] In the present specification, for example, when presented as "1 to 10 w / w %", those skilled in the art can understand that the presentation specifically means 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 w / w %.

[0126] In this specification, any numerical value used to express the content of a component or a numerical range can be interpreted as including the meaning of the term "about" unless otherwise specified. For example, "10 times" can be understood as meaning "about 10 times" unless otherwise specified.

[0127] All the disclosures in the documents cited in this specification should be deemed to be cited in this specification. Those skilled in the art should understand that the relevant disclosures in the prior art documents are cited as part of this specification based on the context of this specification without departing from the spirit and scope of the present invention.

[0128] [Example]

[0129] In order to confirm the effects of the present invention, the following experiments were performed.

[0130] [Experiment 1. Reaction of catalyst and chlorite aqueous solution]

[0131] In this experiment, a simpler version of the device of the present invention was used. Fig. 9 The apparatus shown in the figure was used to conduct a chlorine dioxide generation experiment. The catalyst used was a catalyst in which a platinum masterbatch was supported on titanium (carrier), and the chlorite aqueous solution used was 1L of a 1% sodium chlorite aqueous solution. The air introduction device 11 was used to bubble air into the reaction container 13 containing the chlorite aqueous solution 14 and the catalyst 15 at a flow rate of about 1L / min. On the other hand, as a control group, the apparatus was operated under the same conditions as described above except that no catalyst was used.

[0132] The comparison of chlorine dioxide produced under the two conditions is shown in Fig.10 .like Fig.10As shown, chlorine dioxide is generated under the condition of using a catalyst, but not under the condition of not using a catalyst. In other words, it is confirmed that a catalyst is necessary to generate chlorine dioxide in the device of the present invention.

[0133] [Experiment 2. Qualitative analysis of generated gas]

[0134] The gas produced by the method of Experiment 1 was collected and the components were qualitatively analyzed by ion chromatography. The results are shown in Fig.11 .like Fig.11 As shown, the gas component produced by the reaction of chlorite and the catalyst is actually only chlorine dioxide.

[0135] [Experiment 3. Confirmation of the effect of humidification mechanism]

[0136] The same apparatus as in Experiment 1 was used ( Fig. 9 The device shown in the embodiment 1) and the device of the present invention shown in the embodiment 1 ( Figure 1 The results of the case where the device used in Experiment 1 was used are shown in Fig.12 The results of the case where the device of the present invention shown in Design Example 1 is used are shown in Fig.13 .like Fig.12 As shown in FIG. 1 , although the device without a humidifying mechanism generates chlorine dioxide stably for about one month, the amount of chlorine dioxide generated becomes unstable due to evaporation of the water in the chlorite aqueous solution after about one month. Fig.13 As shown, the device with the humidification mechanism has been stably releasing chlorine dioxide for more than 3 months. As described above, the humidification mechanism of the device of the present invention has been shown to allow the device to operate stably for a long time.

Claims

1. A chlorine dioxide generator, comprising a humidifying mechanism and a bubbling mechanism, wherein: The device comprises a reaction container, a humidification container, an air introduction device, and a blower fan for releasing the chlorine dioxide gas generated in the device to the outside of the device. The reaction container contains a chlorite aqueous solution and a catalyst. The catalyst is a metal catalyst, a mineral catalyst, a carbon catalyst or a combination thereof. The metal catalyst is a catalyst containing platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), or a compound of platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), The mineral catalyst is a catalyst containing silicon (Si) or a silicon-containing compound. The carbon-based catalyst is a catalyst comprising activated carbon, The humidification container contains a humidification solution, The humidification container includes a first conduit for introducing air from outside the device. The humidification container is connected to the reaction container via a second conduit. The humidification container is substantially sealed. The air introduction device is arranged in the flow path of the chlorine dioxide generating device. The humidification container is constructed in the following manner: when the air introduction device is in operation, the air provided through the first conduit is bubbled into the humidification solution to humidify the air in the humidification container; The reaction container is configured in such a manner that the humidified air in the humidification container is bubbled into the chlorite aqueous solution in the reaction container through the second conduit.

2. A chlorine dioxide generator, comprising a humidifying mechanism and a bubbling mechanism, wherein: The device comprises a reaction container, a reaction solution storage container, a humidification container, an air introduction device, and a blower fan for releasing the chlorine dioxide gas generated in the device to the outside of the device. The reaction container contains a catalyst, The catalyst is a metal catalyst, a mineral catalyst, a carbon catalyst or a combination thereof. The metal catalyst is a catalyst containing platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), or a compound of platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), The mineral catalyst is a catalyst containing silicon (Si) or a silicon-containing compound. The carbon-based catalyst is a catalyst comprising activated carbon, The reaction solution storage container contains a chlorite aqueous solution, The humidification container contains a humidification solution, The humidification container includes a first conduit for introducing air from outside the device. The humidification container is connected to the reaction solution storage container via a second conduit. The reaction solution storage container is connected to the reaction container via a third conduit. The humidification container is substantially sealed. The reaction solution storage container is substantially airtight. The air introduction device is arranged in the flow path of the chlorine dioxide generating device. The humidification container is constructed in the following manner: when the air introduction device is in operation, the air provided from the air introduction device through the first conduit is bubbled into the humidification solution to humidify the air in the humidification container; The reaction liquid storage container is configured in the following manner: when the air introduction device is in operation, the humidified air in the humidification container is supplied to the reaction liquid storage container; The reaction container is configured in the following manner: when the air introduction device is operated, the chlorite aqueous solution in the reaction solution storage container is supplied to the reaction container via the third conduit, and then the humidified air in the reaction solution storage container is bubbled into the chlorite aqueous solution in the reaction container via the third conduit; The reaction liquid storage container and the reaction container are configured in the following manner: when the air introduction device stops from an operating state, the reaction liquid moved into the reaction container during the operating state of the air introduction device returns to the reaction liquid storage container via the third conduit.

3. The chlorine dioxide generating device according to claim 2, wherein: The reaction container is arranged above the reaction solution storage container.

4. The chlorine dioxide generating device according to claim 1 or 2, wherein: The chlorine dioxide generating device is configured in such a manner that when the air introducing device is operated, the air in the chlorite aqueous solution bubbled into the reaction container comes into contact with the catalyst.

5. The chlorine dioxide generating device according to claim 1 or 2, wherein: The reaction container is constructed in such a manner that it is at least partially open, and the air containing chlorine dioxide generated in the reaction container is released to the outside of the device.

6. The chlorine dioxide generating device according to claim 1 or 2, wherein: When the air introduction device is in operation, the reaction container contains only the chlorite aqueous solution and the catalyst.

7. The chlorine dioxide generating device according to claim 1 or 2, which does not contain an electrolysis mechanism.

8. The chlorine dioxide generating device according to claim 1 or 2, wherein: The chlorite aqueous solution is an alkali metal chlorite aqueous solution or an alkaline earth metal chlorite aqueous solution.

9. The chlorine dioxide generating device according to claim 8, wherein: The chlorite alkali metal salt aqueous solution is a sodium chlorite aqueous solution, a potassium chlorite aqueous solution or a lithium chlorite aqueous solution. The alkaline earth metal chlorite aqueous solution is a calcium chlorite aqueous solution, a magnesium chlorite aqueous solution or a barium chlorite aqueous solution.

10. The chlorine dioxide generating device according to claim 1 or 2, wherein: The concentration of the chlorite aqueous solution is 0.01 to 45% by weight.

11. The chlorine dioxide generating device according to claim 1 or 2, wherein: The humidifying solution is water.

12. The chlorine dioxide generating device according to claim 11, wherein: The humidifying solution is tap water.

13. The chlorine dioxide generating device according to claim 1 or 2, wherein: The catalyst is supported on a carrier.

14. The chlorine dioxide generating device according to claim 13, wherein: The carrier is a carrier including a material selected from the group consisting of titanium, valve metal, stainless steel, nickel, ceramic, carbon and porous substances.

15. The chlorine dioxide generating device according to claim 1 or 2, wherein: The air introduction device is a device for introducing air into the flow path of the chlorine dioxide generator from the starting point of the flow path of the chlorine dioxide generator, A device for moving the air in the flow path of the chlorine dioxide generating device in one direction, or A device for sucking air in the flow path of the chlorine dioxide generator from the end point of the flow path.

16. The chlorine dioxide generating device according to claim 15, wherein: The air introduction device is an electric air pump.

17. The chlorine dioxide generating device according to claim 1 or 2, wherein The concentration of chlorine dioxide contained in the air released from the device when the device is continuously operated for one month can be maintained at least 50% compared with the concentration of chlorine dioxide contained in the air released from the device when the device is continuously operated for one week.

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