Chlorine Dioxide Generator and Chlorine Dioxide Generation Method

Abstract

[Problem] The present invention addresses the problem of providing an apparatus capable of rapidly generating a sufficient amount of chlorine dioxide with a simpler configuration as compared with a conventional chlorine dioxide generation apparatus.　[Solution] Provided is a novel chlorine dioxide generation apparatus using a reaction of an aqueous chlorite solution, a catalyst, and a salt having a buffering action.

Description

Technical Field

[0001] The present invention relates to a novel chlorine dioxide generator and a chlorine dioxide generation method.

Background Art

[0002] Chlorine dioxide gas is a gas that is safe for the living body of animals at low concentrations (for example, 0.1 ppm or less). However, even at such low concentrations, it is known to have an inactivating effect on microorganisms such as bacteria, fungi, and viruses, as well as a deodorizing effect.

[0003] As a method for generating chlorine dioxide, for example, a method of stably generating chlorine dioxide using a composition containing dissolved chlorine dioxide gas, an aqueous chlorite solution, and a pH adjuster (Patent Document 1), or a method of producing chlorine dioxide by electrolyzing an electrolytic solution containing chlorite is known (Patent Document 2).

[0004] In recent years, an apparatus for generating chlorine dioxide by irradiating solid chlorite with visible light has also been proposed (Patent Document 3).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] An object of the present invention is to provide an apparatus that can generate a sufficient amount of chlorine dioxide rapidly with a simpler configuration compared to conventional chlorine dioxide generators.

Means for Solving the Problems

[0007] The present invention is based on the discovery by the inventors that chlorine dioxide can be stably generated over a long period of time by continuously stirring a reaction solution containing chlorite in the presence of a solid catalyst. The inventors have succeeded in rapidly generating a practically sufficient amount of chlorine dioxide using the above principle by adding a salt having a buffering action to the reaction solution containing chlorite, and have completed the present invention.

[0008] In one embodiment, the present invention is a chlorine dioxide generator comprising a reaction vessel, a reaction start / stop mechanism, a solid catalyst, and a solution stirring mechanism, wherein the reaction vessel contains a reaction solution during the chlorine dioxide generation reaction, the reaction solution contains chlorite and a salt having a buffering action, the reaction start / stop mechanism is designed to start the chlorine dioxide generation reaction by bringing the solid catalyst into contact with the reaction solution, and to stop the chlorine dioxide generation reaction by separating the solid catalyst from the reaction solution, and the solution stirring mechanism is designed to stir the reaction solution during the chlorine dioxide generation reaction. The present invention relates to an apparatus.

[0009] In one embodiment of the present invention, the salt having a buffering action is characterized in that it is a hydrogen carbonate or a hydrogen phosphate.

[0010] In one embodiment of the present invention, the hydrogen carbonate is sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate, or ammonium hydrogen carbonate, and the hydrogen phosphate is disodium hydrogen phosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate, or diammonium hydrogen phosphate.

[0011] In one embodiment of the present invention, the concentration of the salt having a buffering action in the reaction solution is 0.1 to 63% by weight.

[0012] In one embodiment of the present invention, the chlorite is an alkali metal chlorite or an alkaline earth metal chlorite.

[0013] In one embodiment of the present invention, the alkali metal chlorite is sodium chlorite, potassium chlorite, or lithium chlorite, and the alkaline earth metal chlorite is calcium chlorite, magnesium chlorite, or barium chlorite.

[0014] In one embodiment of the present invention, the concentration of the chlorite in the reaction solution is 0.01 to 45% by weight.

[0015] 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.

[0016] In one embodiment of the present invention, the metal-based 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 compounds of these metals, the mineral-based catalyst is a catalyst containing silicon (Si) or a compound containing silicon, the carbon-based catalyst is a catalyst containing activated carbon, and is characterized by this.

[0017] In one embodiment of the present invention, the catalyst is supported on a carrier.

[0018] In one embodiment of the present invention, the carrier is a carrier containing a material selected from the group consisting of titanium, valve metal, stainless steel, nickel, ceramics, carbon, and porous materials.

[0019] In one embodiment of the present invention, the solution stirring mechanism is characterized by being a bubbling type stirring mechanism, a stirrer type stirring mechanism, a stirring blade type stirring mechanism, or a shaking type stirring mechanism.

[0020] In one embodiment of the present invention, the reaction vessel is at least partially open, and air containing chlorine dioxide generated within the reaction vessel is configured to be discharged to the outside of the apparatus.

[0021] Another embodiment of the present invention is a method for generating chlorine dioxide, comprising: continuously or periodically stirring a reaction solution containing chlorite and a salt having a buffering action in the presence of a solid catalyst; and relates to a method.

[0022] Inventions arbitrarily combining one or more of the features of the present invention listed above are also included in the scope of the present invention.

Advantages of the Invention

[0023] The present invention has at least one or more of the following advantages over conventional chlorine dioxide generation methods / generation apparatuses.

[0024] (1) Safety The method and apparatus of the present invention utilize the generation of chlorine dioxide by the reaction of chlorite, a catalyst, and a salt having a buffering action. In this method, the generation of chlorine dioxide can be easily controlled by separating the reaction solution from the catalyst or stopping the solution stirring, and it has been confirmed that no harmful gases other than chlorine dioxide gas are generated. Therefore, the method of the present invention is highly safe compared to methods of generating chlorine dioxide by adding an acidic substance to chlorite or using electrolysis (for example, in chlorine dioxide generation by electrolysis, when the electrolytic solution deteriorates, chlorine gas, hydrogen gas, etc. may be generated).

[0025] (2) Durability of the apparatus Since the device of the present invention has a relatively simple structure, the risk of failure is low, and it is also easy to repair when the device fails.

[0026] (3) Chlorine dioxide generation efficiency Despite having a relatively simple structure, the method and device of the present invention can stably generate chlorine dioxide with high efficiency (see the examples in this specification).

[0027] (4) Miniaturization and cost reduction Since the device of the present invention has a simple structure compared to, for example, a chlorine dioxide generation device by electrolysis, it is possible to miniaturize the device and reduce costs.

Brief Description of the Drawings

[0028]

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Embodiments for Carrying Out the Invention

[0029] Embodiments for carrying out the present invention will be described using the design examples shown in Figs. 1 to 4.

[0030] The simplest design example of the apparatus using the method of the present invention is shown in Fig. 1. Air is bubbled from the gas supply pipe 2 connected to the air introduction device 1 into the reaction vessel 3 containing the reaction solution 4, whereby the reaction solution 4 is stirred. The reaction solution 4 is an aqueous chlorite solution containing the reactant 5 (a salt having a buffering action). By bringing the reaction solution 4 into contact with the solid catalyst 6, a reaction for generating chlorine dioxide is started, and the reaction is stopped by separating the reaction solution 4 from the solid catalyst 6. For the chlorine dioxide generation effect by the method and apparatus of the present invention, refer to the examples of the present application.

[0031] Furthermore, Figs. 2 to 4 show more specific design examples of the apparatus. Fig. 2 shows the external appearance of the apparatus, Fig. 3 shows a cross-sectional view of the apparatus during operation, and Fig. 4 shows a cross-sectional view of the apparatus when the reaction is stopped. The reaction vessel 17 contains a reaction solution 18 (an aqueous sodium chlorite solution containing the reactant 19). The reaction solution 18 is stirred by being bubbled through the gas supply pipe 12 connected to the air introduction device 11. The apparatus includes a reaction start / stop mechanism (13, 14, 15) having a solid catalyst 15. The solid catalyst 15 is connected to the stepping motor 13 via the wire 14 and can move up and down by the operation of the stepping motor 13.

[0032] As shown in Fig. 3, when the solid catalyst 15 is brought into contact with the reaction solution 18, chlorine dioxide is generated. On the other hand, as shown in Fig. 4, when the wire 14 is wound up and the solid catalyst 15 is not in contact with the reaction solution 18, the generation of chlorine dioxide stops.

[0033] In the above, the content of the present invention has been described with reference to design examples. However, the present invention can be embodied in various forms and should not be construed as being limited to the design examples described herein. For example, in one embodiment of the present invention, the apparatus can be optimized by variously changing the container constituting the apparatus, the arrangement of conduits, the reaction start / stop mechanism, and the like.

[0034] The reaction solution used in the method and apparatus of the present invention contains chlorite and a salt having a buffering action.

[0035] Examples of the chlorite used in the present invention include alkali metal chlorites and alkaline earth metal chlorites. Examples of the alkali metal chlorite include sodium chlorite, potassium chlorite, and lithium chlorite. Examples of the alkaline earth metal chlorite include calcium chlorite, magnesium chlorite, and barium chlorite. Among them, sodium chlorite and potassium chlorite are preferred from the viewpoint of easy availability, and sodium chlorite is most preferred. These alkali chlorites may be used alone or in combination of two or more. The concentration of chlorite in the reaction solution is preferably 0.01% by weight to 45% by weight. When the concentration is less than 0.01% by weight, the chlorite required for the generation of chlorine dioxide may be depleted in a short period. When the concentration exceeds 45% by weight, there may be a problem that the chlorite becomes saturated and crystals are likely to precipitate. Considering safety, stability, the generation efficiency of chlorine dioxide, etc., the 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 further preferred range is 2% to 15% by weight.

[0036] As the salt having a buffering action used in the present invention, various known salts can be used as long as they promote the reaction between chlorite and the catalyst. For example, it is preferable to use bicarbonate or hydrogen phosphate. Examples of bicarbonates include sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, ammonium bicarbonate, and the like. Examples of hydrogen phosphates include disodium hydrogen phosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate, diammonium hydrogen phosphate, and the like.

[0037] The concentration of the salt having a buffering action in the reaction solution is preferably 0.1 to 63% by weight. When the concentration of the salt is less than 0.1% by weight, the chlorine dioxide generation reaction may be insufficient, and it may not be possible to obtain the amount of chlorine dioxide required for practical use. Also, when the concentration of the salt is 63% by weight or more, the salt in the reaction solution may become saturated and crystals may precipitate. Considering safety, stability, chlorine dioxide generation efficiency, etc., the preferable range is 1% to 50% by weight, a more preferable range is 5% to 45% by weight, and an even more preferable range is 10 to 40% by weight.

[0038] The catalyst used in the present invention is not limited as long as it reacts with an aqueous chlorite solution to generate chlorine dioxide. However, since it is necessary to be separated from the aqueous chlorite solution at the end of the reaction, it is preferably a solid catalyst (or heterogeneous catalyst). Examples of the solid catalyst that can be used in 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 these metals), mineral-based catalysts (for example, silicon (Si) or a compound containing silicon), and carbon-based catalysts (for example, a catalyst containing activated carbon).

[0039] The above catalyst may be used alone, or a catalyst supported on a carrier may be used. The carrier on which the catalyst is supported is not limited as long as it contributes to improving the reaction efficiency between the chlorite aqueous solution and the catalyst. For example, a carrier containing a material selected from the group consisting of titanium, valve metal, stainless steel, nickel, ceramics, carbon, and porous substances is preferable.

[0040] The reaction start / stop mechanism used in the apparatus of the present invention is designed to start the chlorine dioxide generation reaction by bringing the solid catalyst into contact with the reaction solution and stop the chlorine dioxide generation reaction by separating the solid catalyst from the reaction solution, and may be realized in various forms as long as it meets this requirement. For example, the reaction start / stop mechanism used in the apparatus of the present invention may be either (1) a mechanism that achieves the above object by moving the solid catalyst or (2) a mechanism that achieves the above object by moving the reaction solution. For example, the following non-limiting specific examples can be given.

[0041] (1) Examples of the mechanism for moving the solid catalyst · Hoisting mechanism (Electric or manual): The solid catalyst is directly or indirectly connected to a thin wire such as a wire, and by winding up (or winding down) the thin wire, the solid catalyst is brought into contact with (or separated from) the reaction solution. · Vertical movement mechanism (Electric or manual): The solid catalyst is directly or indirectly connected to a linear motion mechanism, and by driving the linear motion mechanism in the vertical direction, the solid catalyst is brought into contact with (or separated from) the reaction solution.

[0042] (2) Examples of the mechanism for moving the reaction solution · Additional reaction solution holding container : A reaction solution holding container is provided separately from the reaction container. When the reaction is stopped, the reaction solution is moved to the reaction solution holding container to separate the solid catalyst (remaining in the reaction container) from the reaction solution, and when the reaction occurs, the reaction solution is moved to the reaction container to bring the solid catalyst into contact with the reaction solution. The movement of the solution between the containers can be performed using, for example, an electric pump.

[0043] In the apparatus of the present invention, as long as the solution stirring mechanism can continuously or periodically stir the reaction solution, a known solution stirring mechanism can be used. For example, a bubbling type stirring mechanism that stirs the solution with a gas such as air; a stirrer type stirring mechanism that stirs the solution by rotating a stirrer using magnetic force or the like; a stirring blade type stirring mechanism that stirs the solution by rotating a propeller; a shaking type stirring mechanism that stirs the solution by shaking the reaction solution or the reaction vessel containing the reaction solution; and the like can be mentioned.

[0044] As a typical example of the solution stirring mechanism used in the apparatus of the present invention, an air introduction device (for example, an electric air pump or a gas cylinder), which is one of the bubbling type stirring mechanisms, can be mentioned. The supply of electricity to the electric air pump may be performed from a power supply device via a power cable, or a battery may be used. The gas introduced by the air introduction device is typically air, but for example, an inert gas such as nitrogen or argon may be used.

[0045] The apparatus of the present invention may further include a blower fan for discharging the chlorine dioxide gas generated in the apparatus to the outside of the apparatus. By providing the blower fan, the chlorine dioxide gas generated in the apparatus can be efficiently sent out of the apparatus. Also, by adjusting the air volume of the fan, the amount of chlorine dioxide gas sent out of the apparatus can be adjusted. For example, when the generation amount of chlorine dioxide gas is relatively large, by increasing the air volume of the blower fan, the chlorine dioxide gas outside the apparatus is diffused farther, and when the generation amount of chlorine dioxide gas is relatively small, by decreasing the air volume of the blower fan, it is possible to prevent the chlorine dioxide gas outside the apparatus from being diffused more than necessary, and thus adjust the chlorine dioxide gas concentration outside the apparatus to be within a certain range.

[0046] The terms used in this specification are used to describe specific embodiments and are not intended to limit the invention.

[0047] Also, as used herein, the term "comprising" is intended to mean the presence of the stated item (such as a member, step, element, or number), unless the context clearly dictates otherwise, and does not exclude the presence of other items (such as a member, step, element, or number).

[0048] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used herein should be interpreted as having a meaning consistent with the meaning in this specification and the relevant technical field, and should not be interpreted in an idealized or overly formal sense, unless otherwise explicitly defined.

[0049] Embodiments of the present invention may be described with reference to schematic diagrams. However, when they are schematic diagrams, they may be exaggerated for clarity of explanation.

[0050] In this specification, for example, when expressed as "1 to 10 w / w%", those skilled in the art will understand that this expression specifically refers to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 w / w% individually.

[0051] In this specification, any numerical values used to indicate component contents or numerical ranges should be interpreted as including the meaning of the term "about" unless otherwise explicitly stated. For example, "10 times" is understood to mean "about 10 times" unless otherwise explicitly stated.

[0052] All the disclosures of the documents cited in this specification should be regarded as incorporated herein. Those skilled in the art should incorporate and understand the relevant disclosure contents in those prior art documents as part of this specification without departing from the spirit and scope of the present invention according to the context of this specification.

Examples

[0053] [Experiment 1: Examination of a New Method for Generating Chlorine Dioxide] Using the apparatus shown in Fig. 1, a chlorine dioxide generation experiment was conducted. Air was bubbled at a flow rate of approximately 3 L / min from the gas supply pipe 2 connected to the air introduction device 1 into the reaction vessel 3 containing the reaction solution 4. The reaction solution 4 was an aqueous chlorite solution containing the reactant 5 which was potassium hydrogen carbonate, and the solid catalyst 6 was mixed therein. As the solid catalyst 6, a material obtained by supporting a platinum-based catalyst on titanium (carrier) was used ( Condition 1 ). Using a gas detector tube, the chlorine dioxide concentration in the air discharged from the gas discharge pipe 2' to the outside of the apparatus was measured.

[0054] As a control, experiments were conducted under the conditions where the reaction solution did not contain the reactant ( Condition 2) , and where the solid catalyst was not mixed in the reaction solution ( Condition 3 ).

Table 1

[0055] The measurement results of the chlorine dioxide concentration and generation amount under each condition are shown in Tables 2 - 3 and Fig. 5. As shown in Tables 2 - 3 and Fig. 5, under Condition 1, a practically sufficient amount of chlorine dioxide was generated over a long period of time. On the other hand, under Condition 2, only about 3 to 10% of the amount of chlorine dioxide generated under Condition 1 was generated, and under Condition 3, almost no chlorine dioxide was generated.

[0056]

Table 2

Table 3

[0057] [Experiment 2: Examination of Reactants] (1) Regarding hydrogen carbonates An experiment was conducted under the same conditions as Condition 1 except that the reactant (potassium hydrogen carbonate) was changed to sodium carbonate, and the chlorine dioxide concentration in the air discharged from the gas discharge pipe 2' to the outside of the apparatus was measured (Condition 4 )。

[0058] The measurement results are shown in Table 5 and Figure 6. As shown in Table 5 and Figure 6, when the reactant was changed from potassium hydrogen carbonate to sodium carbonate, almost no generation of chlorine dioxide was observed.

Table 4

Table 5

[0059] (2) Regarding hydrogen phosphate An experiment was conducted under the same conditions as Condition 1 except that the reactant (potassium hydrogen carbonate) was changed to dipotassium hydrogen phosphate, and the chlorine dioxide concentration and generation amount in the air discharged from the gas discharge pipe 2' to the outside of the apparatus were measured ( Condition 6 ). As a control, the conditions where the reaction solution does not contain the reactant (the above-mentioned Condition 2 ), and the conditions where the solid catalyst is not mixed in the reaction solution ( Condition 5 ) were used to conduct similar experiments.

Table 6

[0060] The measurement results are shown in Tables 7 - 8 and Figure 7. As shown in Tables 7 - 8 and Figure 7, even when the reactant of Condition 1 (potassium hydrogen carbonate) was changed to dipotassium hydrogen phosphate (Condition 6), a sufficient amount of chlorine dioxide was generated over a long period of time. However, the generation amount of chlorine dioxide was larger when potassium hydrogen carbonate was used as the reactant. On the other hand, in Condition 2, only about 10 - 17% of the amount of chlorine dioxide generated in Condition 6 was generated, and in Condition 5, almost no chlorine dioxide was generated.

[0061]

Table 7

Table 8

[0062] In addition, an experiment was conducted under the same conditions as in Condition 6 except that the reactant (dipotassium hydrogen phosphate) was changed to trisodium phosphate, and the chlorine dioxide concentration in the air discharged from the gas discharge pipe 2' to the outside of the apparatus was measured ( Condition 7 ).

[0063] The measurement results are shown in Table 10 and Figure 8. As shown in Table 10 and Figure 8, when the reactant was changed from dipotassium hydrogen phosphate to trisodium phosphate, almost no generation of chlorine dioxide was observed. [Table 9]

[0064] [Table 10]

[0065] [Experiment 3: Examination regarding start / stop of reaction] An experiment was conducted to confirm that the generation of chlorine dioxide can be controlled by removing the solid catalyst used in the method of Condition 1. In the method of Condition 1, when the solid catalyst was removed 5 minutes after the start of the test and the operation of the apparatus was continued ( Condition 8 )(see Figure 9), and when the operation of the apparatus was continued without removing the solid catalyst ( Condition 9 ), the amounts of chlorine dioxide generated were compared. Furthermore, in Conditions 8 and 9, when the reactant was changed from potassium hydrogen carbonate to sulfuric acid ( Condition 10 , Condition 11 ), the same experiment was conducted and the amounts of chlorine dioxide generated were compared. [Table 11]

[0066] The measurement results are shown in FIGS. 10 and 11. As shown in FIG. 10, in the method of Condition 8, in conjunction with the removal of the solid catalyst, the generation of chlorine dioxide promptly stopped. On the other hand, as shown in FIG. 11, when sulfuric acid was used as the reactant, it was impossible to control the generation of chlorine dioxide by removing the solid catalyst.

[0067] [Experiment 4: Examination on the necessity of stirring] An experiment was conducted to confirm the necessity of bubbling (stirring) the reaction solution in the method of Condition 1. The experiment was carried out under the same conditions as Condition 1 except that bubbling of the reaction solution was not performed, and the concentration of chlorine dioxide in the air discharged from the gas discharge pipe 2' to the outside of the apparatus was measured ( Condition 12 )(see FIG. 12).

Table 12

[0068] The measurement results are shown in FIG. 13. As shown in FIG. 13, when bubbling of the reaction solution was not performed, almost no generation of chlorine dioxide was observed.

Explanation of symbols

[0069] 1, 11: Air introduction device 2, 12: Gas supply pipe 2’: Gas discharge pipe 3, 17: Reaction vessel 4, 18: Reaction solution 5, 19: Reactant 6, 15: Catalyst 13: Stepping motor 14: Wire 16: Apparatus main body

Claims

1. A chlorine dioxide generator comprising a reaction vessel, a reaction start / stop mechanism, a solid catalyst, and a solution stirring mechanism, wherein the reaction vessel contains a reaction solution during the chlorine dioxide generation reaction, the reaction solution contains a chlorite and a hydrogen carbonate or a hydrogen phosphate, the solid catalyst does not dissolve in the reaction solution, the reaction start / stop mechanism is designed to start the chlorine dioxide generation reaction by bringing the solid catalyst into contact with the reaction solution, and to stop the chlorine dioxide generation reaction by separating the solid catalyst from the reaction solution, and the solution stirring mechanism is designed to stir the reaction solution during the chlorine dioxide generation reaction. Device.

2. The device according to claim 1, wherein the hydrogen carbonate is sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate, or ammonium hydrogen carbonate, and the hydrogen phosphate is disodium hydrogen phosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate, or diammonium hydrogen phosphate. Device.

3. The device according to claim 1, wherein the concentration of the hydrogen carbonate or the hydrogen phosphate in the reaction solution is 0.1 to 63% by weight. Device.

4. The device according to claim 1, wherein the chlorite is an alkali metal chlorite or an alkaline earth metal chlorite. Device.

5. The device according to claim 4, wherein the alkali metal chlorite is sodium chlorite, potassium chlorite, or lithium chlorite, and the alkaline earth metal chlorite is calcium chlorite, magnesium chlorite, or barium chlorite. Device.

6. The chlorine dioxide generator according to claim 1, wherein the concentration of the chlorite in the reaction solution is 0.01 to 45% by weight. Device.

7. The device according to claim 1, wherein the solid catalyst is a metal-based catalyst, a mineral-based catalyst, a carbon-based catalyst, or a combination thereof. Device.

8. The device according to claim 7, wherein the metal-based 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 compounds of these metals. The mineral-based catalyst is a catalyst containing silicon (Si) or a compound containing silicon, The carbon-based catalyst is a catalyst containing activated carbon, is, Device.

9. The device according to claim 7 or 8, wherein the solid catalyst is supported on a carrier, Device.

10. The device according to claim 9, wherein the carrier is a carrier containing a material selected from the group consisting of titanium, valve metal, stainless steel, nickel, ceramics, carbon, and porous substances, Device.

11. The device according to claim 1, wherein the solution stirring mechanism is a bubbling stirring mechanism, a stirrer stirring mechanism, a stirring blade stirring mechanism, or a shaking stirring mechanism, Device.

12. The device according to claim 1, wherein the reaction vessel is at least partially open, and air containing chlorine dioxide generated in the reaction vessel is configured to be discharged to the outside of the device, Device.

13. A method for generating chlorine dioxide, continuously or periodically stirring a reaction solution containing chlorite and bicarbonate or hydrogen phosphate in the presence of a solid catalyst, comprising, wherein the solid catalyst does not dissolve in the reaction solution, Method.

14. The method according to claim 13, wherein the bicarbonate is sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, or ammonium bicarbonate, wherein the hydrogen phosphate is disodium hydrogen phosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate, or diammonium hydrogen phosphate, Method.

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