JP7401103B2 - Chlorine dioxide generator - Google Patents

Description

The present invention relates to a novel chlorine dioxide generator.

While chlorine dioxide gas is safe for animal living bodies at low concentrations (for example, 0.1 ppm or less), even at such low concentrations it has a deactivating effect on microorganisms such as bacteria, fungi, and viruses. It is known to have deodorizing effects.

Examples of methods for generating chlorine dioxide include a method for stably generating chlorine dioxide using a composition containing dissolved chlorine dioxide gas, an aqueous chlorite solution, and a pH adjuster (Patent Document 1), A method of producing chlorine dioxide by electrolyzing an electrolytic solution containing an acid salt is known (Patent Document 2).

Additionally, in recent years, a device has been proposed that generates chlorine dioxide by irradiating solid chlorite with visible light (Patent Document 3).

WO/2008/111357 WO/2009/154143 WO/2015/098732

An object of the present invention is to provide an apparatus that can stably generate chlorine dioxide for a long period of time with a simpler configuration than conventional chlorine dioxide generating apparatuses.

As a result of extensive research, the present inventors succeeded in developing a new chlorine dioxide generation device that utilizes the chlorine dioxide generation mechanism through the reaction between a chlorite aqueous solution and a catalyst, and completed the present invention. It has arrived.

That is, one embodiment of the present invention is a chlorine dioxide generator equipped with a bubbling mechanism,
The apparatus includes a reaction container and an air introduction device,
The reaction container contains an aqueous chlorite solution and a catalyst,
The reaction container and the air introduction device are connected by a conduit,
When the air introduction device is operated, air is bubbled into the chlorite aqueous solution in the reaction container, and the bubbled air is configured to come into contact with the catalyst,
The concentration of chlorine dioxide contained in the air released from the device when the device is operated continuously for two weeks is the same as the concentration of chlorine dioxide contained in the air released from the device when the device is continuously operated for one week. The chlorine dioxide concentration is maintained at least 50% compared to the chlorine dioxide concentration.

In one embodiment of the invention, the reaction vessel is at least partially open and configured such that air containing chlorine dioxide produced within the reaction vessel is discharged to the outside of the apparatus. It is characterized by being

One embodiment of the present invention is characterized in that it does not include an electrolysis mechanism.

One embodiment of the present invention is characterized in that the aqueous chlorite solution is an aqueous alkali metal chlorite solution or an aqueous alkaline earth metal chlorite solution.

In one embodiment of the present invention, the aqueous alkali metal chlorite solution is an aqueous sodium chlorite solution, an aqueous potassium chlorite solution, or an aqueous lithium chlorite solution, and the aqueous alkaline earth metal chlorite solution is characterized in that it is a calcium chlorite aqueous solution, a magnesium chlorite aqueous solution, or a barium chlorite aqueous solution.

One embodiment of the present invention is characterized in that the concentration of the chlorite aqueous solution is 0.01 to 45% by weight.

One embodiment of the present invention is characterized in that the catalyst is a solid catalyst.

One embodiment of the present invention is characterized in that the catalyst is a metal catalyst, a mineral catalyst, a carbon catalyst, or a combination thereof.

In one embodiment of the present invention, the metal catalyst is platinum (Pt), ruthenium (Rh), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), or a compound of these metals, and the mineral catalyst contains silica (Si) or , a compound containing silica, and the carbon-based catalyst is a catalyst containing activated carbon,
It is characterized by

One embodiment of the present invention is characterized in that the catalyst is supported on a carrier.

One embodiment of the present invention is characterized in that the carrier includes a material selected from the group consisting of titanium, valve metal, stainless steel, nickel, ceramics, carbon, and porous materials.

In one embodiment of the present invention, the air introduction device is a device that introduces air into the flow path from a starting point of the flow path of the chlorine dioxide generation device, or from an end point of the flow path of the chlorine dioxide generation device. The present invention is characterized in that it is a device that sucks air in the flow path.

One embodiment of the present invention is characterized in that the air introduction device is an electric air pump.

Inventions in which one or more features of the invention listed above are arbitrarily combined are also included within the scope of the invention.

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

(1) Improved safety and durability The present invention utilizes the generation of chlorine dioxide through the reaction between chlorite and a catalyst. In this method,
There is almost no risk of generating a large amount of chlorine dioxide due to a rapid reaction, and it has been confirmed that no harmful gas other than chlorine dioxide gas is generated, so chlorine dioxide can be generated by adding an acidic substance to chlorite. It is safer than a method that generates chlorine dioxide or a method that uses electrolysis (for example, in the generation of chlorine dioxide by electrolysis, chlorine gas, hydrogen gas, etc. can be generated when the electrolyte deteriorates). Further, since the device of the present invention is powered only by the air introduction device, the risk of device failure is low, and repair is easy if the device breaks down.

(2) Maintenance-free Despite the simple structure, the present invention can stably generate chlorine dioxide without maintenance for at least two weeks or more (preferably three weeks or more, more preferably one month or more). I can do it. Further, when the chlorite aqueous solution reaches the end of its service life, the device can continue operating simply by replacing the chlorite aqueous solution.

(3) Downsizing and cost reduction The present invention has an extremely simple structure compared to, for example, a chlorine dioxide generating device using electrolysis, so it is possible to downsize the device and reduce costs.

FIG. 1 shows an example design of the present invention. FIG. 2 shows the results of Experiment 1 (amount of chlorine dioxide generated). FIG. 3 shows the results of Experiment 2 (qualitative analysis of generated gas). FIG. 4 shows the results of Experiment 3.

A mode for carrying out the present invention will be described using a design example shown in FIG.

Design Example A chlorine dioxide generating apparatus according to an embodiment of the present invention shown in FIG. The air introduction device 1 and the reaction container 3 are connected by a conduit 2.

In the reaction vessel 3, chlorine dioxide is produced by the reaction between the chlorite aqueous solution 4 and the catalyst 5. When the air introduction device 1 is activated, air provided via the conduit 2 is bubbled into the reaction vessel 3 and stirs the aqueous chlorite solution 4 and the catalyst 5. When the chlorite aqueous solution 4 and the catalyst 5 are stirred by bubbling, chlorine dioxide generated on the surface of the catalyst 5 is liberated from the catalyst surface, and chlorine dioxide is generated on the surface of the catalyst 5 again. Chlorine dioxide liberated by bubbling is discharged from the conduit 2' provided at the top of the reaction vessel 3 to the outside of the apparatus together with air.

That is, the chlorine dioxide generator of the present invention shown in FIG. Chlorine dioxide can be released outside the device.

Although the content of the present invention has been described above with reference to design examples, the present invention can be embodied in various aspects and should not be construed as being limited to the design examples described herein. . For example, in one embodiment of the invention, the size and shape of the device can be optimized by varying the arrangement of the containers and conduits that make up the device.

Examples of the chlorite used in the present invention include alkali metal chlorite and alkaline earth metal chlorite. 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 chlorite. Examples include barium chlorate. Among these, sodium chlorite and potassium chlorite are preferred, and sodium chlorite is most preferred, because they are easily available. These chlorite oxygen alkalis may be used alone or in combination of two or more. The proportion of alkali chlorite in the aqueous chlorite solution is preferably 0.01% to 45% by weight. If it is less than 0.01% by weight, the chlorite needed to generate chlorine dioxide may be exhausted in a short period of time, and if it exceeds 45% by weight, the chlorite will become saturated and crystals will form. There is a possibility that the problem of easy precipitation may occur. In view of safety, stability, chlorine dioxide generation efficiency, etc., the preferred range is 0.1% to 25% by weight, the more preferred range is 1% to 20% by weight, and the most preferred range is is 2-15%.

The catalyst used in the apparatus of the present invention is not limited as long as it reacts with an aqueous chlorite solution to generate chlorine dioxide, but since it needs to be separated from the aqueous chlorite solution when the reaction is stopped, it is A catalyst (or a heterogeneous catalyst) is preferred. Examples of solid catalysts that can be used in the apparatus of the present invention include metal catalysts (e.g., platinum (Pt), ruthenium (Rh), 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 catalysts (for example, silica (Si), or , a compound containing silica), and a carbon-based catalyst (for example, a catalyst containing activated carbon).

The catalyst used in the apparatus of the present invention may be used alone, or may be supported on a carrier in order to improve the reaction efficiency between the aqueous chlorite solution and the catalyst. 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, and examples thereof include titanium, valve metal, stainless steel, nickel, ceramics, carbon, and porous materials. Preferably, the carrier comprises a material selected from the group consisting of:

The air introduction device 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, but for example, it may be an electric air pump. good. Electricity may be supplied to the electric air pump from a power supply device via a power cable, or by using a battery.

The air introduction device used in the device of the present invention can be installed in various locations as long as the air or aqueous chlorite solution in the flow path of the device can be moved in one direction. For example, an air introduction device may be installed at the starting point of the flow path to introduce air into the flow path, or an air introduction device may be installed in the middle of the flow path to move the air in the flow path in one direction. Alternatively, the air or chlorite aqueous solution in the flow path of the device may be moved in one direction by installing an air introduction device at the end of the flow path and sucking the air in the flow path. good.

In the apparatus of the present invention, the gas introduced into the flow path within the apparatus by the air introduction device is typically air, but an inert gas such as nitrogen or argon may also be used.

The chlorine dioxide generating device of the present invention may further include a blower fan for discharging chlorine dioxide gas generated in the device to the outside of the device. By providing a blower fan, the chlorine dioxide gas generated inside the equipment can be efficiently sent out of the equipment, and by adjusting the air volume of the fan, the amount of chlorine dioxide gas sent outside the equipment can be adjusted. You can also. For example, if the amount of chlorine dioxide gas generated is relatively large, increase the air volume of the blower fan to diffuse the chlorine dioxide gas outside the device further; if the amount of chlorine dioxide gas generated is relatively small, By reducing the air volume of the blower fan to prevent the chlorine dioxide gas outside the device from being diffused more than necessary, the concentration of chlorine dioxide gas outside the device can be adjusted to fall within a certain range.

The terminology used herein is used to describe particular embodiments and is not intended to limit the invention.

Furthermore, the term "comprising" as used herein means that the described matter (member, step, element, number, etc.) is present, unless the context clearly requires a different understanding. It does not exclude the existence of other items (members, steps, elements, numbers, etc.).

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. Terms used herein, unless explicitly defined differently, should be construed to have meanings consistent with their meanings in this specification and in the relevant technical field, and should not be interpreted as idealized or overly formalized. should not be construed in that sense.

Embodiments of the invention may be described with reference to schematic drawings, which may be exaggerated for clarity of explanation.

In this specification, for example, when expressed as "1 to 10 w/w%", a person skilled in the art would understand that the expression is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10w%. Understand that /w% refers specifically to each individual.

In this specification, all numerical values used to indicate component contents or numerical ranges are to be interpreted as including the meaning of the term "about" unless otherwise specified. For example, "10 times" is understood to mean "about 10 times" unless specified otherwise.

The documents cited herein are to be considered in their entirety to be incorporated herein by reference, and those skilled in the art will be able to understand the spirit of the invention according to the context of this specification. and the relevant disclosures in those prior art documents are hereby incorporated and understood without departing from the scope thereof.

In order to confirm the effects of the present invention, the following experiment was conducted.

[Experiment 1. Reaction between catalyst and chlorite aqueous solution]
A chlorine dioxide generation experiment was conducted using the apparatus shown in FIG. The catalyst used was a platinum-based catalyst supported on titanium (carrier), and the chlorite aqueous solution used was 1 L of a 1% sodium chlorite aqueous solution. Using the air introduction device 1, air was bubbled into the reaction container 3 containing the chlorite aqueous solution 4 and the catalyst 5 at a flow rate of about 1 L/min. On the other hand, as a control, the apparatus was operated under the same conditions as above except that no catalyst was used.

Figure 2 shows a comparison of the amount of chlorine dioxide generated under both conditions. As shown in FIG. 2, chlorine dioxide was generated under the conditions where a catalyst was used, but no chlorine dioxide was generated under conditions where no catalyst was used. That is, it was confirmed that a catalyst is required in order to generate chlorine dioxide in the apparatus of the present invention.

[Experiment 2. Qualitative analysis of generated gas]
The gas generated by the method of Experiment 1 was collected, and its components were qualitatively analyzed by ion chromatography. The results are shown in FIG. As shown in FIG. 3, the gas component generated by the reaction between the chlorite and the catalyst was substantially only chlorine dioxide.

[Experiment 3. Verification of long-term operability]
Using the device used in Experiment 1 (the device shown in FIG. 1), a long-term device operation test was conducted. The results are shown in FIG. As shown in FIG. 4, the device of the present invention was able to stably generate chlorine dioxide for about one month.

As described above, the present invention can generate chlorine dioxide stably for a long period of time despite the extremely simple structure compared to conventional chlorine dioxide generators.

Claims (11)

A chlorine dioxide generator equipped with a bubbling mechanism,
The apparatus includes a reaction container and an air introduction device,
The reaction vessel contains an aqueous chlorite solution and a platinum-based catalyst;
The reaction container and the air introduction device are connected by a conduit,
When the air introduction device is operated, air is bubbled into the chlorite aqueous solution in the reaction container, and the bubbled air is configured to come into contact with the catalyst,
The concentration of chlorine dioxide contained in the air released from the device when the device is operated continuously for two weeks is the same as the concentration of chlorine dioxide contained in the air released from the device when the device is continuously operated for one week. The chlorine dioxide concentration is maintained at least 50% or more compared to the chlorine dioxide concentration.
Device. The chlorine dioxide generator according to claim 1,
The reaction vessel is at least partially open and configured such that the air containing chlorine dioxide produced in the reaction vessel is discharged to the outside of the apparatus.
Device. The chlorine dioxide generator according to claim 1,
Characterized by not including an electrolysis mechanism,
Device. The chlorine dioxide generator according to claim 1,
The chlorite aqueous solution is an alkali metal chlorite aqueous solution or an alkaline earth metal chlorite aqueous solution,
Device. The chlorine dioxide generator according to claim 4,
The alkali metal chlorite 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,
characterized by
Device. The chlorine dioxide generator according to claim 1,
characterized in that the concentration of the chlorite aqueous solution is 0.01 to 45% by weight,
Device. The chlorine dioxide generator according to claim 1,
The catalyst is a solid catalyst,
Device. The chlorine dioxide generator according to claim 1,
The catalyst is supported on a carrier,
Device. The chlorine dioxide generator according to claim 8 ,
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,
Device. The chlorine dioxide generator according to claim 1,
The air introduction device is a device that introduces air into the flow path from a starting point of the flow path of the chlorine dioxide generator, or sucks air in the flow path from an end point of the flow path of the chlorine dioxide generator. a device, characterized in that
Device. The chlorine dioxide generator according to claim 10 ,
The air introduction device is an electric air pump,
Device.