TWI813799B - Chlorine dioxide generation apparatus - Google Patents

Abstract

An objective of this invention is to provide an apparatus capable of long-time stably generating chlorine dioxide by easier construction in comparing with the prior chlorine dioxide generation apparatus.

Provided is a novel chlorine dioxide generation apparatus by using the reaction of chlorite aqueous solution with catalyst.

Description

Chlorine dioxide generating device

The present invention relates to novel chlorine dioxide generating apparatus.

Chlorine dioxide is known to be a safe gas for living animals at low concentrations (for example, 0.1 ppm or less). On the other hand, even at such low concentrations, it still has a deactivating effect on microorganisms such as bacteria, fungi, and viruses. , deodorizing effect, etc.

Methods for generating chlorine dioxide are known. For example, a method for stably generating chlorine dioxide from a composition containing dissolved chlorine dioxide gas, a chlorite aqueous solution, and a pH adjuster is known (Patent Document 1); A method for producing chlorine dioxide by electrolyzing an electrolytic solution containing chlorite (Patent Document 2).

In addition, in recent years, a device for generating chlorine dioxide by irradiating solid chlorite with visible light has also been proposed (Patent Document 3).

[Prior technical literature]

[Patent Document]

[Patent Document 1] WO/2008/111357

[Patent Document 2] WO/2009/154143

[Patent Document 3] WO/2015/098732

An object of the present invention is to provide a device that can stably generate chlorine dioxide over a long period of time with a simpler structure than conventional chlorine dioxide generating devices.

As a result of intensive research, the inventors of this case successfully developed a novel chlorine dioxide generating device using a mechanism that generates chlorine dioxide through the reaction of a chlorite aqueous solution and a catalyst, thereby completing the present invention.

That is, one embodiment of the present invention is a chlorine dioxide generating device equipped with a bubbling mechanism, wherein the chlorine dioxide generating device includes a reaction container and an air introduction device, and the reaction container includes a chlorine dioxide generating device. The chlorate aqueous solution and the catalyst, the reaction container and the air introduction device are connected by a conduit, and the chlorine dioxide generation device is configured such that when the air introduction device is operating, air is bubbled into the reaction container In the chlorite aqueous solution, the bubbled air will come into contact with the aforementioned catalyst, causing the aforementioned chlorine dioxide generating device to continue operating for 2 weeks. The chlorine dioxide concentration contained in the chlorine dioxide generating device is at least capable of being maintained compared with the chlorine dioxide concentration contained in the air released from the chlorine dioxide generating device at a time point after the chlorine dioxide generating device is continuously operated for one week. above 50.

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 chlorine dioxide generating device.

In one embodiment of the present invention, the chlorine dioxide generating device does not include an electrolysis mechanism.

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.

In one embodiment of the present invention, the alkali metal chlorite aqueous solution is a sodium chlorite aqueous solution, a potassium chlorite aqueous solution or a lithium chlorite aqueous solution, and the alkaline earth metal chlorite aqueous solution is a calcium chlorite aqueous solution, a chlorite aqueous solution, or a chlorite aqueous solution. Magnesium acid aqueous solution or barium chlorite aqueous solution.

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

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

In one embodiment of the present invention, 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 includes platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), osmium (Os), iron (Fe), Catalysts of copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), or compounds of these metals, the aforementioned mineral-based catalysts containing silicon (Si) or As a catalyst of a silicon compound, the carbon-based catalyst is a catalyst containing activated carbon.

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

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 substances.

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

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

The scope of the present invention also includes an invention in which one or a plurality of the features of the present invention listed above are arbitrarily combined.

Compared with conventional chlorine dioxide generation methods/generation devices, the present invention has at least one or more advantages described below.

(1) Improvement of safety and durability

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

(2) Maintenance-free

Although the structure of the present invention is simple, it can still produce chlorine dioxide stably without maintenance for at least 2 weeks or more (preferably 3 weeks or more, more preferably 1 month or more). In addition, when the life of the chlorite aqueous solution expires, the device can continue to operate as long as the chlorite aqueous solution is replaced.

(3) Miniaturization and cost reduction

The present invention has an extremely simple structure compared to, for example, a chlorine dioxide generating device using electrolysis, so that the device can be miniaturized or the cost can be reduced.

1: Air introduction device

2. 2’: Conduit

3: Container for reaction

4: Chlorite aqueous solution

5:Catalyst

Figure 1 shows a design example of the present invention.

Figure 2 shows the results of Experiment 1 (the amount of chlorine dioxide produced).

Figure 3 shows the results of Experiment 2 (qualitative analysis of generated gases).

Figure 4 shows the results of Experiment 3.

The embodiment of the present invention will be explained using the design example shown in Fig. 1 .

Design example

A chlorine dioxide generator according to an embodiment of the present invention shown in FIG. 1 includes an air introduction device 1 and a reaction container 3 containing a chlorite aqueous solution 4 and a catalyst 5 . The air introduction device 1 and the reaction container 3 are connected by a duct 2 .

In the reaction container 3, chlorine dioxide is generated by the reaction between the chlorite aqueous solution 4 and the catalyst 5. When the air introduction device 1 is operated, the air supplied via the duct 2 is bubbled into the reaction container 3 to stir the chlorite aqueous solution 4 and the catalyst 5 . If the chlorite aqueous solution 4 and the catalyst 5 are stirred by bubbling, the chlorine dioxide generated on the surface of the catalyst 5 will be released from the catalyst surface, and chlorine dioxide will be generated again on the surface of the catalyst 5 . The chlorine dioxide freed by bubbling is released to the outside of the device together with air through the conduit 2' provided at the upper part of the reaction vessel 3.

That is, the chlorine dioxide generating device of the present invention shown in Figure 1 is provided with a bubbling mechanism centered on the air introduction device 1, which can accelerate the reaction between the chlorite aqueous solution 4 and the catalyst 5, and can also cause The generated chlorine dioxide is released outside the device.

In the above description, the content of the present invention is explained with reference to the design examples. However, the present invention can be embodied in various forms and is not to be construed as being limited to the design examples described here. For example, in one embodiment of the present invention, the size and shape of the device can be optimized by variously changing the arrangement of containers and tubes constituting the device.

Examples of the chlorite used in the present invention include alkali metal chlorite or alkaline earth metal chlorite. Examples of alkali metal chlorite salts include sodium chlorite, potassium chlorite, and lithium chlorite, and examples of alkaline earth metal chlorite salts include calcium chlorite, magnesium chlorite, and barium chlorite. Among them, in terms of ease of acquisition, sodium chlorite and potassium chlorite are preferred, and sodium chlorite is most preferred. One type of these chloroxybases may be used alone, or two or more types may be used in combination. The proportion of chlorite base in the aqueous chlorite solution is preferably 0.01% to 45% by weight. When it is less than 0.01% by weight, the chlorite necessary to generate chlorine dioxide may be exhausted in a short time. When it exceeds 45% by weight, there may be a problem that chlorite is saturated and easily precipitates. When considering safety and stability, chlorine dioxide production efficiency, 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 more preferred range is 2 to 15%

The catalyst used in the device of the present invention is not limited as long as it reacts with the chlorite aqueous solution to generate chlorine dioxide. However, it is preferably separated from the chlorite aqueous solution when the reaction is stopped. It is a solid catalyst (or heterogeneous catalyst). Examples of solid catalysts 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 these metals), mineral-based catalysts (such as silicon (Si) or silicon-containing compounds), carbon-based catalysts (such as catalysts containing activated carbon).

The catalyst used in the device of the present invention can be used alone, but in order to improve the reaction efficiency between the chlorite aqueous solution and the catalyst, a catalyst supported on a carrier can be used. The carrier carrying the catalyst is not limited as long as it helps improve the reaction efficiency between the chlorite aqueous solution and the catalyst, but is preferably selected from the group consisting of titanium, valve metal, stainless steel, nickel, and ceramics. The carrier of materials composed of , carbon and porous substances.

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 the chlorite aqueous solution in the flow path of the device in one direction. For example, it can be an electric air pump. The power supply to the electric air pump may be performed by a power supply device via a cable, or a battery may be used.

The air introduction device that can be used in the device of the present invention can be installed in various positions as long as it can move the air or the chlorite aqueous solution in the flow path of the device in one direction. For example: the air introduction device can be placed at the starting point of the flow path to introduce air into the flow path; the air introduction device can also be placed in the middle of the flow path to move the air in the flow path in one direction; or the air introduction device can be placed in the middle of the flow path to move the air in the flow path in one direction; The air introduction device is installed at the end of the flow path, and by sucking the air in the flow path, the air or chlorite aqueous solution in the flow path of the device moves in one direction.

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.

The chlorine dioxide generating device of the present invention may further include a blower fan for releasing chlorine dioxide gas generated in the device to the outside of the device. By having an air supply fan, the chlorine dioxide gas generated in the device can be efficiently sent out of the device. In addition, the air volume of the fan can also be adjusted. To adjust the amount of chlorine dioxide gas sent out of the device. For example: when the production of chlorine dioxide gas is large, the air volume of the air supply fan can be increased to make the chlorine dioxide gas outside the device diffuse farther; when the production of chlorine dioxide gas is small, the air volume of the air supply fan can be increased. Weaken the air volume of the air supply fan to prevent unnecessary diffusion of chlorine dioxide gas outside the device, and adjust the concentration of chlorine dioxide gas outside the device within a certain range.

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

In addition, the word "comprising" used in this specification is intended to indicate the existence of the described matters (components, steps, elements or numbers, etc.), except when it is obvious that it should be understood differently in the context of the article. The existence of matters (components, steps, elements, numbers, etc.) other than those described is excluded.

Unless otherwise defined, all terms (including technical terms and scientific terms) used herein have the same meanings as commonly understood by a person of ordinary skill in the technical field to which this invention belongs. The terms used here, unless a different definition is expressly stated, should be interpreted as having a meaning consistent with the meaning in this specification and related technical fields, and should not be interpreted as being idealized or overly formalized. meaning.

Embodiments of the present invention may be described with reference to schematic diagrams. However, in the case of schematic diagrams, they are presented exaggeratedly for clear explanation.

In this specification, for example, when expressed as "1 to 10 w/w%", those with ordinary knowledge in the relevant technical field can understand that this presentation specifically refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10w/w%.

In this specification, any numerical value used to express the content of an ingredient or a numerical range can be interpreted to include the meaning of the word "approximately" unless otherwise stated. For example, "10 times" can be understood to mean "about 10 times" unless otherwise stated.

Among the documents cited in this specification, all the disclosures should be deemed to be quoted in this specification. A person with ordinary knowledge in the relevant technical field shall not deviate from the spirit and scope of the present invention based on the context of this specification. In this case, it should be understood that the relevant disclosures in such prior technical documents are cited as part of this specification.

[Example]

In order to confirm the effect of the present invention, the following experiments were conducted.

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

Using the apparatus shown in Figure 1, conduct a chlorine dioxide production experiment. The catalyst is a catalyst in which platinum masterbatch is supported on titanium (carrier), and 1L of 1% sodium chlorite aqueous solution is used for the chlorite aqueous solution. The air introduction device 1 was used to bubble air 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, the control group operates the device under the same conditions as above except not using a catalyst.

A comparison of the amount of chlorine dioxide produced under the two conditions is shown in Figure 2. As shown in Figure 2, chlorine dioxide is generated under conditions where a catalyst is used, but no chlorine dioxide is generated under conditions where a catalyst is not used. That is, it was confirmed that in order to generate chlorine dioxide in the device of the present invention, a catalyst is necessary.

[Experiment 2. Qualitative analysis of generated gas]

The gas generated by the method of Experiment 1 was collected, and the components were qualitatively analyzed by ion chromatography. The results are shown in Figure 3. As shown in Figure 3, the gas component produced by the reaction of chlorite and catalyst is actually only chlorine dioxide.

[Experiment 3. Test of long-term operability]

Using the device used in Experiment 1 (the device shown in Figure 1), a long-term device operation test was performed. The test results are shown in Figure 4. As shown in Figure 4, the device of the present invention can stably produce chlorine dioxide for about one month.

As described above, although the structure is extremely simple compared with conventional chlorine dioxide generating devices, chlorine dioxide can be stably generated for a long time.

1: Air introduction device

2. 2’: Conduit

3: Container for reaction

4: Chlorite aqueous solution

5:Catalyst

Claims (12)

A chlorine dioxide generating device provided with a bubbling mechanism, wherein the chlorine dioxide generating device includes a reaction container and an air introduction device, the reaction container includes a chlorite aqueous solution and a catalyst, Here, the catalyst is a solid catalyst, the reaction container and the air introduction device are connected through a pipe, and the chlorine dioxide generating device is configured such that when the air introduction device is operating, air is bubbled into the reaction In the chlorite aqueous solution in the container, the bubbled air will contact the aforementioned catalyst, causing the aforementioned chlorine dioxide generating device to continue operating for 2 weeks. The air released from the aforementioned chlorine dioxide generating device will The chlorine dioxide concentration contained in the chlorine dioxide generating device is at least comparable to the chlorine dioxide concentration contained in the air released from the chlorine dioxide generating device at a time point after the chlorine dioxide generating device is continuously operated for one week. Maintain more than 50%. The chlorine dioxide generating device according to claim 1, wherein the reaction container is configured to be at least partially open, and the air containing chlorine dioxide generated in the reaction container flows toward the chlorine dioxide. External release of chlorine generating device. The chlorine dioxide generating device described in item 1 of the patent application, wherein the chlorine dioxide generating device does not include an electrolysis mechanism. The chlorine dioxide generating device described in claim 1, wherein the chlorite aqueous solution is an alkali metal chlorite aqueous solution or an alkaline earth metal chlorite aqueous solution. The chlorine dioxide generating device described in item 4 of the patent application, wherein, The aforementioned alkali metal chlorite aqueous solution is a sodium chlorite aqueous solution, a potassium chlorite aqueous solution or a lithium chlorite aqueous solution, and the alkaline earth metal chlorite aqueous solution is a calcium chlorite aqueous solution, a magnesium chlorite aqueous solution or chlorite. Barium acid aqueous solution. The chlorine dioxide generating device described in item 1 of the patent application, wherein the concentration of the aforesaid chlorite aqueous solution is 0.01 to 45% by weight. For example, the chlorine dioxide generating device described in item 1 of the patent application, wherein the aforementioned catalyst is a metal catalyst, a mineral catalyst, a carbon catalyst or a combination thereof. The chlorine dioxide generating device described in item 7 of the patent application, wherein the aforementioned metal catalyst includes platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), Catalysts of osmium (Os), iron (Fe), copper (Cu), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), or compounds of these metals, the aforementioned minerals are catalysts The media is a catalyst containing silicon (Si) or a silicon-containing compound, and the carbon-based catalyst is a catalyst containing activated carbon. The chlorine dioxide generating device described in claim 1 of the patent application, wherein the catalyst is carried on a carrier. The chlorine dioxide generating device of 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. The chlorine dioxide generating device of claim 1, wherein the air introduction device is a device that introduces air into the flow path from the starting point of the flow path of the chlorine dioxide generating device, or is a device that introduces air from the starting point of the flow path of the chlorine dioxide generating device, or is a device that introduces air from The end point of the flow path of the chlorine dioxide generating device is a device that sucks the air in the flow path. The chlorine dioxide generating device described in claim 11 of the patent application, wherein the air introduction device is an electric air pump.

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