KR102720554B1 - Chlorine dioxide generator - Google Patents

Abstract

The present invention aims to provide a device capable of generating chlorine dioxide stably for a long period of time with a simpler configuration than conventional chlorine dioxide generating devices. As a means of solving this problem, a novel chlorine dioxide generating device utilizing a reaction between an aqueous chlorite solution and a catalyst is provided.

Description

Chlorine dioxide generator

The present invention relates to a novel chlorine dioxide generating device.

Chlorine dioxide gas is known to be safe for animal life at low concentrations (e.g., 0.1 ppm or less), but even at such low concentrations, it has an inactivating effect on microorganisms such as bacteria, fungi, and viruses, and a deodorizing effect.

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

In addition, a device that generates chlorine dioxide by irradiating solid chlorite with visible light has been recently proposed (Patent Document 3).

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

The present invention aims to provide a device capable of generating chlorine dioxide stably for a long period of time with a simpler configuration compared to conventional chlorine dioxide generating devices.

As a result of repeated research, the inventors succeeded in developing a novel chlorine dioxide generating device utilizing a chlorine dioxide generating mechanism by reaction between an aqueous chlorite solution and a catalyst, and completed the present invention.

That is, the present invention, in one embodiment, is a chlorine dioxide generating device equipped with a bubbling mechanism,

The above device comprises a reaction vessel and an air introduction device,

The above reaction vessel contains a chlorite aqueous solution and a catalyst,

The above reaction vessel and the air introduction device are connected by a conduit,

When the above air introduction device is operated, air is bubbled into the chlorite aqueous solution in the reaction vessel,

The bubbling air is configured to contact the catalyst,

It is characterized in that the concentration of chlorine dioxide contained in air emitted from the device at a time when the device is operated continuously for two weeks is maintained at at least 50% higher than the concentration of chlorine dioxide contained in air emitted from the device at a time when the device is operated continuously for one week.

In one embodiment of the present invention, the reaction vessel is characterized in that it is at least partially open and is configured such that air containing chlorine dioxide generated within the reaction vessel is discharged to the outside of the device.

In one embodiment of the present invention, it is characterized in that it does not include an electrolytic device.

In one embodiment of the present invention, the chlorite aqueous solution is characterized in that it is an aqueous solution of an alkali metal chlorite salt or an aqueous solution of an alkaline earth metal chlorite salt.

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

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

In one embodiment of the present invention, the catalyst is characterized in that it is a solid catalyst.

In one embodiment of the present invention, the catalyst is characterized in that it is a metal-based catalyst, a mineral-based catalyst, a carbon-based catalyst, or a combination thereof.

In one embodiment of the present invention, the metal catalyst is a catalyst including 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, the mineral catalyst is a catalyst including silica (Si) or a compound including silica, and the carbon catalyst is a catalyst including activated carbon.

In one embodiment of the present invention, the catalyst is characterized in that it is supported on a carrier.

In one embodiment of the present invention, the carrier is characterized in that it is a carrier comprising 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 characterized in that it is a device that introduces air into the path from a starting point of the path of the chlorine dioxide generator or a device that sucks air within the path from a ending point of the path of the chlorine dioxide generator.

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

An invention that arbitrarily combines one or more of the features of the present invention mentioned above is also included in the scope of the present invention.

The present invention has at least one of the following advantages over conventional chlorine dioxide generating methods/generating devices.

(1) Improvement of safety and durability

The present invention utilizes the generation of chlorine dioxide by the reaction of chlorite and a catalyst. In this method, there is almost no risk of generating a large amount of chlorine dioxide by a rapid reaction, and it has been confirmed that no harmful gases other than chlorine dioxide gas are generated, so it is highly safe compared to a method of generating chlorine dioxide by adding an acidic substance to chlorite or a method using electrolysis (for example, in generating chlorine dioxide by electrolysis, chlorine gas or hydrogen gas, etc. may be generated when the electrolyte deteriorates). In addition, since the device power of the present invention is only an air introduction device, the risk of device failure is low, and also, when the device fails, repair is easy.

(2) Maintenance free

The present invention, despite its simple structure, can stably generate chlorine dioxide without maintenance for at least two weeks (preferably three weeks or more, more preferably one month or more). In addition, when the chlorite aqueous solution has reached its lifespan, the operation of the device can be continued simply by replacing the chlorite aqueous solution.

(3) Miniaturization, cost reduction

Since the present invention has an extremely simple structure compared to, for example, a device for generating chlorine dioxide by electrolysis, it is possible to miniaturize the device and reduce its cost.

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 gas).
Figure 4 shows the results of Experiment 3.

A form for implementing the present invention will be described using the design example shown in Fig. 1.

Design example

A chlorine dioxide generating device according to one embodiment of the present invention illustrated in Fig. 1 comprises an air introduction device (1) and a reaction vessel (3), and the reaction vessel (3) contains a chlorite aqueous solution (4) and a catalyst (5). The air introduction device (1) and the reaction vessel (3) are connected by a conduit (2).

In the reaction vessel (3), chlorine dioxide is generated by the reaction of the chlorite aqueous solution (4) and the catalyst (5). When the air introduction device (1) operates, air supplied through the conduit (2) bubbles into the reaction vessel (3) to stir the chlorite aqueous solution (4) and the catalyst (5). When the chlorite aqueous solution (4) and the catalyst (5) are stirred by the bubbling, chlorine dioxide generated on the surface of the catalyst (5) is liberated from the catalyst surface, and chlorine dioxide is generated again on the surface of the catalyst (5). The chlorine dioxide liberated by the bubbling is discharged out of the device together with air from the conduit (2') provided at the upper portion of the reaction vessel (3).

That is, the chlorine dioxide generating device of the present invention illustrated in Fig. 1 is equipped with a bubbling mechanism centered on an air introduction device (1), thereby promoting the reaction between the chlorite aqueous solution (4) and the catalyst (5) and releasing the generated chlorine dioxide outside the device.

In the above, the contents of the present invention have been described with reference to design examples, but the present invention can be implemented in various ways and should not 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 variously changing the arrangement of containers or conduits constituting the device.

As the chlorite used in the present invention, examples thereof include alkali metal chlorite and alkaline earth metal chlorite. Examples thereof include sodium chlorite, potassium chlorite and lithium chlorite, and examples thereof include calcium chlorite, magnesium chlorite and barium chlorite. Among these, sodium chlorite and potassium chlorite are preferable because they are easy to obtain, and sodium chlorite is most preferable. These alkali chlorites may be used alone, or two or more may be used in combination. The proportion of alkali chlorite in the chlorite aqueous solution is preferably 0.01 wt% to 45 wt%. If it is less than 0.01 wt%, there is a possibility that the chlorite required for generating chlorine dioxide will be depleted in a short period of time, and if it exceeds 45 wt%, there is a possibility that the problem of chlorite becoming saturated and easily precipitating crystals may occur. Considering safety, stability, and chlorine dioxide generation efficiency, a preferable range is 0.1 wt% to 25 wt%, a more preferable range is 1 wt% to 20 wt%, and an even more preferable range is 2 to 15%.

The catalyst used in the device of the present invention is not limited as long as it is a catalyst that reacts with an aqueous chlorite solution to generate chlorine dioxide. However, since it is necessary to be separated from the aqueous chlorite solution when the reaction is stopped, it is preferably a solid catalyst (or a heterogeneous catalyst). Examples of the solid catalyst that can be used in the device of the present invention include a metal catalyst (for example, 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), a mineral catalyst (for example, silica (Si) or a compound containing silica), and a carbon catalyst (for example, a catalyst containing activated carbon).

The catalyst used in the device of the present invention may be used alone, but may be supported on a carrier in order to improve the reaction efficiency between the chlorite aqueous 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, but is preferably a carrier containing a material selected from the group consisting of, for example, titanium, valve metal, stainless steel, nickel, ceramics, carbon, and porous materials.

The air introduction device used in the device of the present invention is not limited to any device capable of moving air or a chlorite solution in the device's path in one direction, but may be, for example, an electric air pump. Electricity may be supplied to the electric air pump from a power supply device via a power cable, or may be supplied using a battery.

The air introduction device used in the device of the present invention can be installed at various locations as long as it can move the air or chlorite solution in the flow path of the device in one direction. For example, the air introduction device may be installed at the start of the flow path and introduce air into the flow path, the air introduction device may be installed in the middle of the flow path and move the air in the flow path in one direction, or the air introduction device may be installed at the end of the flow path and move the air or chlorite solution in the flow path of the device in one direction by sucking the air in the flow path.

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

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 including the blower fan, chlorine dioxide gas generated inside the device can be efficiently discharged to the outside of the device, and furthermore, the amount of chlorine dioxide gas discharged to the outside of the device can be controlled by controlling the air volume of the fan. For example, when the amount of chlorine dioxide gas generated is relatively large, the air volume of the blower fan is strengthened so that chlorine dioxide gas outside the device is dispersed further, and when the amount of chlorine dioxide gas generated is relatively small, the air volume of the blower fan is weakened so that chlorine dioxide gas outside the device is prevented from dispersing excessively, thereby allowing the concentration of chlorine dioxide gas outside the device to converge within a certain range.

The terms used herein are used to describe particular embodiments and are not intended to limit the invention.

Furthermore, the term "comprises" as used herein, unless the context clearly requires otherwise, is intended to imply the presence of the stated matter (such as an element, step, element, or number), and does not exclude the presence of other matters (such as an element, step, element, or number).

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

Embodiments of the present invention are sometimes described with reference to schematic diagrams; however, in the case of schematic diagrams, they may be expressed exaggeratedly in order to clarify the explanation.

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

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

Any references cited in this specification are to be considered as incorporated herein in their entirety, and a person skilled in the art will understand that the relevant disclosures in their prior art documents are incorporated into this specification as part of the spirit and scope of the present invention, in the context of this specification, without departing from the spirit and scope of the present invention.

Example

To confirm the effectiveness of the present invention, the following experiment was conducted.

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

Using the device shown in Fig. 1, a chlorine dioxide generation experiment was conducted. As a catalyst, a platinum-based catalyst supported on titanium (carrier) was used, and as the chlorite aqueous solution, 1 L of a 1% sodium chlorite aqueous solution was used. Using an air introduction device (1), air was bubbled into a reaction vessel (3) containing the chlorite aqueous solution (4) and the catalyst (5) at a flow rate of about 1 L/min. Meanwhile, as a control, the device was operated under the same conditions as above, except that no catalyst was used.

A comparison of the amount of chlorine dioxide generated under two conditions is shown in Fig. 2. As shown in Fig. 2, chlorine dioxide was generated under the condition using a catalyst, but chlorine dioxide was not generated under the condition not using a catalyst. In other words, it was confirmed that a catalyst is necessary to generate chlorine dioxide in the device of the present invention.

[Experiment 2. Qualitative analysis of generated gas]

The gas generated in the method of Experiment 1 was collected, and its components were qualitatively analyzed by ion chromatography. The results are shown in Fig. 3. As shown in Fig. 3, the gas component generated by the reaction between 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. 4. 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 stably generate chlorine dioxide for a long period of time despite having an extremely simple structure compared to conventional chlorine dioxide generating devices.

Claims (13)

A chlorine dioxide generating device equipped with a bubbling device,
The above device comprises a reaction vessel and an air introduction device,
The above reaction vessel contains a chlorite aqueous solution and a platinum-based catalyst,
The above reaction vessel and the air introduction device are connected by a conduit,
When the above air introduction device is operated, air is bubbled into the chlorite aqueous solution in the reaction vessel, and the bubbled air is configured to contact the catalyst.
A device characterized in that the concentration of chlorine dioxide contained in air emitted from the device at a time when the device is operated continuously for two weeks is maintained at at least 50% higher than the concentration of chlorine dioxide contained in air emitted from the device at a time when the device is operated continuously for one week. In the first paragraph,
A device characterized in that the reaction vessel is at least partially open and is configured such that air containing chlorine dioxide generated within the reaction vessel is discharged to the outside of the device. In the first paragraph,
A device characterized by not including an electrolytic device. In the first paragraph,
A device characterized in that the above chlorite aqueous solution is an alkali metal chlorite aqueous solution or an alkaline earth metal chlorite aqueous solution. In paragraph 4,
The above chlorite alkali metal salt aqueous solution is a sodium chlorite aqueous solution, a potassium chlorite aqueous solution or a lithium chlorite aqueous solution,
A device characterized in that the chlorite alkaline earth metal salt aqueous solution is a calcium chlorite aqueous solution, a magnesium chlorite aqueous solution or a barium chlorite aqueous solution. In the first paragraph,
A device characterized in that the concentration of the above chlorite aqueous solution is 0.01 to 45 wt%. In the first paragraph,
A device characterized in that the catalyst is a solid catalyst. In the first paragraph,
A device characterized in that the above catalyst is supported on a carrier. In Article 8,
A device characterized in that the carrier is a carrier comprising a material selected from the group consisting of titanium, valve metal, stainless steel, nickel, ceramics, carbon, and porous materials. In the first paragraph,
A device characterized in that the air introduction device is a device that introduces air into the path from the starting point of the path of the chlorine dioxide generator or a device that sucks air within the path from the ending point of the path of the chlorine dioxide generator. In Article 10,
A device characterized in that the air introduction device is an electric air pump. delete delete