TW202340080A - Chlorine dioxide generator - Google Patents

Abstract

The present invention aims to provide a chlorine dioxide generator of practical use that is formed by members different from those of conventional chlorine dioxide generators.

The chlorine dioxide generator provided by the present invention has an ozone generator, a gas introduction mechanism, and a reaction vessel.

Description

Chlorine dioxide generating device

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

It is known that the chlorine dioxide gas system is a safe gas for living animals at low concentrations (for example, below 0.1 ppm). On the other hand, at this low concentration, it also has the effect of inactivating microorganisms such as bacteria, fungi, viruses, etc. or deodorizing effect. wait.

Known methods for generating chlorine dioxide include, for example, a method of stably generating chlorine dioxide from a composition containing dissolved chlorine dioxide gas, a chlorite aqueous solution, and a pH adjuster (Patent Document 1); or electrolysis of a composition containing dissolved chlorine dioxide gas. A method for producing chlorine dioxide from an electrolyte of chlorite (Patent Document 2).

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

[Prior technical literature]

[Patent Document]

Patent document 1: WO2008/111357.

Patent document 2: WO2009/154143.

Patent document 3: WO20 15/098732.

An object of the present invention is to provide a practical chlorine dioxide generating device that is constructed differently from conventional chlorine dioxide generating devices.

One embodiment of the present invention relates to a chlorine dioxide generating device, which is provided with an ozone generator, a gas introduction mechanism, and a reaction container. The reaction container contains a chlorite-containing solution during the chlorine dioxide generation reaction. Medicine, the aforementioned device is to deliver the gas containing ozone generated by the aforementioned ozone generator to the aforementioned chlorite in the aforementioned reaction container through the aforementioned gas introduction mechanism, thereby making the aforementioned gas containing ozone and the aforementioned chlorite salt get in touch with.

In one embodiment of the present invention, the ozone generator is a discharge ozone generator, an electrolytic ozone generator, or a UV lamp ozone generator.

In one embodiment of the present invention, the agent containing chlorite in the reaction vessel is a agent containing a chlorite aqueous solution or a solid chlorite.

In one embodiment of the present invention, the chlorite-containing agent in the reaction container is a chlorite aqueous solution, and the device is configured to transfer the ozone-containing gas generated by the ozone generator through The aqueous chlorite solution is bubbled in the reaction container by the gas introduction mechanism.

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

In one embodiment of the present invention, the chlorite-containing agent in the reaction container is a solid chlorite-containing agent, and the device is configured to generate ozone-containing gas generated by the ozone generator. The gas introduction mechanism delivers the solid chlorite-containing agent to the inside of the reaction container, so that the ozone is brought into contact with the solid chlorite.

In one embodiment of the present invention, the agent containing solid chlorite is a agent containing a porous material carrying chlorite.

In one embodiment of the present invention, the porous material carrying chlorite is obtained by impregnating the porous material with a chlorite aqueous solution and further drying the porous material.

In one embodiment of the present invention, the porous material is selected from the group consisting of sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, perlite, and calcium silicate.

In one embodiment of the present invention, the pharmaceutical agent containing solid chlorite is a granular pharmaceutical agent.

In one embodiment of the present invention, a humidification mechanism for supplying moisture into the gas containing ozone generated by the ozone generator is further provided.

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

In one embodiment of the present invention, the alkali metal chlorite salt is sodium chlorite, potassium chlorite, or lithium chlorite, and the alkaline earth metal salt of chlorite is calcium chlorite, magnesium chlorite, or chlorite. Barium chlorate.

In one embodiment of the present invention, the chlorine dioxide generating device further includes the control mechanism of the ozone generator.

In one embodiment of the present invention, the control mechanism of the ozone generator controls the start/stop of the ozone generator according to a predetermined program, thereby controlling the chlorine dioxide production amount of the chlorine dioxide generating device.

Inventions that arbitrarily combine one or more of the features of the invention cited above are also included in the scope of the invention.

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

(1)Safety

The device of the present invention utilizes a device that generates chlorine dioxide by reacting ozone generated by an ozone generator with chlorite. In this device, the generation of chlorine dioxide can be easily controlled by turning the ozone generator on/off. In addition, the chlorite in the material is a substance that can be used as a food additive in Japan. Ozone (O ₃ ) will quickly change into oxygen (O ₂ ) in the air, so it is highly safe.

(2) Durability of the device

The structure of the device of the present invention is relatively simple, so the risk of failure is low, and repair when the device fails is relatively easy.

(3)Chlorine dioxide production efficiency

Although the device of the present invention has a relatively simple structure, it can generate chlorine dioxide stably and efficiently (refer to the embodiments of this specification).

(4) Miniaturization/enlargement and cost reduction

Compared with a device that generates chlorine dioxide by electrolysis, for example, the device structure of the present invention is relatively simple, so it is easy to miniaturize/enlarge the device and reduce the cost.

Figure 1 is a schematic diagram showing the device used in Embodiment 1.

FIG. 2 is a graph showing the results of Example 1.

Figure 3 is a schematic diagram showing the device used in Embodiment 2.

Figure 4 is a schematic diagram showing the device used in Embodiment 3.

FIG. 5 is a graph showing the results of Example 3.

FIG. 6 is a schematic diagram showing the device used in Embodiment 4.

Figure 7 is a schematic diagram showing the device used in Embodiment 5.

FIG. 8 is a graph showing the results of Example 5.

The simplest design example of the device of the present invention is shown in Figure 1. The gas system containing the ozone generated by the ozone generator is bubbled into the chlorite aqueous solution through the gas introduction mechanism, thereby causing the ozone to react with the chlorite to generate chlorine dioxide gas. In addition, the chlorine dioxide production effect of the device of the present invention is based on the examples of this case.

As long as the ozone generator in the device of the present invention is an ozone generator generally available to those with ordinary knowledge in the technical field (such as a discharge ozone generator, an electrolytic ozone generator, a UV lamp ozone generator), it can Use various types of ozone generators. In this disclosure, discharge ozone generators refer to all devices that generate ozone through silent discharge or surface discharge, and electrolytic ozone generators refer to all devices that generate ozone through electrolysis of specific aqueous solutions. UV lamp type ozone generating device refers to any device that generates ozone by irradiating ultraviolet rays to gas containing oxygen.

The gas introduction mechanism in the device of the present invention only needs to be a mechanism that can transport oxygen-containing gas in a fixed direction. For example, an air pump, a gas cylinder, an air compressor, etc. can be used. In addition, the gas delivered through the gas introduction mechanism is not particularly limited as long as it is a gas containing oxygen. For example, if air is used, the cost can be suppressed, and if oxygen or an oxygen-containing gas is used, the ozone generation efficiency can be improved.

In the device of the present invention, the chlorite that becomes the direct raw material of chlorine dioxide can be a chlorite aqueous solution or a solid chlorite. Examples of the chlorite used in the present invention include alkali metal chlorite or alkaline earth metal chlorite. Examples of the alkali metal chlorite salt include sodium chlorite, potassium chlorite, and lithium chlorite, and examples of the alkaline earth metal salt of chlorite include calcium chlorite, magnesium chlorite, and barium chlorite. Among them, sodium chlorite and potassium chlorite are preferred in terms of ease of acquisition, and sodium chlorite is most preferred. These chloroxybases can be used individually by 1 type or in combination of 2 or more types.

In the device of the present invention, when using a chlorite aqueous solution, the concentration of chlorite in the aqueous solution is preferably 0.01% by weight to 45% by weight. When the concentration is less than 0.01% by weight, the chlorite required to produce chlorine dioxide may be used up in a short period of time. When the concentration exceeds 45% by weight, there is a problem that the chlorite is easily saturated and precipitates and crystallizes. Considering safety or stability, chlorine dioxide production efficiency, etc., the preferred range is 0.1 to 25% by weight, the more preferred range is 1 to 20% by weight, and the more preferred range is 2 to 15% by weight. .

In the device of the present invention, when solid chlorite is used, the solid chlorite can be supported on the porous material. By supporting solid chlorite on a porous substance, the surface area of the solid chlorite can be enlarged and the contact efficiency with ozone can be improved. In addition, porous materials easily absorb pollutants in the air Moisture, so by using solid chlorite and porous materials, the moisture required for the reaction of chlorite and ozone can be ensured. Examples of porous materials used in the present invention include sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, perlite, calcium silicate, etc., in order to prevent the decomposition of chlorite. From this point of view, those that show alkalinity when suspended in water are preferred, palygorskite and sepiolite are more preferred, and sepiolite is particularly preferred.

In the present invention, the method of supporting chlorite on the porous material is not particularly limited. For example, a "chlorite-supported porous material" can be obtained by impregnating a porous material with a chlorite aqueous solution and drying it. The moisture content of the "porous material carrying chlorite" is preferably 10% by weight or less, more preferably 5% by weight or less.

The "chlorite-carrying porous material" used in the present invention can have any particle size, and for example, it is suitable to use one with an average particle size of 1 mm to 3 mm.

The average particle diameter of the "chlorite-loaded porous material" in the present invention can be measured, for example, using an optical microscope and subjected to statistical processing. And calculate the mean and standard deviation, and use this to calculate.

The concentration of chlorite in the "chlorite-loaded porous material" used in the present invention is effective when it is 1% by weight or more. If it exceeds 25% by weight, it becomes a highly toxic substance, so it is preferably 1% by weight. % or more and not more than 25% by weight, more preferably not less than 5% by weight and not more than 20% by weight.

In the device of the present invention, when solid chlorite is used, a humidification mechanism for supplying moisture to the gas containing ozone generated by the ozone generator may be further provided. The structure of the humidification mechanism is not limited. For example, a "bubble chamber (where the delivered gas bubbles in water to humidify the gas)" can be provided in the gas delivery path of the device of the present invention. Examples of other humidification mechanisms include Peltier elements, vaporization humidification mechanisms (which allow moisture to penetrate into the humidification material and allow airflow to pass through it, thereby evaporating it), Steam humidification mechanism (uses electric heat to boil water and humidify it), water spray humidification mechanism (uses ultrasonic waves to vibrate water to disperse very small water droplets in the gas).

The device of the present invention is further equipped with a control mechanism of the ozone generator, whereby the amount of chlorine dioxide generated can be controlled. The control mechanism of the ozone generator may be, for example, a mechanism that controls the start/stop of the ozone generator according to a predetermined program, thereby controlling the amount of chlorine dioxide generated by the chlorine dioxide generating device. Non-limiting examples of the control mechanism include, but are not limited to, a switch that stops the ozone generator for a certain period of time if the concentration of chlorine dioxide exceeds a prescribed time, or a switch with a timer that repeats an on/off cycle at a fixed time. .

The device of the present invention may further be equipped with a blower fan for releasing the chlorine dioxide gas generated in the device to the outside of the device. By having a blower fan, the chlorine dioxide gas generated in the device can be efficiently sent out to the outside of the device. Furthermore, by adjusting the air volume of the fan, the amount of chlorine dioxide gas sent out of the device can be adjusted. For example, when the amount of chlorine dioxide gas generated is large, the air volume of the blower fan can be increased to diffuse the chlorine dioxide gas outside the device farther. When the amount of chlorine dioxide gas produced is small, the air volume of the blower fan can be reduced. The air volume prevents excessive diffusion of chlorine dioxide gas outside the device, thereby adjusting the concentration of chlorine dioxide gas outside the device to maintain a certain range.

The terms used in this specification are used to describe specific implementation modes, but not to limit the invention.

In addition, the word "contains" used in this specification refers to the existence of the stated matters (components, steps, requirements, numbers, etc.), except for cases where the context clearly requires different interpretations, but does not exclude other matters. The existence of matters (components, steps, elements or numbers, etc.).

Unless otherwise defined, all terms (including technical terms and scientific terms) used have the same meaning as understood by a person with ordinary knowledge in the technical field to which this invention belongs. in the future Where there are different definitions, the terms used should be interpreted as consistent with their meanings in this specification and related technical fields, and should not be interpreted in an idealized or overly formalized sense.

When describing embodiments of the present invention with reference to schematic diagrams, the schematic diagrams may sometimes be exaggerated for clear explanation.

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

In this specification, various numerical values used to express ingredient content or numerical ranges should be interpreted to include the meaning of the word "about" unless otherwise specified. For example, "10 times" should be understood as "about 10 times" unless otherwise specified.

All disclosures in the cited documents in this specification can be quoted in this specification. Those with ordinary knowledge in the technical field can refer to the relevant disclosures in these prior technical documents according to the context of this specification without departing from the spirit and scope of the present invention. The contents are disclosed and understood as part of this manual.

(Example)

Example 1: Generation of chlorine dioxide gas by the device of the present invention

The composition of the device

In this test, the chlorine dioxide generating device shown in Figure 1 was used. The device is equipped with an air pump, an ozone generator (discharge type), and a reaction container containing a 10% chlorite aqueous solution. The air pump is connected to the ozone generator, and the ozone generator and the reaction container are respectively connected by pipes. By operating the air pump, the ozone generated by the ozone generator is bubbled in the chlorite aqueous solution in the reaction container.

Test method

Run the air pump and introduce air (1L/min) into the aqueous chlorite solution in the reaction container, and then run the ozone generator. The temperature and humidity of the air are not controlled. In addition, the ozone generator operates intermittently between ON=5sec and OFF=20sec.

Determination of chlorine dioxide gas

Use a trapping fluid to capture the gas released from the device outlet. The captured chlorine dioxide gas is measured by iodine titration. In addition, the collection time per time is 30 minutes, and measurement is performed regularly until about 360 hours.

Test results

The measurement data of the chlorine dioxide production amount are shown in Table 1 and Figure 2. In addition, the gas collection time is 30 minutes, so twice the measured value is the generation amount per hour. As shown in Table 1 and Figure 2, the device of the present invention can stably produce 6 to 9 mg/h chlorine dioxide for a long time.

[Table 1]

Example 2: Comparison between discharge ozone generator and lamp ozone generator

The composition of the device

In this test, a chlorine dioxide generating device equipped with a discharge ozone generator (the same device used in Example 1) and a chlorine dioxide generating device equipped with a lamp ozone generator were used to compare the production of ozone and chlorine dioxide. quantity (refer to Figure 3).

Test method

Run the air pump in each device, introduce the chlorite aqueous solution in the reaction container into the air at 1L/min, and then run the ozone generator. The temperature and humidity of the air are not controlled. In addition, all ozone generators operate continuously.

Determination of chlorine dioxide gas

Use a trapping fluid to capture the gas released from the device outlet. The captured chlorine dioxide gas is measured by iodine titration. In addition, the collection time per time is 10 minutes.

Test results

The amount of ozone generated and the amount of chlorine dioxide generated in each device are as follows.

[Table 2]

[table 3]

As shown in the table, compared to the case of using a lamp-type ozone generator, when a discharge-type ozone generator is used, a larger amount of ozone is produced, and ultimately a larger amount of chlorine dioxide is produced. From this result, it can be seen that by using a discharge-type ozone generator in the device of the present invention, it is expected that the device can be miniaturized, the cost can be reduced, and the efficiency can be improved.

Example 3: Stabilization of chlorine dioxide production by adding a humidification mechanism

The composition of the device

In this experiment, changes in chlorine dioxide production efficiency caused by differences in humidity conditions were explored. As shown in Fig. 4, two types of chlorine dioxide generating devices equipped with a discharge ozone generator and two air pumps (for path 1 and for path 2) are prepared. In the device of Figure 4A, humidified air containing ozone is brought into contact with chlorite, and in the device of Figure 4B, dry air containing ozone is brought into contact with chlorite.

In the path 1 of the humidification condition (Fig. 4A), the air is bubbled in the water, thereby delivering the humidified air. In path 1 of the drying condition (Fig. 4B), the air is passed through the desiccant, thereby delivering the dry air. Path 2 is common to both devices, and the air dried with the desiccant is mixed with the ozone generated by the ozone generator and delivered.

Test method

In each device, the air pumps for path 1 and path 2 were operated, and air was introduced into the solid chlorite in the reaction container (the total of 0.5L/min for path 1 and 0.5L/min for path 2 is 1L/min), then operate the ozone generator. In addition, the discharge-type ozone generator operates intermittently with ON=1sec and OFF=36sec.

Determination of chlorine dioxide gas

Use a trapping fluid to capture the gas released from the device outlet. The captured chlorine dioxide gas is measured by iodine titration. In addition, the collection time per time is 30 minutes, and measurement is performed regularly until about 360 hours.

Test results

The amount of ozone generated and the amount of chlorine dioxide produced in each device are as follows.

[Table 4]

[table 5]

As shown in Tables 4, 5 and Figure 5, according to the device of the present invention, chlorine dioxide can be generated for a long time in either humidification conditions or drying conditions. However, in general, the amount of chlorine dioxide produced under dry conditions is less than that under humidified conditions, and the amount of chlorine dioxide produced at each measurement point is also inconsistent.

As described above, in the device of the present invention, when solid chlorite is used as the chlorine dioxide generation source, the amount of chlorine dioxide generated can be increased by providing a humidification mechanism in the air supply path. In addition, by providing a humidification mechanism in the air supply path, chlorine dioxide can be stably generated for a long time.

Example 4: Discussion on delivery method of air

The composition of the device

In this experiment, the method of delivering ozone-containing air to the chlorite in the reaction vessel was explored. As shown in the table below and Figure 6, prepare the method of delivering the chlorite (aqueous solution or solid chemical) and ozone-containing air in the reaction container (to the inside of the solution or solid chemical, or to the solution or solid chemical). Four devices (Devices C, D, E, F) with different combinations of surface). In addition, apparatus A and apparatus B are the control group which does not have an ozone generator.

[Table 6]

Test method

‧Device A

Use an air pump to pass air into 100g of 10% sodium chlorite aqueous solution at a flow rate of 1L/min.

‧Device B

Use an air pump to pass air into 50g of 10% sodium chlorite solid impregnated material at a flow rate of 1L/min.

‧Device C

Use an air pump to supply air to the discharge ozone generator at a flow rate of 1L/min, and pass the generated ozone gas above 100g of 10% sodium chlorite aqueous solution to bring it into contact.

‧Device D

Use an air pump to supply air to the discharge ozone generator at a flow rate of 1L/min, and pass the generated ozone gas over 50g of the 10% sodium chlorite solid impregnated material to bring it into contact.

‧Device E

Use an air pump to supply air to the discharge ozone generator at a flow rate of 1L/min, and pass the generated ozone gas into 100g of 10% sodium chlorite aqueous solution.

‧Device F

Use an air pump to supply air to the discharge ozone generator at a flow rate of 1L/min, and pass the generated ozone gas into 50g of 10% sodium chlorite solid impregnated material.

In addition, in each device, the discharge-type ozone generator performs intermittent operation of ON=0.5 sec and OFF=2 sec.

Determination of chlorine dioxide gas

Use a trapping fluid to capture the gas released from the device outlet. The captured chlorine dioxide gas is measured by iodine titration.

Test results

The amount of chlorine dioxide generated in each device is as follows.

[Table 7]

As shown in Table 7, the device of the present invention is configured so that air containing ozone is delivered to the inside of a chemical containing chlorite, thereby increasing the amount of chlorine dioxide generated. That is, in the device of the present invention, when solid chlorite is used as a source of chlorine dioxide, it is preferably configured so that ozone-containing air is passed into the interior of the solid chlorite. Furthermore, in the device of the present invention, when a chlorite aqueous solution is used as a source of chlorine dioxide, it is preferably configured so that ozone-containing air is bubbled in the chlorite aqueous solution.

Example 5: Control of chlorine dioxide production

The composition of the device

In this test, the controllability of chlorine dioxide generation by turning on/off the ozone generating device was confirmed. As shown in Figure 7, a device (device I) using a chlorite aqueous solution (100g of a 1% sodium chlorite aqueous solution) and a device using a solid chlorite (100g of a 10% sodium chlorite solid impregnated material) are prepared. Device (Device II). As a control group, an aqueous solution containing chlorite and citric acid (1% chlorite 100g sodium aqueous solution + 0.1g citric acid) device (device III). Either device is configured so that air is delivered to the inside of the chemical containing chlorite.

[Table 8]

Test method

For devices I and II, the ozone generator was operated at the beginning of the test and stopped after 30 minutes. Repeat the above pattern twice and conduct the test until 120 minutes. In addition, the air pump is in a constant operating state. In addition, the air flow rate of the air pump in each condition is 1L/min. In device III, an air pump is used to pass air into an aqueous solution containing chlorite and citric acid.

In addition, the discharge-type ozone generator operates intermittently with ON=0.5 sec and OFF=2 sec.

Determination of chlorine dioxide gas

In each device, the gas detection tube 23M is used to measure the chlorine dioxide gas concentration at the gas blowing port every 10 minutes.

The amount of chlorine dioxide produced in each device is shown in Table 9 and Figure 8 below.

[Table 9]

As shown in Table 9 and Figure 8, in the devices I and II of the present invention, if the ozone generator is stopped, the amount of chlorine dioxide generated will decrease rapidly. On the other hand, if the ozone generator is operated again, the amount of chlorine dioxide produced will increase rapidly. That is, it is shown that the amount of chlorine dioxide generated can be controlled by controlling the operation of the ozone generator in the device of the present invention.

Claims (15)

A chlorine dioxide generating device is provided with an ozone generator, a gas introduction mechanism, and a reaction container, The aforementioned reaction vessel contains a chlorite-containing agent when chlorine dioxide is reacted, The aforementioned device delivers the gas containing ozone generated by the aforementioned ozone generator to the aforementioned chlorite in the aforementioned reaction container through the aforementioned gas introduction mechanism, thereby bringing the aforementioned gas containing ozone into contact with the aforementioned chlorite. The chlorine dioxide generating device according to claim 1, wherein the ozone generator is a discharge ozone generator, an electrolytic ozone generator, or a UV lamp ozone generator. The chlorine dioxide generating device according to claim 1 or 2, wherein the agent containing chlorite in the reaction container is a agent containing a chlorite aqueous solution or a solid chlorite. The chlorine dioxide generating device according to claim 3, wherein the agent containing chlorite in the reaction container is a agent containing an aqueous chlorite solution, The device is configured to bubble the aqueous chlorite solution in the reaction vessel through the gas introduction mechanism. The chlorine dioxide generating device according to claim 4, wherein the aqueous chlorite solution contains chlorite at a concentration of 0.01 to 45% by weight. The chlorine dioxide generating device according to claim 3, wherein the agent containing chlorite in the reaction container is a agent containing solid chlorite, The aforementioned device is configured to deliver the gas containing ozone generated by the aforementioned ozone generator to the inside of the aforementioned solid chlorite-containing agent in the aforementioned reaction container through the aforementioned gas introduction mechanism, so that the aforementioned ozone and the aforementioned solid chlorite are mixed. Chlorate exposure. The chlorine dioxide generating device according to claim 6, wherein the agent containing solid chlorite is a agent containing a porous material carrying chlorite. The chlorine dioxide generating device according to claim 7, wherein the porous material carrying chlorite is obtained by impregnating the porous material with a chlorite aqueous solution and further drying the porous material. The chlorine dioxide generating device according to claim 7 or 8, wherein the porous material is selected from the group consisting of sepiolite, palygorskite, montmorillonite, silica gel, diatomaceous earth, zeolite, perlite, and silica A group composed of calcium phosphate. The chlorine dioxide generating device according to claim 7, wherein the agent containing solid chlorite is a granular agent. The chlorine dioxide generating device according to any one of claims 6 to 10, further equipped with a humidification mechanism for supplying moisture into the gas containing ozone generated by the ozone generator. The chlorine dioxide generating device according to any one of claims 1 to 11, wherein the chlorite is an alkali metal chlorite or an alkaline earth metal chlorite. The chlorine dioxide generating device according to claim 12, wherein the alkali metal chlorite salt is sodium chlorite, potassium chlorite, or lithium chlorite, The alkaline earth metal salt of chlorite is calcium chlorite, magnesium chlorite, or barium chlorite. The chlorine dioxide generating device according to any one of claims 1 to 13, further equipped with a control mechanism of the aforementioned ozone generator. The chlorine dioxide generating device as claimed in claim 14, wherein the control mechanism of the ozone generator controls the start/stop of the ozone generator according to a predetermined program, thereby controlling the carbon dioxide of the chlorine dioxide generating device. Chlorine production.

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