KR100860779B1 - Apparatus producing chlorine dioxide and method for chlorine dioxide production using the same - Google Patents

Abstract

Provided is an apparatus for generating gas phase chlorine dioxide that can be used easily by anyone at places requiring the chlorine dioxide by reducing size and weight of the apparatus, operating the apparatus simply, and raising safety of the apparatus as a batch type chlorine dioxide generation apparatus operated for a predetermined time by injecting a predetermined volume of reagent cartridge into the apparatus, and a method for generating chlorine dioxide using the apparatus is provided. An apparatus for generating chlorine dioxide comprises: a reactor case(330): a receiving equipment(110) for mounting a reagent cartridge(400) containing a reagent solution on the reactor case or demounting the reagent cartridge from the reactor case; an acid vessel(200) in which an acid solution(210) is contained, and to which an acid supply tube(230) is connected to supply the acid solution to the reagent solution; and a suction unit for forming a negative pressure in the reactor case to suck gas phase chlorine dioxide generated during a reaction between the reagent solution and the acid solution, wherein the gas phase chlorine dioxide is generated in a unit of the reagent cartridge. The apparatus further comprises aeration tubes(320) of which one ends are exposed to the outside of the reactor case, and of which the other ends are immersed into the reagent solution to form bubbles(410) in the reagent solution by sucking air of the outside during the formation of the negative pressure. The apparatus further comprises a first purifier(510), a second purifier(520), a sodium chlorite column(530), a powder remover(540), filters(524,534), a differential pressure removing tube(220), and a safety tube(310). The receiving equipment includes a reagent cartridge injection stand(350), an air-tightening unit, a guide(360), a slider(114), and an arm(116). Further, the acid supply tube is made of teflon and is opened and closed by a solvent value.

Description

Chlorine dioxide generation device and chlorine dioxide generation method using the same {APPARATUS PRODUCING CHLORINE DIOXIDE AND METHOD FOR CHLORINE DIOXIDE PRODUCTION USING THE SAME}

The present invention relates to an apparatus for producing gaseous chlorine dioxide and a method for generating chlorine dioxide using the same, and more particularly, to produce gaseous chlorine dioxide by the oxidation method of chlorite, or the reduction method of chlorate. A chlorine generating device and a method for generating the same.

Since chlorine dioxide (ClO ₂ ) was first discovered by Humphrey Davy in 1811, it was only commercially available in the 1930s.

The molecular weight of chlorine dioxide is 67.45 g / mol, which differs from chlorine in that it has a boiling point of 11 ° C, a melting point of -59 ° C, and does not react with water or ammonia. It also does not produce chlorinated hydrocarbons even after reaction with hydrocarbons. In general, chlorine dioxide is less corrosive to metals and nonmetallic materials than chlorine.

Chlorine dioxide and chlorine act as oxidants that accept electrons. Looking at the chemical scheme is shown in Scheme 1 below.

Cl ₂ + 2e ^- = 2Cl ^-

_{ClO 2 + 2H 2 O + 5e} - = Cl - + 4OH _

Based on Scheme 1, chlorine takes 33.5 kg while chlorine dioxide requires 13.5 kg to take 1 kg-mol of electrons. Therefore, 1 kg of chlorine dioxide is equivalent to 2.63 kg of chlorine. Chlorine dioxide (ClO ₂ ) can accept 2.5 times as much electrons to form chloride (Cl) than chlorine (Cl ₂ ).

Chlorine dioxide is a light yellow gas with a greenish color similar in appearance and smell to chlorine. Unlike chlorine gas, chlorine dioxide gas is explosive at high temperatures and pressures, so it cannot be compressed and put in a container.It has a disadvantage that it must be produced and used in the place where it is needed. Tend to be.

It is also known to dissolve in water very easily and about 10 times better solubility than chlorine. Chlorine dioxide should be stored in a cool dark place. The chlorine dioxide solution evaporates over time, decreasing its concentration, and the color of the solution gradually changes from light yellow to colorless.

In general, chlorine dioxide, unlike chlorine, does not hydrolyze in water, and bactericidal power is not affected even in the range of pH 6-10. In addition, it is known that when reacting with organic substances does not produce trihalomethans (THMs) known as carcinogens, and does not produce chloroamine by reacting with ammonia.

Chlorine dioxide is a strong oxidizer that has strong oxidizing, sterilizing and deodorizing power and is drawing attention as a substitute for chlorine because it does not produce chlorine disinfection by-products such as trihalomethane (THMs) and organic chlorine compounds. Chlorine dioxide has both chlorine and oxygen disinfection properties, has 2.5 times the oxidizing power of chlorine, and has the characteristic of remaining effectively in a wide range of pH 6-10 level.

Chlorine dioxide is known as an excellent disinfectant as well as a strong oxidizer. The bactericidal, algal, bleaching, and deodorizing properties of chlorine dioxide are described in various literatures. Chlorine dioxide is approximately five times more soluble in water than chlorine gas.

In addition, chlorine dioxide differs from chlorine gas in that it does not react with water or ammonia and does not produce chlorinated hydrocarbons even after reaction with hydrocarbons. In general, chlorine dioxide corrodes metals and nonmetallic materials less than chlorine, which is a very important advantage.

And, chlorine dioxide has a high volatility and may have a light explosive when the concentration is 11% or more. Because of this, compression storage is impossible, and this is why a chlorine dioxide generator that can be produced directly in the field is needed.

Chlorine dioxide is currently consumed in large quantities as a bleaching agent for wood, paper, fats, oils, resins and powders, and it is noted as a substitute for chlorine used as a disinfectant for water and wastewater and as a regulator for taste / odor (T / O). Is getting. Chlorine dioxide is an excellent sulfur remover and is widely used in washing towers in the wastewater, fat refining, gas and oil industries.

And with the recent deregulation, chlorine dioxide has been increasingly used as a disinfectant and disinfectant in the food processing industry. In the United States, chlorine dioxide is licensed for meat, dairy, poultry, fruit and vegetable processing, and processed foods. In most cases, chlorine dioxide does not cause organoleptic damage to food products.

Next, a conventional method for producing chlorine dioxide is introduced.

Initially produced by reacting potassium chlorate (KClO ₃ ) with hydrochloric acid (HCl), in the 1930's a commercial process was developed for producing chlorine dioxide from sodium chlorate (NaClO ₃ ).

Chlorine dioxide is primarily chlorate is manufactured by oxidation _{^{of:: - - (ClO 2 chlorites}} ) or reduction or chlorite of (chlorates ClO _3). In the case of bleaching processes in large paper mills, the production of chlorine dioxide is mainly achieved by reduction of chlorate.

Some manufacturing methods are described as follows.

As a reduction method of chlorate by sulfuric acid,

2NaClO ₃ + H ₂ SO ₄ + SO ₂ → 2ClO ₂ + 2NaHSO ₄

Where SO ₂ as reducing agent Increases the yield and purity of chlorine dioxide.

As the oxidation method of chlorite,

5NaClO ₂ + 4HCl ↔ 4ClO ₂ + 5NaCl + 2H ₂ O

Here, as the acid for oxidizing chlorite, hydrochloric acid, acetic acid, nitric acid, lactic acid and the like may be used.

As an example of the oxidation method of chlorite by chlorine,

2NaClO ₂ + Cl ₂ → 2ClO ₂ + 2NaCl

As another example of the oxidation method of chlorite by chlorine,

2NaClO ₂ + HOCl → 2ClO ₂ + NaCl + NaOH

As a way of obtaining stabilized sodium chlorite,

NaClO ₂ + H + (weak acid) ↔ HClO ₂

On the other hand, the chlorine dioxide generating device for generating chlorine dioxide according to the above reaction formula is required to install a separate device and a safety device for supplying and removing the reaction after the reaction / harmful gases such as SO ₂ , Cl ₂ , HCl, etc. There is a problem. In addition, there is a problem that requires a complex facility such as an electrolysis facility as a device for the reaction.

In order to alleviate the inconvenience of such a gaseous chlorine dioxide generating device, liquid chlorine dioxide is sold like a normal chlorine solution.

The consumer adds a certain amount of acid to this liquid chlorine dioxide solution to generate chlorine dioxide gas, but initially exists as a mixture of chlorine dioxide and chlorite and the conversion to chlorine dioxide is slowed down (slow releasing chlorine dioxide). There is a problem of slow response.

In addition, the reaction formula of the commercially used chlorine dioxide generator is different in the way that each manufacturer, and if the unwanted reaction by-products are generated excessively, the purity of the chlorine dioxide is lowered, so setting the optimum reaction conditions and chemical reactions It is an important requirement.

Next, the problems of the chlorine dioxide production method conventionally used are summarized.

The biggest disadvantage of the conventional method for producing chlorine dioxide is that chlorine dioxide of low yield and low purity is obtained, in which chlorine and chlorite are produced as by-products.

In the process of reducing chlorate in the mass production of chlorine dioxide, there is a burden to install a separate device and a safety device to remove SO ₂ , Cl ₂ , HCl gas to produce high purity products.

The production of gaseous chlorine dioxide can be produced by reacting chlorate with sulfur dioxide. However, chlorate, a raw material used here, is generated through a large electrolysis facility, which requires a high temperature electrolysis facility and high purity chlorate, and a device and a safety device for removing SO ₂ , Cl ₂ , and HCl gas must be accompanied. There are disadvantages.

Recently, a method of obtaining a chlorine dioxide gas by passing a chlorine gas through a chlorite column is used, but there is a problem in terms of stability of the process. In other words, some of the chlorine gas introduced may be released to the outside in the unreacted state, there is a risk of serious corrosion problems and human injury.

On the other hand, when stabilized chlorine dioxide is diluted at low temperature in the treated water at room temperature in an purified water or wastewater treatment plant, anion such as chlorite and chlorate is activated, so it is unlikely to be converted into chlorine dioxide. Therefore, even after a considerable time elapses after the injection of stabilized chlorine dioxide, most of chlorite and chlorate remain in the treated water and the sterilization power is extremely low, and an excessive amount of chlorite may be injected to reinforce it. And if chlorate remains, there is a problem causing cyanosis. In this regard, the US EPA regulates the content of chlorite in drinking water below 0.8 mg / L and domestically below 0.5 mg / L. Due to such a problem, the disinfection method using stabilized chlorine dioxide is currently very limited.

The present invention is to improve the problems of the prior art as described above, the problems caused by the existing continuous reaction process, that is, the controllability due to the use of the metering pump and high-pressure reactor, increased manufacturing cost and complexity of the device This is a dramatic improvement.

That is, a batch type chlorine dioxide generator and a method of generating the reagent cartridge of a predetermined capacity to operate the device for a predetermined time, and are small, lightweight, easy to operate, and improved in safety, and can be easily used by anyone where needed. It is to provide a chlorine dioxide generating device and chlorine dioxide generating method using the same.

In order to achieve the above object, the chlorine dioxide generating device of the present invention, the reactor case; A storage device for attaching and detaching a reagent cartridge containing a reagent solution to the reactor case; An acid container containing an acid solution, to which an acid supply tube for supplying the acid solution to the reagent solution is connected; Suction means for sucking gaseous chlorine dioxide generated during reaction of the reagent solution and the acid solution by forming a negative pressure inside the reactor case; It includes, characterized in that for generating the gaseous chlorine dioxide in the reagent cartridge unit.

In one embodiment, the chlorine dioxide generating device, one end is exposed to the outside of the reactor case and the other end is submerged in the reagent solution to form a bubble in the reagent solution by sucking the outside air when the negative pressure is formed ; It further includes.

In one embodiment, the suction means includes a suction tube connected to the suction port opened in the reactor case, and a vacuum pump connected to the suction tube to form a negative pressure.

In one embodiment, the chlorine dioxide generating device, the chlorine dioxide in the gas phase is sucked from the reactor case sequentially passed, the primary purifier for removing water; A secondary purifier for removing at least one of chlorine gas, hydrochloric acid gas and remaining moisture not removed from the primary purifier; Sodium chlorite column to increase the purity of the chlorine dioxide; It includes more.

In one embodiment, the chlorine dioxide generating device, the chlorine dioxide sucked from the sodium chlorite column is passed through the powder remover to remove the powder contained in the chlorine dioxide; It further includes.

In one embodiment, the secondary purifier is filled with pellets in which silica gel (SiO ₂ Gel) and sodium hydroxide (NaOH) are mixed in a weight ratio of 1: 1 to 5: 1.

In one embodiment, the silica gel (SiO ₂ Gel) and sodium hydroxide (NaOH) can be reused by drying when reaching the saturation state.

In one embodiment, the sodium chlorite column is filled with sodium chlorite powder and silicon oxide powder in a weight ratio of 9: 1 to 7: 3.

In one embodiment, the secondary purifier and the inlet / outlet of the sodium chlorite column are each equipped with a filter for preventing the separation of the internal filling.

In one embodiment, the chlorine dioxide generating device, the differential pressure removing tube for removing the differential pressure inside the acid container by connecting the acid container and the reactor case; It further includes.

In one embodiment, the chlorine dioxide generating device, the safety tube for discharging the chlorine dioxide inside the reactor case while the solenoid valve is opened when the suction means stops; It further includes.

In one embodiment, the acid supply tube, made of Teflon material, is opened and closed by a solvent valve.

In one embodiment, the storage device is provided with a reagent cartridge inlet vertically moved relative to the reactor case by placing the reagent cartridge, and an airtight means for sealing between the reagent cartridge inlet and the reactor case.

In one embodiment, the storage device includes a guide for guiding the movement of the reagent cartridge holder, a slider for vertically moving the reagent cartridge holder by a ball screw with a driving motor, the slider and the reagent cartridge. It is further provided with an arm connecting the charging table.

In one embodiment, the reagent solution is sodium chlorate or sodium chlorite solution.

On the other hand, the chlorine dioxide generation method of the present invention, the step of opening the lid of the reagent cartridge containing the reagent solution and put on the reagent cartridge inlet; Filling an acid solution into an acid container which is opened and closed by a solvent valve; Mounting the reagent cartridge inside the reactor case by bringing the reagent cartridge holder into tight contact with the reactor case by a receiving device; Closing a safety tube connecting the inside of the reactor case with the outside thereof; Opening the solvent valve and feeding the acid solution to the reagent solution by gravity; Operating a suction means to form a negative pressure inside the reactor case to discharge gaseous chlorine dioxide generated during the reaction of the acid solution and the reagent solution to the outside of the reactor case; Characterized in that it comprises a.

In one embodiment, bubbles are formed in the reagent solution by supplying external air to the reagent solution through an aeration tube during the formation of the negative pressure.

As an example, the chlorine dioxide generation method may include sequentially passing chlorine dioxide discharged to the outside of the reactor case through a first purifier, a second purifier, and a sodium chlorite column; Wherein the first purifier removes moisture contained in the chlorine dioxide, and the second purifier removes at least one of chlorine gas, hydrochloric acid gas, and remaining moisture not removed from the primary purifier. One is removed, and the sodium chlorite column is mixed and filled with sodium chlorite powder and silicon oxide powder to increase the purity of the chlorine dioxide.

In one embodiment, the pressure difference inside the acid container is removed by connecting the acid container and the inside of the reactor case with a differential pressure removing tube.

In one embodiment, when the reaction of the reagent solution contained in the reagent cartridge is finished, the solenoid valve is opened to open the safety tube to the outside.

As described above, according to the present invention, a batch is generated in which gaseous chlorine dioxide is generated by operating the apparatus for a predetermined time using a reagent cartridge fractionated by an amount necessary for one-time use of chlorine dioxide without using a conventional continuous process. ) Type, easy to use, and do not use expensive equipment such as metering pump can reduce the production cost of the generator.

In addition, according to the present invention, the chlorine dioxide produced by the reaction of the acid with sodium chlorate or sodium chlorite is extracted in a gaseous state rather than a liquid phase, and the solution used for the reaction remains in the reagent cartridge, so when chlorine dioxide in aqueous solution is generated. There is no concern for the generation of by-products such as chlorite, which has been a problem, and it can fundamentally block the safety problem of using strong acid.

1 shows a chlorine dioxide generating device of the present invention and shows a state before the reagent cartridge is added. Figure 2 is for the chlorine dioxide generating device of the present invention, it shows a state in which the reagent cartridge is added and the reaction.

1 and 2 will be described in detail the configuration and operation of the chlorine dioxide generating device of the present invention.

Reactor cartridge 330 and reagent cartridge 400, which can contain a reagent cartridge 400 (e.g., in the form of a reagent bottle) containing sodium chloride or sodium chlorite solution (also called reagent solution) at a certain concentration, It is supported and the reagent cartridge inlet 350 to move up and down to remove the reagent cartridge 400 to the reactor case 330, the storage device 110 for moving the reagent cartridge inlet 350 up and down is provided.

A plurality of tubes are connected to the upper surface of the reactor case 330 to perform each function. That is, the aeration tube 320 for aeration of the reagent solution contained in the reagent cartridge 400 and the acid solution 210 such as hydrochloric acid or sulfuric acid from the acid container 200 by forming an air bubble 410 by sucking outside air. Acid supply tube 230, which can be supplied to the reagent cartridge 400, suction tube 380 for sucking the generated gaseous chlorine dioxide, safety tube 310 for preventing the explosion of the gaseous chlorine dioxide, acid container ( A differential pressure removing tube 220 or the like for removing the differential pressure in the 200 is connected.

When the reagent cartridge 400 containing a predetermined concentration of sodium chlorate or sodium chlorite solution is placed in the reagent cartridge holder 350 and turned on, the storage device 110 operates and the reagent cartridge 400 is placed in the reactor case 330. Insert tightly. Likewise, when the reaction is completed, the storage device 110 operates to separate the reagent cartridge 400 from the reactor case 330. The storage device 110 includes a drive motor 100, a ball screw 112 rotated by the drive motor 100, a slider 114 connected to the ball screw 112, and a slider 114, a slider 114, and a reagent cartridge. It is preferred to have an arm 116 connecting the feeder 350.

The airtight means is provided to maintain the airtight inside the reactor case 330, an O-ring (340) mounted to the lower portion of the reactor case 330 as an embodiment of the airtight means.

The aeration tube 320 mounted in the reactor case 330 is disposed to be immersed in the reagent solution contained in the reagent cartridge 400, and the gaseous chlorine dioxide is easily volatilized by an air bubble from the aeration tube 320 to externally. And soaking of the acid solution 210 supplied from the acid container 200 and the sodium chlorate or sodium chlorite solution contained in the reagent cartridge 400. The rising height of the reagent cartridge inlet 350 is set such that the aeration tube 320 passes through the inlet 420 of the reagent cartridge 400 so as to be sufficiently immersed in the reagent solution inside the reagent cartridge 400.

The acid vessel 200 is installed on the reactor case 330 and is connected to the acid supply tube 230 so that the acid solution 210 may fall into the reagent cartridge 400 by gravity. The acid feed tube 230 is preferably provided with a Teflon tube to prevent corrosion by the acid solution 210. In addition, the acid supply tube 230 is equipped with a solvent valve (235) (solvent valve) to prevent the acid in the acid container 200 to flow down when the device is not operating.

The driving method of the gas phase chlorine dioxide generator is as follows.

Open the lid of the reagent cartridge 400 containing the appropriate concentration of sodium chlorate or sodium chlorite solution, and then place the reagent cartridge 400 on the reagent cartridge holder 350. Then, an acid solution 210 such as hydrochloric acid or sulfuric acid solution 210 of an appropriate concentration is poured along the acid container 200 and the lid of the acid container 200 is closed.

When the power of the chlorine dioxide generating device is turned on and the “start” button is pressed, the storage device 110 inserts the reagent cartridge holder 350 into which the reagent cartridge 400 is placed in close contact with the reactor case 330. The airtightness is maintained, the solenoid valve attached to the safety tube 310 is closed, and the solvent valve 235 connected to the acid container 200 is opened, so that the acid solution 210 is moved by gravity into the reagent cartridge 400. Start dropping down.

As the solvent valve 235 is opened and the vacuum pump 550 is operated, the pressure inside the reactor case 330 is lower than atmospheric pressure. While negative pressure is generated inside the reactor case 330, air is injected into the inside of the reactor case 330, that is, within the reagent solution of the reagent cartridge 400, causing bubbling or aeration. As the aeration starts in the reagent cartridge 400, the gaseous chlorine dioxide produced through the reaction between the acid solution 210 and the reagent solution (sodium chlorine or sodium chlorite solution) is volatilized, and the reactor is passed through the suction tube 380. It begins to move from the case 330 toward the vacuum pump 550.

The gaseous chlorine dioxide leaving the reactor case 330 is vacuum pumped through a primary purifier 510, a secondary purifier 520, a sodium chlorite column 530 filled with sodium chlorite powder, and a powder remover 540. It enters 550 and is released to the outside. Chlorine dioxide released from the vacuum pump 550 is supplied to the required place.

The vacuum pump 550 of the gas phase chlorine dioxide generator of the present invention is operated for a predetermined operating time corresponding to the time when the capacities of the reagent cartridge 400 all react. That is, the vacuum pump 550 may be controlled by a timer once operation time. One time of operation is preferably set to a time sufficient to remove the unreacted material in the reagent cartridge (400).

When the operation of the vacuum pump 550 is stopped, the solenoid valve 315 in the safety tube 310 of the upper part of the reactor case 330 is opened to vent the inside and the outside of the reactor case 330. Thus, any chlorine dioxide gas that may be generated is released to the outside, and an explosion of chlorine dioxide gas that may be caused by residual pressure is prevented.

Solvent valve 235 is closed at the same time solenoid valve 315 is open. That is, the solvent valve 235 is always locked when the vacuum pump 550 is not operating. Therefore, the acid solution 210 is not leaked until the generator of the present invention is used later.

The primary clarifier 510 removes water that may accompany the flow of gaseous chlorine dioxide, and the secondary clarifier 520 contains 1: 1 to 5: silica gel (SiO ₂ Gel) and sodium hydroxide (NaOH). Pellets mixed at a weight ratio of 1 are filled to remove chlorine (Cl ₂ ) gas and hydrochloric acid (HCl) gas that may accompany the flow of gaseous chlorine dioxide, and to remove moisture not completely removed from the primary clarifier 510. Remove

The sodium chlorite column 530 is filled by mixing sodium chlorite powder and silicon oxide powder in a weight ratio of 9: 1 to 7: 3. Silicon oxide powder prevents the solidification of sodium chlorite powder, thereby improving the reaction efficiency of sodium chlorite powder, gaseous chlorine dioxide and other impurities. At the end of the secondary clarifier 520, in addition to gaseous chlorine dioxide, unremoved chlorine and hydrochloric acid gas may be emitted. They are all converted to gaseous chlorine dioxide while passing through sodium chlorite powder.

Inlets and outlets of the secondary purifier 520 and the sodium chlorite column 530 are equipped with filters 524 and 534 to prevent the contents from being separated. When the silica gel and sodium hydroxide of the secondary purifier 520 is saturated, the contents may be taken out and dried to reuse.

1 shows a chlorine dioxide generator of the present invention, and shows a state before the reagent cartridge is added.

Figure 2 is for the chlorine dioxide generator of the present invention, it shows a state in which the reagent cartridge is added and the reaction.

<Explanation of symbols for the main parts of the drawings>

100 ... drive motor 110 ... storage

112 ... ball screw 114 ... slider

116 Arm 200 Acid Container

210 ... acid solvent 220 ... pressure drop tube

230 ... acid supply tube 235 ... solvent valve

300 ... reactor 310 ... safety tube

315 Solenoid valve 320 Aeration tube

330 ... Reactor case 340 ... O-ring

350 ... Reagent Cartridge Insert 360 ... Guide

370 ... Intake 380 ... Suction tube

400 ... reagent cartridge 410 ... bubble

510 ... Primary Purifier 520 ... Secondary Purifier

524,534 Filter 530 Sodium Chlorite Column

540 ... powder remover 550 ... vacuum pump

Claims (18)

Reactor case; A storage device for attaching and detaching a reagent cartridge containing a reagent solution to the reactor case; An acid container containing an acid solution, to which an acid supply tube for supplying the acid solution to the reagent solution is connected; Suction means for sucking gaseous chlorine dioxide generated during reaction of the reagent solution and the acid solution by forming a negative pressure inside the reactor case; To include, Chlorine dioxide generation device characterized in that for generating the gaseous chlorine dioxide in the reagent cartridge unit. The method of claim 1, An aeration tube whose one end is exposed to the outside of the reactor case and the other end is immersed in the reagent solution, and which forms air bubbles in the reagent solution by sucking external air when the negative pressure is formed; Chlorine dioxide generation device characterized in that it further comprises. The method of claim 1, The suction means, Chlorine dioxide generation apparatus comprising a suction tube connected to the suction port opened in the reactor case, and a vacuum pump connected to the suction tube to form a negative pressure. The method of claim 1, As the chlorine dioxide in the gas phase sucked from the reactor case is sequentially passed, A primary purifier to remove moisture; A secondary purifier for removing at least one of chlorine gas, hydrochloric acid gas and remaining moisture not removed from the primary purifier; Sodium chlorite column to increase the purity of the chlorine dioxide; Chlorine dioxide generation device characterized in that it further comprises. The method of claim 4, wherein A powder remover through which chlorine dioxide sucked in the sodium chlorite column is passed and removes the powder contained in the chlorine dioxide; Chlorine dioxide generation device characterized in that it further comprises. The method of claim 4, wherein The sodium chlorite column is filled with sodium chlorite powder and silicon oxide powder is mixed in a weight ratio of 9: 1 to 7: 3 chlorine dioxide generator. The method of claim 4, wherein Chlorine dioxide generator, characterized in that the inlet / outlet of the secondary purifier and the sodium chlorite column is equipped with a filter for preventing the separation of the internal filling. The method of claim 1, A differential pressure removing tube for removing the differential pressure inside the acid container by connecting the acid container and the reactor case; Chlorine dioxide generation device characterized in that it further comprises. The method of claim 1, A safety tube opening the solenoid valve when the suction means stops and discharging chlorine dioxide inside the reactor case to the outside; Chlorine dioxide generation device characterized in that it further comprises. The method of claim 1, The acid feed tube, Chlorine dioxide generator, characterized in that made of Teflon material, which is opened and closed by a solvent valve. The method of claim 1, The storage device, A reagent cartridge feeder moved up and down relative to the reactor case by placing the reagent cartridge thereon; And an airtight means for sealing between the reagent cartridge holder and the reactor case. The method of claim 11, The storage device, A guide for guiding movement of the reagent cartridge holder; A slider for moving the reagent cartridge tray up and down by being linearly moved by a ball screw with a drive motor; A chlorine dioxide generating device further comprising an arm connecting the slider and the reagent cartridge inlet. The method of claim 1, The reagent solution, Chlorine dioxide generator, characterized in that the sodium chlorate or sodium chlorite solution. Opening the lid of the reagent cartridge containing the reagent solution and placing it on the reagent cartridge holder; Filling an acid solution into an acid container which is opened and closed by a solvent valve; Mounting the reagent cartridge inside the reactor case by bringing the reagent cartridge holder into tight contact with the reactor case by a receiving device; Closing a safety tube connecting the inside of the reactor case with the outside thereof; Opening the solvent valve and feeding the acid solution to the reagent solution by gravity; Operating a suction means to form a negative pressure inside the reactor case to discharge gaseous chlorine dioxide generated during the reaction of the acid solution and the reagent solution to the outside of the reactor case; Chlorine dioxide generation method comprising a. The method of claim 14, And forming air bubbles in the reagent solution by supplying external air to the reagent solution through an aeration tube during the formation of the negative pressure. The method of claim 14, Sequentially passing chlorine dioxide discharged out of the reactor case through a first purifier, a second purifier, and a sodium chlorite column; More, The first purifier removes the water contained in the chlorine dioxide, The second purifier removes at least one of chlorine gas contained in the chlorine dioxide, hydrochloric acid gas and the remaining moisture not removed from the primary purifier, The sodium chlorite column is filled with a mixture of sodium chlorite powder and silicon oxide powder to increase the purity of the chlorine dioxide generation method. The method of claim 14, Chlorine dioxide generation method characterized in that to remove the differential pressure inside the acid container by connecting the acid vessel and the inside of the reactor case with a differential pressure removal tube. The method of claim 14, When the reaction of the reagent solution contained in the reagent cartridge is chlorine dioxide generation method characterized in that to open the safety tube by opening the solenoid valve.

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