KR100817730B1 - A chlorine dioxide generator and method - Google Patents

Abstract

An apparatus for generating chlorine dioxide and a process for producing chlorine dioxide are provided to produce chlorine dioxide in a safe and economical manner by using chlorite hardly having aging characteristics produced locally by a salt electrolyzing method, and enable the cathodic electrolyzed water to be used repeatedly by neutralizing cathodic electrolyzed water with hydrochloric acid. An apparatus for generating chlorine dioxide comprises: an anodic electrolyzed water tank(20) for supplying anodic electrolyzed water that is an electrolysis raw material through a salt water pipe(21); a cathodic electrolyzed water tank(28) for supplying cathodic electrolyzed water that is an electrolysis raw material through a salt water pipe(23) and receiving hydrogen through a hydrogen exhaust pipe(27); electrolyzed water injectors(22,24) installed on the salt water pipes to inject electrolyzed water into the salt water pipes; an electrolyzer(25) which is divided into an anode and a cathode by an ion exchange membrane, and receives the anodic electrolyzed water and the cathodic electrolyzed water from the anodic electrolyzed water tank and the cathodic electrolyzed water tank; a chlorite tank(30) for storing chlorite that is a reaction raw material; a hydrochloric acid tank(34) for storing hydrochloric acid; a hydrochloric acid metering pump(35) into which a fixed quantity of hydrochloric acid is supplied from the hydrochloric acid tank, and which enables the neutralized sodium hydroxide to be reused as cathodic electrolyzed water by neutralizing sodium hydroxide in the hydrochloric acid tank; a mixer(32) for mixing hypochlorite or chlorine generated in an anode region of the electrolyzer with chlorite to generate chlorine dioxide; and an aqueous solution storage and gas separation tank(40) for storing chlorine dioxide generated from the mixer.

Description

Chlorine dioxide generator and method

1 is a schematic configuration diagram of a chlorine dioxide generating device of the present invention

2 is another embodiment of FIG. 1

3 and 4 are views for explaining the chlorine dioxide gas generator and the chlorine dioxide solution of the present invention

<Explanation of symbols for main parts of drawing>

20: anode electrolytic water tank 21.23: brine pipe

22,24: Electrolyzed water injector 25: Brine electrolyzer
26: anode electrolytic water pipe 27: hydrogen exhaust pipe
28: cathode electrolytic water tank 30: chlorite tank

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31: Chlorine chlorine injector 32: Mixer

33: Chlorine dioxide transport pipe 34: Hydrochloric acid tank

35: hydrochloric acid fixed pump 40, 60: aqueous solution storage and gas separation device

41: Pressurized air inlet 43, 44: Valve

42,63: Microfiber filter 50: Ion exchange membrane

51: anode 52: cathode

61: Pressurized air ejector 62: Air inlet

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The present invention relates to a chlorine dioxide generating apparatus and a manufacturing method having a bactericidal disinfection and deodorizing effect.

Generally, chlorine dioxide has strong oxidizing power, sterilizing power, deodorizing power, and unlike other chlorine disinfectant disinfectants, carcinogenic organic substances such as trihalomethane (THMs), halo acetic nitrate (HAAs), and halo acetonitrile (HANs) It does not generate and does not produce organic chlorine compounds by reacting with other organic materials, so it is widely used as a tap water purification plant, sewage / wastewater disinfection and deodorant, and is known as an eco-friendly disinfectant that has no residue because it is rapidly decomposed by sunlight or temperature.

The conventional method for producing chlorine dioxide is to produce chlorine by electrolyzing salt at high temperature without unfavorable membrane when producing in large capacity (several to several hundred tons by weight of chlorine dioxide) and reducing the chlorate with reducing sulfite or hydrochloric acid Was synthesized.

(전기분해)→

또는

(Electrolysis) →

or

　→

→

→

→

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In addition, where chlorine dioxide is needed for several tens to hundreds of kilograms per day, chlorine dioxide is oxidized to produce chlorine dioxide. The following methods are known.

1) chlorite and chlorine method

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→

2) chlorite, hypochlorite and inorganic acid method

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3) When chlorine dioxide is produced by reacting with chlorite and hydrochloric acid or sulfuric acid, the reaction rate is faster than a certain concentration of chlorine or inorganic acid, but a lot of by-products are generated due to a slow reaction rate at too diluted concentration.

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→

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,

,

,

등의 부산물이 최소화되게 억제할 수 있는 반응조건을 알아내는 것이 대단히 중요하다.As shown in the above methods, the reaction does not proceed simply by reaction, but chlorine dioxide is produced while chlorine acid produces an intermediate decomposition reaction with hypochlorous acid or chloric acid.

,

,

,

It is very important to find out the reaction conditions that can suppress the by-products such as to minimize.

In other words, these reactions can minimize the side reactions by controlling the ratio and concentration of the reactants and the method of rapid and uniform mixing of the reactants, proper acidity and concentration, so that high purity chlorine dioxide can be obtained.

When chlorine dioxide is prepared using chlorite as a starting material, high pressure toxic chlorine gas or hypochlorite may cause severe change over time and storage difficulties, and chlorite and high concentration of hydrochloric acid or sulfuric acid. In order to minimize the reactants, it is not easy to control the reaction conditions, and technical personnel with expertise and expensive safety facilities for accidents are essential.

,

)이 부착되어 전극의 효율이 떨어지고 오래 지속되면 거의 전기분해가 일어나지 않으며 다시 전극판을 산으로 재생하여 사용하여야 하는 번거로움이 있다. In addition, conventionally, hydrogen and caustic soda are generated at the cathode during the electrolysis of salt and trace impurities (Ca, Mg) are present in the electrolytic water and high purity salt.

,

), The efficiency of the electrode decreases, and if it lasts for a long time, almost no electrolysis occurs and there is a need to regenerate the electrode plate with acid again.

In the present invention, using a salt electrolysis method known long time ago, chlorine dioxide produced in the country and using little chlorite with little change over time can be produced in a safe and economical way, re-repetitive by neutralizing the cathode electrolytic water with hydrochloric acid It is to provide a chlorine dioxide generator and a manufacturing method that can be used.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1 and 2 is a schematic configuration diagram of the present invention, the configuration of the other parts are all the same, but in the case of Figure 1 shows a case further provided with an ejector 61.

)가 아염소산염과 혼합하여 이산화염소를 발생시키는 혼합기(32)와, 상기 혼합기(32)로부터 발생된 이산화염소를 저장하는 수용액저장 및 기체분리탱크(40)와, 상기 수용액저장 및 기체분리탱크(40)로부터 배출되는 가스상태의 이산화염소의 개폐를 제어하는 밸브(44) 및 액상상태의 이산화염소의 개폐를 제어하는 밸브(43)와, 상기 수용액저장 및 기체분리탱크(40)에 고압공기를 제공하는 이젝터(61)를 포함하여 구성된 것이다.As shown in the drawing, the positive electrode electrolyzed water tank 20 for supplying the positive electrode electrolyzed water as the electrolytic raw material through the brine pipe 21 and the negative electrode electrolyzed raw material as the electrolytic raw material through the brine pipe 23 and the hydrogen exhaust pipe 27 Cathode electrolytic water tank (28) receiving hydrogen through the), the electrolyzed water injectors 22, 24 installed through the brine pipes (21, 23) to feed the electrolytic water, and through the ion exchange membrane (50) An electrolysis tank 25 separated from the positive electrode 51 and the negative electrode 52 and receiving the positive and negative electrolytic water from the positive and negative electrolytic water tanks 20 and 28, and a hydrochloric acid tank 34 containing hydrochloric acid. ) And a chlorite tank (30) storing chlorite as a reaction raw material, a hydrochloric acid metering pump (35) for supplying a fixed amount of hydrochloric acid from the hydrochloric acid tank (34), and an anode region of the electrolysis tank (25). Hypochlorous acid (HClO) or chlorine

Is mixed with chlorite to generate chlorine dioxide 32, an aqueous solution storage and gas separation tank 40 for storing the chlorine dioxide generated from the mixer 32, and the aqueous solution storage and gas separation tank ( The valve 44 for controlling the opening and closing of the gaseous chlorine dioxide discharged from the gas 40 and the valve 43 for controlling the opening and closing of the chlorine dioxide in the liquid state, and the high pressure air in the aqueous solution storage and gas separation tank 40 It is configured to include an ejector 61 to provide.

3 and 4 show the gas and liquid phase of the aqueous solution storage and gas separation tank 40, the case of Figure 4 shows the case where the ejector 61 is further added.

First, in the case of Figure 3, the pressurized air inlet 41 for introducing air into the aqueous solution storage and gas separation tank 40, the chlorine dioxide transport pipe 33 for introducing the chlorine dioxide, the aqueous solution storage and gas Valve 44 is installed at the top of the separation tank 40 for discharging chlorine dioxide in the gas state, and valve for discharging the chlorine dioxide in the liquid state is installed at the bottom of the aqueous solution storage and gas separation tank 40 It is composed of (43).

4, the air inlet 62 for introducing air into the aqueous solution storage and gas separation tank 60, the chlorine dioxide transport pipe 33 for introducing the chlorine dioxide, and the aqueous solution storage and gas separation. It is installed at the upper end of the tank 60, the pressurized air ejector 61 for introducing air, and the valve 43 for discharging the chlorine dioxide in the liquid phase is installed at the lower end of the aqueous solution storage and gas separation tank 40 It is composed.

Referring to the operation of the present invention configured as described above is as follows.

)가 아염소산염과 혼합하여 이산화염소가 발생되는 혼합기(32), 또 혼합기(32)에서 발생된 이산화염소 수용액을 저장하는 수용액저장 및 기체분리탱크(40)로 구성되어 있다.Chlorine dioxide generator according to the present invention is a salt water (NaCl) tank (20,28) of the electrolytic raw material and chlorite tank (30) of the reaction raw material, hypochlorous acid (HClO) or chlorine (HClO) generated in the anode region of the electrolysis tank

) Is composed of a mixer 32 in which chlorine dioxide is generated by mixing with chlorite, and an aqueous solution storage and gas separation tank 40 for storing an chlorine dioxide aqueous solution generated in the mixer 32.

The chlorine dioxide aqueous solution storage and gas separation tank 40 is sterilized and sterilized and deodorized in a gaseous phase by extracting and evaporating chlorine dioxide into an aqueous solution or air according to the purpose of use.

The gas method is equipped with a microporous generation filter 42, which is a porous filter made of fine porous (less than 10μm) porcelain or porcelain installed at the bottom of the aqueous solution storage and gas separation tank 40, and pressurized air inlet 41 from the outside. Through the input of compressed air, fine air bubbles rise and chlorine dioxide is extracted and discharged together with air.

In addition, Figure 4 shows another embodiment of the present invention, by using a pressurized air ejector 61 chlorine dioxide aqueous solution storage and gas bubbles generated by the pressure generated in the gas separation tank 60, the fine air bubbles, the droplets are top Chlorine dioxide is extracted and discharged together with air while rising to the air, and the micro-bubble generation filter 63 is installed inside the chlorine dioxide aqueous solution storage and gas separation tank 60.

The electrolysis tank 25 is provided with an ion exchange membrane (Membrane) 50 for separating the anode region and the cathode region.

)가 발생되며, 이 염소 분자는 물에서 가수분해되어 차아염소산과 염산이 만들어진다.Salt, which is a raw material, is dissociated from water and separated into Na + and Cl- ions.

), These chlorine molecules are hydrolyzed in water to form hypochlorous acid and hydrochloric acid.

The cathode electrolyzed water is introduced into the mixer 32 through the anode electrolyzed water pipe 26. In the mixer 32, the chlorite as a reactant is mixed from the chlorite tank 30 to generate chlorine dioxide, thereby storing an aqueous solution of chlorine dioxide. It is stored in the gas separation tank (40).

This process is represented by the following formula.

→

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→

anode

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+

→

+

→

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+

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+

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The chlorine dioxide aqueous solution thus generated is stored in the aqueous solution storage and gas separation tank 40 and the chlorine dioxide aqueous solution is used as a disinfectant disinfectant and deodorant in the liquid or gas phase according to the purpose. As it is discharged through the valve 43, when used as a gas is to be discharged through the valve 44 of the aqueous solution storage and gas separation tank 40, the gas can be used as a gas type.

)이 부착되지 않아 음극판의 효율을 극대화 할 수 있다.Hydrogen generated at the cathode is discharged to the atmosphere, and caustic soda can be neutralized by hydrochloric acid metering pump 35 in hydrochloric acid tank 34 to be reused as cathode electrolytic water. Scale on negative plate due to repeated use

) Is not attached, so the efficiency of the negative electrode plate can be maximized.

<Example 1>

2% of brine is added to the electrolysis tank 25 at 100ml / min. At this time, the voltage is fixed at 5V (8A) to electrolyze. Electrolyzed water and chlorite solution 100ml / min (0.342%) When introduced into the mixer 32, chlorine dioxide (351 ppm) is generated.

<Example 2>

2% of brine is added to the electrolysis tank 25 at 50ml / min, and the voltage is electrolyzed by fixing at 5V (11A), and 50ml / min (0.152%) of electrolytic water and chlorite solution produced at the anode When introduced into the mixer 32, chlorine dioxide (1,133 ppm) is generated.

<Example 3>

Add 3% brine to the electrolysis tank 25 at 100ml / min, and fix the voltage at 5V (12A) to electrolyze, and mix electrolyzed water and chlorite solution 100ml / min (0.3%) When added to (32), chlorine dioxide (1,119 ppm) is generated.

<Example 4>

3% of the brine is added to the electrolysis tank 25 at 50 ml / min, and the electrolysis is performed by fixing the voltage at 5 V (16 A), and 50 ml / min (0.452%) of the positive electrode electrolyzed water and the chlorite solution are mixed (32 ) Produces chlorine dioxide (3,371 ppm).

<Example 5>

Aqueous chlorine dioxide solution (3,370ppm) was put into an aqueous solution storage and gas separation tank 40 (10 cm in diameter and 100 cm in length) with a micro-bubble filter 42 having a 10 μm fine pore, and injected with 200 ml of air per minute for 15 minutes. About 80% of chlorine dioxide was extracted by microbubbles.

<Example 6>

Aqueous chlorine dioxide solution (3,370ppm) is placed in an aqueous solution storage and gas separation tank (60) (10 cm in diameter and 100 cm in length) with a 10-micron fine pore micro-bubble filter (63) attached to the ejector (61). When operating, the decompression was carried out inside the column, and fine bubbles were generated at the bottom of the aqueous solution storage and gas separation tank 60, and ascending, chlorine dioxide was extracted 83% after about 18 minutes.

Unlike the chlorinated disinfectant, the present invention as described in detail above does not generate carcinogenic organic chlorine compounds (THMs, HAAs, HANs) and has strong sterilization and deodorizing power after ozone.

In addition, the present invention can be used even without specialized knowledge because the chlorine dioxide production apparatus is simple and there is no risk, and there is an effect that can significantly reduce the cost of electricity, production raw materials.
In addition, the present invention has the effect that can be used even where the liquid sterile disinfection and deodorant can not be used by using pure chlorine dioxide gas as air.

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Claims (5)

The anode electrolyzed water tank 20 supplies the anode electrolyzed water as an electrolytic raw material through the brine pipe 21, and the cathode electrolyzed water as the electrolytic raw material through the brine pipe 23, and supplies hydrogen through the hydrogen exhaust pipe 27. The anode 51 and the cathode through the receiving cathode electrolytic water tank 28, the brine pipes 21 and 23, and the electrolyzed water injectors 22 and 24 for introducing the electrolyzed water, and the ion exchange membrane 50. An electrolysis tank 25, which is separated into 52 and receives the anode electrolyte and the cathode electrolyte from the cathode electrolytic water tank 20 and the anode electrolyzed water tank 28, is a hydrochloric acid tank 34 containing hydrochloric acid and a reaction raw material. Hydrochloric acid fixed quantity pump (35) and the chlorite tank 30, the chlorite is stored in the hydrochloric acid tank 34, and the caustic soda is neutralized in the hydrochloric acid tank (34) to be reused as a cathode electrolytic water and Hypochlorous acid or chlorine generated in the anode region of the electrolysis tank 25 Chlorine dioxide generator, characterized in that it comprises a mixer 32 for mixing with chlorite to generate chlorine dioxide, and an aqueous solution storage and gas separation tank 40 for storing the chlorine dioxide generated from the mixer 32 . According to claim 1, wherein the aqueous solution storage and gas separation tank 40, the micro-bubble generating filter 42 for generating fine air bubbles when compressed air flows from the outside, and a valve for discharging chlorine dioxide in the liquid state And a valve (44) for discharging the chlorine dioxide converted into the gas state by the bubbles generated from the microbubble generation filter (42). The method of claim 1, wherein the ejector 61 is installed on the outside of the aqueous solution storage and gas separation tank 40, the pressure reduction is formed in the aqueous solution storage and gas separation tank 40, characterized in that configured to generate bubbles Chlorine Generator. delete delete

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