KR20090110785A - High Efficient Apparatus and method for manufacturing of aqueous chlorine dioxide using un-divided electrochemical cell - Google Patents

Abstract

PURPOSE: A method for manufacturing aqueous chlorine dioxide using a high efficiency un-divided electrochemical cell and a manufacturing method thereof are provided to reduce resistance of fluid and power consumption with simple structure. CONSTITUTION: A method for manufacturing aqueous chlorine dioxide using a high efficiency un-divided electrochemical cell includes a sodium chlorate feed port(10), a sodium chloride feed part(20), a mixing part(30), a feed pump(40), an electrolytic cell, and a control part(60). The mixing part mixes the supplied sodium chlorate and sodium chloride. The feed pump supplies a mixture. The electrolytic cell is comprised of a housing(51), an anode board(52), and a cation board(53). The electrolytic cell generates the chlorine dioxide oxidation by electrolyzing the mixture.

Description

High-efficiency Apparatus and method for manufacturing of aqueous chlorine dioxide using un-divided electrochemical cell}

The present invention is an apparatus and method for producing chlorine dioxide oxidized water using a highly efficient membrane-free electrolysis cell that generates chlorine dioxide by electrolysis into a membrane-free electrolysis cell using a solution of sodium chloride (NaClO ₂ ) and sodium chloride (NaCl). It is about.

Chlorine dioxide, which has attracted much attention as a new disinfectant and disinfectant to replace the existing chlorine (Cl ₂ ) oxidation water, has not only 10 times higher solubility in water than chlorine, but also about 2.5 times higher oxidation power than chlorine. Have Unlike chlorine, chlorine dioxide does not react with ammonia in the water treatment process and does not produce chloramine, which is a toxic substance.It also reacts with natural organic matter (NOM) in water and THMs (Trihalomethanes) or HAAs (Haloacetic acids). Does not produce carcinogenic disinfection by-products such as). Due to these advantages, chlorine dioxide is gradually increasing in various fields from water purification process to sterilization and disinfection of fruits and vegetables, meat and seafood sterilization, and sewage and wastewater treatment process. However, chlorine dioxide is a very unstable substance, and there is a risk of explosion at a partial pressure of 30 mmHg or more, and it is difficult to transport or store for a long time. In general, chlorine dioxide is an acidic sodium chlorite (NaClO ₂ ) or sodium chlorate (NaClO ₃ ) solution, sulfur dioxide, methanol, oxalic acid, hydrogen peroxide, sodium chloride It is mainly manufactured by chemical method using reducing agent such as (sodium chloride) and electrolysis method of diaphragm electrolytic cell method using porous or selective ion permeable membrane. The domestic application patent related to the chemical method relates to a method for the continuous production of chlorine dioxide under non-crystallization conditions in two reaction vessels. Korean Patent Application No. 10-2007-7009258 (name of the invention: a method for producing chlorine dioxide) ) And an apparatus and a method for producing chlorine dioxide by converting a chlorine dioxide generating solution into chlorine dioxide by exposure to ultraviolet rays. Korean Patent Application No. 10-2007-7009258 (Invention: Method for producing chlorine dioxide) And Korean Patent Application No. 10-2004-0059680 (name of the invention: Chlorine Dioxide Production Device), etc., which relates to a chlorine dioxide production device using a chlorite solution and an acid reaction. Patents related to the preparation of a non-membrane solution containing an aqueous pit solution containing a chlorite containing a positive electrode (Anode) and a negative electrode (Cathode) Transformation to chlorine dioxide using a cell, Korean Patent Registration No. 10-0575036 (name of the invention: chlorine dioxide generation electrolytic cell) and electrolysis type chlorine dioxide generating apparatus and method using a cation exchange membrane Patent registration No. 10-0445756 (name of the invention: electrolytic chlorine dioxide generator and method) and sodium chlorite (NaClO ₂ ) in a container containing a certain amount of water and then in the form of a sprayer with an electrolytic cell The present invention relates to an electrolytic sterilizing water production apparatus and method using the spray module connected to a container has been disclosed Korean Patent Registration No. 10-0643591 (name of the invention: an electrolytic sterilizing water production apparatus and its manufacturing method).

The methods are not economical due to the high cost of sodium chlorite (NaClO ₂ ), which is expensive, and has a problem that the concentration of chlorine dioxide oxidized water is lowered compared to the requirement of sodium chlorite (NaClO ₂ ). In addition, since the resistance imposed on the electrolytic cell is large, the power consumption is large, there is a problem uneconomical.

The present invention is to improve the above problems, an object of the present invention is to reduce the required amount of sodium chlorate to economically improve the concentration of chlorine dioxide (ClO ₂ ) oxidized water production of chlorine dioxide oxidized water using a highly efficient membrane-free electrolytic cell It is to provide an apparatus and a manufacturing method.

In addition, another object of the present invention is to provide an apparatus and method for producing chlorine dioxide oxidized water using a highly efficient membrane-free electrolytic cell that generates chlorine dioxide oxidized water economically by reducing power consumption by reducing the resistance imposed on the electrolytic cell. will be.

In addition, another object of the present invention to improve the generation efficiency of chlorine dioxide oxidized water by presenting the configuration sequence of the positive electrode and the negative electrode, as well as the separation interval between the positive electrode and the negative electrode, which is a factor affecting the efficient generation of chlorine dioxide It is to provide a chlorine dioxide oxidation water production apparatus and a manufacturing method using a high-efficiency membrane-free electrolysis cell.

An apparatus for producing chlorine dioxide oxide water using a high efficiency non-deposited membrane electrolysis cell of the present invention includes a sodium chlorate supply unit 10 for supplying sodium chlorate (NaClO ₂ ); A sodium chloride supply unit 20 for supplying sodium chloride (NaCl); A mixing unit 30 for mixing sodium chlorate and sodium chloride supplied from the sodium chlorate supply unit 10 and the sodium chloride supply unit 20, respectively; A supply pump 40 for supplying the mixed solution mixed by the mixing part 30; It consists of a housing 51, the positive electrode plate 52 and the negative electrode plate 53 which is installed at a predetermined interval inside the housing 51, the supply pump between the positive electrode plate 52 and the negative electrode plate 53 An electrolytic cell 50 for generating chlorine dioxide (ClO ₂ ) oxide water by electrolyzing the mixed solution supplied from 40 by applying a voltage to the positive electrode plate 52 and the negative electrode plate 53; And a controller 60 for controlling power and current supplied to the electrolysis cell 50. Characterized in that comprises a.

In addition, two positive electrode plates 52 are disposed in parallel, and the negative electrode plates 53 are spaced apart at regular intervals between the positive electrode plates 52.

In addition, between the positive electrode plate 52 and the negative electrode plate 53 is characterized in that the spacer 54 is further provided to be spaced apart from each other at a predetermined interval.

In addition, the spacers 54 are spaced apart from each other and are arranged alternately left and right to form a zigzag flow path.

In addition, the mixing unit 30 is characterized in that the venturi mixer or line mixer.

In addition, a preheater 70 is provided between the supply pump 40 and the electrolytic cell 50 and preheats the mixed solution of sodium chlorate and sodium chloride supplied to the supply pump 40. .

The concentration of sodium chlorate (NaClO ₂ ) is 0.2-1.0 g / L, the concentration of sodium chloride (NaCl) is 2-10 g / L, and the pH of the sodium chlorate (NaClO ₂ ) / sodium chloride (NaCl) mixed solution is It is characterized by being 2-5.

In addition, the current density of the positive electrode plate 52 and the negative electrode plate 53 is characterized in that 1 ~ 10 A / dm ² .

In addition, the injection flow rate of the sodium chlorate (NaClO ₂ ) / sodium chloride (NaCl) mixed solution by the feed pump 40 into the membrane-free electrolytic cell 50 is characterized in that 30 ~ 150 ml / min.

In addition, the positive electrode plate 52 and the negative electrode plate 53 is characterized in that the electrode of any one selected from DSA electrode, Pt electrode, Ti electrode made of IrO ₂ / Ti or RuO ₂ / Ti.

In addition, the positive electrode plate 52 and the negative electrode plate 53 is characterized in that the porous electrode in the form of a mesh.

In addition, the separation distance between the positive electrode plate 52 and the negative electrode plate 53 is characterized in that 0.6 ~ 2.0 mm.

The present invention can reduce the required amount of sodium chlorate very economically can improve the concentration of chlorine dioxide oxidized water, and can reduce the power consumption by reducing the resistance imposed on the electrolytic cell, the feed solution flows out through the electrolytic cell It is suitable for industrial use that does not require purity by adopting continuous flow type rather than recycling part of the ion, and the ion exchange membrane or between porous anode and cathode plates Since no porous material is used, the resistance of the fluid is relatively low.

Hereinafter, a chlorine dioxide oxidized water production apparatus and a manufacturing method using a high efficiency non-capacity electrolytic cell according to the present invention will be described with reference to the accompanying drawings.

1 is a view showing an electroless apparatus of a membrane-free electrolytic cell type for the production of chlorine dioxide, Figure 2 is a cross-sectional view of the membrane-free electrolytic cell, Figure 3 is an exploded perspective view of the membrane-free electrolytic cell.

As shown, an apparatus for producing chlorine dioxide oxidized water using a membrane-free electrolytic cell according to the present invention includes a sodium chlorate supply unit 10 for supplying sodium chlorate (NaClO ₂ ); A sodium chloride supply unit 20 for supplying sodium chloride (NaCl); A mixing unit 30 for mixing sodium chlorate and sodium chloride supplied from the sodium chlorate supply unit 10 and the sodium chloride supply unit 20, respectively; A supply pump 40 for supplying the mixed solution mixed by the mixing part 30; An electrolysis cell 50 for supplying a mixed solution from the supply pump 40 and having a positive electrode plate 52 and a negative electrode plate 53 spaced apart from each other and electrolyzing the supplied mixed solution; And a controller 60 for controlling power and current supplied to the electrolysis cell 50. It is made, including.

The mixing unit 30 serves to mix sodium chlorate and sodium chloride supplied from the sodium chlorate supply unit 10 and the sodium chloride supply unit 20, respectively. The mixing unit 30 is preferably a venturi mixer or line mixer.

The electrolytic cell 50 is supplied with a mixed solution of sodium chlorate and sodium chloride supplied from the supply pump 40 and serves to electrolyze the supplied mixed solution and form a membrane.

The electrolytic cell 50 is a positive electrode plate 52 and a negative electrode of the electrolyte solution consisting of a mixed solution of sodium chlorate and sodium chloride is injected through the injection port 55 and the sodium chlorate and sodium chloride mixed solution spaced apart from each other inside the housing 51 Passed between the plates 53. At this time, the electrolytic solution is electrolyzed by applying a voltage to the positive electrode plate 52 and the negative electrode plate 53 to generate chlorine dioxide (ClO ₂ ) oxide water. The generated chlorine dioxide oxidized water is discharged through the outlet 56.

In the drawing, two positive electrode plates 52 are arranged in parallel, and a negative electrode plate 53 is interposed between the positive electrode plates 52.

In addition, the electrolytic cell 50 is made of a non-aluminum membrane that does not use an ion exchange membrane or any porous material between the porous anode and anode plates (Cathode) so that the resistance of the fluid is relatively low.

In addition, since the electrolytic cell 50 uses a continuous flow type rather than a part of the effluent after the feed solution passes, it is suitable for industrial use that does not require purity and is simple in structure.

Preferred electrode composition of the membrane-free electrolytic cell is RuO ₂ / Ti as the positive electrode plate (Anode) by using IrO ₂ / Ti electrode of the DSA electrode as the positive electrode plate (Anode), Pt electrode as the cathode electrode (Cathode). cathode) if a or the positive electrode plate (Anode) the case of using Ti with the IrO ₂ / Ti as Pt, the negative electrode plate (cathode), the IrO ₂ / Ti, a negative electrode plate (cathode) a positive electrode plate (Anode) with Ti Chlorine dioxide (ClO ₂ ) can be more effectively generated than the non-diaphragm electrolytic cell.

In addition, the positive electrode plate 52 and the negative electrode plate 53 is more preferably a porous electrode in the form of a mesh.

The distance between the positive electrode plate 52 and the negative electrode plate 53 is preferably 0.6 ~ 2.0 mm. If the separation distance is too large, the chlorine dioxide oxidant generation concentration is too low, if the separation distance is too small it is preferable to have a suitable separation distance because the fluidity of the mixed solution is less.

In addition, the spacers 54 may be spaced apart from each other and arranged alternately left and right to form a zigzag flow path. When the spacer 54 is spaced apart from each other to form a zigzag flow path, the concentration of the chlorine dioxide oxidized water can be increased by extending the time for the electrolyte to contact the electrode plate.

It is preferable that the controller 60 for controlling the power and current supplied to the electrolytic cell 50 is provided.

It is preferable that the preheater 70 is provided between the supply pump 40 and the electrolytic cell 50 to preheat the mixed solution of sodium chlorate and sodium chloride supplied to the supply pump 40. As the preheater 70 is provided, the electrolysis efficiency can be increased, thereby increasing the generation efficiency of chlorine dioxide oxidized water.

1. Experimental Materials and Equipment

In this experiment, precursors of chlorine dioxide (starting material) were purchased using NaClO ₂ (manufacturer: Kanto Chemical Co. Inc. Japan) and NaCl (manufacturer: Daejung Chemicals & Metals Co. Ltd., Korea), and the pH of the solution Was adjusted using H ₂ SO ₄ (manufacturer: DC Chemical Co. Ltd., Korea). The current supplied to the electrolytic cell was constantly supplied using a DC power supply (10V, 50A, Korea Switching Inc., Korea).

2. Experiment and Analysis Method

NaClO ₂ solution concentration was 0.2 ~ 1.0 g / L, NaCl concentration was 2 ~ 10 g / L experiments were carried out under various conditions, pH range of NaClO ₂ / NaCl mixture solution is 2.5 ~ 5, the reaction temperature is At room temperature (about 19-20 ° C.). Mesh type DSA electrodes (IrO ₂ / Ti, RuO ₂ / Ti), Pt and Ti electrodes were used as electrodes of the non-diaphragm electrolytic cell, and the supplied current density was performed in the range of 1 to 10 A / dm ² . . The concentration of chlorine dioxide generated by the membrane-free electrolysis of NaClO ₂ / NaCl mixture solution was measured using a UV / Vis spectrophotometer (λ = 445 nm, HACH DR 2500, USA).

3. Example 1

A Ti electrode coated with RuO ₂ as an anode and Ti as a cathode. A 1 mm thick Teflon spacer 44 was used to separate the positive electrode plate 52 and the negative electrode plate 53. The experimental conditions were sodium chlorite (NaClO ₂ ) concentration of 4.7 mM (0.54 g / L), sodium chloride (NaCl) concentration of 100 mM (6.0 g / L), electrolyte injection rate of the precursor solution 120 ml / min, initial pH of the precursor solution. 2.3, the current was applied to the electrolytic cell was 0.6 A (5 A / dm ² ) to perform the experiment under the same conditions, the results are shown in [Table 1].

[Table 1] shows the chlorine dioxide oxidized water generation concentration according to the composition of the electrode combination and the spacer zigzag flow path.

[Table 1] Chlorine Dioxide Oxidation Water Concentration According to Composition of Electrode Combination and Spacer in Zigzag Channel

※ Explanation of Symbols: A = Anode, C = Cathode

As shown in Table 1, the separation distance between the positive electrode plate 52 and the negative electrode plate 53 is fixed at 1.0 mm in the high-performance non-aqueous electrolyte cell, and the spacer 54 constitutes a zigzag flow path, and the zigzag flow path is not provided. As a result of measuring the concentration of chlorine dioxide generated by varying the amount of chlorine, it was found that the combination of the electrode having the highest chlorine dioxide generation efficiency was ACA. Even in the same ACA combination, the concentration of chlorine dioxide generated when the spacer 54 constitutes a zigzag flow path and when the spacer 54 is not formed is 360 mg / L and 420 mg / L, respectively. The effect of chlorine dioxide on the surface of the electrode surface where chlorine dioxide is generated and the effect of turbulence on the flow path were affected by the electrode arrangement and structure of the electrolytic cell. Judging by

4. Example 2

Figure 4 is a positive electrode plate (Anode) to the concentration of IrO ₂ / Ti, a negative electrode plate (Cathode) of the concentration of NaClO ₂ in a non-membrane electrolysis cell with a Pt 0.4 g / L, NaCl shown in Figs 10 g / L, the pH of the solution is 9.5, the chlorine dioxide concentration of the effluent generated by the electrolytic cell injection flow change under the conditions of the supplied current density 5A / dm ² .

The chlorine dioxide concentration in the effluent stabilized within about 5 to 10 minutes, and as the flow rate increased, the concentration of chlorine dioxide generated in the effluent increased, but the flow rate increased over 90 ml / min due to the high flow rate. The degassing rate of heavy chlorine dioxide was increased and decreased. The concentration of chlorine dioxide measured at a flow rate of 90 ml / min was about 254 ppm.

5. Example 3

5 is delivered free diaphragm when the pH of the concentration of NaClO ₂ to a concentration of 0.4 g / L, NaCl to 10 g / L and, NaClO ₂ and NaCl mixture is hayeoteul to 9.58, the electrolytic cell injection flow rate to 90 ml / min It shows the chlorine dioxide concentration in the effluent according to the change of the current density supplied to the cell. At a current density of 1A / dm ² 10 A / increases until dm ² proportional increase in the concentrations 144 ppm of chlorine dioxide in the effluent to 339 ppm, however, the electrolytic measured voltage due to the increase in resistance will be charged to the cell is also 2.4 Increased from V to 4.0 V.

6. Example 4

6 shows that the concentration of NaClO ₂ is 0.4 g / L, the concentration of NaCl is 10 g / L, the electrolyte injection rate is 90 ml / mi, and the current density supplied to the electrolyte cell is 5 A / dm ² . When the pH of the NaClO ₂ and NaCl mixture solution changes, the chlorine dioxide concentration changes in the effluent. The concentration of ClO ₂ in the electrolysis effluent at high pH of NaClO ₂ / NaCl mixture was about 280 ppm, but when the pH was 3 ~ 3.5, the ClO ₂ concentration rapidly increased from 230 ppm to 180 ppm. There was a slow decrease between pH 3.5 and 5 and a decrease from 180 ppm to 165 ppm. This, and a more stable chlorine dioxide at a low pH range, when the pH increases the hydroxide ion (OH ^-) in water to have the chlorine dioxide reaction Chlorite (ClO ₂ ^-) or Chlorate (ClO ₃ ^-) predicted due to form an ion do. The optimum pH was about 2.9 ~ 3 considering the dose of H ₂ SO ₄ injected and the concentration of chlorine dioxide injected for pH adjustment.

7. Example 5

7 shows that the concentration of NaCl is 10 g / L, the injection flow rate of the electrolytic cell is 90 ml / min, the pH of the NaClO ₂ and NaCl mixture solution is 2.93, and the current density supplied to the electrolysis cell is 5 A / dm ² . When the concentration of NaClO ₂ was increased from 0.2 g / L to 0.9 g / L, the concentration of chlorine dioxide in the effluent was shown. As the concentration of NaClO ₂ increased, the concentration of chlorine dioxide in the eluate increased, but the concentration of chlorine dioxide in the eluate slowed down at concentrations above 0.5 g / L. At a concentration of 0.5 g / L NaClO _{2, the} concentration of chlorine dioxide was about 255 ppm.

8. Example 6

8 shows the concentration of NaClO ₂ as 0.5 g / L, the injection flow rate of the electrolytic cell was 90 ml / min, the pH of the NaClO ₂ and NaCl mixture solution was 2.93, and the current density supplied to the electrolysis cell was 5 A / dm ² . When the concentration of NaCl increases from 2 g / L to 10 g / L shows the change in the concentration of chlorine dioxide in the effluent. As the concentration of NaCl in the NaClO ₂ / NaCl mixture increased, the concentration of chlorine dioxide generated also increased, and the voltage applied to the non-deposited electrolyte cell also decreased. This is because NaCl acts as an electrolyte, reducing the resistance imposed on the electrolytic cell, thereby increasing the electrolytic cell efficiency, and NaCl is also converted into chlorine dioxide along with NaClO ₂ to increase the concentration of chlorine dioxide in the eluate.

9. Comparative Example

9 and 10 show that the concentration of NaClO ₂ is 0.5 g / L, the concentration of NaCl is 10 g / L, the electrolytic cell injection flow rate is 90 ml / min, the pH of the NaClO ₂ and NaCl mixture solution is 2.93, It shows the change of chlorine dioxide generation concentration and the change of voltage across electrolytic cell when the supplied current density is 5 A / dm ² and when NaClO ₂ is injected without NaCl at the same pH, current density, and electrolytic cell injection flow rate. will be. When NaClO ₂ alone is used, the maximum concentration of chlorine dioxide is about 80 ppm and the voltage on the electrolytic cell is about 9.8 V. However, the concentration of chlorine dioxide in the mixed solution with NaCl is about 200 ppm, electrolytic The voltage across the cell was about 3V. This can not only effectively improve the concentration of ClO ₂ when using a solution in which NaCl is mixed with NaClO ₂ than in the case of using NaClO ₂ alone in a membrane-free electrolysis cell reactor to generate chlorine dioxide, It shows that there is an advantage that the added voltage can be lowered efficiently.

1 is a view showing an electrolysis device of the membrane-free electrolysis cell method for producing chlorine dioxide water.

2 is a cross-sectional view of a non-diaphragm electrolytic cell.

Figure 3 is an exploded perspective view of the non-diaphragm electrolysis cell.

Figure 4 is a graph showing the concentration of chlorine dioxide in the effluent generated according to the flow rate of the membrane-free electrolytic cell injection of NaClO ₂ / NaCl mixture solution.

5 is a graph showing the change in the concentration of chlorine dioxide in the effluent and the voltage change of the electrolytic cell according to the supplied current density.

Figure 6 is a graph showing the chlorine dioxide concentration change and pH change in the effluent according to the pH change of the NaClO ₂ / NaCl mixture solution.

7 is a graph showing the change in the concentration of chlorine dioxide in the effluent according to the change in NaClO ₂ concentration in the NaClO ₂ / NaCl mixture solution.

8 is a graph showing the change in chlorine dioxide concentration in the eluate according to the change in NaCl concentration in NaClO ₂ / NaCl mixture solution.

9 is a graph showing a comparison of chlorine dioxide generation concentrations of NaClO ₂ single solution and NaClO ₂ / NaCl mixed solution.

Figure 10 is a graph showing the comparison of the electrolytic cell voltage required for the electrolysis of NaClO ₂ single solution and NaClO ₂ / NaCl mixture solution.

* Description of the symbols for the main parts of the drawings *

10: sodium chlorate supply 20: sodium chloride supply

30: mixing section 40: supply pump

50: electrolytic cell 51: housing

52: positive electrode plate 53: negative electrode plate

54: spacer 60: control unit

70: preheater

Claims (13)

Sodium chlorate supply unit 10 for supplying sodium chlorate (NaClO ₂ ); A sodium chloride supply unit 20 for supplying sodium chloride (NaCl); A mixing unit 30 for mixing sodium chlorate and sodium chloride supplied from the sodium chlorate supply unit 10 and the sodium chloride supply unit 20, respectively; A supply pump 40 for supplying the mixed solution mixed by the mixing part 30; It consists of a housing 51, the positive electrode plate 52 and the negative electrode plate 53 which is installed at a predetermined interval inside the housing 51, the supply pump between the positive electrode plate 52 and the negative electrode plate 53 An electrolytic cell 50 for generating chlorine dioxide (ClO ₂ ) oxide water by electrolyzing the mixed solution supplied from 40 by applying a voltage to the positive electrode plate 52 and the negative electrode plate 53; And A controller 60 for controlling power and current supplied to the electrolytic cell 50; Chlorine dioxide oxidized water production apparatus using a high-efficiency membraneless electrolytic cell comprising a. The method of claim 1, The two positive electrode plates 52 are arranged in parallel, and the negative electrode plate 53 is an apparatus for producing chlorine dioxide oxide water using a high efficiency non-aqueous electrolyte cell, which is spaced apart at regular intervals between the positive electrode plates 52. . The method of claim 2, Chlorine dioxide oxidized water production apparatus using a high efficiency non-deposited membrane electrolytic cell, characterized in that the spacer 54 is further provided between the positive electrode plate 52 and the negative electrode plate 53 to be spaced apart from each other at a predetermined interval. The method of claim 3, wherein The spacer (54) is a plurality of spaced apart and arranged to the left and right alternately to form a zigzag flow path chlorine dioxide oxidized water production apparatus using a high efficiency non-aluminum electrolytic cell, characterized in that arranged. The method of claim 4, wherein The mixing unit 30 is a chlorine dioxide oxidized water production apparatus using a high-efficiency membraneless electrolytic cell, characterized in that the venturi mixer or line mixer. The method of claim 5, wherein It is provided between the supply pump 40 and the electrolytic cell 50, the high efficiency zero, characterized in that further provided with a preheater 70 for preheating the mixed solution of sodium chlorate and sodium chloride supplied to the supply pump 40 Chlorine dioxide oxidation water production apparatus using a diaphragm electrolysis cell. The method of claim 6, The concentration of sodium chlorate (NaClO ₂ ) is 0.2-1.0 g / L, the concentration of sodium chloride (NaCl) is 2-10 g / L, and the pH of the mixed solution of sodium chlorate (NaClO ₂ ) / sodium chloride (NaCl) is 2- Chlorine dioxide oxidized water production apparatus using a highly efficient membrane-free electrolytic cell, characterized in that 5. The method of claim 7, wherein The current density of the positive electrode plate 52 and the negative electrode plate 53 is 1 ~ 10 A / dm ² Chlorine dioxide oxidized water production apparatus using a high efficiency non-deposited membrane electrolytic cell, characterized in that. The method of claim 8, The high flow rate membrane-free electrolytic cell, characterized in that the injection flow rate of the sodium chloride chlorine (NaClO ₂ ) / sodium chloride (NaCl) mixed solution by the supply pump 40 into the membrane-free electrolytic cell 50 is 30 ~ 150 ml / min Chlorine dioxide oxidation water production apparatus using. The method of claim 9, The positive electrode plate 52 and the negative electrode plate 53 are made of any one electrode selected from a DSA electrode, a Pt electrode, and a Ti electrode of IrO ₂ / Ti or RuO ₂ / Ti. Chlorine dioxide oxidation water production apparatus using. The method of claim 10, The positive electrode plate 52 and the negative electrode plate 53 is a chlorine dioxide oxidized water production apparatus using a high-efficiency membrane-free electrolytic cell, characterized in that the porous electrode in the form of a mesh. The method of claim 11, The distance between the positive electrode plate 52 and the negative electrode plate 53 is chlorine dioxide oxidized water production apparatus using a high efficiency non-deposited electrolytic cell, characterized in that the 0.6 ~ 2.0 mm. A method for producing chlorine dioxide oxidized water using a highly efficient membrane-free electrolytic cell, characterized by producing chlorine dioxide oxidized water using the apparatus according to any one of claims 1 to 12.

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