KR20060057838A - Repair methods of persistent contaminated soil by using high concentrated ozone water and its device - Google Patents

Abstract

The present invention relates to a method and apparatus for restoring a hardly degradable contaminated soil using high concentration ozone water.

Conventionally, there are problems such as deterioration of physical and chemical properties of soil and generation of secondary pollutants by directly treating redox agents with contaminated soil. To remove the pollutants in an environmentally friendly way, but by improving the ozone generator to increase ozone generation and increase the dissolved ozone concentration in the water, the ozone water, which has greatly improved chemical activity, is treated with contaminated soil to remove organic pollutants in the soil. By improving the physical and chemical properties of the soil, preventing the generation of secondary pollutants, and eco-friendly restoration of the contaminated soil by the existing chemical treatment, such as the rapid treatment efficiency, the efficiency, promptness and environmental friendliness In addition to restoration of contaminated soil, It is designed to handle fires and wastes.

Soil, ozone, eco-friendly, ozone water, high concentration, pollution, restoration, field treatment, pesticide, indigenous

Description

REPAIR METHODS OF PERSISTENT CONTAMINATED SOIL BY USING HIGH CONCENTRATED OZONE WATER AND ITS DEVICE}

1: shows various factors affecting ozone production characteristics.

2 is a block diagram of an embodiment of the present invention.

3 is a configuration of a cooling cycle of the raw material gas cooling device of the present invention.

4 is a schematic diagram of source gas cooling according to an embodiment of the present invention.

5 is a schematic diagram of source gas cooling according to another embodiment of the present invention.

6 is a plan view of an embodiment of the present invention ozone generator.

7 is a partially enlarged cross-sectional view of the present invention FIG.

8 is an arrangement diagram of the ozone generating tube of the ozone generating device of the present invention.

9 is a partial cross-sectional view of a member constituting the water cooling chamber of the external electrode cooling device of the present invention.

10 is a front view of the air supply chamber part of the ozone generating device of the present invention.

11 is a front view of the cover portion of the ozone generating device of the present invention.

12 is a front view of an exhaust chamber part of the ozone generator according to the present invention.

13 is a plan view of another embodiment of the ozone generator of the present invention.

14 is an exemplary view of the flow path configuration of the ozone generating tube of the present invention.

15: ozone production concentration characteristics table when the ozone generating tube is 2 cells in the present invention.

Fig. 16: Schematic diagram of the anion measurement of the present invention.

17 is an ozone production characteristics analysis apparatus of the present invention.

18 is a graph comparing the ozone generation characteristics according to the composition of the ozone generating pipe flow path in the present invention.

19 is a graph comparing the ozone generation characteristics with or without cooling of the ozone generator in the present invention.

20 is an output voltage waveform diagram of an anion generator of the present invention.

21 is a waveform diagram of discharge characteristics of one cell of the ozone generating tube of the present invention.

22 is a column diagram for investigating changes in soil physicochemical properties by ozone water treatment in the present invention.

Figure 23 is a graph of the results of measuring the dissolved ozone amount by varying the reaction time of the 250 ml sample solution at 2 ℃, 15 ℃, 25 ℃ temperature conditions.

24: In the present invention, the result of examining the change of dissolved ozone amount according to the settling time of ozone water aerated for 30 minutes by adjusting the initial temperature to 40 ℃ tap water in 15 ℃.

FIG. 25 is a graph showing the results of examining the amount of dissolved oxygen according to the settling time in order to investigate the effect of the amount of dissolved ozone in the aqueous solution in the present invention.

26: In the present invention, the result of aeration of the aqueous solution, ozone and air, respectively, and a graph of the results of the pH change according to the reaction time.

27: In the present invention, when the 1 mg / L chlorosalonyl (TPN) and chlorpyrifos solution was aerated with ozone and air to investigate the change of the aqueous solution according to the reaction time graph.

28: In the present invention, 100 ml of a 1 mg / kg chlorosalonyl (TPN) solution was examined for the amount of volatilized and decomposed by bubbles and ozone at 15 ° C. for 30 minutes.

29: In the present invention, 100 ml of 1 mg / kg chlorpyrifos solution was examined for the amount of volatilized and decomposed by bubbles and ozone at 15 ° C. for 30 minutes.

FIG. 30 is a graph showing the volatilization and decomposition of pesticides by treating bubbles and ozone at 15 ° C. for 30 minutes at different pHs of a solution containing 1 ml / l chlorosalonyl (TPN).

FIG. 31 is a graph showing the volatilization and decomposition of pesticides by treating bubbles and ozone at 15 ° C. for 30 minutes by varying the pH of a solution containing 1 ml / l chlorpyrifos.

32: In the present invention, dissolved in 100ml of a solution in which a certain concentration of hydrogen peroxide was added to chlorosalonyl (TPN) and ozone treatment for 30 minutes to examine the pesticide removal rate graph.

33: In the present invention dissolved in 100ml of a solution of a certain concentration of hydrogen peroxide added to chlorpyrifos (chlorpyrifos) and ozone treatment for 30 minutes to investigate the pesticide removal rate graph.

34: Graph of the result of ozone treatment for 30 minutes with different volume of chlorosalonyl (TPN) in the present invention.

35: Graph of the result of ozone treatment for 30 minutes with different volume of chlorpyriphos in the present invention.

36 to 39: extracted with hexane, dichloromethane, ethyl acetate in the present invention, concentrated and re-dissolved in acetone and analyzed by GC-Mass graph.

40: Pictures of the bactericidal effect of ozone water for Fusarium in the present invention.

41: Pictures of the bactericidal effect of ozone water on Rhizoctonia in the present invention.

42: Pictures of the bactericidal effect of ozone water according to subculture for Fusarium in the present invention.

43: Pictures of the bactericidal effect of ozone water according to subculture for Rhizoctonia in the present invention

44: Photo activity change according to ozone water treatment of indigenous microorganisms in the present invention.

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

(1)-air compressor (2)-air filter

(3)-oil mist filter (4)-pressure regulator

(5)-1st dehumidifier (6)-flow regulator

(7)-purge amount regulator (8) -secondary dehumidifier

(9)-Raw gas cooler (10)-Ozone generator

(11)-External Electrode Chiller (12)-Cooling Water Circulation Pump

(13)-negative ion generator (14)-power supply unit for ozone generation

(15)-Power supply for negative ion generation (16)-Charge chamber

(17)-Exhaust chamber (18) (19)-Support member

(20)-Supply vent (21)-Exhaust vent

(22)-Ciro (23)-Dielectric

(24)-External Electrode (25)-Internal Electrode

(26)-Joining Holes (27)-Conduit

(28)-Slope (29)-Heat Shrink Tubing

(30) (31)-Power Supply Line (30a) (31a)-Jumper Wire

(32)-Discharge Power (33)-Coolant

(34)-Water Cooling Room (35) (36)-Side Plate

(37) (38) (39) (40)-plate (41)-via

(42)-Sewer (43)-Coolant

(44)-Drain (45)-Indentation Groove

(46)-O-Ring (Packing) (47) (48)-Cover

(49) (50)-Reinforcement member (51)-Coupling member

(52)-Blower (C1)-(C14)-Connector

(G1) to (G15)-ozone generator tube (d1)-diameter of internal electrode

(d2)-distance between internal electrodes

The present invention relates to a method and apparatus for eco-friendly restoration of hardly degradable contaminated soil using high concentration ozone water, and in detail, to restore and restore environmentally friendly soil contaminated using high concentration ozone water. The improved ozone generator increases ozone generation and increases the dissolved ozone concentration in the water to treat contaminated soil and contaminated water with ozone water with high chemical activity to remove organic contaminants in soil or contaminated water more efficiently and quickly. In addition, secondary pollution is prevented.

Crop and water pollution caused by various harmful substances and soil pollution by their long-term use has already reached a level of concern. In particular, over-dispersion of hardly degradable and toxic pesticides, over-use of chemical fertilizers, and salt accumulation due to long-term use have a great influence on the quality and productivity of agricultural products as well as loss of the original function of the soil. Recently, the use of chemical fertilizers and pesticides is extremely limited, and the preference for organic products produced using compost is increasing rapidly.

However, no matter how the cultivation method in the contaminated soil, the crops produced are contaminated, and once contaminated soil is rarely recovered to the soil before pollution. As a result, new researches and extensive researches are underway to restore soils severely contaminated by complex and diverse sources.

Among the contaminated soil restoration techniques, the chemical restoration technique using the oxidation-reduction reaction plays a complementary role with the biological restoration technique, and thus many studies have been conducted because the application method is easy. However, when the strong oxidizing agent or reducing agent is directly applied to the soil, its physical and chemical properties deteriorate, and its utilization is limited due to problems such as decreased efficiency and secondary pollutants caused by the treatment time.

Therefore, in order to restore organic polluted soils and salt integrated soils, there is an urgent need for an environmentally friendly treatment technique that has excellent oxidizing power and combines stability, speed, economy and high functionality.

Chemical soil restoration consists of the process of insolubilizing, decomposing and detoxifying pollutants by chemical reactions such as precipitation, adsorption and desorption and oxidation-reduction. In particular, the chemical treatment method by the oxidation reaction has the advantage that can quickly remove contaminants as well as the treatment of wastewater and toxic pollutants.

However, the conventional chemical treatment method is that the oxidation-reducing agent is directly treated to contaminated soil, so that the physical and chemical properties of the soil are deteriorated, the efficiency according to the treatment time is decreased, and secondary pollutants are generated. As there is a problem, there is an urgent need for technology development to overcome this problem.

On the other hand, studies on the decomposition mechanism of organic soil pollutants by the strong oxidizing agent and the reducing agent and their efficacy have been established in considerable part. For example, KMnO ₄ (potassium permanganate), KClO ₃ (potassium chlorate), H ₂ O ₂ (hydrogen peroxide) Oxidation-reduction reactions using strong oxidants such as O ₃ (ozone) and reducing agents such as Fe (iron), Zn (zinc) and Co (cobalt) have been actively studied in the field of catalysts as well as decomposition of organic harmful substances. .

In particular, oxidants such as KMnO ₄ and KClO ₃ are chlorinated aliphatics, chlorinated aromatics and chlorinated biphenyls (PCBs) and halogenated organic compounds present in air, water and soil. It is used for the removal of (HOCs), and the research on the jet cutting method which oxidizes and processes a phenol compound in situ is also in progress at home and abroad .

On the other hand, ozone (O ₃ ) has a much stronger oxidizing power than chlorine, so it is used for the sterilization, decolorization of organic wastewater, water purification, and deoxidation of organic matters. . In recent years, its application has been researched and developed in sterilization, disinfection, deodorization, decolorization, bleaching, freshness maintenance, pesticides and heavy metals removal, and food.In the water treatment process, it is used to deodorize and improve the taste of drinking water. In sewage treatment, it is used for the purpose of color, deodorization and sterilization.

The plant is also used to remove odorous components contained in the exhaust gas, and in particular, it has an excellent effect on the removal of ammonia. In addition, it is used for preventing corruption of processed foods, maintaining freshness and removing mold, and is used in medical fields such as blood circulation and metabolism promotion.

To date, there have been few systematic studies on the restoration of polluted soil using ozone water. Existing restoration treatment methods for treating chemicals of strong oxidizing agents or reducing agents with high chemical activity directly on contaminated soils can change the physical and chemical properties of the soil, reduce the reaction efficiency according to the treatment time, and as degradation products or intermediate metabolites. Since there are problems such as generation of secondary pollutants, its utility is limited.

Until now, much research has been conducted to oxidize and decompose pollutants by using ozone water in wastewater and water treatment facilities. However, there are few studies on the use of ozone water to restore polluted soil.

In addition, by treating ozone water with high chemical activity and excellent degradability of organic pollutants, but without residuals, the soil is removed by decomposing various organic pollutants such as pesticides and oils as well as salt accumulation and nematode contamination. There is an urgent need for research on eco-friendly restoration techniques that combine economical efficiency and efficiency.

Therefore, in the present invention, ozone water having high chemical activity and excellent resolving ability of organic pollutants and no residual property is treated to contaminated soil and contaminated water through the greatly improved ozone generator to decompose various organic pollutants such as pesticides and oils. In addition, the aim of the present invention is to provide a method and apparatus for eco-friendly contaminated soil restoration that combines rapid and high functionality to improve salt accumulation and nematode soil.

In addition, the present invention in the production of high concentration ozonated water to improve and restore the contaminated soil by greatly improving the ozone generation through the improvement of the ozone generator and dissolved in water to increase the dissolved ozone concentration significantly to increase the ozone water with high chemical activity. By removing the organic pollutants in the soil by treating them with contaminated water, it is possible to solve the problems of pollution soil restoration technology by conventional chemical treatment such as improvement of soil physical and chemical properties, prevention of secondary pollutant generation and rapid treatment efficiency. It is intended to contribute greatly.

In order to achieve the above object, in the embodiment of the present invention, the method comprises the steps of compressing the source gas from which impurities are removed with an air compressor, removing moisture from the compressed source gas with a dehumidifying device, and removing the moisture from an oil mist filter. Removing the oil in the gas, adjusting the supply pressure of the source gas with a flow controller, and discharging the source gas with an ozone generator to generate high concentration ozone. To be treated in an environmentally sound manner.

In another aspect, the present invention is the step of generating and discharging the negative ion ozone by the negative ion generator installed in the ozone outlet, the step of cooling the external electrode of the ozone generator with a cooling device in which the coolant is circulated by the circulation pump, and the purge amount regulator The method may further include adjusting a purge amount of the source gas.

In addition, the present invention is dissolved ozone in ozone water is 0.02ppm ~ 2ppm, anion generated water is 4.4 × 10 ⁶ / cc ~ 6.0 × 10 ⁶ / cc, dissolved oxygen after ozone dissolved for 30 minutes ~ 2 hours 6.0 mg / l to 12.0 mg / l, source gas cooling temperature is -20 ° C to -30 ° C, cooling water temperature of external electrode cooling device of ozone generator is 3 ° C to 6 ° C, humidity of dehumidified source gas Is characterized in that 15% to 25%. Of course, depending on the circumstances, the value can be believed or exceeded.

The present invention also provides an air compressor for compressing the raw material gas from which impurities are removed, an oil mist filter for removing oil in the compressed raw material gas, a dehumidifying device for removing moisture from the raw material gas, and a flow rate for adjusting the supply gas supply amount. A regulator, a dehumidifier that removes moisture in the source gas again, a source gas cooling device that cools the dehumidified source gas to a predetermined temperature, and one or more ozone generations that discharge and generate high concentration ozone by discharging the supplied source gas. A device, an anion generator installed at the ozone outlet for discharging anion ozone water, an external electrode cooler for cooling the external electrode of the ozone generator with circulating cooling water, and an operating power source using the ozone generator and the anion generator. Each of the power supplies is composed of a refractory soil recovery device using high concentration ozone water.

In addition, in the present invention, the ozone generating device has a plurality of ozone generating pipes installed in parallel between left and right support members having a supply / exhaust chamber, and end portions of the ozone generating tubes protruding into the supply chamber and the exhaust chamber are each connected to a plurality of connecting members. One side of the first ozone generating tube is connected to the air supply chamber, so that the compressed source gas flowing into the air supply port is introduced, and the other side of the last ozone generating tube is connected to the exhaust chamber to form a single series flow path having a large discharge area. .

In the present invention, the raw material gas cooling device is composed of a refrigeration compressor, a condenser, an expander, an evaporator, one cycle, an evaporator of the raw material gas cooling device which is immersed in the antifreeze in an insulating storage container in which the antifreeze is stored, and an air pipe through which the raw material gas passes. The ozone generating tube is composed of a tubular dielectric through which raw material gas passes, an external electrode provided in close contact with the outer surface of the dielectric, and an internal electrode provided in a coil structure inside the dielectric.

And, the dielectric of the ozone generating tube is forcibly coupled to the coupling hole formed in the support member and the tubular portion, the inclined surface is formed round the inlet portion of the coupling hole, the tubular portion protrudes in the opposite direction of the air supply chamber and the exhaust chamber, respectively In this case, the outer circumferential surface of the tubular part and the outer circumferential surface of the dielectric are bonded and fixed by a heat shrink tube.The outer electrode of the ozone generating tube is connected by a conductive jumper line, respectively, and then connected to a power supply line, and the inner electrode passing through the connecting member is connected by another jumper line The discharge power is supplied by connecting to another power supply line.

The improvement of the ozone generator includes the development and adoption of ozone generator peripheral devices such as a cooling device and a raw material dehumidification device to greatly increase the ozone generation efficiency, thereby improving the ozone generating capacity and increasing the power of the power supply device supplied to the ozone generator. In order to increase the concentration of dissolved ozone and to generate hydroxyl radical (OH-radical) which has better sterilizing power than ozone (O ₃ ), the output voltage of the negative ion generating power supply is increased to increase the negative ion generating water and increase ozone water with high chemical activity. To get it.

In addition, the present invention is chlorosalonyl (TPN: chlorothalonil), a fungicide widely used as a hardly decomposable organic chlorine-based pesticide in order to identify a method for restoring organic polluted soil by ozone water treatment, and chlorpyrifos, an insecticide. (chlorpyrifos) was selected to investigate the decomposition of ozone water and to determine the soil change by ozone water treatment. To establish. In addition, in order to investigate the change of soil biological environment by ozone water treatment, the activities of ozone water treatment on indigenous soil microorganisms, pathogenic microorganisms and root-knot nematodes were investigated and compared.                         

Existing methods treat redox directly in contaminated sites, so there are various problems such as deterioration of physicochemical properties of soil and generation of secondary pollutants. Therefore, it is urgent to develop alternative technologies. Accordingly, the present invention is to provide an environmentally friendly treatment method for removing contaminants by treating ozone water with excellent resolving power of organic pollutants but without residuals in soil for long-term use in contaminated soil.

In describing the present invention, the same elements in the drawings are denoted by the same reference numerals as much as possible, and detailed descriptions of related well-known structures or functions will be omitted in order not to obscure the subject matter of the present invention. Hereinafter, described in detail with reference to the accompanying drawings a preferred embodiment of the present invention.

There are various types of ozone generators, for example, silent discharge method, creepage discharge method, electrolytic method, irradiation method, high frequency electric field method, photochemical reaction, etc., but in the present invention, it is suitable for large-capacity ozone generation and stable in production and performance. The method is preferred, and the internal electrode is dispersed in several dielectrics to dissipate the heat of discharge, thereby reducing the ozone concentration caused by heat and changing the flow rate of the source gas and the flow of the source gas. Will be described later.

1 illustrates various factors affecting ozone generation characteristics, and examples of the factors include source gas, cooling effect, discharge state, and the like. In the case of source gas, the type, purity, temperature, and dryness affect ozone production characteristics.In the cooling effect, the degree of electrode cooling and the temperature of the cooling water affect ozone production characteristics. The flow rate, the shape and distance of the electrode, the flow of gas, the type of power source, and the density of the discharge power affect the ozone generation characteristics.

Therefore, the present invention is to maximize the ozone production efficiency by improving the cooling and dryness of the raw material gas having a high impact among these factors affecting the ozone production characteristics. To this end, a cooling device and a dehumidifying device are added to greatly improve its performance. As the power supply device of the ozone generator, a high frequency transformer (frans fomer) is applied to reduce the size, and the characteristics of the power supply device are confirmed with an oscilloscope as shown in FIG. 20 under a high voltage applied to the ozone generator. ) To maximize the number of anions generated from the anion generator.

The present invention is obtained by supplying the generated ozone to the negative ion generator by supplying and discharging the compressed source gas dehumidified and cooled and dehumidified by the ozone generator to dissolve the negative ion ozone generated in water to obtain the negative ion ozone water, To restore the soil in an environmentally sound manner.

That is, compressing the source gas from which impurities are removed with an air compressor, removing moisture from the compressed source gas with a dehumidifier, removing oil from the compressed source gas from which moisture is removed with an oil mist filter, and flow rate. Adjusting the supply pressure of the raw material gas with a regulator, generating a high concentration of ozone by discharging the raw material gas with an ozone generating device, by treating the ozone water dissolved in the ozone in the water to restore the environment.

The method further includes the step of generating and discharging negative ion ozone by an anion generator installed at the ozone outlet, and supplying the ozone to the negative ion generator to treat the soil with anion ozone water dissolved in the anion ozone generated in water. Restore it.

Further, the step of cooling the external electrode of the ozone generator to a cooling device in which the coolant is circulated by the circulating pump to cool not only the source gas but also the ozone generator having a high calorific value so as to obtain a high concentration of ozone.

2 illustrates an ozone generator according to an embodiment of the present invention, in which an air compressor 1 for compressing and supplying air, which is raw material gas, and air for filtering and removing foreign substances or impurities in the source gas supplied from the air compressor 1. A filter 2, an oil mist filter 3 for removing oil and the like contained in the source gas, a pressure regulator 4 for adjusting the pressure of the source gas from which the oil has been removed, and water in the source gas whose pressure is controlled. A primary dehumidifier 5 for removing the gas, a flow regulator 6 for adjusting the supply amount of the source gas, a purge amount controller 7 for adjusting the purge amount of the source gas, and water in the source gas. The secondary dehumidifier 8 to remove again, the raw material gas cooling device 9 for cooling the dehumidified raw material gas to a predetermined temperature, and when the cooled raw material gas flows in, it is discharged at high pressure to generate high concentration ozone (O ₃ ). One or more ozone generators (10) And a cooling device 11 for circulating the cooling water to cool the external electrode of the ozone generator 10, a cooling water circulation pump 12 for circulating the cooling water, and an outlet of the ozone generator 10. Supplying an operating power to an anion generator 13 for discharging anion ozone water, an ozone generator power supply 14 for supplying operating power to the ozone generator 10, and an anion generator 13 It consists of a power supply unit 15 for generating negative ions.

Some of the above components except for the necessary components may be omitted.

The ozone generator 10 is preferably to use a silent discharge that is suitable for large-capacity ozone generation, easy to manufacture, and stable performance, the primary dehumidifier 5 is a silica gel or gas separation membrane For example, the filter mesh mesh of the oil filter 2 is preferably around 5 µm, and the filter mesh mesh of the oil mist filter 3 is preferably around 0.01 µm.

3 shows a basic cooling cycle of the raw material gas cooling device 9, wherein the refrigeration compressor, the condenser, the expander, and the evaporator are constituted by one cycle, so that the cooling required for the raw material gas cooling is achieved.

4 shows a schematic diagram of source gas cooling, in which a source gas cooling device 9, that is, an evaporator of a refrigerator system and an air pipe through which source gas passes, are installed in an antifreeze inside a reservoir in which an antifreeze is stored. Thus, the antifreeze is cooled to a predetermined temperature by an evaporator, and the cooled temperature is transferred to the air pipe to cool the source gas passing through the air pipe. In addition, the outside of the reservoir is cooled with insulation and the antifreeze is replenished through an inlet (not shown) installed in the upper portion of the reservoir.

The cooling water may use distilled water or a general constant, but the reason for using the antifreeze is to prevent freezing due to cooling, and the piping through which the raw material gas passes for a sufficient cooling of the raw material gas has a length of 1 m to 8 m depending on the raw material gas supply amount. By immersing completely in antifreeze, optimum cooling efficiency can be achieved.

FIG. 6 is a plan view of an embodiment of the ozone generator 10 of the present invention, and FIG. 7 is a partial cross-sectional view of the ozone generator 10 having a supply / exhaust port 20 (21) and a supply / exhaust chamber 16 (17). A plurality of ozone generating pipes G1 to G15 are installed in parallel between the right support members 18 and 19 to be connected to one another.

That is, the end portion of the ozone generating tube protruding into the supply / exhaust chambers 18 and 19 of the left and right support members 18 and 19 may have a plurality of connection members C1 as shown in FIGS. 8, 10, and 11. ) And (C14), respectively, but one side of the first ozone generating pipe (G1) is connected to the air supply chamber 16 so that the compressed source gas flowing into the air supply port 20 is introduced, and the last ozone generating pipe The other side of (G15) is connected to the exhaust chamber 17 so that one series path or series flow path 22 is formed as a whole, so that the high concentration of ozone generated in each ozone generating pipe (O) ₃ ) is discharged to the exhaust port 21 through the exhaust chamber 17.

In this way, the overall length and volume of the ozone generator 10 can be reduced while maintaining the efficiency of ozone generation (generation) at high efficiency, and the ozone generator tubes are all gathered between the left and right support members 18 and 19. Therefore, efficient cooling of the ozone generating pipes G1 to G15 is possible. Each ozone generating pipe (G1) ~ (G15) is connected in series, so that the total discharge area is greatly expanded, the ozone generation efficiency is maximized, the efficiency is further improved by the cooling device, the inner diameter or length and the number of connections It depends on the amount of ozone you need.

In the ozone generating pipes G1 to G15, discharge electrodes are respectively provided inside and outside the tubular dielectric 23 so that source gas can pass therethrough. As the dielectric 23, a quartz glass tube or the like is used, and the external electrode is completely adhered to the entire surface of the dielectric 23 with a copper tape having a thickness of 0.03 mm to 0.5 mm, or the copper pipe is tightly bonded. The internal electrode 25 provided in the dielectric 23 is wound around a stainless wire having a diameter of 0.5 mm to 2.0 mm in a coil shape, and is almost in close contact with the inner circumferential surface of the dielectric 23. It is constructed by installing in a structure.

As the ozone generating tube has a larger inner diameter or longer length, the ozone generating efficiency is further improved. As the separation distance between the internal electrodes 25 is higher, the ozone generating efficiency is increased, but heat generation and power consumption are increased. In the present invention, the separation distance d2 between the internal electrodes 25 is preferably maintained in a range of 1/3 to 2 of the diameter d1 of the internal electrodes 25.

The dielectric 23 is fitted into the coupling hole 26 and the tubular portion 27 formed in the support members 18 and 19 in a press fit manner, respectively, into the air supply chamber 16 and the exhaust chamber 17, respectively. At the end portions of the protruding ozone generating pipes G1 to G15, the connecting members C1 to C14 are hermetically coupled as shown in FIG. 8 to form one series flow path.

An inclined surface 28 is formed around the inlet portion of the coupling hole 26 so that the dielectric 23 is easily coupled, and the tubular portion 27 is provided in the opposite direction of the air supply chamber 16 and the exhaust chamber 17. Each protrusion is formed so that the end portions of the inner circumferential surface of the dielectric 23 are coupled to each other, and the heat shrink tube 29 is watertightly bonded and fixed to the outer circumferential surface of the tubular portion 27 and the outer circumferential surface of the dielectric 23.

Since the heat shrink tube 29 is further contracted by the cooling water, the watertight watertightness is maintained, as well as the watertight watertightness is applied to the outer circumferential surface of the heat shrinkage tube 29 and the tubular portion 27 by being applied as a binder or watertightly retained by a seal ring member. Since it is maintained, the cooling water 33 does not flow out into the air supply chamber 16 and the exhaust chamber 17.

In the present invention, the outer electrode 24 is formed on the outer circumferential surface of the dielectric 23 between the left and right heat-shrink tubes 29, and the inner electrode 25 is disposed to be located over the entire inner circumferential surface of the dielectric 23 so that the discharge efficiency is maximized. It is preferable to construct.

In the present invention, the cross-sectional shape of the dielectric 23 may be variously formed into a triangle, a square, an ellipse, a polygon, or a modified shape thereof, but the manufacturing shape of the inner and outer electrodes 24 and 25 and the manufactured electrode may be It is desirable to form a circle so that it can be easily installed.

In addition, the external electrodes 24 of the ozone generating tubes G1 to G15 are connected to the conductive jumper wires 30a, respectively, and then connected to the power supply line 30, so that the external electrodes 24 are required for silent discharge. The power supply 32 is supplied, and the external electrodes 24 of the ozone generating pipes G1 to G15 are hermetically maintained through the connecting members C1 to C14, and the air supply chamber 16 or the exhaust chamber 17 is maintained. And then connected to a jumper wire 31a and connected to another power supply line 31 drawn out of the ozone generator 10 to supply power 32 necessary for silent discharge to each external electrode 24. To be. The discharge power supply 32 is supplied from the ozone generating power supply unit 14.

A water cooling chamber 34 is provided between the supporting members 18 and 19 so that the cooling water 33 can be forcedly circulated. The water cooling chamber 34 is fixed to the support members 18 and 19, respectively, to the rectangular side plates 35 and 36 which are fixed in watertightness, and the upper and lower parts and the front and rear parts of the side plates 35 and 36, respectively. And the upper and lower plate bodies 37 and 38 and the front and rear plate bodies 39 and 40 which are watertightly maintained, and the two side plates 35 and 36 can be forcibly coupled to the support members 18 and 19. 41 is formed.

The side plates 35, 36 and the plate bodies 37, 38, 39, and 40 are bonded or integrally injection molded with a transparent resin having a thickness and durability sufficient to withstand the cooling water 33 hydraulic pressure. The watertight is maintained by a method such as the above, and the inside of the water cooling chamber 34 can be viewed by forming a transparent body.

One end of the plate body 37 is provided with a water supply port 42 through which the cooling water 33 is supplied by the cooling water circulation pump 12, and a drain port 43 through which the cooling water 33 is discharged. The jumper wire 30 penetrates through the plate 37 and is drawn out, and the lead portion is kept watertight.

The air supply port 20 is connected to the raw material gas cooling device 9, and the exhaust port 21 is connected to the negative ion generating device 13 and ozoneized while passing the compressed and dehumidified raw material gas. In addition, the water supply port 42 is connected to the external electrode cooling device 11, the drain port 43 is connected to the cooling water circulation pump 12, the cooling water 33 is circulated while the ozone generating pipe (G1) (G15) Forced cooling. In addition, both support members 18 and 19 are maintained at a separation distance by the plurality of spaces 44.

The compressed raw material gas is supplied to the air supply chamber 16, and ozone gas is discharged to the exhaust chamber 17, so that it is isolated from the outside and kept airtight.

That is, each concave groove 45 is formed in the outer surface portion of the support member 18, 19 of the cylindrical shape, the concave groove 45, the packing or O-ring 46 is respectively coupled, O-ring The outer side of the cover 46 is in contact with the cover 47, 48 having the air supply port 20 and the exhaust port 21, respectively, and the reinforcing members 49, 50 are in contact with the outer surface of the cover 47, 48. The cover 47 and 48 are tightly coupled to the support members 18 and 19 and the O-ring 46 by using the plurality of coupling members 51 in the state.

The coupling member 51 may use a fastening member composed of riveting or bolt nut, and the like. In another embodiment, the outer and outer peripheral surfaces of the support members 18 and 19 and the inner peripheral surfaces of the lids 47 and 48 are male and female. It can also be comprised by methods, such as forming and fastening a screw part, respectively.

By combining the cover (47, 48) can be separated / combined by the ozone generating pipe (G1) ~ (G15) and the space 44, the coupling of the connection member (C1) (C14), jumper wire (31a) ) Wiring work can be done easily, and parts can be repaired or replaced.

In the present invention, the connecting members (C1) to (C14) may be made of a metal material or synthetic resin having resistance to strong oxidizing power without shortening the life of ozone. Then, the portion of the flow path in contact with ozone, most (O ₃₎ is a non-metallic material, for example it is preferable to ensure that the life is not shortened in ozone (O ₃₎ and consists of a synthetic resin material or the like. Of course, the internal electrode 25 is preferably using an oxidation-resistant conductive metal, such as stainless steel.

In the present invention, a plurality of ozone generating pipes are connected in series to greatly expand the discharge area, thereby minimizing the overall length and maximizing the ozone generating efficiency. Such a structure has a simple cooling structure and maximizes cooling efficiency.

In addition, since the temperature generated by the discharge is cooled by the source gas cooling device 9 and the external electrode cooling device, respectively, not only the life of the generated ozone is greatly extended, but also the ozone generating efficiency is greatly improved.

The cooling device may use a combination of water cooling or air cooling, or water cooling and air cooling. In the case of the air-cooling system, as shown in FIG. 13, an air blower 52 that is rotated by a motor may be installed at the upper portion, the lower portion, or the upper and lower portions of the ozone generating tube, and forced cooling may be performed by air cooling. What is necessary is just to install a blower in the upper part or the lower part of the ozone generator 10 with which the water cooling chamber 34 is provided.

In the present invention, the raw material gas compressed, cooled, and dehumidified is supplied to the air supply port 20 of the ozone generator 10, and a voltage 32 necessary for discharge is applied to the internal and external electrodes 24 and 25, When the cooling device is operated, ozone generated by the silent corona discharge is pumped to the negative ion generator 13 through the exhaust port 21 by the compressed gas supplied, and a large amount of negative ions generated by the negative ion generator 13 Anion ozone is discharged while being mixed with the ozone, and the anion ozone is dissolved in the water to obtain anion ozone water, and then treated, such as watering, pouring, spilling, or spraying polluted soil, to restore the environment.

On the other hand, in the case of general water, the water particles tend to be large and the amount of dissolved oxygen is absorbed in the state of holding the soil when absorbed into the soil, so that the water is well accumulated and the drainage is not good. Since the anion is dissolved, it is a hexagonal water state in which dissolved oxygen is high and organic substances are removed. In addition, dissolved ozone and anions oxidize and decompose contaminants in the soil, and contaminated soil is restored. The soil is provided with air permeability, which greatly promotes the growth and growth of crops and prevents damage to crops.

Meanwhile, as shown in FIG. 14, when the ozone generating tube 2 cell is configured as one ozone generating device, the ozone generating characteristics are changed while changing the input power of the power supply and the flow rate of the raw material gas. (25ℓ / min → 10ℓ / min) The higher the input power (35W → 55W), the higher the concentration of ozone produced, so that a maximum ozone concentration of 1,020ppm was obtained.In the case of ozone generation, the flow rate was 25ℓ / min and the input power was 55W. The maximum ozone generation amount was 2.02g / h.

In general, in the case of ozone concentration, when the flow rate is low, the heat generated inside the ozone generator increases as the power increases, and the ozone concentration rapidly decreases due to the rapid decomposition of ozone due to heat.

In the present invention, in order to prevent the rapid decomposition of ozone due to the heat of the external electrode 24 generated by forced circulation of the cooling water 33 before and after 5 ℃ as a result as shown in Figure 15 regardless of the increase in power and increase or decrease in flow rate It can be seen that concentration increases.

Looking at Table 1 below, it can be seen that the amount of ozone is slightly different according to the change of flow rate under each same power, which can be seen as a slight effect due to the variation of the internal temperature of the ozone generating tube according to the flow rate. Rather than analyzing ozone production effects by the experiments, it is thought that it is desirable to discharge the flow rate and power in favor of ozone production through repeated experiments and data accumulation.

Table 1. Comparison table of ozone generation by ozone concentration for 2 cells of ozone generating tube. (Unit: [ppm] * [g / h])

Flow rate [ℓ / min] ＼ Electric power [W] 35 40 45 50 55 10 Concentration 507 721 829 885 1,020 Occurrence 0.60 0.85 0.98 1.04 1.20 15 Concentration 397 547 662 812 895 Occurrence 0.70 0.97 1.17 1.44 1.58 20 Concentration 370 502 607 725 848 Occurrence 0.89 1.18 1.43 1.71 2.00 25 Concentration 305 407 523 590 687 Occurrence 0.90 1.20 1.54 1.74 2.02

The characteristics of the ozone generator were compared by comparing the flow paths (the input and discharge paths of the raw material gas) in parallel when two cells of the ozone generator were connected to one generator.

In this embodiment, as shown in the bottom of Fig. 14, the flow paths were configured in series, and as a result of the examination, the maximum ozone concentration was 369 ppm and the maximum ozone generation amount was 0.18 g as shown in Table 2 and Fig. 18 below. / h more generated.

Since the ozone generating tube of one cell can not be lengthened indefinitely, in the present invention, when combining several ozone generating tube cells, not only the configuration of the flow paths in series but also in series can bring better ozone generating characteristics. It can reduce the volume and is a preferable configuration for cooling.

Table 2. Comparison of Ozone Production Concentration Characteristics of 2 Cells of Ozone Generating Pipes by Units (ppm)

Flow rate power 35 W 40 W 45 W 50 W 55 W  Euro series 10 [ℓ / min] 760 971 1,084 1,185 1,389 15 [ℓ / min] 556 814 856 950 1,157 20 [ℓ / min] 375 578 672 758 917 25 [ℓ / min] 303 440 528 619 747  Euro parallel 10 [ℓ / min] 507 721 829 885 1,020 15 [ℓ / min] 397 547 662 812 895 20 [ℓ / min] 370 502 607 725 848 25 [ℓ / min] 305 407 523 590 687

There are various ways to cool the ozone generator 10. For example, in the case of cooling the dielectric 23 (discharge tube), a method of cooling the outside of the dielectric 23 includes water cooling and air cooling, and a method of cooling the inside of the dielectric 23 uses raw material gas introduced into the dielectric 23. There is a method of cooling.

In the present invention, two methods of cooling the outside of the dielectric 23 and cooling the source gas flowing into the dielectric 23 are applied in parallel. In the case of the ozone generating device to which the cooling device is applied and the ozone generating device to which the cooling device is not applied, as shown in Table 3 and FIG. 19 below, the ozone concentration increased to the maximum value between about 1 to 3 minutes and then, at about 5 minutes, In this case, the concentration decreased up to 35.4%, while the ozone generator 10 with cooling system decreased only up to 5.1%, and the maximum ozone concentration of the initial value (within 1-3 minutes) was not applied without the cooling system. 1,609 ppm more was produced. In addition, in the case of the ozone generator 10 that is not cooled, it can be seen that the decrease in ozone concentration increases from 65 W to 105 W as the power increases.

In addition to the increase in power, most of the power loss is consumed by heat, and the large amount of heat generated promotes the decomposition of ozone, which in turn lowers the ozone generation and may also shorten the life of the ozone generating electrode.

Table 3. Comparison table of ozone production concentrations for 10 cells of ozone generator. (Unit: ppm)

Power @ time 3 minutes 5 minutes 7 minutes 9 minutes 15 minutes 30 minutes 50 minutes   No cooling 65 W 1,187 1,066 1,025 1,009 1,005 998 1,000 75 W 1,489 1,243 1,196 1,172 1,170 1,165 1,163 85 W 1,557 1,209 1,168 1,145 1,128 1,112 1,121 95 W 1,515 1,201 1,129 1,092 1,088 934 937 105 W 1,631 1,053 891 846 817 799 784  Cooling 75 W 2,429 2,308 2,312 2,315 2,340 2,323 2,329 85 W 2,786 2,644 2,624 2,649 2,654 2,666 2,663 95 W 2,989 2,976 2,957 2,933 2,910 2,905 2,899 105 W 3,240 3,183 3,185 3,197 3,185 3,193 3,196

In an embodiment of the present invention, the ozone generator is configured by connecting a series of 10 cells of the ozone generator tube in series to form one ozone generator, and Table 4 below compares the inlet temperature and the outlet temperature of the cooling device 9. . As shown in the previous table, cooling of the ozone generator 10 is essential for generating high concentration ozone with dehumidification of source gas.

Table 4. Temperature Comparison Table of Inlet and Outlet of Cooling System

Flow rate [ℓ / min] Chiller outlet temperature [℃] Ozone tube inlet temperature [℃] Temperature measuring device 15 -20.3 -3.6   Hanna (HI93530) 20 -22.0 -6.5 25 -23.1 -11.1 30 -24.0 -14.0 35 -24.0 -15.6

In the above table, the lower the flow rate of the raw material gas, the lower the cooling effect. When the flow rate is low, the heat exchange time in the antifreeze is sufficient. This is because there is a large amount of heat lost to the air due to the slow flow rate.

In the case of the cooling device 11 of the external electrode 24, distilled water was used instead of the antifreeze in the same principle as the cooling device 9 of the source gas, as shown in FIG. 5. At this time, in order to prevent freezing of the distilled water, the cooling temperature was maintained at 3 ℃ ~ 6 ℃ do not fall below 3 ℃.

The dehumidifier and the dehumidifier (5) (8) applied dehumidification using a gas separator and dehumidification using silica gel in combination with the compressed moisture, and maintained a humidity of 15% to 25% when the ozone generator 10 was operated.

The DC output high voltage of the negative ion generating power supply unit 15 is fixed at -9.0kv to -9.5kv and the amount of negative ions generated and the equipment used for the measurement are shown in Table 5 below.

Table 5. Overview of Anion Measurement and Analysis Equipment

Product Name Model Specification manufacturer Anion measuring instrument SC-50 10 to ⁷ pcs / cc Signatec DC high voltage meter 149-30A DC 30㎸ Kikusui Digital oscilloscope TDS 3054B 500 MHz, 5 GS / S Tectronics High voltage voltage divider EP 50K 2000: 1 Pulse electronic

As shown in FIG. 16, the ionizer was fixed at a distance of 5 cm from the ion connector to 5 cm, and then 100 times were measured by holding the holder (HOLD) at an interval of 30 seconds, and the number of times was 4.4 × 10 ⁶ / cc ~ 6.0 It was measured at × 10 ⁶ pcs / cc, with an average value of 5.2 × 10 ⁶ pcs / cc.

In the present invention, the negative ion generating device 13 is provided with an anion generating electrode inside the tubular body coupled to the outlet of the ozone generating device 10 or the outlet of the ozone generating device 10, as the negative ion generating electrode- Anion is generated by applying a DC high voltage of 9.0kv to -9.5kv. As shown in FIG. 16, a sharp needle is formed at the end of the anion generating electrode to concentrate charges, and an anion generating electrode is formed. The needle is positioned in the direction in which anions and ozone are discharged. The negative ion generating electrode is downsized in size so as not to interfere with the discharge of negative ions and ozone.

On the other hand, in order to verify the ozone generation amount, as shown in FIG. 14, two ozone generating pipes were connected in series or parallel to form an ozone generating device, and high voltage was applied to each ozone generating device using the power supply unit 14. After the two ozone generators 10 were configured using the ozone generation characteristic analyzer of FIG. 17, the maximum ozone generation amount was 20.9 g / h under the condition that the input power of the power supply was 450 W and the raw material gas flow rate was 35 L / min. It was.

Dissolved ozone analysis was carried out using the Indigo method using a UV-Spectrophotometer (Hitachi U-2001). As a result of analyzing the dissolved ozone according to the state of water temperature, the ozone generator 10 was about 10 minutes regardless of the temperature conditions. At the time of operation, dissolved ozone became saturated and the dissolved ozone concentration of each temperature was 1.13ppm at 2 ℃, 0.65ppm at 15 ℃, and 0.40ppm at 25 ℃. When the ozone generator was operated for about 5 minutes, the dissolved oxygen content was 7.9 ppm. Of course, the amount of dissolved oxygen varies depending on the quality of the ozone dissolved water in the present invention. That is, depending on the water quality, after dissolved (aerated) ozone for 30 minutes to 2 hours, the dissolved oxygen amount was measured in the range of 6.0 mg / l to 12.0 mg / l.

FIG. 17 is a device for analyzing ozone generation characteristics of an ozone generating device. The ozone concentration is measured by fixing a flow rate of sample gas flowing into an ozone monitor at 1 l / min. The discharge characteristics were confirmed on the oscilloscope screen by constructing a 50 Ω non-inductive resistor between the external electrode and ground.

Data as shown in Table 6 and Table 7 below were obtained using the ozone generator of FIG. 14 and the ozone generating characteristic analyzer of FIG. 17. Table 6 below shows the ozone generation characteristics analysis device and analysis equipment specifications, Table 7 is a comparison of the ozone generation concentration of the ozone generator, Table 8 is a table comparing the ozone generation amount of the ozone generator.

Table 6. Specifications of ozone generation characterization equipment.

Product Name Model Specification manufacturer Digital oscilloscope TDS 3054B 500 MHz, 5 GS / S Tectronics High voltage voltage divider EP 50K 2000: 1 Puise electronic Digital power meter 2534 2㎾ YOKOGAWA Ozone meter 1008-HC 60,000 ppm Dasibi thermometer HI 93530 -200 ℃ ~ 1,370 ℃ Hanma

In the present embodiment, in the case of the ozone generator applied to the ozone generator, one ozone generator 10 is connected by connecting 13 ozone generator cells in series with each other, and as shown in FIG. 2, two ozone generators 10 are provided. Connected in series to form a serial flow path.

In addition, each power supply unit 14 was connected to each ozone generator 10 to apply a high voltage, and the humidity of the peripheral device of the ozone generator 10 was maintained at 15% to 25%. The antifreeze temperature of 9) was maintained between -20 ℃ and -30 ℃ to increase the reliability of the data as the average value of the data repeated at least 10 times for each input power for each flow rate. Table 8 is a comparison table of the ozone generation amount of the ozone generator.

Table 7. Comparison table for ozone production concentration of ozone generator (unit: ppm)

Flow rate (ℓ / min) Power distribution 250 W 290 W 350 W 390 W 450 W    15 3 4,405 4,495 4,486 3,650 3,122 5 4,312 4,301 4,085 3,336 2,463 10 4,274 4,218 4,056 3,219 2,269 15 4,290 4,198 4,006 3,072 2,147 20 4,266 4,193 3,983 3,007 2,071 25 4,253 4,170 3,951 2,992 2,041 30 or more 4,223 4,176 3,924 2,930 1,997    20 3 4,336 4,616 4,541 5,008 5,029 5 4,293 4,533 4,423 4,876 4,641 10 4,269 4,527 4,387 4,850 4,583 15 4,257 4,509 4,378 4,836 4,468 20 4,239 4,516 4,386 4,778 4,372 25 4,209 4,503 4,372 4,751 4,283 30 or more 4,213 4,515 4,369 4,729 4,157   25 3 4,044 4,554 4,805 4,897 5,185 5 3,994 4,512 4,762 4,662 5,010 10 3,982 4,516 4,753 4,552 4,892 15 3,971 4,506 4,703 4,499 4,738 20 3,955 4,524 4,698 4,450 4,712

25 25 3,982 4,537 4,671 4,409 4,693 30 or more 3,986 4,535 4,592 4,341 4,651    30 3 3,853 4,313 4,692 5,177 5,381 5 3,688 4,222 4,660 5,025 5,274 10 3,662 4,226 4,586 5,020 5,212 15 3,652 4,228 4,577 5,012 5,193 20 3,627 4,212 4,601 4,996 5,158 25 3,641 4,218 4,607 4,963 5,157 30 or more 3,627 4,230 4,587 4,913 5,111    35 3 3,336 4,116 4,399 4,837 5,240 5 3,330 4,095 4,313 4,662 5,201 10 3,346 4,069 4,384 4,627 5,162 15 3,364 4,088 4,439 4,652 5,153 20 3,358 4,072 4,464 4,679 5,105 25 3,372 4,040 4,436 4,655 5,075 30 or more 3,361 4,054 4,374 4,682 5,011

Table 8. Comparison table of ozone generation amount of ozone generator (unit: g / h)

Flow rate (ℓ / min) Power distribution 250 W 290 W 350 W 390 W 450 W    15 3 7.8 7.9 7.9 6.5 5.5 5 7.6 7.6 7.2 5.9 4.4 10 7.6 7.5 7.2 5.7 4.0 15 7.6 7.4 7.1 5.4 3.8 20 7.5 7.4 7.0 5.3 3.7 25 7.5 7.4 7.0 5.3 3.6 30 or more 7.5 7.4 6.9 5.2 3.5    20 3 10.2 10.9 10.7 11.8 11.9 5 10.1 10.7 10.4 11.5 10.9 10 10.1 10.7 10.3 11.4 10.8 15 10.0 10.6 10.3 11.4 10.5 20 10.0 10.6 10.3 11.3 10.3 25 9.9 10.6 10.3 11.1 10.1 30 or more 9.9 10.6 10.3 11.1 9.8   25 3 11.9 13.4 14.2 14.4 15.3 5 11.8 13.3 14.0 13.7 14.8 10 11.7 13.3 14.0 13.4 14.3 15 11.7 13.3 13.9 13.3 14.0 20 11.7 13.3 13.8 13.1 13.9

25 25 11.7 13.4 13.8 13.0 13.8 30 or more 11.7 13.4 13.5 12.8 13.7    30 3 13.6 15.2 16.6 18.3 19.0 5 13.0 14.9 16.5 17.8 18.6 10 12.9 14.9 16.2 17.7 18.4 15 12.9 14.9 16.2 17.7 18.4 20 12.8 14.9 16.3 17.7 18.2 25 12.9 14.9 16.3 17.5 17.5 30 or more 12.8 15.0 16.2 17.4 17.4    35 3 13.8 17.0 18.1 19.9 21.6 5 13.7 16.9 17.8 19.2 21.5 10 13.8 16.8 18.1 19.1 21.3 15 13.9 16.9 18.3 19.2 21.3 20 13.8 16.8 18.4 19.3 21.1 25 13.9 16.7 18.3 19.2 20.9 30 or more 13.9 16.7 18.0 19.3 20.9

Looking at the ozone production characteristics in the above table, the highest condition for the ozone concentration was the highest when the input power of the power source was 450W and the flow rate of the source gas was about 5,100ppm, and the amount of ozone generation was 450W, 35ℓ / The highest yield was 20.9 [g / h] at min.

As mentioned above, as the power of the ozone generator 10 increases, the ozone generation amount decreases as the flow rate of the source gas decreases. In addition, under the same power condition, the amount of ozone generated increased as the flow rate of raw material gas increased.

The yield of the ozone generator 10 is an important factor to evaluate the efficiency of the ozone generator 10. In general, the ozone generation yield of the silent discharge type ozone generating device is theoretically 1,200 g / kwh or about 90 g / kwh when air is used as a raw material.

In the case of the ozone generator 10 of the present invention, the yield under the condition of maximum ozone generation (20.9g / h) 450W, 35L / min is 46.4g / kwh, while the flow rate 35L / min, power 290W The yield of ozone generation (16.9g / h) under the conditions was 58.3g / h, rather, the ozone generation efficiency was good.

It is considered that ozone production efficiency is decreased because the heat generated inside the ozone generating pipe is not discharged at the power of 290W or higher. If the flow rate of raw material gas is more than 35ℓ / min for sufficient heat emission, the maximum ozone generation amount and ozone production yield It is assumed that this will be high.

On the other hand, since ozone has a strong oxidizing power, it is also known to be excellent in microbial sterilization and discoloration, deodorization, toxic substance decomposition and decomposition of organic substances. Because ozone is composed of oxygen atoms, it generates oxygen when it is decomposed, so ozone treatment does not produce harmful reaction products that may occur when treating chlorine-based oxidants. Toxicity is not as strong as chlorine, which makes handling easier than chlorine. .

In addition, when active anions are generated simultaneously, it is known that the decomposition of pesticides is increased. However, the existing data on this may overlook the removal of pesticides by volatilization by the physical force of bubbles when ozone is generated. The amount of residual pesticides removed by the oxidizing power or radical reaction of ozone and the amount removed by volatilization by air bubbles should be accurately distinguished.

Therefore, in the present invention, the decomposition and volatilization by ozone were investigated in comparison with air aeration using chlorosalonyl as a fungicide and chlorpyridose as a pesticide, which is widely used among organochlorine pesticides.

1. Restoration experiment of organic soil by ozone water treatment

Experiments to confirm the restoration of organic soils by ozone water treatment are as follows.

end. Experimental material

(1) pesticide

 Chlorallonil (TPN: 99.9% purity), a fungicide widely used as an organic chlorine-based pesticide, and chlorpyrifos (purity 99.7%) as a pesticide are standardized by Merk Chemical Co. (Japan). It was purchased from and used, and the physical and chemical properties are shown in Table 9 below.

Table 9. Comparison of physical and chemical properties of crorosalonyl and chlorpyrifoss.

Characteristic Chlorosalonyl Chlorpyrifoss    Chemical structure

 Chemical Name 2,4,5,6-tetrachloro-1,3-benzenebenzenecarbonitrile O, O-diethyl-O- (3, 5, 6 -trichloro-2-pyridyl) -phosphorothioate Molecular expression C ₈ Cl ₄ N ₂ C ₉ H ₁₁ Cl ₃ NO ₃ PS Molecular Weight 265.9 350.6 Melting degree 0.6 mg / l (20 ° C) 2.0 mg / l (20 ° C) Melting point 250 ℃ 43 ℃ Poison Castle (LD ₅₀ & TLm) Rat: 10,000 mg / ℓ Fish: 0.1 mg / ℓ Rat: 136 ~ 163 mg / ℓ Fish: 0.13 mg / ℓ

These standard products were dissolved in acetone (acetone) to prepare a mother liquor of 100 mg / L, and then diluted with distilled water to the required concentration, and 5% of acetone was added in consideration of the solubility of chlorosalonyl and chlorpyrifoss.

(2) reagent

As a solvent used for the analysis of chlorosalonyl and chlorpyriphos, hexane, dichloromethane, ethyl acetate, or HPLC grade (high-performance liquid chromatography grade) for residual analysis was used. Indigo reagent used to determine the amount of dissolved ozone was used C ₁₆ H ₇ N ₂ O ₁₁ S ₃ K ₃ (potassium indigo trisulfonate) purchased from Sigma chemicla Co.

(3) Bubble generator

In order to investigate the chlorosalonyl and chlorpyrifos removed by the bubbles generated in the ozone generator 10, the same amount of bubbles are produced as the ozone generator 10, and then the bubble generator 10 Bubbles were generated with (Fig. 17).

(4) How to measure ozone dissolved amount

Indigo method is used to investigate the dissolved amount of ozone generated in the ozone generator (10). Was used. The principle of measuring dissolved ozone is that in acidic solutions, ozone rapidly decolorizes indigo reagents. Since ozone reacts with the indigo reagent in mole to molar ratio, the degree of discoloration is measured using an UV-spectro photometer at an absorbance of 600 nm [0.42 ± 0.01 / cm / mg / l (Δε = 20,000 / M · cm)] was calculated by the following formula (1) in comparison with the ultraviolet absorption amount (ε = 2,950 / M · cm) of pure ozone at 258 nm.

---------------------------------------------- 식(1)

---------------------------------------------- Formula (1)

ΔA = difference between sample and blank and absorbance

b = path length of ozone generator cell (cm)

v = volume of sample in ml

f = 0.42

(5) ozone oxygen amount measurement

Oxygen is generated during the decomposition of dissolved ozone, so to determine the correlation between dissolved ozone and dissolved oxygen, water is collected in 40 l of solution according to the aeration time of the ozone generator 10 (Hanna, HI 9141). Was measured.

I. Experiment method

(1) pH change measurement

Chloralonyl and chlorpyrifos measured the pH of a solution that changed when ozone was generated because hydrolysis occurred rapidly under strong alkali conditions of pH 10 or higher. Using a pH meter of Orion Co., Ltd., ozone was generated in 100 ml of chlorosalonyl and chlorpyriphos at a concentration of 1 mg / L, and the pH was measured hourly (0 to 60 minutes).

(2) Decomposition of pesticides by ozone treatment

Ozone was generated in a constant time (2 minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes, 60 minutes) in 100 ml of the experimental solution dissolved to a concentration of chlorosalonyl and chlorpyriphos at 1 mg / l, followed by hexane The amount of decomposition of chlorosalonyl and chlorpyridose by ozone was investigated. Each experiment was divided into two cases: ozone generation and air bubble generation.

In addition, to determine the effect of the volume of the reaction solution on the decomposition of chlorosalonyl and chlorpyriphos, the volume of the initial solution was varied to 50ml, 100ml, 250ml, 500ml and the amount of decomposition was investigated. In order to investigate the effect of the pH of the initial solution on the decomposition of chlorosalonyl and chlorpyriphos, the amount of decomposition was examined by varying the pH of the initial solution to 3, 5, 7, 9.

(3) Effect of hydrogen peroxide (H ₂ O ₂ )

After making 1mg / ℓ of chlorosalonyl and chlorpyriphos solution, hydrogen peroxide was added at different concentrations, for example, 10, 25, 50, and 100 mM in order to generate a lot of OH radicals. The amount of decomposition of chlorosalonyl and chlorpyrifos was investigated in comparison with the case where it occurred.

(4) Quantitative analysis of chlorosalonyl and chlorpyrifoss

For quantitative analysis of chlorosalonyl and chlorpyriphos, each sample was extracted with hexane, redissolved with acetone, and analyzed by HPLC. HPLC analysis conditions are shown in Table 10 below.

(5) Analysis of metabolites

In order to identify the metabolites of chlorosalonyl and chlorpyriphos by ozone treatment, 200 ml of 3 mg / L chlorosalonyl and chlorpyriphos solution was ozonated for 30 minutes, and then the sample was subjected to hexane, dichloromethane, Each was extracted with ethyl acetate and redissolved with acetone and analyzed by GC-Mass. The analysis conditions of GC-Mass are similarly shown in Table 10 below.

Table 10. GC-Mass Analysis Conditions

Model SHIMADZU-10A Detector UV 254nm Column μ-Bondapak C18 (3.9mm × 15mm) Temperature Room temperature Mobile phase Water: Acetonitrile (6: 4) Flow rate 1.0ml / min Sample volume 20 μl

In order to investigate the effect on the soil physicochemical properties by treating ozone water with high chemical activity, glass wool was put on the bottom of a 100 ml column as shown in FIG. Then, 50 ml of ozone water or distilled water was repeatedly added four times, and the change in physicochemical properties of the soil after the reaction with the leachate discharged each time was investigated.

Table 11 and Table 12 below are the results of examining the physicochemical properties and heavy metal content of the four soils (Soil-I, Soil-II, Soil-III, Soil-IV) used in the present invention. Soil-I is the general soil soil, Soil-II is high in organic matter, Soil-III is high salt, and Soil-IV is heavy metal. Each of these high soils was selected to investigate the effect of ozone water treatment on the properties of each soil.

Table 11. Results Table of the Physicochemical Content of Soil.

 Soil type pH (1: 5) EC (µS / cm) T-N (%) O.M (%) P ₂ O ₅ (mg / kg) Ex. cations ^* (mg / kg) Ca Mg K Na Soil-Ⅰ 5.41 70 1.19 1.5 186 1,886 192 174 25 Soil-Ⅱ 5.73 999 3.61 10.9 2,875 1,845 179 484 116 Soil-Ⅲ 5.81 1,620 2.49 4.2 297 2,651 437 347 318 Soil-IV 6.49 43 0.36 0.7 100 1,183 171 118 38

Table 12. Table of results of investigation of heavy metal content in soil.

Soil type Heavy metal content (mg / kg) Mn Cu Zn Pb CD Cr Soil-Ⅰ 64.6 2.3 4.5 3.5 0.1 0.1 Soil-Ⅱ 65.2 12.7 23.5 2.7 0.2 0.5 Soil-Ⅲ 52.8 6.9 4.0 8.3 0.2 1.3 Soil-IV 50.9 21.7 25.1 22.5 0.6 0.7

2. Ozone Water Sterilization Test

The sterilization test of ozone water against soil pathogens is as follows.

end. Experiment Content

Oxidation of contaminated soils by ozone water treatment affects not only the general physicochemical properties of the soil, but also the native microbes in the soil. In other words, by investigating the effects on the activity of soil microorganisms according to the treatment concentration, treatment amount and treatment time of ozone water, the optimum treatment concentration, treatment amount and treatment time of ozone water were investigated to maximize the efficiency.

① Subsequent culture of each strain after addition of ozone water to Potato Dextrose Agar medium.

-Experiment with different concentrations of ozone water at 100%, 80%, 50%, 30% and 10%.

② Subsequently culture each bacteria and add ozonized water after 24 hours.

Experiment by varying the amount of ozone water to 200 ml, 400 ml and 600 ml.

③ Each experiment was processed within 5 minutes considering the characteristics of ozone water.

I. Effects of Ozone Water Treatment on Indigenous Microorganisms

In order to examine the effect of ozone water treatment on soil indigenous microorganisms, 1 ml of soil extract water was diluted in each test tube. The dilution method was 3 treatments as follows.

① Control: 1 ml of soil extract + 1 ml of distilled water

② 2x ozone dilution zone: Soil extract 1ml + ozone water 0.5ml + distilled water 0.5ml

③ Ozone water treatment zone: 1 ml of soil extract water + 1 ml of ozone water

Soil extract water was added 10ml sterilized 0.85% NaCl solution in 1g of the sample and mixed for 2 minutes with a vortexer (diluted with 0.85% NaCl (sodium chloride) solution) was used as soil extract water. As a medium for separating soil microorganisms, bacteria were used as TSA (Tryptic Soy Agar) media, actinomycetes as YMA (Yeast extract-Malt extract Agar) media, and fungi PDA (Potato Dextrose Agar) media. 100 μl of the diluted sample of the fungal sample was spread on each medium, and bacteria were incubated at 37 ° C. for 3 days, actinomycetes at 30 ° C. for 5 days, and mold at 28 ° C. for 7 days.

All. Root-knot nematode control effect

(One). Isolation of Root-knot Nematodes

Root-knot nematodes were collected from the nematode cultivation site of Seongju Fruit and Vegetable Research Center of Gyeongsangbuk-do Agricultural Research and Development Institute, and 300 cm ³ of soil was collected and the nematodes were separated by centrifugation (Southey, 1986). The type of nematodes growing here was Peanuts Root Nematodes (Meloidogyne arenaria), and the isolated nematodes were the second larvae (J ₂ ). The isolated nematodes were placed in a counting dish and collected under the dissecting microscope to distinguish corrosive nematodes and peanut root-knot nematodes.

(2) Nematode Effect Test on Root-knot Nematodes of Ozone Water

The ozone water used was operated for about 15 minutes using the ozone generator 10 to dissolve the generated ozone in water to obtain ozone water, and then immediately add 0.6 mg / l ozone water to the vial containing the separated nematode. Survival was confirmed after 1 hour, 2 hours, 3 hours, 4 hours, 6 hours, 12 hours, 24 hours, and 48 hours. The survival of nematodes was visually confirmed by observing nematodes under a dissecting microscope and touching the nematodes with saliva.

In addition, the separated nematodes were placed in a sieve having a size of 50 μm, and the top of the sieve was covered with a sieve of the same size again and put in an ozone generator to generate ozone for 20 minutes. The nematode survival was directly confirmed by touching the movement with saliva.

la. Growth and quality of facility cultivation melon by ozone water irrigation

Melon cultivation was carried out in a farm house (50m in length × 6m in width), and the melon varieties were cladded with new earthen squash with gold leaf, silver spring, and large tree. The soil of the test package was silty loam, and the area of ridge was 1.8m and covered with green polyethylene mulching film. The test area of Gugu was 13.77m ² (1.8m × 7.65m), which was used for ozone water and water supply by installing a drip hose for middle water.

Before the experiment, the ratio of urea was 9.7kg / 10a based on the nitrogen content, phosphate was 6.3kg / 10a based on the amount of phosphate, 5.1kg / 10a based on the amount of chlorine chloride, and Murabi was added every 20 days. Compound fertilizer (N 9-P 0-K 9-B 0.18-S 7.2) was dissolved in water and irrigated at 500-fold concentration. Ozone water and irrigation were irrigated 7 times at intervals of about 10 days at 10 liters per test zone from the 20th day after the establishment. The ozone water was irrigated immediately by connecting the underwater motor to the drip hose immediately after ozone was generated. The harvest of melon was harvested three times from the 80th day to the 90th day. The test zones were subjected to two complete randomization methods.

Since ozone (O ₃ ) is a gas, its solubility in water is greatly affected by temperature, pressure and contact method. In general, according to Henry's law, ozone is known to dissolve more at lower temperatures near 0 ° C, at higher pressures, and at higher contact areas. Therefore, in the present invention, the amount of dissolved ozone was measured under conditions of 2 ° C., 15 ° C., and 25 ° C. that can be artificially controlled.

FIG. 23 is a result of measuring the dissolved ozone amount by varying the reaction time in a 250 ml sample solution at a temperature of 2 ℃, 15 ℃ and 25 ℃. The amount of dissolved ozone increased rapidly as the initial temperature of the reaction solution decreased. The maximum amount of dissolved ozone reached within 10 minutes at all temperature conditions. At 2 ℃, 1.13 mg / ℓ was dissolved after 10 minutes of ozone generation, 0.65 mg / ℓ at 15 ℃ and 0.40 mg / ℓ at 25 ℃. This is because the lower the temperature of the solution, the higher the solubility of ozone.

In the present invention, ozone water generated by generating ozone for 30 minutes under the condition of 15 ° C. in which the temperature of the solution is easily controlled is used for the experiment.

FIG. 24 shows the result of investigating the change of dissolved ozone amount according to the settling time of ozone water aerated for 30 minutes by adjusting the initial temperature of 40 L of tap water to 15 ° C. The dissolved ozone amount was 0.65mg / l after 30 minutes of aeration, but the dissolved ozone amount decreased rapidly as the settling time passed.

The half-life of the dissolved ozone calculated by the equation y = 0.5874e ^{-0.0131 x} was 45.2 minutes, 0.27 mg / l after 60 minutes and 0.12 mg / l after 120 minutes.

In general, the case where ozone and anion are simultaneously generated is known to have a shorter half-life than when only ozone is generated. When ozone and anion are simultaneously generated in an ozone generator, it is reported that anion with good solubility in aqueous solution destroys dissolved ozone faster than when only molecular ozone is generated, but it is not clear.

In order to investigate the effect of dissolved ozone in the dissolved oxygen in the aqueous solution, the dissolved oxygen amount was investigated as shown in FIG. 25. The dissolved oxygen content of the initial aqueous solution was 6.4 mg / l, but the dissolved oxygen amount slightly increased by aeration of ozone or air. The maximum amount of dissolved oxygen reached 7.3 mg / l within 10 minutes when the air was aerated, and the maximum amount of dissolved oxygen reached 7.9 mg / l within 5 minutes when the air was aerated. The amount of dissolved oxygen increased slightly due to aeration of ozone, but it was low as 81.4% and 75.3% compared with 9.7 mg / l, which is the dissolved ozone saturation at 15 ℃.

In order to analyze the residual amount of chlorosalonyl and chlorpyriphos present in water, the mixture was treated with 100 ml of distilled water so that the concentration of chlorosalonyl and chlorpyriphos was 1 mg / l, and then extracted twice with dichloromethane. The results showing the recovery rate are shown in Table 13 below.

Table 13. Recovery value extracted twice with dichloromethane after treatment of 100 mL distilled water to have a concentration of chlorosalonyl and chlorpyriphos at 1 mg / L.

Pesticide Recovery rate (%) Chlorosalonyl 100.8 ± 0.2 Chlorpyrifoss 99.6 ± 0.2

In Table 11, the recovery rate of chlorosalonyl was 100.8 ± 0.2%, and in the case of chlorpyriphos, 99.6 ± 0.2% showed satisfactory recovery.

As a result of investigating the change of pH according to the reaction time by aeration of ozone and air in the aqueous solution, respectively, as shown in FIG. 26. The pH of the initial aqueous solution was 6.2, but the pH of the ozone-aerated aqueous solution rapidly decreased to 10 minutes and was 3.2 after 60 minutes. However, the pH of the aqueous solution by the bubble generator, which only generates bubbles, was almost unchanged as 5.9 even after 60 minutes.

These results suggest that low pH decreases because ozone reacts with OH ^- ions to form OH radicals in the initial reaction stage where ozone reacts with water, and hydrogen ions are generated as it is hydrolyzed. Initiation reaction of ozone in water is as follows.

O₃ + OH ^- → O₂ and ^- + HO₂ and ^{k₁ = 70 M - 1 s -} 1

HO₂ · ↔ O₂ · ^- + H ⁺ pKa = 4.8

In this initial stage of reaction between ozone and water, hydrogen ions (H ⁺ ) are generated, thereby lowering pH and changing to acidic conditions.

FIG. 27 shows the results of investigating the pH change of the aqueous solution according to the reaction time when the 1 mg / L chlorosalonyl and chlorpyrifos solution were aerated with ozone and air.

The presence of pesticides in water showed a large change in pH due to ozone aeration. That is, as shown in FIG. 26, the pH was continuously decreased until 30 minutes of reaction in water. When chlorosalonyl and chlorpyrifos were present, the pH of the initial aqueous solution was 5.8 to 6.0, but after 5 minutes of reaction. 3.9 showed a tendency to decrease rapidly. These results are presumably because organic compounds such as pesticides react with ozone to promote the generation of hydrogen ions.

3. Pesticide decomposition experiment by ozone

end. Kinetics of Pesticide Decomposition by Ozone

In order to investigate the effect of ozone dissolved in water on the decomposition of chlorosalonyl and chlorpyriphos, bubbles, air bubbles, and ozone generators, which generate only bubbles (air bubbles) at 15 ° C, are used for time, pH, After reacting with different amounts of pesticide and hydrogen peroxide (H ₂ O ₂ ), the residual amounts of chlorosalonyl and chlorpyriphos were measured and investigated.

FIG. 28 and FIG. 29 show the results of volatilization and decomposition removal of 1 mg / kg of chlorosalonyl and chlorpyrifos solution by bubbles and ozone at 15 ° C. for 30 minutes.

Volatilization and degradation patterns of chlorosalonyl and chlorpyriphos showed similar trends. In the case of chlorosalonyl, the bubble was continuously increased up to 30 minutes by reaction, but thereafter, the removal amount was greatly decreased. Ozone treatment increased significantly up to 10 minutes of reaction compared to bubble treatment, but showed a constant trend thereafter. After 10 minutes, only 25% of bubbles were removed by ozone, but about 55% were removed by ozone treatment. After 60 minutes of reaction, 57% and 87% were removed by bubbles and ozone, respectively. Therefore, about 30% of the chlorosalonyl substantially decomposed by ozone was found.

Bubble treatment of chlorpyrifos removed 35% after 10 minutes, but 62% was removed by ozone treatment. After 30 minutes, 53% and 89% were removed by bubble and ozone treatment, and after 60 minutes, 63% and 97% were removed, respectively. Thus, chlorpyrifose, which is substantially degraded by ozone, was found to be about 40%.

In view of the above results, it is assumed that the removal of chlorosalonyl and chlorpyridose by ozone treatment simultaneously causes volatilization by bubbles and decomposition by ozone. In addition, judging from the pattern removed by air bubbles and ozone treatment, decomposition of pesticides by ozone was completed in 10 minutes for chlorosalonyl, and chlorpyriphos in 30 minutes, and then volatilized by bubbles. Judging.

In general, the initial and production reactions of ozone in water occur by the following reactions.

O₃ + OH ^- → O₂ and ^- + HO₂ and ^{k₁ = 70 M - 1 s -} 1

HO₂ · ↔ O₂ · ^- + H ⁺ pKa = 4.8

O₃ + O₂ ^- → O ₃ and _{^{- + O₂ k 2 = 1.6 10}} 9 M -1 s -1

HO ₃ ㆍ ↔ O ₃ ㆍ ^- + H ⁺ pKa = 6.2

HO ₃ ㆍ → OH + O₂ k _{2 =} 1.1 10 ⁸ M ^-1 s ^-1

In the initial stage, ozone combines with OH ^- ions to form O 2 ^-- ions and hydrooxyl radicals, which are hydrolyzed to O 2 ^-- and hydrogen ions. Leading to ozone and O₂ and at step Radical Chain ^- ions react with O _{3 and} ^- forming ions and oxygen, and is formed with a _{3 and} HO radical. When OH radical is finally formed by HO _{3 ·} radical, it reacts with chlorosalonyl and chlorpyriphos to cause decomposition.

I. pH influence

Figures 30 and 31 show the effects of bubbles and air bubbles at 15 ° C for 30 minutes by varying the pH of a solution containing 1 mg / L chlorosalonyl and chlorpyriphos to investigate the effect of the pH of the initial solution on the decomposition of pesticides. It is the result of investigating volatilization and decomposition of pesticide by treating ozone

The removal patterns of chlorosalonyl and chlorpyriphos showed a similar tendency according to the pH of the initial solution. The higher the pH at the time of bubble treatment, the higher the removal rate of chlorosalonyl and chlorpyriphos was. This result is considered to be because volatilization by bubbles is easier as the pH of the initial solution increases.

Although the removal rate of pesticides increased a little by the increase of pH during ozone treatment, it is thought to be caused by bubbles rather than the ozone effect. However, the slightly increased removal rate of pesticides during ozone treatment at pH 3 is estimated to be acid-degraded because the pH of the solution is lowered to 1.4 by the ozone effect.

The difference in the removal rate of chlorosalonyl and chlorpyriphos was 25% and 40%, respectively. These results indicate that the solubility in water is chlorosalonyl 0.6 mg / ℓ, chlorpyriphos 2.0 mg / ℓ, chlorpyriphos is higher.

All. Hydrogen peroxide (H ₂ O ₂ ) Impact of treatment

Hydrogen peroxide (H ₂ O ₂ ) is a strong oxidizing agent that quickly forms OH radicals and is known to induce decomposition of pesticides by OH radicals generated from H ₂ O ₂ . H ₂ O ₂ reacts with two molecules of ozone to form two molecules of OH radicals as shown in the following equation.

_{2O 3 + H 2 O 2 →} 2OH and + 3O ₂

The addition of H ₂ O ₂ to the ozone generator is expected to produce more OH radicals than the amount of OH radicals produced by ozone. Therefore, the effect of large amount of OH radical on the decomposition of pesticides was investigated.

32 and 33 are results of dissolving the amount of removal of the two pesticides by dissolving in 100ml of a solution in which a constant concentration of hydrogen peroxide was added to chlorosalonyl and chlorpyriphos at 1 mg / L and ozone treatment for 30 minutes.

As the amount of hydrogen peroxide increased, the removal rate of chlorosalonyl and chlorpyriphos tended to decrease. This is different from the effect of hydrogen peroxide, which is commonly used as an adjuvant to increase the production of OH radicals in photodegradation or oxidation mechanisms of hazardous organic compounds. These results indicate that the higher the concentration of hydrogen peroxide, the lower the dissolved amount of ozone, which is the same oxidant, in the solution. In addition, it is estimated that hydrogen peroxide volatilizes in part by the bubble produced at the time of ozone generation.

la. Influence of volume

In order to investigate the effect of the volume of the solution on the decomposition of pesticides, ozone treatment for 30 minutes with different volumes of 1 mg / L chlorosalonyl and chlorpyriphos solution was as shown in FIGS. 34 and 35.

Chlorosalonyl tended to decrease as the volume of initial solution increased. In the case of 50ml and 500ml volumes of the initial solution, 90.1% and 24.8%, respectively, the removal rate decreased rapidly as the volume increased. However, the total removal rate of chlorosalonyl per ozone generation increased with increasing volume of solution.

Chlorpyrifos was 98.9% and 78.1%, respectively, when the volume of the initial solution was 50 ml and 500 ml, respectively, and the removal rate decreased slightly as the volume was increased.

From these results, volatilization and decomposition of the pesticide by ozone is judged to be different depending on the chemical structure of the pesticide, the solubility in water and the characteristics of the active group. Compared to chlorosalonyl, chlorpyriphos has high solubility in water and contains sulfur (S) group, which is thought to be easy to remove by ozone due to easier oxidative reaction.

In order to investigate the reaction product of the decomposition of chlorosalonyl by ozone, 5 mg / l and 200 ml were ozone-treated for 20 minutes, extracted with hexane, dichloromethane and ethyl acetate, concentrated and redissolved with acetone and analyzed by GC-Mass. One result was the same as FIG. 36, FIG.

The settling time of chlorosalonyl was 15.74 minutes, and 12.66, 14.81, 16.85 and 16.95 appeared in the form of unknown peaks. The molecular weight was 266 at the standard peak of chlorosalonyl, and the peak at 275 was found at the peak of 17.213 minutes which is expected as the reaction product.

As such, the decomposition product is a secondary metabolite in which one CN group is substituted with one Cl group among four Cl groups and two CN groups in the benzene ring in the structure of chlorosalonyl by oxidation of ozone. It seems to be. In general, the final degradation products of organic compounds are known to be water and carbon dioxide, but other metabolites are not clear.

Decomposition of Chlorpyriphos by Ozone To investigate the reaction product, 200ml of 5mg / L solution was ozoneized for 20 minutes, extracted with hexane, dichloromethane and ethyl acetate, concentrated and redissolved with acetone. The results of analysis by GC-Mass (GC-Mass) were the same as FIG. 38, 39.

The retention time of chlorpyrefoss was 17.31 minutes and unknown peaks were observed at 14.81, 16.86, 16.94 and 19.69 minutes. The standard peak of chlorpyripas showed a molecular weight of 351, and a peak of 335 molecular weight appeared at the peak of 17.219 minutes which is expected as a reaction product. These substances are the peaks in which sulfur in chlorpyrifos is replaced with oxygen by the oxidation of ozone.

Phosphoric acid is bonded by crosslinking oxygen to the benzene ring of chlorpyripas, and three oxygen and one sulfur are bonded to phosphoric acid. Thus, it was confirmed that sulfur bonded to phosphoric acid was oxidized by ozone and replaced with oxygen.

4. Experimental Changes in Soil Physicochemical Properties of Ozone Water Treatment

end. Effect of Ozone Water on the Elution of Soil Components

On the other hand, there are various organic and inorganic compounds in the soil, and the reactivity of ozone to organic and inorganic compounds is classified into the oxidation reaction by the ozone molecule and the oxidative reaction by OH radical generated in the aqueous solution. Higher. Direct reaction by ozone molecule is achieved by selective action with other materials as spherical, nucleophilic and 1,3 dipole depending on the four types of resonance structure of the molecule, OH radical is the high redox potential of its own To react directly with other substances in a short time (10 ^-5 sec).

Like most organic substances in the soil, ozone is decomposed to produce low molecular weight substances by acting on unsaturated bonds or aromatic rings. Ozone deodorization, decolorization is due to the decomposition of these functional groups. Ozone is also iron ions (Fe ^2+), manganese ion (Mn ^2+, Mn ^4+), cyanide (CN ^-), ammonia (NH ₃₎ by the oxidation of inorganic material such as known to precipitate to a hydroxide or decomposition have.

In order to investigate the effect of ozone water on the physicochemical properties of soil, the pH and electrical conductivity of leachate discharged every time by filling ozone water or distilled water four times by filling various soils in the column are shown in Table 14 below. .

The pH of soil leachate treated with ozone or distilled water increased slightly with the number of treatments. In particular, the organic matter content was 10.9% and 4.2%, respectively, and the pH of soil II and soil III was increased with distilled water and ozone water. The initial pHs of soils II and III were 5.7 and 5.8, but the pH of four washes with distilled water increased to 6.5 and 7.0, respectively, and to 6.6 and 6.8, respectively. Similar trend was observed in soil I, but there was little change in pH in soil IV with low organic matter and nitrogen content. The electrical conductivity of leachate tended to decrease as the number of treatments increased, and the electrical conductivity of leachate treated with ozone water was higher than that of leachate treated with distilled water. These results suggest that the salts affecting the electrical conductivity are easily dissolved when ozone water or distilled water is treated, and more salts in the soil are released by the reaction with ozone than distilled water.

Table 14. Results of distilled water and ozone water repeated four times in various soils and the pH and electrical conductivity of the leachate discharged each time.

 Soil type Washing time Distilled water Oh john can One 2 3 4 One 2 3 4  pH (1: 5) Soil-Ⅰ 6.2 6.4 6.2 6.2 6.2 6.0 6.1 6.0 Soil-Ⅱ 5.9 6.6 6.6 6.5 5.8 6.4 6.4 6.6 Soil-Ⅲ 6.0 6.7 6.9 7.0 6.0 6.7 6.7 6.8 Soil-IV 6.3 6.6 6.5 6.7 6.4 6.6 6.5 6.5  EC (㎲ / cm) Soil-Ⅰ 53 20 11 8 128 102 89 91 Soil-Ⅱ 1,052 84 64 70 1,210 185 145 112 Soil-Ⅲ 1,530 110 70 57 1,660 175 139 128 Soil-IV 44 9 8 5 120 88 94 92

In particular, salts that are not easily released by water, such as soil I and soil IV, are also easily eluted by ozone water.

Therefore, when ozone water is treated in the soil, the pH of the leachate is slightly increased, and it is considered that there is an improvement effect of the salt accumulated soil in view of the sharp decrease in the electrical conductivity.

In order to investigate the effect of ozone water on the physicochemical properties of soil, the concentration of substituted cations in the leachate discharged every time by filling ozone water or distilled water four times by filling various soils in the column is shown in Table 15 below.

Compared to the leachate of the soil treated with distilled water, the leachate content of the soil treated with ozone water was higher. As the number of treatments of ozone or distilled water increased, the concentration of substituted cations in the leachate decreased.

Table 15. A table of the substitutional cation concentration in the leachate discharged every time by distilled water and ozone water four times in the soil. (Unit: mg / l)

Soil type  metal Washing time Distilled water Oh john can One 2 3 4 One 2 3 4   Soil-Ⅰ Ca 47.2 10.1 20.4 11.9 102.6 90.2 87.9 93.4 Mg 7.9 5.3 4.6 4.3 20.9 13.5 11.2 10.9 K 21.8 21.4 19.2 17.3 45.5 33.0 25.3 20.2 Na 28.9 12.5 5.8 11.3 45.6 33.5 31.3 35.0   Soil-Ⅱ Ca 427.9 35.3 28.4 36.2 563.3 100.9 88.6 96.6 Mg 221.0 11.2 10.3 15.3 290.2 34.4 26.2 24.7 K 801.2 154.5 149.4 143.1 979.2 235.4 173.8 118.3 Na 128.7 26.3 15.6 17.1 170.5 42.9 41.8 34.3   Soil-Ⅲ Ca 584.4 42.4 34.8 36.3 705.3 100.9 46.0 43.2 Mg 309.4 14.9 13.9 11.2 380.5 23.6 22.0 23.2 K 1,093.2 180.3 160.9 92.9 1,203.0 235.7 150.4 104.4 Na 145.1 23.7 16.0 15.2 194.9 36.4 36.2 36.5   Soil-IV Ca 27.2 15.4 13.4 8.3 101.3 189.9 93.3 80.3 Mg 8.5 5.6 3.6 3.1 20.2 16.4 16.9 16.0 K 30.5 17.6 18.2 12.9 55.2 33.1 23.8 18.1 Na 16.7 14.9 17.5 13.0 39.2 34.4 35.5 33.6

In order to investigate the effect of ozone water on the physicochemical properties of soil, the change of heavy metal content of the leachate discharged every time by filling ozone water or distilled water four times by filling various soils in the column is shown in Table 16 below.

Table 16. Results of heavy metal content of leachate discharged every time by filling ozone water or distilled water four times by filling various soils in column. Unit (mg / l)

 Soil type  heavy metal Washing time Distilled water Oh john can One 2 3 4 One 2 3 4   Soil-Ⅰ Mn 0.21 0.09 0.02 - 1.15 0.74 0.92 0.81 Cu 0.41 0.22 0.56 0.25 0.28 0.25 0.12 0.06 Zn 0.12 0.11 0.15 0.05 0.50 0.32 0.33 0.16 Pb 0.62 0.60 0.61 0.75 0.86 0.56 0.49 0.12 CD 0.12 0.12 0.11 0.10 0.49 0.12 0.15 0.51 Cr 0.21 0.15 0.23 0.17 0.17 0.10 0.05 0.02   Soil-Ⅱ Mn 3.21 0.10 0.02 - 4.47 0.63 0.17 0.05 Cu 5.83 3.55 3.16 3.05 12.16 5.79 2.45 1.98 Zn 8.88 1.72 1.57 1.51 7.46 2.49 2.77 2.14 Pb 3.71 3.18 3.14 4.37 7.88 3.92 4.99 3.05 CD 2.95 1.97 1.87 2.35 2.49 1.85 0.78 1.15 Cr 1.24 1.12 1.97 1.22 0.81 1.12 0.87 1.24

  Soil-Ⅲ Mn 11.87 1.25 0.51 0.12 14.45 10.41 3.98 2.13 Cu 0.75 1.26 0.37 0.31 1.02 0.43 0.87 0.32 Zn 1.24 0.78 0.52 0.37 0.86 0.29 0.21 0.16 Pb 0.98 0.73 1.12 0.87 0.92 1.05 0.74 0.70 CD 0.75 0.50 0.16 0.21 0.24 0.18 0.36 0.81 Cr 0.17 0.24 0.24 0.21 0.12 0.21 0.19 0.20   Soil-IV Mn 0.28 0.17 0.08 - 0.79 0.18 0.25 0.49 Cu 0.62 0.32 0.27 0.20 0.12 0.08 0.04 0.21 Zn 0.21 0.12 0.08 0.10 0.17 0.20 0.24 0.34 Pb 0.75 0.49 0.74 0.62 0.33 0.21 0.29 0.12 CD 0.16 0.12 0.14 0.11 0.30 0.15 0.08 0.26 Cr 0.17 0.13 0.22 0.15 0.20 0.11 0.08 0.03

The content of heavy metals in leachate was higher in ozone leachate than in distilled leachate. However, the difference in the number of treatments was not significant in the leachate. Table 17 below shows the change in soil chemical properties after treatment with ozone or distilled water.

I. Effect of Ozone Water on the Chemical Properties of Soil

Table 17 below shows the change in the chemical properties of soil after treatment with ozone or distilled water.

Table 17. Table showing the change in soil chemistry after treatment with ozone or distilled water

 process Soil type pH (1: 5) EC (㎲ / cm) T-N (%) O.M (%) P ₂ O ₅ (mg / kg) Metal (mg / kg) Ca Mg K Na  Raw soil Soil I 5.41 70 1.19 1.5 186 1,699 192 174 25 Soil Ⅱ 5.73 999 3.61 10.9 2,875 1,845 479 484 116 Soil III 5.81 1,620 2.49 4.2 297 2,651 437 347 318 Soil IV 6.49 43 0.36 0.7 100 1,183 171 118 38  Distilled water Soil I 5.27 103 0.92 1.3 182 1,605 207 137 29 Soil Ⅱ 6.35 105 2.43 10.5 2,795 1,628 472 271 - Soil III 6.48 110 2.00 4.0 215 2,287 429 267 - Soil IV 6.49 27 0.32 0.6 81 1,197 168 94 -  Ozone water Soil I 5.37 125 0.95 1.3 174 1,631 189 124 23 Soil Ⅱ 6.26 150 2.80 9.9 2,771 1,578 476 264 - Soil III 6.54 100 2.14 3.7 189 2,225 419 223 - Soil IV 6.39 39 0.33 0.5 76 1,228 140 71 -

Regardless of soil characteristics, ozone water or distilled water treatment resulted in lower inorganic and organic contents in soil than untreated soil, and ozone water treatment was more effective in removing salt than distilled water treatment.

5. Test of bactericidal power of ozone water against soil pathogens

First, the results of examining the bactericidal power of ozone water against soil pathogens Fusarium and Rhizoctonia were as shown in FIG.

The bactericidal activity of ozone water was not shown for each bacterium, and Fusarium bacteria showed a significant growth promoting effect in the ozone water-added medium compared to the untreated group. Rhizoctonia was only slightly grown and did not differ significantly from the untreated.

After the ozone water was added to the PDA (Potato Dextrose Agar) medium for the soil pathogens Fusarium and Rhizoctonia , each strain was passaged and examined for the bactericidal power of ozone water as shown in FIG. 42 and FIG. 43.

If the addition of ozone water in the passage a culture is Fusarium strain exhibited some growth promotion effect as a whole as compared to untreated, the growth of Rhizoctonia strains were of the ozone water treatment effect is almost not see some growth promoting effects compared to untreated Could.

As a result of culturing soil extract water in PDA, YMA, and TSA medium to investigate the ozone water treatment of indigenous microorganisms, it was as shown in FIG. 44.

In the case of fungi growth medium (PDA medium), ozone water treatment group showed lower activity than control group, and bacterial medium (TSA medium) showed higher activity of microorganisms according to ozone water treatment. YMA medium) did not have a clear tendency, and the results of investigating the control effect of root-knot nematodes according to ozone water treatment were shown in Table 18 below.

Table 18. Comparison of Root-knot Nematode Control Effects by Ozone Water Treatment.

division 30 minutes 1 hours 2 hours 3 hours 4 hours 6 hours 12 hours 24 hours 48 hours Minutes survival survival survival survival survival survival survival survival survival Body seal survival survival survival survival survival survival survival survival survival

In the above, 'preparation' is when the ozone water is put into the vial containing the nematode, and 'body seal' is when the nematode is sealed in the sieve and immersed in the ozone generator

As shown in the table above, when the nematode was treated with ozone water (preparation), it survived even after 48 hours, and the nematode used in this experiment was found to survive even when placed in an ozone generator (sealing seal) to increase the effect of ozone. Is not killed at an ozone concentration of 0.6 mg / l.

The results of investigating the effects on the quality and yield of facility melon by ozone water irrigation are shown in Table 19 below.

Table 19. Effect on Ozone Water Irrigation Quality and Yield Results

process (G / piece) And sheet (cm) And width (cm) Sugar (Brix) Quantity (kg / 10a) Goods and (pieces) Ozone water 310a 11.6a 7.9a 14.3a 1,520a 51a Control 315a 11.4a 8.0a 14.1a 1,630a 49a

※ 270g overweight with the product.

As shown in the table above, ozone water irrigation was higher in sugar content, commodity and water than in control, but statistically insignificant.

In the present invention, the content of soil organic matter and the substitution of cation concentration according to the treatment of ozone water resulted in the increase of the elution of soil salts by ozone water, and the concentration of salts in the soil by ozone water treatment, the indigenous microorganisms, pathogenic microorganisms and root nodules. By comparing the activities of ozone water treatment with nematodes, and by comparing and inspecting the quantity and quality of ozone water irrigation for facility melon, the experiments confirmed that soil restoration was restored by the change of soil biological environment by ozone water treatment. there was.

In addition, the present invention is treated with high concentration ozone water having a dissolved ozone concentration of 0.02ppm ~ 2ppm by contaminating soil, watering, spraying, etc., oxidatively decomposes pesticides and / or fungicides and other pollutants in the soil, organic The salt direct drops significantly and the soil chemistry is restored to its original soil state.

In addition, in the soil, various fungi such as white mold are parasitic breeding, so that oxygen is blocked, but the activity of aerobic microorganisms, which are indigenous microorganisms, is suppressed, but in the present invention, since a large amount of oxygen is supplied by ozone, ozone, and anions, there are no anaerobic microorganisms. And aerobic microorganisms that are beneficial to various crops.

In the case of general water, the water particles tend to be large and the amount of dissolved oxygen is small so that it is not absorbed well in the soil and becomes high. However, in the case of the present invention, a large amount of ozone and anions are dissolved, so that dissolved oxygen is high and organic materials are used. As the hexagonal water is removed, it is absorbed more than twice as much as it is not accumulated in the soil. Soil ozone and anions oxidize and decompose pollutants in the soil, which restores the contaminated soil and imparts breathability to the soil. It is greatly promoted, and serial damage is prevented.

In addition, the present invention is not only capable of in-situ method, but also contributes greatly as an alternative technology of the existing chemical treatment method as an advanced technology that combines efficiency, promptness and environmental friendliness, and functional agricultural materials, water purification and waste treatment. In addition, the technology developed for the restoration of polluted soil is expected to have a large ripple effect in related fields because of its simple application and easy transfer of technology.

The present invention described above is capable of various substitutions and modifications within the scope without departing from the spirit of the present invention for those of ordinary skill in the art to which the present invention pertains to the above-described embodiments and the accompanying drawings. It is not limited to.

As described above, in the present invention, in generating high concentration ozone water for improving and restoring the contaminated soil, the ozone generator is improved through the improvement of the ozone generator and the dissolved ozone concentration in the water is treated to the soil and the contaminated water. Soil removal technology by existing chemical treatments such as improvement of soil physical and chemical properties, prevention of secondary pollutants and rapid treatment efficiency by inducing removal of organic pollutants in soil and promoting change of soil physicochemical properties There is an effect that can greatly contribute to the solution of the problem.

The present invention also improves the ozone generator through the performance analysis of the ozone generator and ozone generator cooling apparatus. The development and adoption of ozone generator peripherals, such as dehumidification system of raw material gas, greatly improves the ozone generating capacity and increases the power of the power supply to the ozone generator to increase ozone generation, increase dissolved ozone concentration, and sterilization ability better than ozone. In order to help generate radicals, anion generating water is increased by increasing the output voltage of an anion generator.                     

In addition, since the present invention treats the redox agent directly to contaminated soil, instead of the conventional soil treatment method which has various problems such as deterioration of physicochemical properties of soil and generation of secondary pollutants, the present invention contaminates ozone water having excellent resolution of organic pollutants but not residuals. By treating the soil for a long time, there is an effect that the pollutants of the soil are environmentally friendly.

In addition, the present invention is excellent in the effect of improving the soil physicochemical properties due to the rapid removal of soil pathogens and the improvement of salt accumulation soil by treating ozone water in the long-term soil of the chemical fertilizer, and by treating the soil with oxidizing power ozone water oxidative It can be expected to maximize the activity, and the ozone water treatment penetrates into the deep part (soil) of the soil, which is difficult to penetrate the solid phase oxidant, and has the effect of showing rapid reaction characteristics with the liquid pollutant.

In addition, the present invention is a high-functionalization technology for improving salt accumulation and nematode contaminated soil as well as restoring soil contaminated with various harmful substances, as well as the development of environmentally friendly contaminated soil restoration technology as well as sterilization, disinfection, deodorization, decolorization, freshness maintenance, As it can be used in various fields such as the removal of harmful gases and heavy metals, it is expected to have a great technical ripple effect. Especially, high-functional polluted soil technology is not only capable of in-situ method but also efficiency, speed and environmental friendliness. It will contribute greatly as an alternative technology to the existing chemical treatment method with advanced technology, and the technology to be developed for functional agricultural materials, water purification, waste disposal as well as contaminated soil restoration is simple to apply and easy to transfer technology. There is an excellent effect expected to have a large ripple effect.                     

In addition, the present invention can be used not only in the restoration of the contaminated soil using ozone water, but also in the field of catalytic agriculture as well as in functional agricultural materials, water purification and waste treatment requiring oxidative activity. It is easy to have a ripple effect in related fields.

In addition, the present invention is the development of a technology that can quickly and efficiently restore and improve the organic contaminated soil and salt accumulation soil is a very useful invention that has the effect that can greatly contribute to the domestic environment conservation as the next-generation advanced technology.

Claims (14)

Impurities are removed and cooled, dehumidified and compressed source gas is discharged into an ozone generator having a cooling means to generate ozone, dissolved ozone in water to obtain ozone water, and the ozone water is treated in soil to make the soil contaminated. Hardly decomposable soil recovery method using a high concentration of ozone water, characterized in that to restore to. The impurities are removed and the dehumidified and compressed raw gas is discharged into an ozone generator having a cooling means to generate ozone, and the generated ozone is supplied to an anion generator to generate anion ozone, and the anion ozone is dissolved in water. By obtaining the anion ozone water, and treating the anion ozone water in the soil to restore the contaminated soil in an environment-friendly, hardly decomposable soil recovery method using high concentration ozone water. The method according to claim 1 or 2; Dissolved ozone in ozone water is a method for restoring soils with degradable soil using high concentration ozone water, characterized in that 0.02ppm ~ 2ppm. The method according to claim 2; Dissolved ozone in ozone water is 0.02ppm ~ 2ppm, anion water is 4.4 × 10 ⁶ / cc ~ 6.0 × 10 ⁶ / cc The hardly decomposable soil recovery method using high concentration ozone water. The method according to claim 1 or 2; After dissolved ozone for 30 minutes ~ 2 hours dissolved oxygen amount is 6.0mg / ℓ ~ 12.0mg / ℓ. The method according to claim 1 or 2; Raw material cooling temperature is -20 ℃ ~ -30 ℃, cooling temperature of the cooling means is 3 ℃ ~ 6 ℃, humidity of the dehumidified raw material gas is 15% to 25%, difficult to decompose pollution using high concentration ozone water Soil restoration method. Compressing the source gas from which impurities are removed with an air compressor, removing moisture from the compressed source gas with a dehumidifier, removing oil from the compressed source gas from which moisture is removed by an oil mist filter, and using a flow controller. Adjusting the supply pressure of the source gas, generating the high concentration ozone by discharging the source gas with an ozone generator, cooling the external electrode of the ozone generator with a cooling device in which cooling water is circulated by a circulation pump, A method of restoring a degradable contaminated soil using high concentration ozone water, wherein the contaminated soil is environmentally restored by treating the ozone water dissolved in the ozone in the soil. The method according to claim 7, Anion ozone is generated and discharged by an anion generator installed at an ozone outlet, and the anion ozone water in which the negative ion ozone generated by supplying the ozone to the anion generator is dissolved in water is treated with soil. Hardly decomposable soil recovery method using a high concentration of ozone water, characterized in that to restore environmentally friendly. An air compressor for compressing the raw material gas from which impurities are removed, an oil mist filter for removing oil in the compressed raw material gas, a dehumidifying device for removing moisture in the raw material gas, a flow regulator for controlling the supply gas supply amount, and a raw material gas A dehumidifier for removing moisture in the water again, a raw material gas cooling device for cooling the dehumidified raw material gas to a predetermined temperature, one or more plural ozone generating devices for discharging the supplied raw material gas to generate and discharge high concentration ozone, and the ozone External electrode cooling device that cools the external electrode of the generator with circulating cooling water, an anion device installed at the ozone outlet to discharge negative ion ozone water, and a power supply device for supplying operating power to the ozone generator and the anion generator, respectively. Hardly decomposable contaminated soil restoration system using high concentration ozone water. The method according to claim 9; The ozone generator is provided with a plurality of ozone generating pipes in parallel between the left and right support members having a supply / exhaust chamber, and the ends of the ozone generating tubes protruding into the supply chamber and the exhaust chamber are connected with a plurality of connecting members, respectively. One side of the generating pipe is connected to the air supply chamber so that the compressed source gas flowing into the air supply port is introduced, and the other side of the last ozone generating pipe is connected to the exhaust chamber so that one series flow path is formed. Polluted soil recovery device. The method according to claim 9 or 10; The raw material gas cooling system is composed of a refrigeration compressor, a condenser, an expander, and an evaporator in one cycle, an evaporator of the raw material gas cooling device which is immersed in the antifreeze in an adiabatic reservoir containing an antifreeze, and an air pipe through which the raw material gas passes. Refractory soil recovery device. The method of claim 10; The ozone generating tube is composed of a tubular dielectric through which raw material gas passes, an external electrode installed in close contact with the outer surface of the dielectric, and an internal electrode provided in a coil structure inside the dielectric, and the external electrode has a copper thickness of 0.03 mm to 0.5 mm. One of tape or copper pipe and the inner electrode is stainless wire of 0.5mm to 2.0mm diameter, and the outer electrode of ozone generating pipe is connected by conductive jumper line, and then connected to the power supply line. A decomposable soil recovery device that is connected to another power supply line connected by another jumper wire so that discharge power can be supplied. The method of claim 10; Dielectric of the ozone generating tube is forcibly coupled to the coupling hole formed in the support member and the tubular portion, the inlet portion of the coupling hole is formed around the inclined surface, the tubular portion protrudes in the opposite direction of the air supply chamber and the exhaust chamber, respectively, The outer circumferential surface and the outer circumferential surface of the dielectric are bonded and fixed by a heat shrink tube, and the external electrode cooling device is provided by side plates fixed to both support members, and upper and lower plates and front and rear plates that are secured to be watertightly fixed to upper and lower parts and front and rear parts of the side plates. Refractory soil recovery device consisting of a water cooling chamber, a cooling water supply port and a cooling water drainage port installed in a plate. The method according to claim 9 or 10; Concave grooves are formed on the outer surface of the support member on both sides, O-rings are coupled to the concave grooves, a cover having an air supply port and an exhaust port on the outer side of the O-ring contact, a reinforcing member abuts on the outer surface of the cover, a plurality of A decomposable soil recovery device, which is tightly coupled to a cover and a support member by two coupling members.

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