KR20070073679A - Method and potable type equipment for treatment of polychlorinated biphenyls in wasted insulation oil - Google Patents

Abstract

A method for disposing waste insulation oil containing polychlorinated biphenyl and portable disposing equipment for carrying out the same are provided to quickly remove the polychlorinated biphenyl from the waste insulation oil, and to achieve simplified disposing process. The portable disposing equipment of waste insulation oil comprises: a controller(50), controlling the whole of the equipment; a reaction container(15), chemically reacting the waste insulation oil, containing the polychlorinated biphenyl, with a metallic sodium as a reagent; a high speed motor(10), arranged on the reaction container(15); a rotating axis(90), and a stirring blade(100), both of which are arranged inside the reaction container(15); wherein the motor(10), the container(15), and the axis(90) generate a vortex in the insulation oil, mixed with the reagent; a temperature controlling and heating device(30), bringing about the reaction of the insulation with the reagent; a temperature sensor(40), detecting the temperature of the insulation oil; a level sensor(20), detecting a level of the insulation oil; and two motor pumps(70,80) and many hoses for inputting the insulation oil into the reaction container(15) and a transformer container(160) or discharging it from the latters.

Description

Method and potable type Equipment for Treatment of Polychlorinated Biphenyls in wasted Insulation Oil}

1 is an overall configuration diagram of a processing apparatus of the present invention.

2 is a mounting view of the processing apparatus vehicle of the present invention.

<Description of the code | symbol about the principal part of drawing>

10: high speed rotation motor 20: level sensor

30: heating part 40: temperature sensor

50: control device 60: power cord

55: control console

70: outflow motor pump 80: inflow motor pump

90: rotating shaft 100: stirring blade

110: reagent storage container 120: outflow hose

130: level sensor 140: temperature sensor

150: nozzle 160: transformer barrel

170: iron core and core 180: connecting wire

200: vehicle 210: control console

220: controller 230: container

240: reactor 250: outflow inlet hose

260: transformer

The present invention relates to a method for environmentally harmlessly decomposing waste insulating oil containing polychlorinated biphenyls (PCBs), and to a mobile processing apparatus for decomposing and treating waste insulating oil containing PCBs, which are persistent organic pollutants, in a storage location. will be.

PCBs are used for various purposes such as insulating oil, heat medium, lubricating oil, plasticizer, etc., and are used for various purposes because of their high value, incombustibility, no fear of thermal deterioration, excellent insulating or electrical properties, and very chemical stability.

Polychlorinated biphenyl is basically a compound in which hydrogen bonded to ten hydrogen atom positions of biphenyl (C ₆ H ₅ -C ₆ H ₅ ) is substituted with 1 to 10 chlorine atoms, and there may theoretically be 242 isomers. However, about 100 species are actually used. The polychlorinated biphenyl is not decomposed even when heated, is insoluble in water, and has excellent electrical insulation, and thus has been widely used in electrical products such as transformers and capacitors.

Polychlorinated biphenyls are introduced into sewage treatment plants after use, causing environmental damage and ecological changes. These polychlorinated biphenyls are used as environmental pollutants without any special measures. Since then, production and use of it has ceased worldwide. However, in the world, 1 million tons of polychlorinated biphenyls have been released to the natural world, and the amount of disposal disposal reaches 2 million tons, and in Korea, it is known that a large amount of polychlorinated biphenyls to be treated is present. There is an urgent need.

According to the US Environmental Protection Agency (US EPA), more than 90 kinds of technologies are reported to be able to process polychlorinated biphenyls. Until now, technologies for treating harmful chemicals such as polychlorinated biphenyls have been largely biochemical treatment technologies, Physical and chemical treatment techniques, thermal treatment techniques, and techniques for irradiating and treating electron beams are known.

In the case of biological treatment using an enzyme or the like which is effective in treating polychlorinated biphenyls, it is applicable to various media contaminated with polychlorinated biphenyls and has the advantage of minimizing the generation of residues. The disadvantage is that the efficiency is greatly influenced by the polychlorinated biphenyl concentration.

The thermal treatment technology has advantages in that the treatment speed is high and the volume of the treated waste is small. However, it is limited to be applied to liquid and gaseous media, which is relatively expensive, and requires further treatment of residues generated after the treatment. There are disadvantages. In addition, incineration of polychlorinated biphenyl-containing products by general methods has been reported to produce polycyclic aromatic hydrocarbons, such as dioxins, which are more toxic than polychlorinated biphenyls, as by-products. There is a limit to the safe handling of insulating oils. In particular, since it is known that harmful dioxins are produced and discharged, due to the strong opposition of the residents in the area where incinerators are installed, they are often exported to foreign countries for consignment or long-term storage. There is also a high risk of polychlorinated biphenyls being released into the environment and contaminate the environment.

Decomposition by ultraviolet light has a disadvantage of low decomposition efficiency, and chemical decomposition by oxidizing agent can decompose in several hours, but corrosion of device material by oxidizing agent is a problem, and oxidative decomposition by supercritical water consumes energy. There is a problem that is too large.

In the case of chemical treatment technology, there is a disadvantage that additional treatment of residues generated after treatment is required like thermal treatment technology. However, the treatment speed is fast and can be applied to various media contaminated with polychlorinated biphenyls. Although it can be used as a recycling technology, the chemical decomposition reaction of commercially available polychlorinated biphenyls includes metal sodium dispersion method (North Sea, Japan), dechlorination method (Toyoda, Japan), and alkaline catalyst decomposition method (US, Japan). , Australia) Hydrogenation Dechlorination Catalysis (Osaka, Japan), Dechlorination (Kyushu, Canada, Japan), Hydrothermal Oxidation (Tokyo), Organometallic Alkalysis (Japan), Chemical Extraction (Japan) and Supercritical Water Oxidation method (USA, Japan).

In addition, Japanese Patent Application Laid-open No. Hei 10-316798 discloses dechlorination by adding ethyl alcohol, ethylene glycol, and alkaline hydroxide to insulating oil containing polychlorinated biphenyl for treatment of polychlorinated biphenyl contained in insulating oil. Japanese Patent Laid-Open No. 2001-29942 discloses a method for treating polychlorinated biphenyls contained in insulating oil using titanium oxide as a photocatalyst.

There is a method of removing polychlorinated biphenyl contained in the insulating oil by irradiating electron beam, but the installation equipment is expensive and there is a disadvantage that chlorine molecules may remain in the insulating oil during treatment, and thus must be reprocessed.

In the process of the Japanese commercialization company using the metal sodium dispersion method for chemical dechlorination decomposition reaction, a large building with a land area of about 24000m ² is used to process 0.5 tons of insulating oil containing polychlorinated chloride per day. The pre-treatment process is performed to remove the oil from the transformer and to remove the polychlorinated chloride attached to the transformer from the transformer to perform a vacuum heating separation process, and then to crush the transformer and then clean the transformer member. Next, in the reactor, metal sodium was added to the insulating oil to treat polychlorinated biphenyls. In this case, the pretreatment process is complicated, so a large site factory is required. In addition, since the contact probability between dechlorination reagent and polychlorinated biphenyl is increased by heat dispersion in the process of performing sodium dispersion method in the reactor, the temperature is increased to improve the reaction time between reagent molecules and polychlorinated biphenyl molecules. Doing. Therefore, by maintaining a high temperature reaction temperature (160 ~ 170 degrees Celsius) there is a problem in that a large amount of energy is consumed in the reactor to increase the cost during processing.

The present invention is to provide a polychlorinated biphenyl chemical decomposition treatment method of a novel process that eliminates the problems in the treatment process of the prior art metal sodium dispersion method pointed out above.

In the prior art metal sodium dispersion method using chemical dechlorination reaction, a solvent washing facility and a vacuum heat separation facility treatment process are required to remove polychlorinated biphenyls remaining in a transformer or the like. Provides a treatment method and apparatus for quickly removing polychlorinated biphenyls having an insulating flow rate containing polychlorinated biphenyls and decomposing polychlorinated biphenyls remaining in components (containers, iron cores, paper trees, etc.) in transformers. Its purpose is to. In addition, the introduction of a simplified treatment process provides a mobile treatment apparatus that can be processed on a scale that is installed on a vehicle without a large treatment plant site.

In addition, in the prior art process of performing the sodium dispersion method in the reactor, the contact probability between the molecules of the dechlorinated reagent and the polychlorinated biphenyl is increased by thermal dispersion. Therefore, by increasing the temperature to improve the reaction opportunity between the reagent molecules and polychlorinated biphenyl molecules, it is necessary to maintain a high reaction temperature (160 ~ 170 degrees Celsius) as possible. Because of this, there is a problem that consumes a lot of energy in the reactor to increase the cost during processing. The present invention provides a method of improving the contact probability between the dechlorination reagent component and the polychlorinated biphenyl molecules of the insulating flow rate by physical dispersion as well as thermal dispersion to sufficiently generate a desired reaction even at a low temperature of 110 degrees. have.

Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings.

1 is a block diagram of a method for treating waste insulating oil containing a polychlorinated biphenyl and a mobile treatment apparatus according to the present invention.

Figure 1 (10) is a high-speed rotation motor to put the reaction reagent in the insulating oil contained in the reaction vessel 15 serves to rotate the insulating oil at high speed, 20 is a revel sensor to the reaction vessel (15) ) Is a sensor that detects whether the insulating oil to be processed has reached full water level.

Denoted at 30 is a portion for heating the insulating oil in the reaction vessel 15 to the reaction temperature with a heating unit, and 40 is a sensor for detecting the reaction temperature of the insulating oil in the reaction vessel with a temperature sensor. A control device for controlling the whole of the device and 60 is a power cord for supplying power to the device.

Reference numeral 70 is an outflow motor pump for allowing the insulating oil in the reaction vessel 15 to flow into the transformer cylinder 160, and 80 is an inflow motor pump for introducing the insulating oil in the transformer cylinder into the reactor. . (90) is a rotating shaft that is mounted in the reactor vessel 15 is connected to the high-speed rotary motor 10, the rotation shaft is rotated, (100) is a stirring vane attached to the rotating shaft 90 to rotate together with the insulating oil and reagents of the reactor vessel Are physically distributed to each other to increase the probability of physical contact to promote the reaction.

Reference numeral 110 denotes a reagent reservoir, and 120 denotes an outlet and inlet hose through which high temperature insulating oil passes, and is made of a material that can withstand high temperatures up to 200 degrees. Revel sensor for detecting the (140) is a temperature sensor for detecting the temperature of the insulating oil in the transformer cylinder, 150 is a nozzle for the insulating oil flows into and out of the transformer cylinder.

Reference numeral 170 is an iron core and a core in the transformer barrel and 180 is a connection wire interconnected between the iron core and core in the transformer barrel and the control device 50.

FIG. 2 shows a mounting view of the processing apparatus vehicle of the present invention.

2, 200 is a vehicle equipped with the processing apparatus of the present invention, 210 is a control console to be operated by an operator as a control panel to operate the processing apparatus, and 220 is an electronic device to control the reaction apparatus of the present invention. A control device with a control device, 230 is a container inherent and protected by the present treatment device, and 240 is a reaction device for reacting and treating polychlorinated biphenyls of insulating oil. Numeral 250 denotes a hose for flowing and injecting insulating oil into a transformer, and numeral 260 denotes a transformer container containing insulating oil containing polychlorinated biphenyls.

Referring to Figure 1 will be described the operation of the waste insulating oil containing polychlorinated biphenyl of the present invention and the operation principle of a mobile treatment device.

First, when the power cord 60 is connected to a power outlet, the control device 50 initializes the control device itself of the present invention and receives the initial state of the processing device from each sensor.

Next, each part of the processing apparatus of this invention is initialized. First, the power of the heating unit 30 is turned off and the operation stops, and the high speed rotary motor 10, the inflow motor pump 80, and the outflow motor pump 70 are stopped. Next, the temperature of the reaction vessel is determined through the temperature sensor 40, and whether the insulation oil is contained in the reaction vessel is detected by the level sensor 20, and the current state is displayed on the display of the control console attached to the control device. do. Next, the control console display unit of the control device 50 detects the temperature of the insulating oil and the level of the insulating oil contained in the transformer from the temperature sensor 140 and the level sensor 130 attached to the nozzle 150 contained in the transformer barrel. Mark on. Next, the processing apparatus of the present invention completes initialization and enters an operation standby state in a state in which power supply is cut off from the control device 50 to the connection wire 180 connected to the transformer core core 170.

Next, when the nozzle 150 is mounted at the inlet of the transformer barrel containing the polychlorinated biphenyl, the level sensor 130 and the temperature sensor 140 are impregnated with the insulating oil in the transformer barrel. When the operation button is pressed on the control console console 55, the control device starts the operation of the processing device of the present invention to treat the insulating oil in the transformer containing polychlorinated biphenyls. First, the inlet motor pump 80 drives the control device 50 to introduce the insulating oil in the transformer barrel 160 into the reaction vessel through the nozzle 150 and the inlet / outlet hose 120. Inflowing insulating oil is to reach the top of the reaction vessel 15 so that no air remains above the reaction vessel (15). Whether the insulating oil flowed up to the top of the reaction vessel is detected by the level sensor 20 and the control device 50 detects the full water level signal from the level sensor to stop the driving of the inflow motor pump 80. The metal sodium is then transferred into the reagent vessel in a reagent vessel. The controller then supplies power to the heating unit to raise the temperature of the insulating oil in the reaction vessel. The control device continuously monitors the temperature of the insulating oil in the reaction vessel with the temperature sensor 40, and when the temperature is less than 100 degrees Celsius, the high speed rotation motor 10 is gradually rotated at the low speed of the first stage so that the insulating oil in the reaction vessel is uniform in each part. Allow temperature. When the temperature of the insulating oil in the reaction vessel exceeds 100 degrees, the sodium metal gradually begins to disperse in the insulating oil.

At this time, a chemical reaction occurs between the chlorine atom and the sodium metal atom of the polychlorinated biphenyl in the insulating oil. The scheme is as follows.

Ar. Cl + Na (metal) = Ar + NaCl

In this case, polychlorinated biphenyls and metal sodium dispersed in a small amount (tens of PPM) in the insulating oil are innocuous by reacting between chlorine atoms and sodium metal atoms of polychlorinated biphenyls in a random motion by thermal dispersion. Decomposition with NaCl.

Under the condition that the temperature of the reaction vessel is between 100 and 120 degrees, the control unit rotates the high-speed rotating motor at high speed for a specified time, and in addition to the thermal dispersion between the polychlorinated biphenyl molecules and the metal sodium atoms in the insulating oil in the reaction vessel, In this case, the stirring vane is forcibly attached to the rotating shaft, causing strong vortices in the insulating oil liquid to maximize the probability of encountering metal sodium and polychlorinated biphenyl molecules, thereby promoting chemical reaction. Polyvinylation of Insulation Velocity by Driving Rotational Motor 90 connected to this motor by driving high speed rotation motor for a prescribed time and Stirring Blade 100 attached to this rotation shaft to rotate at Insulation velocity and form strong vortex in Insulation oil When the biphenyl molecule and the metal sodium atom fully react with each other to change the chlorine atom of the polychlorinated biphenyl chemically to sodium chloride, the insulating oil is harmless because the toxicity of the polychlorinated biphenyl is removed.

Next, the controller 50 drives the outflow motor pump 70 to drain the insulating oil in which the polychlorinated biphenyl in the reaction vessel is harmlessly chemically treated to the transformer barrel 160. At this time, the control device 50 checks whether the insulating oil leaked through the level sensor attached to the nozzle 150 reaches the full water level of the transformer barrel 160. If the water level is reached, the control device 50 immediately stops the operation of the outflow motor pump 70.

Next, during the prescribed time, the heat of the insulating oil is transferred to the transformer core and the core 170 in the transformer barrel 160 so that the non-impregnating member (container, iron core) and the impregnating member of the transformer core and the core portion ( The polychlorinated biphenyls in the penetration into the paper tree) are eluted by the insulating oil in the transformer box. At this time, the chlorine atom of the polychlorinated biphenyl in the eluted member is chemically reacted with the sodium metal remaining in the insulating flow to become sodium chloride, thereby making it harmless.

Next, the control device 50 applies electric power to the core of the transformer iron core and the core part 170 through the connecting wire 180 for heating for a predetermined time to elute the polychlorinated biphenyl that has penetrated the impregnating member more strongly. . In other words, the polychlorinated biphenyl remaining in the impregnated and non-impregnated members of the inner container, iron core and core part in the transformer is eluted by heat transfer to make it chemically react with the sodium metal remaining in the insulating flux to make it harmless.

In the treatment apparatus of the present invention, the chlorine atoms of the polychlorinated biphenyls contained in the insulating flow rate are chemically reacted with the sodium metal to remove the toxic compounds. Such treatment may be repeated two or three times to completely remove the polychlorinated biphenyl remaining in the impregnated and non-impregnated members of the transformer casing by complete elution and chemical reaction.

In addition, the transformer barrel is filled with high temperature insulating oil immediately after the treatment, so that polychlorinated biphenyl which may remain until the impregnating member in the core of the transformer is continuously eluted. Continue the reaction so that it can continue to be harmless. Next, press the operation completion button on the control console, remove the nozzle from the transformer barrel, put it in the insulating oil of the transformer barrel to be processed next, and continue the detoxification treatment described above.

By the above-described operating principle, the treatment apparatus of the present invention makes the polychlorinated biphenyl contained in the insulating flow rate harmless, and also the polychlorinated biphenyl in the iron core and core impregnating member in the transformer barrel.

In the metal sodium dispersion method using the chemical dechlorination reaction of the prior art, the solvent cleaning equipment and the vacuum heat separation equipment treatment process are required, but the treatment method of the present invention elutes polychlorinated biphenyls by electrothermally heating the core and the core of the transformer. By quickly removing polychlorinated biphenyls by chemical reaction with metal sodium atoms in the insulating flow rate, the polychlorinated biphenyls remaining in the components of the transformer are harmless without the prior art solvent cleaning and vacuum heat separation facilities. In addition, the prior art processing method and apparatus for decomposing polychlorinated biphenyls in a member (container, iron core, paper tree, etc.) in a transformer should be cleaned by crushing the transformer member. And electrothermally heating the core to elute the polychlorinated biphenyl, thereby chemically reacting with the metal sodium atom of the insulating flow rate to quickly remove the polychlorinated biphenyl, thereby eliminating the need for a separate expensive crushing device. By introducing such treatment process, it is possible to make polychlorinated biphenyls harmless at low cost and easily by providing a mobile treatment device that can process polychlorinated biphenyls in insulating oil even on a scale that can be installed on a vehicle without a large processing plant site. It has an effect.

Conventional metal sodium dispersion method increases the contact probability between dechlorine reagent and polyvinyl chloride molecule by thermal dispersion in process. Therefore, the reaction temperature between the reagent molecule and the polychlorinated biphenyl molecule should be improved by increasing the temperature, so that the reaction temperature (160 ~ 170 degrees Celsius) should be maintained as high as possible. There is this rising problem. In the present invention, the effect of improving the contact probability between the dechlorination reagent component and the polychlorinated biphenyl molecules of the insulating flow rate by physical dispersion as well as thermal dispersion is sufficient to cause a rapid reaction even at a low reaction temperature of about 110 degrees. have.

The metal sodium dispersion method of the prior art has a problem in that a large amount of energy is consumed in the reactor by maintaining a high temperature reaction temperature (160 to 170 degrees Celsius) to increase the cost during treatment. The present invention improves the contact probability between the dechlorination reagent component and the polychlorinated polychlorinated molecule of the insulating flow rate by physical dispersion as well as thermal dispersion, thereby sufficiently causing the desired chemical reaction even at a low temperature of 110 degrees. There is an effect that can economically harm the biphenyl chloride.

Claims (6)

Waste treatment oil containing a polychlorinated biphenyl of the present invention and a mobile treatment apparatus High speed motors, rotary shafts, and agitator blades that cause vortices in the reaction vessel that chemically reacts the insulating oil including polychlorinated biphenyl with the metal sodium as a reagent, and the reagent oil in the reaction vessel. , Temperature control heating unit for reacting reaction oil and reagent in reaction vessel, temperature sensor to detect temperature of reaction vessel insulation oil, level sensor to detect the level of insulation oil, inlet and outflow of insulation oil into reaction vessel and transformer barrel Treatment device characterized in that consisting of inlet and outlet motor pump and hose. In the process of dispersing sodium in the reaction vessel, not only thermal dispersion to secure contact probability between dechlorination reagent and polychlorinated biphenyl by heat dispersion, but also physical dispersion by high speed rotary motor and vortex by stirring vane. By increasing the probability of contact between the dechlorination reagent component and the polychlorinated biphenyl molecules of the insulating flow rate, it is possible to cause harmless reactions even at low temperatures (110 degrees) to economically and quickly detoxify the polychlorinated biphenyls of the insulating flow rate. Treatment method characterized in that In order to remove the polychlorinated biphenyl remaining in the transformer member, there is no need for processing such as solvent cleaning equipment and vacuum heat separation equipment, which are required in the conventional metal sodium dispersion method. The treatment method of the present invention is characterized in that the polychlorinated biphenyl is eluted by electrothermal heating on the core and the core of a transformer to chemically react with the sodium metal atom at an insulating flow rate, thereby making the polychlorinated biphenyl harmless in the transformer casing. The insulating oil containing polychlorinated biphenyl in the transformer barrel is immediately flowed into the transformer barrel through the outflow pump, and the iron core and core are heated by the heat of the insulating oil in the transformer barrel. The polychlorinated biphenyl remaining in the transformer member is eluted to extract it at an insulating flow rate, and is removed by reacting with a metal sodium reagent remaining in the insulating flow rate to remove it. Treatment method characterized by detoxifying biphenyl chloride There is a revel sensor in claim 1, the controller is introduced into the reaction vessel to the full water level to remove the air in the reaction vessel to remove the polychlorinated biphenyl contained in the insulating oil in the reaction vessel without a separate nitrogen gas injection Processing method The iron core and core are supplied to the core wire from the transformer barrel and heated to elute the polychlorinated biphenyls remaining in the transformer member, extracted into the insulating flow rate, and removed by reacting with the metal sodium reagent remaining in the insulating flow rate to remove the transformer element. Treatment method characterized in that the polychlorinated biphenyl remaining in the member is harmless by the heat of the treated insulating oil and the remaining reagent.

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