JP2000312820A - Fluid heating device and organic halogen compound decomposition device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluid heating device capable of supplying a fluid in a stable manner, and to provide an organic halogen compound decomposing device which stabilizes plasma and realizes an improvement in processing capacity. To do. SOLUTION: The fluid heating device includes a sealed container 18f, water (heating medium) 18a housed in the sealed container 18f,
A heater 18b for heating the heating medium 18a;
8f, the flow paths 34a, 3a through which the fluid flows.
4b.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for decomposing an organic halogen compound, and a fluid heating apparatus for heating a fluid such as water used in the apparatus for decomposing an organic halogen compound.

[0002]

2. Description of the Related Art Organic halogen compounds such as freon, trichloromethane, and halon containing fluorine, chlorine, and bromine in a molecule are widely used in a wide range of applications such as refrigerants, solvents, and fire extinguishers. Is very important.
However, these compounds have high volatility, and if released untreated into the environment such as air, soil, and water, they may have adverse effects on the environment, such as formation of carcinogenic substances and destruction of the ozone layer. It is necessary to perform detoxification treatment from the viewpoint of environmental protection.

[0003] Conventionally, there have been reported methods for treating organic halogen compounds, which mainly utilize a decomposition reaction at a high temperature, and this treatment method is further roughly classified into an incineration method and a plasma method. In the incineration method, the organic halogen compound is incinerated together with ordinary waste such as resin.On the other hand, in the plasma method, the organic halogen compound is reacted with water vapor in plasma to produce carbon dioxide, hydrogen chloride, and fluorine. It decomposes into hydrogen.

[0004] Furthermore, as the latter apparatus for decomposing an organic halogen compound according to the plasma method, an apparatus which generates plasma using microwaves has recently been developed. The decomposition apparatus includes an exhaust gas treatment tank containing an alkaline solution, a reaction tube disposed with the open lower end immersed in the alkaline solution, and a cylindrical waveguide extending vertically above the reaction tube. A tube, a discharge tube disposed inside the cylindrical waveguide and penetrating the lower end thereof and communicating with the reaction tube, and a rectangular waveguide extending in the horizontal direction and connected to the cylindrical waveguide near one end thereof. It comprises a tube, a microwave transmitter mounted on the other end of the rectangular waveguide, and the like.

[0005] In this decomposition apparatus, while the Freon gas and the water vapor are supplied to the discharge tube, the microwave transmitted from the microwave transmitter is transmitted to the cylindrical waveguide through the rectangular waveguide. Then, a discharge is caused by the microwave electric field formed inside the cylindrical waveguide, and the fluorocarbon gas is decomposed by the thermal plasma in the reaction tube. For example, in the case of Freon R12, a chemical reaction represented by the following formula occurs, and Freon is decomposed. CCl ₂ F ₂ + 2H ₂ O → 2HCl + 2HF + CO ₂

At this time, in order to stably decompose the chlorofluorocarbon, it is necessary to heat water to form steam, and to uniformly mix the chlorofluorocarbon with the chlorofluorocarbon gas at a constant rate. Therefore, a fluid heating device as shown in FIG. 7 has been studied.

In the fluid heating device 64, the pipe 64
a, a flow path 34a through which the chlorofluorocarbon gas and water flow,
34b is provided, and a flow path 34 is provided around the pipe 64a.
a, a heater 64b for heating the fluid flowing in the inside 34b. When water evaporates, a resistor 3 is provided in the water flow path to prevent bumping and stabilize the flow rate.
5 are filled. In this fluid heating device, liquid water and chlorofluorocarbon gas are introduced into flow paths 34a and 34b, respectively, and while passing through the flow paths, chlorofluorocarbon and water are heated to a temperature at which water does not condense. Thereafter, the water and the chlorofluorocarbon are uniformly mixed by a mixer, and are subjected to plasma decomposition.

[0008]

By the way, in the above-mentioned fluid heating device, the heater 64b and the flow paths 34a, 34
The space b is separated from the space b. The heater 64b does not directly heat the flow path, but heats the fluid in the flow path through this space. Therefore, because the time required for heat to conduct across the space is required, when the flow rate of the fluid fluctuates,
There will be a difference in the heating temperature. In particular, in heating water, although the resistor 35 is provided, since the load of the fluid in the flow path fluctuates due to vaporization, the heating amount of water,
That is, the amount of vaporization becomes unstable. In addition, it is necessary to control the heater to control the amount of heating of the fluid.However, heating the fluid to the target temperature by controlling the output of the heater must take into account the amount of heat leaking to the outside. Not easy. As a result, there is a problem that the amount of water vapor supplied to the discharge tube is not stable, the decomposition reaction of chlorofluorocarbon is not stable, and in some cases, plasma may be lost.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a fluid heating device capable of supplying a fluid stably. Another object of the present invention is to provide an apparatus for decomposing an organic halogen compound, which stabilizes plasma and realizes an improvement in processing capacity.

[0010]

Means for Solving the Problems In order to solve the above problems, the present invention employs the following constitution. Claim 1
The described fluid heating device is a closed container, a heating medium contained in the closed container, a heater for heating the heating medium,
And a flow path through which the fluid flows through the inside of the closed container.

In this fluid heating device, first, the inside of the closed vessel is evacuated, and a heating medium such as water is sealed therein and sealed. In this state, a liquid and a gas heating medium are mixed in the container. When the liquid heating medium is heated by the heater, a part thereof is vaporized. This gas is cooled by the fluid in the flow path and condenses.
That is, since the gaseous heating medium, which is a heat source, directly heats the flow path by condensation heat transfer, the heat conduction time is very short, and stable heating can be performed. The condensed heating medium is heated again by the heater and vaporized, and the same operation as described above is repeated. Therefore, the gaseous heating medium as the heat source can be continuously and stably supplied.

[0012] The fluid heating device according to the second aspect is the first aspect.
In the fluid heating device according to the aspect, the closed container includes a vaporization chamber provided with the heater, and a liquefaction chamber provided above the vaporization chamber, communicating with the vaporization chamber, and penetrating the flow path. It is characterized by being.

In this fluid heating device, the heating medium vaporized in the vaporization chamber moves to the liquefaction chamber side. The heating medium that has released heat and condensed in the liquefaction chamber moves to the lower vaporization chamber side according to gravity, is heated again by the heater, and the same operation as described above is repeated. Therefore, the gaseous heating medium as the heat source can be continuously and stably supplied.

According to a third aspect of the present invention, there is provided a fluid heating apparatus.
In the fluid heating device described above, the liquefaction chamber has an inclined bottom surface, and the liquefaction chamber and the vaporization chamber communicate with each other at a lower end of the bottom surface.

In this fluid heating device, since the bottom of the liquefaction chamber is inclined, the heating medium condensed in the liquefaction chamber flows on the bottom according to gravity and moves into the vaporization chamber. Therefore, the condensed heating medium quickly moves to the vaporization chamber side, and is heated again and vaporized. Therefore, the gaseous heating medium as the heat source can be continuously and stably supplied.

According to a fourth aspect of the present invention, there is provided a fluid heating apparatus.
Or in the fluid heating device according to 3, wherein the flow path is:
It is characterized by being inclined in the length direction.

In this fluid heating device, since the flow path is inclined, the heating medium condensed on the pipe surface forming the flow path flows on the pipe surface according to gravity and moves into the vaporization chamber. The heating medium is heated again in the vaporization chamber and is vaporized. That is, the condensed heating medium is quickly removed from the flow path, and the flow path is heated by the new gas. Therefore, the gaseous heating medium as the heat source can be continuously and stably supplied.

According to a fifth aspect of the present invention, there is provided a fluid heating apparatus.
5. The fluid heating device according to any one of items 1 to 4, wherein a resistor is provided in the flow path.

In this fluid heating device, a resistor that gives resistance to the fluid moving in the flow path is filled, so that the vaporized fluid in the flow path cannot flow smoothly. . Therefore, a certain amount of vaporized fluid always stays in the flow path. For this reason, pulsation and scattering due to bumping are prevented, the outflow amount of the vaporized fluid is stabilized, and the flow rate fluctuation is suppressed.

The fluid heating device according to the sixth aspect is the first aspect.
6. The fluid heating device according to any one of to 5, further comprising: a pressure detector that detects a pressure of the heating medium; and a pressure control device that controls an output of the heater based on an output of the pressure detector. It is characterized by the following.

In this fluid heating device, the heating temperature of the fluid is determined by adjusting the pressure. That is, although there is a slight variation depending on the amount of evaporation of the heating medium in the closed container, the volume of the gas portion in the closed container may be considered to be constant. Therefore, the temperature of the heating medium is uniquely determined by the pressure in the system. That is, the heating temperature of the fluid is determined by the pressure in the system. In this fluid heating device, a pressure detector for detecting the pressure of the heating medium is provided, and the output of the pressure detector is fed back to the heater via the pressure control means. Can be set to

An organic halogen compound decomposing apparatus according to claim 7, wherein the fluid heating apparatus is provided with a fluid heating device for heating water, wherein the fluid heating device is housed in the hermetically sealed container. Heating medium, and a heater for heating the heating medium, penetrating through the closed container,
And a flow path through which a fluid flows.

In the fluid heating device provided in the organic halogen compound decomposing device, the inside of the closed vessel is evacuated, and a heating medium such as water is sealed therein and sealed. In this state, a liquid and a gas heating medium are mixed in the container. When the liquid heating medium is heated by the heater, a part thereof is vaporized. This gas is cooled by the fluid in the flow path and condenses. That is, since the gaseous heating medium, which is a heat source, directly heats the flow path by condensation heat transfer, the heat conduction time is very short, and stable heating can be performed. The condensed heating medium is heated again by the heater and vaporized, and the same operation as described above is repeated. Therefore, the gaseous heating medium as the heat source can be continuously and stably supplied. From the above, in this apparatus for decomposing an organic halogen compound, the steam to be reacted when decomposing an organic halogen compound such as chlorofluorocarbon is stably supplied, so that the organic halogen compound can be decomposed stably. .

[0024]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to FIGS. In FIG. 4, the rectangular waveguide 1 extending in the horizontal direction is provided with a microwave transmitter 2 for transmitting a microwave having a frequency of 2.45 GHz at the start end (left end), and from the start end to the end (right end). Transmit microwave to.

As shown in FIG. 2, the rectangular waveguide 1 prevents the reflected wave from affecting the transmitting side by absorbing the microwave reflected at the terminal end and returning to the starting end. An isolator 3 and a tuner 6 that adjusts the wave mismatch amount of the radio wave by moving a plurality of wave adjustment members 4 in and out respectively to converge the radio wave to the discharge tube 5 are provided.

This operation will be described in detail. The microwave transmitter 2 is placed at one end of a waveguide having a rectangular cross section, and drives a magnetron to emit an electromagnetic wave of a predetermined frequency. The characteristics of this electromagnetic wave propagation phenomenon can be grasped by solving Maxwell's wave equation relating to the electromagnetic wave. As a result, the electromagnetic wave propagates as an electromagnetic wave TE wave having no electric field component in the propagation direction.

[0027] indicated by arrows the direction examples of the first-order component TE ₁₀ alternates the propagation direction of the rectangular waveguide of Figure 2. The annular cavity of the double-cylindrical waveguide formed of a double-cylindrical conductor at the other end of the rectangular waveguide 1 has conductors 9 for electromagnetic waves propagating in the waveguide 1 and electromagnetic waves reflected at the tube end. , A TM wave having an electric field component in the traveling direction is generated in the annular cavity. The TM ₁₀ wave is the primary component are also shown by the arrows in the annular cavity of FIG. The fine adjustment caused by the second or higher harmonics related to the propagation of the electromagnetic wave is adjusted by the tuner 4. The isolator 3 prevents the transmitter 2 from causing fundamental damage.

As shown in FIG. 3, the cylindrical waveguide 7 is composed of an outer conductor 8 and an inner conductor 9 having a smaller diameter than the outer conductor 8. It is connected so that it may extend in the vertical direction while communicating with 1. The inner conductor 9 is fixed to the upper portion of the rectangular waveguide 1 and surrounds the discharge tube 5 made of quartz while enclosing the end plate 8 of the outer conductor 8.
A, and extend this portion to the probe antenna 9.
a.

The discharge tube 5 is composed of an inner tube 11 and an outer tube 12, and is disposed so as to be coaxial with the central axis of the cylindrical waveguide 7. A Tesla coil 14 that generates heat by an ignition device 13 is inserted into the inner tube 11 of the discharge tube 5.

Further, the distal end (lower end) of the inner tube 11 is disposed at a predetermined distance inward from the distal end of the probe antenna 9a.

On the other hand, the distal end of the outer tube 12 penetrates the end plate 8A of the outer conductor 8 and communicates with the copper reaction tube 15;
The proximal end (upper end) of the outer tube 12 is attached with a gap between the outer tube 12 and the inner conductor 9. Reference numeral 17 denotes an optical sensor 17 directed to the outer cylinder 12 exposed between the end plate 8A of the outer conductor 8 and the reaction tube 15. This optical sensor 1
Numeral 7 monitors the state of plasma generation by detecting the luminous intensity.

Then, a gas supply pipe 16 is inserted into the gap along the tangential direction of the outer pipe 12, and argon gas,
Freon gas (organic halogen compound), air, and water vapor are supplied to the discharge tube 5 via the gas supply tube 16. These argon gas, chlorofluorocarbon gas, and air are selectively sent to the fluid heating device 18 from the respective supply sources by opening and closing the solenoid valves 19a, 19b, and 19c shown in FIG.

The argon gas is supplied to facilitate ignition prior to generation of plasma, and is stored in the argon cylinder 21. This argon cylinder 21
A pressure regulator 22 and a pressure switch 23 are provided between the solenoid valve 19a and the solenoid valve 19a.

The air is supplied from the air compressor 24 in order to remove water remaining in the system to enhance the stability of ignition and to discharge gas remaining in the system. , Nitrogen gas, argon gas and the like are used. Water vapor is necessary to decompose Freon gas.
It is generated by sending water in the water storage tank 26 to the fluid heating device 18 by the plunger pump 25. The water storage tank 26 is provided with a level switch 27 for detecting a change in water level.

The Freon gas is stored in a liquid in a collected Freon cylinder 28, and the collected Freon cylinder 28 and the solenoid valve 1 are stored.
9b, the squeezing device 31, the mist separator 3
2, and a pressure switch 33 are provided. The throttle device 31 is provided for quantifying the flow, and is constituted by, for example, a combination of a capillary tube and an orifice.

The mist separator 32 is for removing oil (lubricating oil) and water contained in the chlorofluorocarbon gas, and is of a collision type or a centrifugal type. The fluid heating device 18 not only generates water vapor to be reacted with the chlorofluorocarbon gas, but also avoids a problem that the chlorofluorocarbon gas or the like is preliminarily heated so that the water vapor is cooled to the chlorofluorocarbon gas and recondensed in the device. Intentionally provided.

The fluid heating device 18 comprises a water 18a as a heating medium, a heater 18b for heating the water 18a, and a tubular vaporizing chamber 1 containing the water 18a and the heater 18b.
8c and a tubular liquefaction chamber 18e provided above the vaporization chamber 18c and penetrated by flow paths 34a and 34b through which a fluid flows.
And a communication pipe 18d through which gas and liquid water 18a are circulated between the vaporization chamber 18c and the liquefaction chamber 18e. The vaporization chamber 18c, the liquefaction chamber 18e, and the communication pipe 18d constitute a closed vessel 18f. are doing. The liquefaction chamber 18e and the flow paths 34a and 34b have their length directions inclined with respect to the horizontal plane, and a communication pipe 18d is connected to the inclined lower end of the bottom surface of the liquefaction chamber 18e.

Here, the fluid heating device 18 of the present embodiment
First, from the viewpoint of facilitating the production, first, the vaporization chamber 18c
And the liquefaction chamber 18e through which the flow paths 34a and 34b pass,
Each of the communication pipes is vertically connected to the communication pipe 18d. Then, when attaching to the decomposition device of the organic halogen compound,
The liquefaction chamber 18e is disposed so as to be inclined. That is, the inclination of the liquefaction chamber 18e and the flow paths 34a and 34b is formed when the fluid heating device 18 is arranged. Also, the vaporization chamber 18
c also inclines, but the vaporization chamber 18c does not need to be inclined, and the presence or absence of the inclination, or the direction of the inclination,
The present invention is not limited to this embodiment. Needless to say, a substance other than water can be used as the heating medium.

The flow paths 34a and 34b are inclined in parallel with each other. Freon gas, argon gas and air are introduced into one flow path 34a, and water is introduced from the water storage tank 26 into the other flow path 34b. To produce steam. The flow path 34b on the side that generates the water vapor is filled with a resistor 35 that gives resistance to the water vapor moving in the flow path 34b, so that the water vapor cannot flow smoothly through the flow path. Has become.

As the resistor 35, an inorganic or organic granular, fibrous, or porous material or a molded product thereof is used. From the viewpoint of preventing deterioration at high temperatures, SiO ₂ , Al, and the like are used. ₂ O ₃ , TiO ₂ , MgO, ZrO ₂
And inorganic materials such as oxides, carbides, nitrides and the like. A thermocouple 36 is provided near the outlet of the fluid heating device 18.

A pressure detector 18g for detecting the pressure of the water 18a and a pressure controller 18h for controlling a power supply 18i of the heater 18b based on the output of the pressure detector 18g are provided to keep the pressure constant. While maintaining the flow path 34a,
The fluid passing through 34b can be heated.

However, the fluorocarbon gas and the like having passed through the fluid heating device 18 and the water vapor are mixed in the mixer 37 and then supplied to the discharge tube 5 through the gas supply tube 16.
As shown in FIG. 5, an orifice 38 is provided inside the mixer 37, and the opening 38a has a diameter of 0.1 mm to 5 mm.
Is set to The outlet-side end surface 37A of the mixer 37 facing the opening 38a has an inclined surface such that the cross section of the flow path gradually decreases.

The exhaust gas treatment tank 41 is provided to neutralize and render harmless the acidic gases (hydrogen fluoride and hydrogen chloride) generated when the fluorocarbon gas is decomposed. Is contained therein. For example, if the decomposed Freon gas is Freon R12 for a refrigerant recovered from a waste refrigerator, the following formula 1 is used.
The generated gas generated by the decomposition reaction shown in (2) is rendered harmless by the neutralization reaction shown in equation (2).

(Formula 1) CCl ₂ F ₂ + 2H ₂ O → 2HCl + 2HF + CO ₂ (Formula 2) 2HCl + Ca (OH) ₂ → CaCl ₂ + 2H ₂ O 2HF + Ca (OH) ₂ → CaF ₂ + 2H ₂ O

The neutralized products (calcium chloride and calcium fluoride) produced by the neutralization reaction of the formula (2) have a low solubility, so that a part of them is dissolved in an alkaline solution, but most of them are present as a slurry. Further, the carbon dioxide generated by the decomposition reaction of the formula 1 and the acid gas reduced to a very small amount equal to or less than the emission reference value by the neutralization reaction of the formula 2 are connected to the exhaust duct 42 connected above the exhaust gas treatment tank 41. Is discharged out of the system by the blower 43.

Inside the exhaust gas treatment tank 41, a blowing pipe 45 connected to the reaction pipe 15 via an exchange joint 44 is provided.
It is arranged to extend vertically with its lower end immersed in an alkaline solution. The tip 4 of this blowing pipe 45
5a is formed so as to be inclined at a predetermined angle with respect to the vertical direction.

A cooler 46 provided with a chilled water pipe (not shown) is provided at an intermediate portion in the axial direction of the reaction tube 15 so as to surround the peripheral surface thereof. The cooler 46 cools a gas produced by the decomposition reaction of the formula 1, and the reaction tube 1
In order to prevent the re-condensation of the residual water vapor in 5, it is controlled not to cool below the dew point. In the present embodiment, the cooling is performed to about 400 ° C.

The cooling water (warm water) of the cooler 46 warmed by cooling the reaction tube 15 is used as a heating source of the recovered freon cylinder 28. That is, a heater 4 provided with a hot water pipe (not shown) is provided around the recovered CFC cylinder 28.
7 is provided, and when the cooling water used for cooling the reaction tube 15 flows through the hot water pipe, the recovered CFC cylinder 28 is heated.

As shown in FIG. 3, the exchange joint 44 is detachably connected between the reaction tube 15 and the blowing tube 45, and the water injection nozzle 51 communicates toward the inside thereof. Cooling water is discharged from the water injection nozzle 51, and the resin-made, for example, Teflon-made blowing pipe 45 is rapidly cooled to its heat-resistant temperature range. Incidentally, when the blowing pipe 45 is a Teflon pipe, it is cooled to 100 ° C. or lower.

The reason why the blowing pipe 45 is made of resin is that the blowing pipe 45 has good corrosion resistance to both the acidic liquid formed by dissolving the acidic gas in the cooling water and the alkaline liquid in the exhaust gas treatment tank 41. This is because it is difficult to achieve this with a metal. On the other hand, in the case of the reaction tube 15,
Since the inside is always in a dry state, there is little possibility of corrosion and heat resistance is required. Therefore, the life is extended by using copper.

From the tip (lower end) of the blowing pipe 45, the gas produced by the decomposition reaction of the formula 1 is released as bubbles into the alkaline liquid. The neutralization reaction in the alkaline solution is accelerated as the contact area between the bubbles and the alkaline solution increases and the time until the bubbles reach the liquid surface is increased. A bubble dividing means 52 for promoting the neutralization reaction of Formula 2 by dividing is provided.

The bubble separating means 52 includes a shaft 52b that is driven to rotate by a motor 52a, a disk-shaped blade holder 52c fixed to the tip of the shaft 52b, and an outer edge of the blade holder 52c. And six blades 52d.

The shaft 52a and the blade holder 52
Each of c and the blade 52d is made of a SUS material, and the blade 52d intersects the blade holding portion 52c and is fixed by silver brazing at equal intervals in the circumferential direction. The reason why the silver brazing is employed is that the general welding is highly corrosive to an alkaline solution.

The bubble separating means 52 includes a blade holder 52
The center of c is arranged so as to be located above the tip of the reaction tube 15, and the air bubbles that float from the tip of the reaction tube 15 are:
When the blade 52d rotates at 300 rpm, it is finely divided into bubbles having a diameter of about 3 to 5 mm. The bubble separating means 52 also plays a role of forming a suspension of water and water-insoluble calcium hydroxide by stirring the calcium hydroxide powder charged into the exhaust gas treatment tank 41.

Further, the exhaust gas treatment tank 41 is provided with a cooler 53 for cooling the temperature in the tank below the heat-resistant temperature of the blowing pipe 45 because the neutralization reaction of the formula 2 is an exothermic reaction. In the cooler 53, a part of a pipe connected to a heat radiating part 53b cooled by a fan 53a is inserted through the exhaust gas treatment tank 41, and a cooling medium such as water flows through the pipe to generate heat. And the heat dissipating part 53
Heat is dissipated in b. Incidentally, the temperature in the tank is detected by the thermocouple 54.

Further, the exhaust gas treatment tank 41 has a pH value
A sensor 55 is provided. The pH value of the alkaline solution is
It is constantly monitored by the control device 61 via the pH sensor 55. For example, when the pH value is 9 (11 to 11 when the operation is started).
In the case of 12), the alarm means is activated by a command from the control device 61, and the disassembling operation is stopped. As the warning means, any means can be used as long as it can draw attention to the surroundings. For example, means such as blinking a lamp or sounding a horn is adopted.

Since the slurry in the exhaust gas treatment tank 41 gradually increases as the operation time elapses, the slurry is received by the solid-liquid separator 62 together with the alkali liquid after the operation is stopped.
After solid-liquid separation, it is disposed of as waste or used for other purposes. On the other hand, the separated alkaline liquid is returned to the exhaust gas treatment tank 41 again and reused. Incidentally, the fluctuation of the liquid level in the exhaust gas treatment tank is detected by the level switch 56.

In the organic halogen compound decomposing apparatus having the above structure, the opening / closing operation of the electromagnetic valve and the ignition operation of the Tesla coil 14 are controlled by the control device 61 as shown in FIG. As is clear from this figure, in this decomposition apparatus, the decomposition of the chlorofluorocarbon gas is performed by batch processing in which one cycle is performed for 8 hours.

That is, before supplying Freon gas or water vapor, first, air is supplied for a predetermined time (3 minutes) for the purpose of removing residual moisture, and after the supply is stopped, argon gas is supplied for the purpose of improving ignition stability. Start supplying. Then, during the supply of the argon gas, the microwave is transmitted to ignite the gas by the Tesla coil, and the steam and the chlorofluorocarbon gas are supplied. Thereafter, the supply of the argon gas is stopped.

After the decomposition operation is stopped, air is supplied for a predetermined time (5 minutes) to ensure the safety, and the residual acid gas is purged.

In the above steps, the supply of the argon gas and the supply of the chlorofluorocarbon gas may overlap with each other. However, the time between the start of the supply of the chlorofluorocarbon gas and the stop of the supply of the argon gas may be very small. The reason is,
This is because, as long as the ignition state is stabilized, it is not necessary to continuously supply the argon gas, and it is necessary to keep the argon consumption low from the viewpoint of cost reduction. In particular, compared to other plasmas, for example, high-frequency induction plasma, plasma by microwave has high stability,
Even if the supply of the argon gas is stopped, there is almost no effect on the formation of plasma from Freon soot.

Further, the control device 61 controls the pressure switch 2
3, 33, thermocouples 36, 54, level switches 27, 5
6. By receiving signals from various sensors such as the optical sensor 17, the supply pressure of the argon gas and the fluorocarbon gas to the fluid heating device 18, the liquid level in the water storage tank 26, the plasma generation state, and the The temperature and the liquid level are constantly monitored, and if these deviate from the specified values, the operation is stopped because there is a possibility that the operation is not performed normally or efficiently. After the operation is stopped, air is supplied as described above to ensure safety, and the residual gas in the apparatus is scavenged.

Hereinafter, the operation of the decomposition apparatus according to the present embodiment will be described. In this disassembly apparatus, first, the solenoid valve 19
a, 19b are closed and the solenoid valve 19c is opened to supply air from the air compressor 24 to the discharge tube 5 via the gas supply tube 16 for 3 minutes. This air passes through the fluid heating device 18,
Since the heating is performed at 180 ° C., the residual moisture in the apparatus is surely removed.

Next, the solenoid valve 19c is closed and the solenoid valve 19a is opened, and argon gas is supplied to the discharge tube 5. At this time, since the argon gas is supplied from the tangential direction of the outer tube 12 and flows down spirally, stagnation is formed near the tip of the inner tube 11 and plasma is easily held.

The gas supply amount at this time is 4 to 40.
l / min, desirably 15 l / min or more. In this setting range, the stagnation is effectively formed, the plasma is more easily held, and the discharge tube 5 is hardly affected by the thermal influence of the plasma, so that melting deformation and breakage thereof are effectively prevented. Become.

Then, a microwave is transmitted from the microwave transmitter 2 at a constant interval from the start of the supply of the argon gas. The microwave is transmitted to the rear end side by the rectangular waveguide 1 and further transmitted to the cylindrical waveguide 7.

At this time, as the electric field in the cylindrical waveguide 7, a TM ₀₁ mode having a large electric field intensity is formed, and the electric field mode in the rectangular waveguide 1 and the TM ₀₁ mode are formed by the inner conductor 9. The electric field inside the cylindrical waveguide 7 is stable because the electric field mode inside the cylindrical waveguide 7 is coupled. As a matter of course, the magnetic field is generated in a direction orthogonal to the electrolysis. The gas introduced into the discharge tube 5 is heated to a plasma state by the oscillating electromagnetic field.

Next, the Tesla coil 1 is
4 is heated to ignite. At this time, the interior of the discharge tube 5 is easily ignited because moisture is removed by air and an easily ignited argon gas is supplied in advance. Next, water is sucked from the water storage tank 26 by the plunger pump 25, and is passed through the fluid heating device 18 to generate steam, and the generated steam is supplied to the discharge tube 5.

In the fluid heating device 18, heating by condensation heat transfer with water 18 a as a heating medium, and the action of the resistor 35 filled in the flow path 34 b,
The water in the flow path 34b becomes stable water vapor, prevents pulsation and scattering due to bumping, stabilizes the flow rate of the water vapor flowing out of the flow path 34b, and effectively suppresses the flow rate fluctuation on the upstream side of the mixer 37. it can.

Specifically, first, the inside of the fluid heating device 18 is evacuated, and the water 18a is sealed therein and hermetically sealed.
In this state, a part of the water 18a evaporates, and a state is obtained in which steam and liquid water are mixed in the closed container 18f. When the water 18a in the vaporization chamber 18c is heated by the heater 18b, a part is vaporized and moves to the liquefaction chamber 18e. In the liquefaction chamber 18e, the water vapor is cooled and condensed by the fluid in the flow paths 34a and 34b. That is, the steam as a heat source is directly condensed and transferred by the flow paths 34a and 34b.
Is heated, the heat conduction time is very short, and the water in the flow path 34b can be stably heated and vaporized. Therefore, it is possible to prevent a change in the amount of vaporization due to a change in the fluid.

The heating temperature can be controlled by controlling the pressure. In other words, the volume of water vapor in the sealed container 18f may be considered to be constant, although there is some variation depending on the amount of water 18a evaporated in the sealed container 18f. Therefore, the temperature of steam is uniquely determined by the pressure in the system. In the fluid heating device 18, since the pressure control device 18h controls the output of the heater 18b based on the output of the pressure detector 18g, the temperature of the heating medium can be easily controlled, and the fluid can be stably formed. Can be heated.

Further, the resistor 35 filled in the flow path 34b prevents the vaporized vapor in the flow path 34b from flowing smoothly. Accordingly, a certain amount of water vapor stays in the flow path 34b.
For this reason, scattering due to pulsation and bumping is prevented, the outflow amount of steam is stabilized, and fluctuations in the flow rate on the upstream side of the mixer 37 can be effectively suppressed.

On the other hand, the water 18a as a heating medium condensed in the liquefaction chamber 18e moves to the lower part of the liquefaction chamber 18e according to gravity, and moves into the vaporization chamber 18c via a communication pipe 18d connected to the lower part. I do. Thereby, the condensed water 18a does not stay on the surfaces of the flow paths 34a and 34b,
It will be quickly removed and will always be heated by fresh steam. Then, it is heated again by the heater 18b and vaporized, and the same operation as described above is repeated. That is, steam as a heat source is continuously and stably supplied,
The fluid in the flow paths 34a and 34b is stably heated.

As described above, the steam is stably supplied to the discharge tube 5, the plasma is stabilized without causing the plasma to disappear, and the processing capability can be improved.

Next, the solenoid valve 19b is opened to supply Freon gas to the discharge tube 5. At this time, the chlorofluorocarbon gas flowing out of the collected chlorofluorocarbon cylinder 28 is supplied to the mist separator 3.
2 to remove oil and moisture.
For this reason, the generation of dirt and by-products from piping and the like due to the lubricating oil in the CFC gas is suppressed, and an efficient and stable supply of CFC gas and the like can be performed. Does not occur. Therefore, it is possible to stabilize the plasma and improve the processing capability.

The water vapor, the argon gas, and the fluorocarbon gas flowing into the mixer 37 after passing through the fluid heating device 18 not only promote mixing due to the pressure loss when passing through the opening 38a of the orifice 38, but also promote the mixing. Since the mixing is promoted by colliding with the outlet side end face 37A, the mixture flows out of the mixer 37 in a more uniformly mixed state and is supplied to the discharge tube 5. For this reason,
Since the decomposition reaction of the formula 1 is sufficiently performed, generation of by-products such as chlorine gas and carbon monoxide can be suppressed.

When the microwave is applied to the Freon gas supplied to the discharge tube 5 in this way, the discharge tube 5
High electron energy and temperature of 2,000K ~
Thermal plasma increased to 6,000 K is generated. At this time, not only the chlorofluorocarbon gas and water vapor but also the discharge tube 5
Since the argon gas is supplied at the same time, the plasma does not disappear.

Further, since the distal end of the inner tube 11 is disposed inside the distal end of the probe antenna 9a by a predetermined distance, it is possible to avoid the thermal effect of the generated plasma,
Melt breakage of the inner tube 11 is prevented. As a result, a stable decomposition operation can be performed without remarkable deformation of the plasma shape.

However, the generation of thermal plasma causes the fluorocarbon gas to be easily dissociated into chlorine, fluorine and hydrogen atoms, and is easily decomposed by reacting with water vapor as shown in equation 1. When the plasma is stabilized, the electromagnetic valve 19a is closed to stop the supply of the argon gas.

The gas generated by the decomposition reaction is supplied to the exchange joint 44.
Then, the gas is discharged into the alkaline liquid in the exhaust gas treatment tank 41 through the blowing pipe 45. However, since these generated gases are extremely high in temperature, they are first cooled to about 400 ° C. by the cooler 46 attached to the lower part of the reaction tube 15 before flowing into the blowing tube 45.

At this temperature, since the residual water vapor does not re-condensate inside the reaction tube 15, the reaction tube 15 is kept in a dry state, and the plasma does not disappear. On the other hand, the cooling water of the cooler 46 heated to about 50 ° C. by cooling the reaction tube 15 is led to the heater 47 attached to the recovered freon cylinder 28, and the liquid freon in the recovered freon cylinder 28 is vaporized. In addition to preventing the formation of frost in the cylinder 28 and the downstream pipe that occurs when the pressure is reduced, the pressure fluctuation due to the temperature drop is also suppressed. In addition, the cooling water from which heat has been deprived can be reused as the cooling water for the cooler 46, and the water consumption can be reduced.

The product gas cooled by the cooler 46 is
While passing through the exchange joint 44, the water injection nozzle 51
Is rapidly cooled to about 100 ° C. or less by the cooling water discharged from the apparatus. Thereby, the resin blowing tube 45 can be used within its heat-resistant temperature range, and can be protected from thermal damage due to high temperature.

At this time, since the gas produced by the decomposition reaction of the formula (1) is dissolved in the cooling water to generate an acidic solution, the exchange joint 44 is gradually corroded. It can be replaced accordingly. That is, on the downstream side of the reaction tube 15, only the exchange joint 44 needs to be exchanged due to corrosion, so that the cost can be reduced and the exchange operation can be facilitated.

The product gas discharged into the alkaline liquid through the blowing pipe 45 is rendered harmless by the neutralization reaction of the formula 2, and is discharged from the exhaust duct 42. Since this neutralization reaction is an exothermic reaction, the temperature of the alkaline solution is set to 70 ° C. by the cooler 53 in order to prevent thermal damage to the blowing pipe 45.
It is kept below.

The generated gas discharged as bubbles from the tip of the blowing pipe 45 is supplied to the blade 52 of the bubble dividing means 52.
Since it is finely divided at d, the contact area with the alkaline liquid increases and the time to reach the liquid surface increases, thereby promoting the neutralization reaction. As a result, the amount of acidic gas exceeding the reference value is not discharged out of the system due to insufficient neutralization.

The neutralized product produced by the neutralization reaction is
Although present as a slurry in the alkaline liquid, the slurry is received by the solid-liquid separator 62 together with the alkaline liquid after the decomposition operation is stopped, and is continuously subjected to solid-liquid separation. Since the separated liquid is returned to the exhaust gas treatment tank 41 and reused, in the present decomposition apparatus, the water consumption is significantly reduced in combination with the reuse of the cooling water. Further, after the decomposition operation is stopped, the air compressor 24 is driven to scavenge the acid gas remaining in the apparatus, so that the safety is improved.

The apparatus for decomposing an organic halogen compound according to the present invention is not limited to the above embodiment, but includes the following embodiments. (1) In the present embodiment, the inclination directions of the flow paths 34a and 34b are the same as the inclination directions of the bottom surface of the liquefaction chamber 18e. However, the present invention is not limited to this, and the inclination directions may be reversed. . In this case, the water condensed around the flow paths 34a and 34b once moves to the bottom of the liquefaction chamber 18e according to the inclination, and flows toward the vaporization chamber 18c according to the inclination of the bottom. Further, the direction of the flow path flowing in the flow paths 34a and 34b may be a direction in which the flow path descends or rises with respect to the inclination of the flow path. Furthermore, the flow paths 34a and 34b need not be linear, but may be, for example, coil-shaped. In this case, the inclination of the flow paths 34a and 34b becomes a curve constituting each winding of the coil. Also, the number of flow paths is not limited to this embodiment. (2) In the present embodiment, the bottom of the liquefaction chamber 18e is inclined in one direction, but the communication pipe 18d is
e, and the bottom surface of the liquefaction chamber 18e may be lowered from both ends of the liquefaction chamber 18e toward the central communication pipe 18d. The liquefaction chamber 18e and the vaporization chamber 18c are tubular, but are not limited thereto, and may have any shape. In addition, as described above,
It is not necessary for the vaporization chamber 18c to be inclined.
Alternatively, the direction of the inclination is not limited to the present embodiment.

(3) The number of communication pipes 18d provided for communicating the liquefaction chamber 18e and the vaporization chamber 18c is not limited to one, but may be plural. Further, the liquefaction chamber 18e and the vaporization chamber 18c may be directly communicated without passing through the communication pipe 18d. Further, the liquefaction chamber 18e
And the vaporization chamber 18c may be integrated.

(4) As a means for promoting the mixing in the mixer 37, beads or the like may be filled in the mixer 37 instead of the orifice 38. In this configuration, the mixing of the flon gas and the steam is promoted because the gas randomly flows through the gap formed in the mixer 37.

Further, a plurality of baffles may be provided on the inner peripheral surface of the mixer 37, for example, alternately vertically or horizontally at intervals (static mixer). In this configuration, the mixing of the flon gas and the water vapor is promoted since the gas flows in a meandering manner.

Further, a pipe connected to the inlet side of the mixer 37 may be inclined with respect to the flow direction, and a guide plate extending spirally may be provided on the inner peripheral surface of the mixer 37 (swirl mixer). . In this configuration, since the CFC gas and the steam flow while drawing a spiral, mixing is promoted.

(5) As a means for preventing the acid gas from being discharged out of the system due to insufficient neutralization treatment, the motor current value may be controlled instead of the pH control of the alkaline liquid. That is, when the motor speed decreases or stops,
In some cases, the bubbles released from the blowing pipe 45 are not sufficiently divided, and the neutralization reaction is not sufficiently performed. Therefore, the abnormality of the motor rotation is detected based on the motor current value, and the control device 6
If the operation of the decomposer is stopped in accordance with the command from 1, it is possible to prevent the acid gas from being discharged outside the system.

(6) Since the inside of the reaction tube 15 is kept in a dry state, there is almost no influence of corrosion by the acid gas generated by the decomposition reaction of the formula 1. However, in order to further enhance safety, a simple booth containing the reaction tube 15 is installed, and the booth and the reaction tube 1 are installed.
An exhaust gas sensor for detecting a CO ₂ gas, a CO gas or the like may be provided between the exhaust gas sensor 5 and the exhaust gas sensor 5.

In this configuration, the corrosion state of the reaction tube 15 can be constantly monitored by the control device 61 via the exhaust gas sensor. Even if the acid flows out of the system, the operation of the decomposition device is stopped by a command from the control device 61, and the generated gas that has flowed out is sucked, thereby preventing the acid gas from being discharged out of the system. In this case, the gas suction is also performed by the blower 43 provided in the exhaust duct 42.

(7) Since the slurry in the exhaust gas treatment tank 41 is settled if left overnight after the operation is stopped, the high-concentration slurry that has settled is pumped up by a pump, and the slurry is separated into solid and liquid for disposal. It may be. In this case, since only the high-concentration slurry can be pumped without mixing with the free alkali solution, efficient slurry treatment can be performed. In addition, if a granulating agent, a coagulant, or the like is added to the alkaline solution to increase the number of slurry particles, the sedimentation time can be reduced, and the slurry treatment can be performed more efficiently.

(8) Connect the tip of the Tesla coil 14 to the discharge tube 5
May be arranged outside the discharge tube 5 to ignite by spark discharge. (9) Instead of heating the recovered Freon cylinder 28 to make it into a gas state and allowing Freon gas to flow out, instead of inverting the recovered Freon cylinder 28 and allowing the recovered Freon to flow out in a liquid state, a throttling device such as a differential pressure control valve , The flow may be quantified, heated and vaporized, and sent to the fluid heating device 18 side. In this case, by heating the expansion device and the piping, the flow rate fluctuation due to the temperature drop is suppressed.

(10) In order to heat the recovered CFC cylinder 28, the cooling device 5 used for cooling the slurry in the exhaust gas treatment tank 41 is used instead of the cooling water used for cooling the reaction tube 15.
3 cooling water may be used. (11) The distance at which the distal end of the inner tube 11 is separated inward from the distal end of the probe antenna 9a is set to be equal to the distance between the distal end of the probe antenna 9a and the energy concentration portion by the microwave unless the inner tube 11 is melted. Although it is optimal, it may be changed appropriately in consideration of melting of the inner tube 11.

(12) The bubble dividing means 52 may be of a screw type in which a propeller is fixed to the tip of a shaft. In addition, the bubble dividing means 52 includes
The b, 52c, and 52d may be made of resin such as Teflon, and these may be screw-connected. In this configuration, there is no welded portion, and each component 52b, 52
Since c and 52d are made of resin, the corrosion resistance is extremely excellent.

(13) Instead of inclining the distal end of the blowing pipe 45 by a predetermined angle with respect to the vertical direction, the blowing pipe 45 may be formed in a substantially U-shape. (14) The neutralized liquid stored in the exhaust gas treatment tank 41 is:
Not limited to the above alkaline suspension, an alkaline aqueous solution such as an aqueous sodium hydroxide solution may be used.

[0100]

As is apparent from the above description, the present invention has the following effects. (A) According to the fluid heating device of the first aspect, the heating medium is vaporized by the heater, and the fluid is heated by the condensation heat transfer. Therefore, the heating medium as the heat source can be continuously and stably supplied, the fluid is stably heated, and the fluid can be stably supplied.

(B) According to the fluid heating device of the second aspect, the heating medium condensed in the liquefaction chamber is vaporized again in the vaporization chamber, so that the heating medium as a heat source can be continuously and stably supplied. As a result, the fluid is stably heated, and a stable supply of the fluid is possible.

(C) According to the fluid heating device of the third aspect, since the bottom surface of the liquefaction chamber is inclined, the condensed heating medium quickly moves to the vaporization chamber. Therefore, the heating medium as the heat source can be continuously and stably supplied, the fluid is stably heated, and the fluid can be stably supplied.

(D) According to the fourth aspect of the present invention, since the flow path is inclined, the heating medium condensed on the surface of the pipe forming the flow path is quickly removed. Therefore, the heating medium as the heat source can be continuously and stably supplied, the fluid is stably heated, and the fluid can be stably supplied.

(E) According to the fluid heating device of the fifth aspect, since the resistor is provided in the flow path, fluctuation of the flow rate due to vaporization of the fluid in the flow path is suppressed, and the fluid is stabilized. And a stable supply of fluid is possible.

(F) According to the fluid heating device of the sixth aspect, the provision of the pressure detector and the pressure control device makes it possible to easily control the temperature of the heating medium,
The fluid is stably heated, and stable supply of the fluid is possible.

(G) In the organic halogen compound decomposing apparatus according to the seventh aspect, since the fluid can be stably heated, the processing capacity can be improved without losing the plasma.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view showing one embodiment of a fluid heating device according to the present invention.

FIG. 2 is a system diagram showing an embodiment of the decomposition apparatus according to the present invention.

FIG. 3 is a perspective view showing an entire configuration of the disassembling apparatus.

FIG. 4 is an enlarged view of a main part of the decomposition apparatus.

FIG. 5 is a sectional view of a main part of a mixer provided in the decomposition apparatus.

FIG. 6 is a comparison diagram showing the time when microwaves, argon gas and the like are supplied and the time of ignition in the decomposition apparatus over time.

FIG. 7 is a perspective view showing an example of a fluid heating device.

[Explanation of symbols]

 Reference Signs List 18 fluid heating device 18a water (heating medium) 18b heater 18c vaporization chamber 18e liquefaction chamber 18f closed vessel 18g pressure detector 18h pressure control device 34a, 34b flow path 35 resistor

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masahiro Bessho 1F, Takamichi, Iwazuka-cho, Nakamura-ku, Nagoya-shi, Aichi F-term in Nagoya Laboratory, Mitsubishi Heavy Industries, Ltd. F-term (reference) 2E191 BA12 BB00 BD18 4D002 AA21 BA07 BA09 CA20 DA35 EA06 GB20 4D034 AA26 CA04 CA21 4G075 AA37 AA61 BA05 BB02 BB04 CA02 CA12 CA15 CA26 CA48 CA51 EB21 EB27

Claims (7)

[Claims] 1. A closed container, a heating medium accommodated in the closed container, a heater for heating the heating medium, and a flow passage penetrating through the closed container and through which a fluid flows. A fluid heating device. 2. The fluid heating device according to claim 1, wherein the closed vessel is provided with a vaporization chamber provided with the heater, and is provided above the vaporization chamber and communicates with the vaporization chamber, and the flow path is penetrated. A fluid heating device comprising: 3. The fluid heating apparatus according to claim 2, wherein the liquefaction chamber has an inclined bottom surface, and the liquefaction chamber and the vaporization chamber communicate with each other at an inclined lower end of the bottom surface. Fluid heating device. 4. The fluid heating device according to claim 2, wherein the flow path is inclined in a length direction thereof. 5. The fluid heating device according to claim 1, wherein a resistor is provided in the flow path. 6. The fluid heating device according to claim 1, wherein a pressure detector that detects a pressure of the heating medium, and a pressure that controls an output of the heater based on an output of the pressure detector. A fluid heating device comprising a control device. 7. An organic halogen compound decomposing device provided with a fluid heating device for heating water, wherein the fluid heating device heats the heating medium contained in the closed container, the heating medium contained in the closed container. An organic halogen compound decomposing apparatus, comprising: a heater that performs a heating operation; and a flow path that penetrates through the closed container and through which a fluid flows.