JPH11221440A - Method and apparatus for decomposition treatment of hardly decomposable substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To decompose an environmental pollutant such as a fluorocarbon gas, polyethylene, plastic, wood or the like and, further, an org. compd., other industrial waste or the like by reacting the same by induction heating and electromagnetic heating due to electromagnetic Raves generated by induction heating and to further decompose the pollutant by the combination reaction of hydrolysis, reducing reaction and oxidation reaction. SOLUTION: A substance to be subjected to decomposition treatment and a solvent are mixed to be introduced into a hollow cylindrical reactor 29 subjected to induction heating and reacted by the heating due to the induction heating of the reactor and electromagnetic heating due to electromagnetic waves generated by induction heating to be decomposed. Concretely, the substance to be subjected to decomposition treatment and the solvent are introduced into a heater 25 to be mixed under heating and the resulting mixture is introduced into the hollow cylindrical reactor 29 having an induction heating coil 10 wound around the outer peripheral part thereof and subjected to induction heating and reacted by the heating due to the induction heating of the reactor 29 and electromagnetic heating due to electromagnetic waves generated by induction heating during the circulating flow within the reactor 29 to be decomposed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for decomposing hardly decomposable substances such as environmental pollutants, and more particularly to fluorocarbon, polyethylene, plastic, wood, organic compounds having a benzene nucleus, and other industrial waste. Decomposes environmental pollutants such as substances by reacting them by induction heating and electromagnetic wave heating by electromagnetic waves generated by induction heating, and further decomposes by a combination reaction of hydrolysis, reduction reaction and oxidation reaction. The present invention relates to a processing method and an apparatus therefor.

[0002]

2. Description of the Related Art It has been pointed out that chlorofluorocarbon and halon gas used as a refrigerant and a spray agent are environmental pollutants, and the detoxification of these substances protects the global environment. From the viewpoint, various countermeasures have been proposed as global concerns. For example, as a method for treating CFCs, a hydrothermal reaction method, an incineration method, an explosion reaction decomposition method, a microbial decomposition method, an ultrasonic decomposition method, a plasma reaction method, and the like have been proposed.

[0003] Among these treatment methods, the hydrothermal reaction method is not limited to chlorofluorocarbon gas and the like, but is applicable to all decomposed substances mainly composed of industrial solvents such as organic solvents such as trichlene, waste oil, dioxin, PCB, and manure. On the other hand, it is used as a versatile processing method. In this hydrothermal reaction method, for example, fluorocarbon gas can be decomposed into a safe substance such as sodium chloride and carbon dioxide.

[0004] Regarding the apparatus for realizing the hydrothermal reaction method, a processing experiment using an autoclave in a laboratory, for example, a mixing ratio of caustic soda solution, ethanol and fluorocarbon solution, a set value of temperature, a set value of pressure and a reaction value Experiments have been conducted on the set time, but usually the hydrothermal reaction is 3
It is performed while maintaining the high temperature and high pressure conditions of 100 to 250 (kg / cm ² ) at 00 to 450 ° C.

[0005] The applicant of the present application has previously filed Japanese Patent Application No. 8-155599.
By heating the mixture of the substance to be decomposed and the solvent to a predetermined temperature to form superheated steam, the superheated steam is allowed to elapse in a normal pressure reactor heated to a predetermined temperature over a predetermined time. A method for decomposing hardly decomposable substances, which decomposes a substance to be decomposed by passing through it, is proposed. Further, according to Japanese Patent Application No. 8-340560, a heater in which water or hydrogen peroxide is used as a solvent, and a mixture of a substance to be decomposed and a solvent is reacted with superheated steam to generate hydrogen is arranged. And the reaction device is heated to a predetermined temperature to produce superheated steam, which is passed through the reaction device over a predetermined period of time, thereby reducing the decomposition target material with hydrogen generated in the heater or the reaction device. A method of decomposing by hydrolysis reaction with superheated steam was proposed.

An example of a conventional reaction apparatus will be described with reference to FIG. 9. Reference numeral 1 denotes an apparatus main body, and a bypass for gas flow is formed by partition walls 2 and 2 arranged in the apparatus main body 1. Reference numeral 3 denotes an inlet for a mixed gas of the substance to be decomposed and the solvent, and reference numeral 4 denotes an outlet for the gas. Further, a plurality of heaters 5, 5 are inserted and arranged from the side of the apparatus main body 1, and the mixed gas flowing in a bypass manner as shown by the arrow a is heated by the heaters 5, 5 to generate superheated steam. As described above, the decomposition treatment of the hardly decomposable substance is performed by the reduction reaction with hydrogen and the hydrolysis reaction with superheated steam.

FIG. 10 shows another example of the conventional reaction apparatus, in which a plurality of heaters 6 and 6 are arranged so as to cover the outer peripheral portion of the apparatus main body 1. The electrode terminals 6a, 6a are connected to a power supply 8 via a controller 7. The mixed gas of the substance to be decomposed and the solvent flowing from the mixed gas inlet 3 is heated in the apparatus main body 1 by the heaters 6 and 6 at the temperature set by the controller 7, and the decomposition of the hardly decomposable substance is performed by the above-described action. And exits from the gas outlet 4.

[0008]

As described above, the conventional reaction apparatus employs a heating method using a plurality of heaters 5 and 5 inserted from the side (an example shown in FIG. 9) or the outer periphery of the apparatus main body. A heating method using a plurality of heaters 6 and 6 arranged so as to cover the portion (the example in FIG. 10) is used, but the heating means for the mixed gas by such a heater is not always efficiently resolvable. There is a drawback that the decomposition treatment of the substance cannot be performed, and a high reaction temperature and a long reaction time are required until the decomposition is completed. Further, the temperature at which the temperature can be raised by the heating means using a heater is about 700 ° C., and the temperature cannot be raised any more. As a result, a long reaction time is required, the decomposition efficiency is reduced, or the decomposition is performed at all. You can't do anything.

Therefore, the present invention solves the above-mentioned problems in a system for decomposing environmentally polluting substances such as chlorofluorocarbon, polyethylene, plastic, wood, organic compounds having a benzene nucleus, and other hardly decomposable substances such as industrial waste. It is another object of the present invention to provide a method and an apparatus for decomposing a hardly decomposable substance that can be decomposed efficiently by accelerating the decomposition rate.

[0010]

In order to achieve the above object, the present invention provides a method for decomposing a hardly decomposable substance by introducing a substance to be decomposed into an induction-heated reactor, and heating the reactor by induction heating. A method of reacting and decomposing by heating and an electromagnetic wave generated by the electromagnetic wave generated due to the induction heating, and a method of mixing a substance to be decomposed and a solvent, introducing the mixture into the induction-heated reaction apparatus, and induction heating the reaction apparatus. The present invention basically provides a method of reacting and decomposing by heating by electromagnetic wave and electromagnetic wave heating by electromagnetic wave generated by induction heating.

As a specific treatment method, the object to be decomposed is introduced into a hollow cylindrical reactor in which an induction heating coil is wound around the outer periphery and is induction-heated, and is circulated around the reactor. A method of reacting and decomposing by heating by induction heating of a reaction apparatus and electromagnetic wave heating by electromagnetic waves generated due to induction heating, introducing an object to be decomposed and a solvent into a heater, heating and mixing, and then mixing with an outer peripheral portion The induction heating coil is wound around and introduced into a hollow cylindrical reactor heated by induction heating. Provided is a method of decomposing by reacting by electromagnetic wave heating by generated electromagnetic waves.

[0012] The object to be decomposed and the solvent are introduced into a heater and mixed by heating to produce superheated steam. The superheated steam is wound around an outer periphery of the induction heating coil to form a hollow cylindrical reaction tube. Provided is a method of decomposing by introducing into an apparatus and reacting by heating by induction heating of the reaction apparatus and electromagnetic heating by electromagnetic waves generated by the induction heating while bypassing the reaction apparatus.

Furthermore, a substance which reacts with the mixed gas to generate hydrogen is disposed in one or both of the heater and the reactor, and a reduction reaction by hydrogen generated in the heater or the reactor, and a superheating A method in which a decomposition target is reacted with a solvent by a combination of a hydrolysis reaction by steam, a heating by induction heating, and a decomposition reaction by electromagnetic wave heating by electromagnetic waves generated due to the induction heating. Using one or more substances selected from iron, carbon, and carbon steel as a substance that generates hydrogen by
Provided is a method using water or hydrogen peroxide as a solvent.

The decomposition processing apparatus comprises a reaction apparatus in which an induction heating coil is wound around the outer periphery and a detour of the decomposition target substance is formed inward, and the introduced decomposition target substance is placed in the reaction apparatus. Heating by induction heating of the reactor while circulating around, and a decomposition treatment device for hardly decomposable substances that react and decompose by electromagnetic wave heating by electromagnetic waves generated due to induction heating, and an induction heating coil on the outer periphery A reactor that is wound and has a detour of a mixed gas of the substance to be decomposed and the solvent formed inside, and the induction heating of the reactor is performed while the introduced mixed gas is bypassed in the reactor. The present invention provides an apparatus for decomposing a hardly decomposable substance, which is decomposed and decomposed by heating by electromagnetic wave heating and electromagnetic wave generated by induction heating.

As a specific configuration, a heater for heating and mixing the object to be decomposed and the solvent, an induction heating coil wound around the outer periphery, and a detour of a mixed gas of the object to be decomposed and the solvent are formed inside. Reactor, a cooler communicating with the piping led out of the reactor, a gas-liquid separator communicating with the piping led out of the cooler, and a neutralization in which the piping led out of the gas-liquid separator is inserted. A heat insulating material is arranged at a position covering the periphery of the reaction device, and an outer member is provided outside the heat insulating material to provide a structure in which the device itself is a hermetically sealed structure.

According to the method and the apparatus for decomposition, the hardly decomposable substances such as CFCs, organic compounds having a benzene nucleus and other industrial wastes are supplied to the reactor alone or as a mixed gas together with a solvent. During the bypass flow, the reaction is caused by the heating by the induction heating of the reactor and the electromagnetic wave heating by the electromagnetic wave generated by the induction heating, and the decomposition action proceeds at normal pressure. If a substance that reacts with the mixed gas to generate hydrogen is placed in one or both of the heater and the reactor, the reduction reaction by the hydrogen generated in the heater or the reactor, and the induction heating of the reactor, The reaction proceeds by a combination of the heating by the electromagnetic wave and the decomposition reaction by the electromagnetic wave generated by the electromagnetic wave generated by the induction heating.

When the material to be decomposed and the solvent are heated to form superheated steam, the hydrolysis reaction by the superheated steam and the heating by induction heating of the reactor, and the heating by electromagnetic waves by electromagnetic waves generated by induction heating. Due to the combination of the decomposition reactions, the substance to be decomposed and the solvent react, and thermal decomposition proceeds. Thereafter, the decomposed gas is cooled and liquefied and discharged.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments of a method and apparatus for decomposing hardly decomposable substances according to the present invention will be described below with reference to the drawings. The inventors of the present application have conducted various improved experiments on the conventional technical means, and as a result, by employing induction heating as a means for heating the reactor, the reactor is heated and heated by the induction current of the induction heating. Along with
It has been found that electromagnetic waves generated by induction heating cause electromagnetic heating. That is, when an electric current is supplied to the induction heating coil to perform electromagnetic wave heating, an eddy current is generated in the reactor by the magnetic flux generated at this time, and heat is generated by Joule heat to heat the reactor. At the same time, passing an electric current through the induction heating coil generates not only a magnetic flux but also an electric field. That is, an electromagnetic wave is generated (the frequency at this time is the electromagnetic wave of the frequency used for the induction heating), and this electromagnetic wave causes a secondary increase in friction and collision of molecules, and the object to be decomposed by the electromagnetic wave heating. Will be heated. In the present invention, together with the heating of the reaction apparatus by the induction heating, the heating efficiency is enhanced by positively utilizing the electromagnetic wave heating by the electromagnetic waves generated by the induction heating, and the collision of molecules is further promoted by activating the molecular motion. The number of times and the collision force are increased to enhance the decomposition efficiency.

First, an object to be decomposed such as chlorofluorocarbon is gasified by heating with a heater using water or hydrogen peroxide as a solvent, and a mixed gas of the object to be decomposed and the solvent is heated by induction heating in a reactor. By reacting in the atmosphere of electromagnetic wave heating by electromagnetic waves generated due to induction heating,
The decomposition of the hardly decomposable substance was able to proceed efficiently while keeping the inside of the reactor at a normal pressure without keeping the inside of the reactor at a high pressure. In addition, it generates superheated steam of the substance to be decomposed and the solvent, or is brought into contact with iron, carbon, carbon steel, or another substance that reacts with the mixed gas to generate hydrogen by heating to about the same temperature as the mixed gas. In addition, the decomposition target material such as chlorofluorocarbon was decomposed by the reduction reaction with the hydrogen generated in the reactor, and at the same time, the decomposition target material could be decomposed by hydrolysis. Hereinafter, specific embodiments will be described.

The present invention decomposes hard-to-decompose substances such as environmental pollutants such as chlorofluorocarbon gas under normal pressure, and the target hard-to-decompose substances are organic and inorganic compounds that are stable or harmful. Although there is no particular limitation, organic solvents such as Freon gas and trichlene, waste oil, dioxin, P
It covers all kinds of industrial waste such as CB and manure, wood, paper, rubber and the like, and its state is not particularly limited, regardless of whether it is solid, liquid or gas. It is mainly useful as an organic compound, but is difficult to treat after use or harmful, such as trichloroethane, PCB, and chlorofluorocarbon (halogen carbon compound). And non-harmful but difficult to process, for example, polyethylene, plastic, rubber and the like.

These are often made from petroleum and can be converted to oil when cracked.
The purpose is to disassemble so that it can be recycled. Further, in the case of rubber, it is another object of the present invention to detoxify the organic compound or to decompose the organic compound so that it can be recycled. Further, the decomposition of paper, wood, and the like is for decomposing cellulose to glucose, and aims to convert those having little utility value to useful ones.

The solvent used in the present invention may be any solvent as long as it gasifies or generates hydrogen by heating, but the most suitable solvent is water, and hydrogen peroxide can also be used. . If hydrogen peroxide solution is used as a solvent, the amount of oxygen increases, and wet oxidation can be effectively performed. In the present invention, only the substance to be decomposed may be supplied to the reactor without using a solvent.

Further, according to the present invention, it is possible to open the benzene ring, and the benzene to be decomposed in the present invention is a basic compound of an aromatic hydrocarbon, and is represented by C ₆ H _6. And monochlorobenzene is represented by C ₆ H ₅ Cl. Examples of the organic compound having a benzene nucleus include phenols. These phenols are a general term for organic compounds in which an OH group is bonded to a benzene nucleus, and are represented by C ₆ H ₅ OH. Further, according to the present invention, dioxins and PCBs having a benzene ring as a skeleton structure can be decomposed and made harmless.

FIG. 1 is a system diagram schematically showing an embodiment of the present invention. In the figure, reference numeral 21 denotes a tank for decomposed substances such as chlorofluorocarbon, 22 denotes a pump for decomposed substances, 23 denotes a water tank as a solvent, and 24 denotes a water tank as a solvent. Is a water pump, 25 is a heater, and an internal heater 26 and an external heater 27 are arranged in the heater 25,
Further, a plurality of iron plates 28, 28 are disposed in the heater 25 as a substance that reacts with the mixed gas to generate hydrogen. A pump capable of pumping an object to be decomposed according to the object to be decomposed is selected as the object to be decomposed pump 22. A slurry pump having a high pumping force capable of pumping a high-concentration slurry, a powder mixed slurry, etc., and having a good volumetric efficiency. It is appropriate to use In some cases, it is not necessary to use a substance that generates hydrogen by reacting with the mixed gas. In addition to the iron plate 28, carbon, carbon steel, or the like may be used as the substance.

Numeral 29 denotes a hollow cylindrical reactor utilizing heating by induction heating and electromagnetic wave heating by electromagnetic waves generated by the induction heating. The reactor 29 is provided with the introduced substance to be decomposed and a solvent. Has a function of decomposing by reacting the mixed gas and hydrogen at a predetermined temperature for a predetermined time. The reactor 29 is provided with a power supply 30 and a matching transformer 31.
The induction heating coil 10 taken out of the reactor is wound around the outer periphery of the reactor 29. The inside of the induction heating coil 10 is hollow as shown in FIG. 3, and cooling water is circulated through the hollow portion. In addition, it is also possible to arrange a substance that reacts with the mixed gas such as the iron plate to generate hydrogen in the reaction device 29.

The inside of the reactor 29 is not pressurized,
The outlet is open to normal pressure. That is, the pressure of the pipe on the mixed gas inlet side has a pressure gradient of only pressure loss due to the pipe. A slight pressure is spontaneously generated in the reaction device 29 by the mixed gas, and a pressure gradient is formed to transfer the decomposition products. The normal pressure in the present invention indicates a state in which the discharge port is opened without forcibly increasing the pressure to a high pressure.

Reference numeral 32 denotes a cooler, in which a pipe 33 communicating with a pipe led out of the reactor 29 is disposed. 34 is an inlet of cooling water, and 35 is an outlet of cooling water. 36 is a gas-liquid separator, 37 is a neutralization device, and the other end of a pipe 38 led out of the cooler 32 is inserted into the gas-liquid separator 36 and is led out of the gas-liquid separator 36. The other end of the pipe 39 is inserted into the neutralization device 37. Reference numeral 40 denotes a processing liquid discharge port.

FIG. 2 is a side view showing a specific example of mounting the reactor 29, and FIG. 3 is a longitudinal sectional view of the reactor 29. As shown in FIG. 2, a hollow cylindrical reactor 29 is mounted on support bases 41, 41. The induction heating coil 10 is wound around the outer periphery of the reactor 29, and the power terminals 10 a, 10a. Further reaction device 2
A heat insulating material 42 is disposed at a position covering the periphery of the heat insulating member 9, and an outer member 47 is provided outside the heat insulating material 42, so that the reaction device 29 itself is entirely sealed.

As shown in FIG. 3, the reactor 29 has a detour through which the mixed gas flows formed by the partition walls 43 and 44 disposed therein. Of the induction heating coil 1 while bypassing the inside of the reactor 29 as shown by the arrow a in the figure.
The material to be decomposed is decomposed by being heated by the action of 0.

The operation of this embodiment will be described.
Taking the case of decomposing fluorocarbon gas, which is an environmental pollutant, as an example, chlorofluorocarbon is charged into the decomposed substance tank 21 and the decomposed substance pump 22 and the water pump 24 are activated, so that the fluorocarbon and water as a solvent are removed. It is sent to the heater 25 through the pipe and mixed at an appropriate ratio.

The internal heater 2 previously arranged in the heater 25
6 and the external heater 27 are operated to make the inside of the heater 25 5
By heating the mixture to 00 ° C. to 750 ° C., the mixed gas of the CFC gas and the solvent is heated to a predetermined temperature and sent into the next reactor 29. Since the temperature required for the decomposition treatment varies depending on the decomposition target, each temperature is set according to the decomposition target. For example, in the case of chlorofluorocarbon gas, it is appropriate to set the temperature to 500 ° C. to 750 ° C., and to set the temperature to about 400 ° C. for polyethylene. Further, depending on the type of the decomposition target, it is effective to generate a superheated vapor of the decomposition target and the solvent.

When the iron plates 28 are heated to substantially the same temperature in the heater 25, the mixed gas contacts the iron plate 28 to generate magnetite and hydrogen by the following reaction formula. _{3Fe + 4H 2 O → Fe 3} O 4 + 4H 2 ......... (1) where generated hydrogen is extremely reducing power is strong, has an action of decomposing the object to be decomposition products bound to many substances.

The mixed gas of the chlorofluorocarbon gas and the solvent is sent into the reactor 29 at the next stage, and flows through the bypass formed by the partition walls 43 and 44. Heat is generated by Joule heat due to eddy current induced by magnetic flux generated by energizing the induction heating coil 10 wound around the outer peripheral portion of the reactor 29, and the reactor 29 is heated to heat the mixed gas. The thermal decomposition of the chlorofluorocarbon gas proceeds.
Simultaneously, when an electric current is applied to the induction heating coil 10, not only a magnetic flux but also an electric field are generated at the same time.
That is, an electromagnetic wave is generated (the frequency at this time is the electromagnetic wave of the frequency used for induction heating), and this electromagnetic wave causes a secondary increase in molecular friction and collision, and the mixed gas is also generated by the electromagnetic wave heating. Heating causes the thermal decomposition of the chlorofluorocarbon gas to proceed. In the present invention, together with the heating of the reaction apparatus by the induction heating, the heating efficiency is enhanced by positively utilizing the electromagnetic wave heating by the electromagnetic waves generated by the induction heating, and the collision of molecules is further promoted by activating the molecular motion. It is characterized in that the number of times and the collision force are increased to increase the decomposition efficiency. Note that the frequency used for induction heating can be from several kHz to several hundred kHz, and in the example, a frequency of 80 kHz was used.

When a substance that reacts with the mixed gas to generate hydrogen is disposed in the reactor 29, the reaction of the above formula (1) is promoted, and a complex decomposition reaction utilizing the reducing power of hydrogen proceeds. I do. Along with this, the decomposition rate of the object to be decomposed is increased and the decomposition rate is also improved, and the object is transferred to the next cooler 32 by a pressure gradient.

In the cooling device 32, cooling water is supplied from an inlet 34 of the cooling water and discharged from the outlet 35,
The gas of the decomposition product decomposed in the pipe 33 communicating with the reactor 29 is cooled and liquefied. The temperature in the cooler 32 may be any temperature at which the gas of the decomposed product can be liquefied. By liquefying in this way, the generation of by-products is prevented, and there is no fear of secondary pollution due to release in the gaseous state and scattering into the atmosphere.

The discharged liquid enters a gas-liquid separator 36 through a pipe 38, where the gas-liquid is separated, and the liquid material flows into a neutralization device 37. And stored in a drain tank (not shown). The cooler 32
It is also possible to incorporate a heat exchanger into the heat exchanger and recover and reuse the heat cooled by the heat exchanger.

In the above description, only water as a solvent is heated by the heater 25 and continuously supplied to the reactor 29, and the substance to be decomposed is supplied to the reactor 29 in the solvent atmosphere and the predetermined amount is supplied. The decomposition treatment can be performed after the reaction time of the above has elapsed. This configuration is suitable for decomposing solid substances to be decomposed other than fluid or gaseous substances, for example, PE, plastic, rubber, wood, paper, etc. It is preferable to supply the substance to the reaction apparatus 29 and to provide a means for transferring the substance to be decomposed such as a feeder in the reaction apparatus 29.

FIG. 4 shows (a) the CFCs R12 and R2
Water 70 (g / mi) for each 70 (g / min) of 2
4 is a graph showing the relationship between the temperature and the decomposition rate when superheated steam is generated by adding n) as a solvent and reacted by an induction heating method reactor to which this example is applied. (B) and (c) are similar graphs when the same sample is reacted by a conventional reaction device using heater heating means.

In the graph (a), the decomposition rate has already reached 99.76% and 99.73% at the temperature of 500 ° C., and it has slightly increased to 99.99% before the temperature reaches 1000 ° C. On the other hand, in the graphs (b) and (c), the temperature is as low as 95.36% and 93.12% at around 550 ° C, and reaches 99.14% and 99.74% at 800 ° C. As can be understood from FIG. 4, the reaction by the induction heating method and the reaction by the heater were performed under the same temperature conditions even under the same temperature condition.
There is a great difference in the decomposition rate of No. 2.

FIG. 5A shows 20 g / chlorobenzene (C ₆ H ₅ Cl), which is an organic substance having a benzene nucleus.
a graph showing the relationship between the temperature and the decomposition rate when superheated steam is generated by adding water (g / min) as a solvent with respect to min. (B) is a similar graph in the case where the same sample is reacted by a conventional reaction device using heater heating means.

Graph (a) has a decomposition rate of 99.16% at a temperature of 500 ° C. and 99.99% at a temperature of about 750 ° C., whereas graph (b) has a temperature of 600 ° C.
At 92.98% and 96.24% at 800 ° C
Has been reached. FIG. 5 also shows that the reaction by the induction heating method and the reaction by the heater have a large difference in the decomposition rate of chlorobenzene even under the same temperature conditions.

FIG. 6 shows an induction heating method in which Freon R113 and water as a solvent are put into a reactor having a weight ratio of 1: 1 and a volume of 1000 (cm ³ ), and the present embodiment is applied under the reaction conditions of 650 ° C. 7 is a graph showing the relationship between the reaction time (second) and the decomposition rate when using a conventional heater heating means.

According to the induction heating method, the reaction time was 1 second and the decomposition rate had already reached 99.96%.
In the case of heater heating, the reaction time is about 2 seconds and the decomposition rate is 4
0.08%, reaching 99.99% with a reaction time of 30 seconds. Therefore, it can be seen that the reaction by the induction heating method and the reaction by the heater have a large difference in the reaction time required for decomposition even under the same temperature conditions.

FIG. 7 shows that chlorofluorocarbon R12 alone was introduced into a reactor having a volume of 1000 (cm ³ ) without using a solvent,
6 is a graph showing the relationship between the reaction time (second) and the decomposition rate when using an induction heating method to which the present embodiment is applied and a conventional heater heating means under respective reaction temperature conditions of ℃, 750 ° C. and 850 ° C.

In the case of heating with a heater, the decomposition of chlorofluorocarbon hardly progressed at any of the reaction temperatures of 650 ° C. and 750 ° C., and the decomposition effect occurred only at the reaction temperature of 850 ° C., and the reaction time was 60 seconds. While the decomposition rate reached 79.1%, according to the induction heating method, 650 ° C., 750 ° C.,
Decomposition of chlorofluorocarbon has progressed from 1 second at each reaction temperature condition of 850 ° C., and particularly at 850 ° C., the decomposition rate has already reached 99.9% in a reaction time of 60 seconds. Therefore, it can be seen that the reaction occurs promptly without using a solvent by using the induction heating method.

FIG. 8 shows that chlorobenzene (C
₆ H ₅ Cl) alone into a reactor having a volume of 1000 (cm ³ ), and reacted by the induction heating method to which the present embodiment was applied under the respective reaction temperature conditions of 850 ° C. and 950 ° C. It is a graph which shows the relationship between the reaction time (second) at the time of making it react at 850 degreeC using a heater heating means, and a decomposition rate.

In the case of heating with a heater, the decomposition of chlorobenzene hardly progresses even at a reaction temperature of 850 ° C., whereas according to the induction heating method, the decomposition rate after 5 seconds at a reaction temperature of 850 ° C. is 22. .1%, 44.3% after 70 seconds
Has been reached. Further, under the reaction temperature condition of 950 ° C., the decomposition rate after 5 seconds reaches 63.0%, and after 75 seconds reaches 92.5%. Therefore, it is understood that chlorobenzene can be decomposed without using a solvent by using the induction heating method.

Here, the principle of heat generation of the reactor 29 utilizing heating by induction heating and electromagnetic wave heating by electromagnetic waves generated due to induction heating in the present invention will be briefly described. Generally, induction heating is a method of heating a conductive resistor by a non-contact electromagnetic induction action. For example, in the case of a general transformer, there are coils on the primary side and the secondary side, respectively.The induced magnetic field generated by the primary side coil generates an induced voltage on the secondary side by an amount corresponding to the coupling with the secondary side coil. Supply current to the load circuit connected to the secondary side.

An electromotive force is generated in a metal body placed in the induction heating coil 10 through high-frequency alternating current as in the present invention, and an eddy current as an induced current flows. This eddy current concentrates on the surface of the metal body, and decreases exponentially as it goes inside, causing a "skin effect" having a constant penetration depth, which is a characteristic of high-frequency induction heating, with a phase delay. The eddy current loss that causes the heat generation phenomenon is a resistance loss (joule's loss) caused by the eddy current, and the electric power that generates the heat generation effect on the cylindrical conductive metal is the electric current flowing through the induction heating coil 10 when the frequency increases. Proportional to the square of the number of turns of the coil, proportional to the square root of the frequency, proportional to the square of the radius of the cylinder, proportional to the square root of the relative permeability of the material, and proportional to the resistivity of the material. It is proportional to the square root.

Therefore, the heat generation increases as the AC frequency increases, but the branch point between the heat generation and the generated power is called a critical frequency of induction heating, and one of the problems is to select which frequency. The optimal frequency must be selected. On the other hand, an electric field is simultaneously generated in the hollow portion of the reaction device 29 by the eddy current (secondary current). Since this electric field is generated in a direction that prevents a change in magnetic flux generated by the primary current, an electromagnetic wave is generated in the reaction device 29.
This electromagnetic wave causes a secondary increase in molecular friction and collision, and the object to be decomposed is heated by electromagnetic wave heating.

The features of induction heating are that the time required for heat conduction is shortened, and high thermal efficiency and high-speed response are obtained.
Moreover, since the object to be heated itself generates heat simultaneously as a heating element, uniform heating is possible regardless of the shape of the object to be heated. In this embodiment, a magnetic field H is generated when the coil current I flows with the total length of the reactor 29 being L and the number of turns of the coil being N. The intensity of the magnetic field H is [NI / L].

Assuming that the magnetic permeability of the cylindrical reactor 29 is μ, the magnetic flux density B becomes: magnetic flux density B = μNI / L, the magnetic flux A becomes: magnetic flux A = μSNI / L, and the magnetic flux density B becomes The larger the magnetic susceptibility μ, the larger. Therefore, a large amount of magnetic flux passes through the cylindrical portion of the reactor 29.

Next, the principle of decomposition of the object to be decomposed and the principle of measurement of the result will be described. When chlorofluorocarbon gas was used as the substance to be decomposed, the following products were confirmed. First, the gas is CO ₂ , H ₂ , HCl, HF, CO (a trace amount), and the liquid is HCl, HF, Fe ³ +. Solid is Fe ₂ O ₄ , C
(Graphite), FeF ₂ , FeF ₂ .4H ₂ O, FeC
l ₂ , FeCl ₂ .4H ₂ O. In addition, as a measuring method,
Gas is GC-MC method, H ₂ and CO are GC-TCD method, H
Cl and HF were measured by ion chromatography, CO ₂ was measured by a detector tube, metals were measured by ICP emission, and solids were measured by X-ray diffraction.

The decomposition reaction of CFC-12 is as follows. [When water is used as a solvent] CCl ₂ F ₂ + 2H ₂ → + 2HCl + 2HF + C (2) CCl ₂ F ₂ + 2H ₂ O → 2HCl + 2HF + CO ₂ (3) 2CCl ₂ F ₂ + 3H ₂ O → 2HCl + 2HF + CO ₂ + CO + H ₂ (4)

The equation (2) represents the decomposition of the reduction reaction by hydrogen,
The equations (3) and (4) are hydrolysis by water, and the reaction of the equation (3) is mainly performed in view of the amount of CO. As a whole, the reactions of the equations (2) and (3) are 95% or more. , (4) is about 5%.

Further, the hydrochloric acid gas and the hydrofluoric acid gas of the products act on iron, and the following reaction occurs. Fe + 2HCl → FeCl ₂ + H ₂ (5) Fe + 2HF → FeF ₂ + H ₂ (6)

When this is cooled by the cooler 32, it absorbs the moisture in the air and receives FeCl ₂ .4H ₂ O and FeF _2.
Changes to 4H ₂ O.

Next, a reaction formula when carbon or carbon steel is used in place of the iron plate 28 will be described. That is, when superheated steam of water as a solvent acts on carbon, C + H ₂ O → CO + H ₂ (7) is obtained, and a water gas as a mixed gas of CO and H ₂ is generated. The obtained hydrogen causes the reactions of the above formulas (1) to (6) to decompose the fluorocarbon gas. However, when carbon is used, the amount of generated hydrogen is slightly lower than when iron or carbon steel is used, and it takes about 10 seconds to achieve a decomposition rate of 99.99. Slightly lower.

In the above formula (1), the magnetite (Fe
₃ O ₄ ) is a passivation having high corrosion resistance to acid, and adheres to the surface of a container or the like to form a protective film. The magnetite adhering to the iron plate 28 reacts with the carbon to become Fe ₃ O ₄ + 2C → 3Fe + 2CO ₂ (8) and also reacts with CO to become Fe ₃ O ₄ + 4CO → 3Fe + 4CO ₂ (9) The iron required for the reaction of the formula (1) is recycled. However, in many cases, expansion and contraction due to heat progress, magnetite peels off, a new iron surface is exposed, and the reaction continues.

When water is used as the solvent for the chlorofluorocarbon, the mixture becomes strongly acidic due to the action of hydrochloric acid and hydrofluoric acid generated by the reaction of the above formula (2), and the corrosion of pipes and tubes becomes severe. May be shortened. Therefore, as shown in the following equation (10), caustic soda NaOH is added according to the concentration of chlorofluorocarbon to convert carbon dioxide into sodium bicarbonate NaHCO _3. And then (1
In some cases, sodium fluoride NaF is generated by the reaction of caustic soda and hydrofluoric acid as shown in equation 2). NaOH + CO ₂ → NaHCO ₃ (10) NaOH + HCl → NaCl + H ₂ O (11) NaOH + HF → NaF + H ₂ O (12)

[When Hydrogen Peroxide Solution is Used as Solvent] Hydrogen peroxide solution is thermally decomposed to produce water and oxygen. 2H ₂ O ₂ → 2H ₂ O + O ₂ (13) Therefore, in addition to hydrolysis by H ₂ O and O ₂ , the next reaction by oxygen occurs simultaneously. CCl ₂ F ₂ + O ₂ → CO ₂ + Cl ₂ + F ₂ (14) Equation (14) is an oxidation reaction. Cl ₂ and F ₂ obtained by the oxidation reaction are changed to HCl and HF as Cl ₂ + H ₂ → 2HCl (15) F ₂ + H ₂ → 2HF (16)

When hydrogen peroxide solution is used as a solvent as described above, in addition to the above-described hydrolysis and reduction reactions,
Since the above-mentioned oxidation reaction proceeds simultaneously, the decomposition rate is fast, and the decomposition target material changes from early to a stable substance,
No extra by-products are produced.

This embodiment is for decomposing a fluid or gaseous substance to be decomposed. In addition to an environmental pollutant, it decomposes a liquid substance of a halogenated carbon compound such as chlorobenzene and trichloroethane as an environmental pollutant. Although it is possible, the temperature in the heater 25 and the reactor 29 was set to 650 ° C., and the temperature of the pipe 33 in the cooler 32 was set to 18 ° C. as the experimental conditions in the case of CFC gas. In addition, the solvent (water or hydrogen peroxide solution) was selected to be in excess in molar ratio. That is, Freon gas: water (or hydrogen peroxide solution) =
1: 3. The decomposition rate at this time is to the extent that CFCs are not detected by gas chromatography, in other words, 99.
A decomposition rate of 99% or more was obtained.

Next, the decomposition reaction of trichloroethane (CH ₃ · CCl ₃ ) and chlorobenzene (C ₆ H ₅ Cl) which is an organic substance having a benzene nucleus according to the present embodiment will be described.
The reaction temperature was 650 ° C.

First, trichloroethane (CH ₃ .CCl ₃ )
Is decomposed, the reaction proceeds as follows.

[When water is used as a solvent] When water is used as a solvent, the hydrolysis proceeds as follows: CH ₃ · CCl ₃ + H ₂ O → 3HCl + CO + C + H ₂ (17) CH ₃ · CCl ₃ + 2H ₂ O → 3HCl + CO ₂ + C + 2H ₂ (18) Meanwhile, the (1) decomposition by hydrogen superheated steam is generated in contact with the iron plate 28 as shown in expression decomposition during the gas qualitative analysis, first, the decomposition reaction of the product, CH ₃ · CCl ₃ + 3H ₂ → CH ₃ .CH ₃ + 3HCl (19) A substitution reaction with hydrogen was observed, and further, CH ₃ .CH ₃ + H ₂ → 2CH ₄ (20) decomposition proceeded, CH ₄ → C + 2H ₂ (21) Therefore, in this decomposition reaction, CO ₂ , C
Decomposed into O, H ₂ , C, HCl.

[When hydrogen peroxide solution is used as a solvent] When hydrogen peroxide solution is used as a solvent, CH ₃ · CCl ₃ + 2O ₂ → 2CO ₂ + 3HCl is used in addition to the above-mentioned hydrolysis and decomposition by hydrogen. 22) A decomposition reaction by oxidation takes place, and the CH ₄ generated in the equation (20) is also partially oxidized to be CH ₄ + 2O ₂ → CO ₂ + 2H ₂ O (23), which is hydrolyzed and produced by hydrogen. The decomposition and oxidative decomposition of the reduction reaction occur in parallel, and the decomposition efficiency is further improved.

Next, when chlorobenzene (C ₆ H ₅ Cl) is decomposed, the reaction proceeds as follows.

[When water is used as a solvent] When water is used as a solvent, the hydrolysis is performed as follows: C ₆ H ₅ Cl + H ₂ O → C ₆ H ₅ OH + HCl (24) As shown in the equation (1), the decomposition by hydrogen generated by the contact of the superheated steam with the iron plate 28 is as follows.
The gas in the middle of decomposition is qualitatively analyzed, and the decomposition reaction of the product is first replaced with H, resulting in C ₆ H ₅ Cl + H ₂ → C ₆ H ₆ + HCl (25). Hydrochloric acid is generated, and H is further added to form C ₆ H ₆ + 3H ₂ → C ₆ H ₁₂ (26), cyclohexane (C ₆ H ₁₂ ) is generated, and the ring is further opened to form methane. Is decomposed into ethane and the like. C ₆ H ₁₂ + 6H ₂ → 6CH ₄ (27) This methane becomes CH ₄ → C + 2H ₂ (28) and is decomposed into C (graphite), hydrochloric acid and hydrogen.

[0070] [If using hydrogen peroxide as a _{solvent] C 6 H 5 Cl + 6O} 2 → 6CO 2 + HCl + 2H 2 ......... other degradation by hydrolysis and hydrogen described above and using aqueous hydrogen peroxide in a solvent ( 29) occurs simultaneously.

[0071]

As described above in detail, according to the present invention, a non-decomposable substance such as a fluorocarbon gas, an organic compound having a benzene nucleus, and other industrial waste is supplied to a reactor as a mixed gas together with a solvent, and the reaction is carried out. Heating by induction heating of the reaction device and electromagnetic wave heating by electromagnetic waves generated by induction heating while reacting with the object to be decomposed and the solvent during the bypass circulation in the device to cause thermal decomposition at normal pressure It can be performed efficiently. In particular, since heating at normal pressure is the main process, a high-pressure pump is not required, and there is no concern that valves and piping may be damaged. Furthermore, since the reaction is a closed system in which all reactions take place in the reactor, there is obtained an effect that there is no secondary contamination.

When a substance that reacts with the mixed gas to generate hydrogen is disposed in one or both of the heater and the reactor, a reduction reaction using hydrogen generated in the heater or the reactor, a reaction in the reactor, Heating by induction heating of
The reaction proceeds by the combination of the decomposition reaction by electromagnetic wave heating due to the electromagnetic wave generated by induction heating, and when the material to be decomposed and the solvent are heated to superheated steam, the hydrolysis reaction and reaction by superheated steam The reaction between the object to be decomposed and the solvent proceeds by a combination of heating by induction heating of the apparatus and a decomposition reaction by electromagnetic wave heating by electromagnetic waves generated due to the induction heating. Thereafter, the decomposed gas can be cooled and liquefied and discharged.

The degree of decomposition can be controlled by arbitrarily setting the reaction time and temperature of the heater and the reactor. The degree of decomposition of polyethylene can be changed, and the rubber can be used again as rubber. Cellulose in wood can be processed under conditions that can be recycled as useful glucose.

Particularly, in the case of the conventionally known catalyst method, there is a problem that the catalyst is deteriorated by oxidation or the like, whereas in the case of the present invention, the above-mentioned problem is caused because the catalyst is not used. There is no point, and it can be applied not only to CFCs but also to other industrial wastes and organic substances having a benzene nucleus.

Further, according to the present invention, since the process proceeds at a low pressure, the material can be arbitrarily selected as long as it can withstand a predetermined high temperature, and can withstand mechanical strength and tensile stress or thermal stress. Therefore, there is an advantage that no design is required, and measures against breakage of various devices are easy and automation of the device itself is also easy.

[Brief description of the drawings]

FIG. 1 is a system diagram showing a basic embodiment of the present invention.

FIG. 2 is a side view of the reaction apparatus used in the present embodiment.

FIG. 3 is a longitudinal sectional view showing a structural example of a reaction apparatus.

FIG. 4 is a graph showing the relationship between the temperature and the decomposition rate when Freon R12 and R22 are reacted by induction heating using water as a solvent.

FIG. 5 is a graph showing the relationship between temperature and decomposition rate when chlorobenzene is reacted by induction heating using water as a solvent.

FIG. 6 is a graph showing the relationship between the reaction time and the decomposition rate when Flon R113 is reacted using water as a solvent in this example and a conventional heater heating means.

FIG. 7 is a graph showing the relationship between the reaction time and the decomposition rate when only Example 1 and conventional heating means are used under the respective reaction temperature conditions for only Freon R12.

FIG. 8 is a graph showing the relationship between the reaction time and the decomposition rate when only chlorobenzene is used at each reaction temperature condition and the present example and a conventional heating means are used.

FIG. 9 is a longitudinal sectional view of a main part for explaining an example of a conventional reaction apparatus.

FIG. 10 is a schematic diagram for explaining an example of another conventional reaction apparatus.

[Description of Signs] 21: Decomposed substance tank 22 ... Decomposed substance pump 23 ... Water tank 24 ... Water pump 25 ... Heater 26 ... Internal heater 27 ... External heater 28 ... Iron plate 29 ... (Induction heating) reactor 30 ... Power supply 31 ... Matching transformer 32 ... Cooler 36 ... Gas-liquid separator 37 ... Neutralization device 41 ... Support table 42 ... Insulation material 43,44 ... Partition

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B01D 53/74 B01D 53/34 117G B09B 3/00 B09B 3/00 302A H05B 6/10 302Z

Claims (13)

[Claims] 1. A method in which an object to be decomposed is introduced into a reactor heated by induction heating, and is decomposed by being heated by induction heating of the reactor and heated by electromagnetic waves generated by electromagnetic waves caused by the induction heating. A method for decomposing difficult-to-decompose substances. 2. An object to be decomposed is introduced into a hollow cylindrical reaction device in which an induction heating coil is wound around an outer periphery thereof and is induction-heated. A method for decomposing a hardly decomposable substance, characterized by reacting and decomposing by heating by induction heating and electromagnetic wave heating by electromagnetic waves generated by induction heating. 3. An object to be decomposed and a solvent are mixed, introduced into a reactor heated by induction heating, and reacted by heating by induction heating of the reactor and electromagnetic wave heating by electromagnetic waves generated by the induction heating. A decomposition treatment method for a hardly decomposable substance, characterized in that it is decomposed by decomposition. 4. An object to be decomposed and a solvent are introduced into a heater and mixed by heating. Then, an induction heating coil is wound around an outer peripheral portion and introduced into a hollow cylindrical reaction apparatus heated by induction to perform a reaction. A method for decomposing a hardly decomposable substance, characterized by reacting and decomposing by heating by induction heating of a reactor and electromagnetic heating by electromagnetic waves generated due to induction heating while being bypassed in the apparatus. 5. A hollow cylindrical reaction in which an object to be decomposed and a solvent are introduced into a heater and mixed by heating to form superheated steam, and the superheated steam is induction-heated by winding an induction heating coil around an outer peripheral portion thereof. The method is characterized in that it is introduced into the apparatus and is decomposed by reacting by heating by induction heating of the reaction apparatus and electromagnetic heating by electromagnetic waves generated due to the induction heating while being bypassed in the reaction apparatus. Decomposition method of decomposed substances. 6. A substance which reacts with a mixed gas to generate hydrogen in one or both of a heater and a reactor, and a reduction reaction by hydrogen generated in the heater or the reactor, and superheating The decomposition treatment is performed by reacting a substance to be decomposed with a solvent by a combination of a hydrolysis reaction by steam, a heating by induction heating, and a decomposition reaction by electromagnetic wave heating by electromagnetic waves generated due to the induction heating. Decomposition method for hardly decomposable substances. 7. The method according to claim 6, wherein one or more substances selected from iron, carbon, and carbon steel are used as the substance that generates hydrogen by reacting with the superheated steam. 8. The method according to claim 3, wherein water or hydrogen peroxide solution is used as the solvent. 9. The hardly decomposable gas according to claim 1, wherein the gas after the decomposition treatment is cooled by a cooler to be liquefied and discharged. Decomposition method of the substance. 10. An induction heating coil is wound around an outer peripheral portion,
It consists of a reactor in which a detour of the substance to be decomposed is formed inside, and is used for heating by induction heating and induction heating of the reactor while the introduced substance to be decomposed is bypassed in the reactor. An apparatus for decomposing hardly decomposable substances, characterized by reacting and decomposing by electromagnetic wave heating by electromagnetic waves generated due to the electromagnetic waves. 11. An induction heating coil is wound around an outer peripheral portion,
A reaction device in which a detour of a mixed gas of the substance to be decomposed and the solvent is formed inward, and heating by induction heating of the reaction device while the introduced mixed gas is bypassed in the reaction device, An apparatus for decomposing hardly decomposable substances, characterized by reacting and decomposing by electromagnetic wave heating by electromagnetic waves generated due to induction heating. 12. A reaction in which a heater for heating and mixing an object to be decomposed and a solvent and an induction heating coil wound around an outer peripheral portion and a detour of a mixed gas of the object to be decomposed and the solvent are formed inward. The apparatus, a cooler communicating with the piping derived from the reactor, a gas-liquid separator communicating with the piping derived from the cooler, and a neutralization device into which the piping derived from the gas-liquid separator is inserted. And reacting and decomposing by heating by induction heating of the reactor and electromagnetic heating by electromagnetic waves generated due to the induction heating while the introduced mixed gas is bypassed in the reactor. Characteristic decomposition equipment for hardly decomposable substances. 13. A heat insulating material is arranged at a position covering the periphery of the reactor, and an outer shell member is provided outside the heat insulating material.
13. The decomposition processing apparatus for hardly decomposable substances according to claim 10, wherein the apparatus itself is configured as a closed structure.