JP2003221216A - Method and apparatus for manufacturing fullerenes - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for manufacturing fullerenes economically on a large scale in a mass production. <P>SOLUTION: In an apparatus 10 for manufacturing fullerenes which apparatus has the first reaction zone 13 that forms a high temperature combustion gas flow by supplying an oxygen-containing gas and a fuel gas via the first burner 12 into a reaction furnace 11 and burning them, and the second reaction zone 16 that is situated in the downstream side of the first reaction zone 13, has discharge spouts 15 of the second burner 14 for supplying the raw material hydrocarbons into the combustion gas flow and produces fullerenes by reacting the raw material hydrocarbons supplied in a gasified state in the combustion gas flow, the apparatus is characterized in that the discharge spouts 15 of the second burner 14 are formed in the upstream side of the second reaction zone 16 in great numbers and with clearances therebetween and dispersively discharge the raw material hydrocarbons into the combustion gas flow. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing fullerenes and an apparatus therefor.

[0002]

2. Description of the Related Art Fullerenes (hereinafter sometimes simply referred to as fullerenes) are a general term for a third carbon allotrope after diamond and graphite, and have a five-membered ring as represented by C ₆₀ and C _70. It is a hollow shell-shaped carbon molecule closed by a network of 6-membered rings. The existence of fullerenes was finally confirmed in 1990, which is a relatively new carbon material, but it was recognized that it has unique physical properties due to its special molecular structure. For example, innovative application development is rapidly expanding in a wide range of fields such as the following. (1) Application to ultra-hard material: Since fullerene is used as a precursor to purify artificial diamond having fine crystal particles, it is expected to be used as a wear-resistant material with added value. (2) Application to pharmaceuticals: The use of C ₆₀ derivatives and optical devices for anticancer agents, therapeutic agents for AIDS, osteoporosis and Alzheimer's drugs, contrast agents, stent materials, etc. is being studied. (3) Application to superconducting materials: It has been discovered that doping a fullerene thin film with metallic potassium can produce a superconducting material having a high transition temperature of 18K, and is attracting attention from various fields. (4) Application to semiconductor manufacturing: Utilizing that the resist structure is further strengthened by mixing C ₆₀ with the resist,
Application to next-generation semiconductor manufacturing is expected.

Among the fullerenes having various carbon numbers, C ₆₀ and C ₇₀ are relatively easy to synthesize, and therefore, it is expected that future demand will increase explosively. The currently known methods for producing fullerenes include the following methods. (1) Laser vapor deposition method This is a method in which a carbon target placed in a rare gas is irradiated with a pulsed laser having a high energy density, and carbon atoms are vaporized to synthesize the carbon target. A quartz tube through which a noble gas flows is placed in an electric furnace and a graphite sample is placed in the quartz tube. When the graphite sample is irradiated with a laser from the upstream side of the gas flow to evaporate it, soot containing fullerenes such as C ₆₀ and C ₇₀ adheres to the inner wall of the cooled quartz tube near the outlet of the electric furnace. Since the amount of evaporation per shot of the laser is small, it is not suitable for mass production. (2) Resistance heating method This is a method in which a graphite rod is electrically heated and sublimated in a container under reduced pressure filled with helium gas. Since the electric resistance loss in the circuit is large, it is not suitable for mass production.

(3) Arc discharge method A method of sublimating carbon of the anode by lightly contacting two graphite electrodes in helium gas of several tens of kPa or by causing arc discharge in a state of being separated by about 1 to 2 mm. Is. It is currently used for mass production of fullerenes on a factory scale. (4) High-frequency induction heating method Instead of using resistance heating or arc discharge, this is a method in which a high-frequency induction causes an eddy current to flow in the raw graphite to evaporate the raw graphite by heating. (5) Combustion method This is a method of incompletely combusting a hydrocarbon raw material such as benzene in a mixed gas of an inert gas such as helium and oxygen. The production efficiency is low because a few percent of benzene fuel becomes soot, and about 10% of it becomes fullerenes, but the soot produced as a by-product (fullerene etc.) can be used as liquid fuel etc., and the production equipment is simple. In this respect, it is attracting attention as a mass production method that is opposed to the arc discharge method. (6) Naphthalene Thermal Decomposition Method This is a method in which naphthalene is thermally decomposed at about 1000 ° C.

As described above, various methods for synthesizing fullerenes have been proposed so far, but none of the methods has been established so far for inexpensively producing large quantities of fullerenes. The cheapest of these methods,
A combustion method is considered to be one of the efficient manufacturing methods. For example, Patent Document 1 describes a method for manufacturing fullerenes by burning a carbon-containing material in a flame and collecting a condensate. . This method is a method of producing fullerenes by burning a carbon-containing material in a flame, and the fuel for combustion and the raw material of the fullerene are substantially the same carbon-containing material. Fullerene is produced by being contained in soot-like substance, and a part of this soot-like substance is so-called carbon black.

The furnace method, the channel method, the thermal method, the acetylene method and the like are known as methods for producing carbon black, and the furnace method is mentioned as an industrially general method. This method uses, for example, a cylindrical carbon black production apparatus (reaction furnace), and supplies an oxygen-containing gas such as air and fuel to the first reaction zone of the reaction furnace in a horizontal direction or a vertical direction with respect to the furnace axis. And burned, and the resulting combustion gas flow is moved to the second reaction zone which is installed downstream in the axial direction of the furnace and has a reduced cross-sectional area, and feed hydrocarbon (feed oil) is fed into the gas flow to react. In this way, carbon black is produced, and then the reaction is stopped by rapidly cooling the gas by spraying cooling water to the gas flow in the third reaction zone downstream thereof.

[0007]

[Patent Document 1] Japanese Patent Publication No. 6-507879

[0008]

However, the above-mentioned ordinary method for producing carbon black hardly produces fullerenes. In the production of fullerenes, how to increase the proportion of fullerenes contained in the soot-like substance obtained is a major issue. Generally, fullerene is produced under reduced pressure, and a diluent may be introduced into the reaction zone in some cases. It is known that the degree of reduced pressure and the concentration of the diluent affect the yield of the fullerene.

The above-mentioned Patent Document 1 describes a method of increasing the flame temperature in order to improve the yield of fullerene, and a method of supplying further energy to the flame from an external energy source as a means thereof. Preferred energy sources include electrical resistance heating, which directly heats the flame, microwave heating, discharge heating, and countercurrent heating, which heats the flame by heat exchange with hot gases.

In the above-mentioned Patent Document 1, pure oxygen is used as the oxidant for the combustion reaction, and argon is used as the diluent. This is considered to have the effect of increasing the yield of fullerene. However, pure oxygen requires a dedicated cylinder or supply facility, and especially when producing fullerenes on an industrial scale, the amount of oxygen required for combustion also becomes large and a special oxygen supply is required. Equipment is required, and as a result, fullerenes are expensive to produce.

Therefore, in order to reduce the manufacturing cost in the combustion method, it can be easily analogized to use air as an oxidant for combustion, but the flame is not stable and the nitrogen is not stable because the oxygen concentration is lower than that of pure oxygen. Has not been put to practical use because the combustion temperature becomes low due to the large proportion of the above, and the volume increases and the speed at which the particles pass through the nozzle increases especially during operation under reduced pressure. Fullerene is a new material for the next generation,
As a new material, it has been drawing attention from various fields, and it is desired to develop a technique for manufacturing fullerenes in large quantities at low cost and easily.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a method for producing fullerenes and an apparatus for producing the fullerenes in a large amount at low cost and easily.

[0013]

DISCLOSURE OF THE INVENTION As a result of various studies on the optimal combustion method and production apparatus capable of producing fullerene in large quantities and at low cost, the present inventors have supplied an oxygen-containing gas and a fuel to the reactor. A first reaction zone for forming a high-temperature combustion gas stream by combustion and combustion, and a raw hydrocarbon feed port for feeding the raw hydrocarbon to the combustion gas stream, and reacting the raw hydrocarbon to produce fullerene It was found that a fullerene can be stably produced in a large amount by using a device for producing fullerenes having two reaction zones and keeping the pressure in the second reaction zone below atmospheric pressure.

That is, the method for producing fullerenes according to the first aspect of the present invention, which meets the above-mentioned object, is the first method for supplying an oxygen-containing gas and a fuel into a reaction furnace and burning them to form a high temperature combustion gas flow. It is characterized by having a reaction zone and a raw material hydrocarbon supply port for supplying the raw material hydrocarbon in the middle of the combustion gas flow, and having a second reaction zone for reacting the raw material hydrocarbon to produce fullerenes. An apparatus for producing fullerenes is used and the pressure in the second reaction zone is set to be less than atmospheric pressure. Since the fuel and the oxygen-containing gas are supplied and burned in the first reaction zone, for example, complete combustion can be easily achieved and a high-temperature combustion gas stream can be formed. Then, by supplying the raw material hydrocarbon into the obtained high-temperature gas stream, the raw material hydrocarbon can be easily thermally decomposed and the production efficiency of fullerenes can be improved. In addition, the pressure in the second reaction zone is set below atmospheric pressure,
By diluting the mixed state of the raw material hydrocarbon and the combustion gas, the thermal decomposition of the raw material hydrocarbon proceeds uniformly and the production efficiency of fullerenes can be improved.

In the method for producing fullerenes according to the first aspect of the present invention, it is preferable that the second reaction zone is downstream of the first reaction zone. By providing the second reaction zone on the downstream side of the first reaction zone, the high temperature combustion gas formed in the first reaction zone can be immediately introduced into the second reaction zone. As a result, the temperature of the second reaction zone can be increased. In the method for producing fullerenes according to the first aspect, it is preferable that the temperature of the second reaction zone is 1000 ° C. or higher. The temperature of the second reaction zone is set to 1000
By setting the temperature to not less than 0 ° C, the supplied raw material hydrocarbon can be reliably pyrolyzed in a short time.

The apparatus for producing fullerenes according to the second aspect of the invention, which meets the above-mentioned object, supplies an oxygen-containing gas and a fuel gas into the reaction furnace through the first burner, and burns them to obtain a high temperature. A first reaction zone for forming a combustion gas flow, and a discharge port of a second burner downstream of the first reaction zone for supplying the raw material hydrocarbon to the combustion gas flow, which are gasified and supplied. It has a second reaction zone in which the raw material hydrocarbons thus reacted are reacted in the combustion gas stream to produce fullerenes. Since the combustion of the fuel is performed in the first reaction zone, it becomes easy to control the combustion state, and it is possible to easily form high-temperature combustion gas. The resulting hot combustion gas stream is
Since it is introduced into the reaction zone and the raw material hydrocarbon is supplied into this high temperature gas stream for thermal decomposition, the gas flow conditions such as the temperature, flow velocity and flow rate of the high temperature combustion gas stream and the feed condition of the raw material hydrocarbon are adjusted. By doing so, it becomes easy to control the thermal decomposition of the raw material hydrocarbons.

In the apparatus for producing fullerenes according to the second aspect of the invention, a large number of discharge ports of the second burner are formed with a gap upstream of the second reaction zone, and the raw material hydrocarbon is It is preferred to disperse and release into the combustion gas stream. By forming the discharge port of the second burner for supplying the raw material hydrocarbon on the upstream side of the second reaction zone, the raw material hydrocarbon can be directly supplied into the high temperature combustion gas stream flowing from the first reaction zone. Therefore, the raw material hydrocarbon can be easily pyrolyzed. Further, since the raw material hydrocarbons are dispersedly discharged into the combustion gas from a large number of outlets, the raw material hydrocarbon can be uniformly thermally decomposed in the combustion gas in a short time. In the apparatus for producing fullerenes according to the second aspect of the present invention, it is preferable that the second burner includes a large number of small-diameter discharge pipes arranged so as to penetrate the first reaction zone. Since the raw material hydrocarbon is supplied through a large number of small-diameter discharge pipes, the raw material hydrocarbon can be uniformly dispersed and released into the high temperature combustion gas stream in the second reaction zone. Further, since the small-diameter discharge pipe is arranged so as to penetrate through the first reaction zone, the raw material hydrocarbon is gradually heated by the high-temperature combustion gas while passing through the small-diameter discharge pipe, and the high-temperature combustion in the second reaction zone is performed. Pyrolysis in a gas stream can be accelerated.

In the apparatus for producing fullerenes according to the second aspect of the present invention, the first burner is provided with a plurality of oxygen-containing gas nozzles and fuel gas nozzles, which emit the oxygen-containing gas and the fuel gas independently of each other. May be. With such a configuration, the supplied oxygen-containing gas and fuel gas can be mixed by diffusion to form a uniform mixed state and be present in the first reaction zone. Further, in the fullerene manufacturing apparatus according to the second aspect of the invention, the head of the first burner is made of a porous member and is jetted from the surface in a state where the oxygen-containing gas and the fuel gas are mixed. Can be With such a configuration, the oxygen-containing gas and the fuel gas can be premixed and supplied to the first reaction zone.

In the apparatus for producing fullerenes according to the second aspect of the invention, the oxygen-containing gas and the fuel gas are mixed in the first burner, and the oxygen-containing gas and the fuel are mixed in the first burner. The fuel gas may be independently supplied through a separate pipe. Since the oxygen-containing gas and the fuel gas are mixed in the first burner, it is not necessary to separately provide a premixing unit for the oxygen-containing gas and the fuel gas, and the configuration of the fullerene-type manufacturing apparatus is simplified. Second
In the apparatus for producing fullerenes according to the present invention, the oxygen-containing gas and the fuel gas can be premixed and supplied to a pressure accumulating chamber provided under the head. Since the oxygen-containing gas and the fuel gas are premixed and supplied to the pressure accumulating chamber below the head, the structure of the first burner can be simplified.

In the apparatus for producing fullerenes according to the second aspect of the present invention, the first burner has a header tube in which a large number of small-diameter jet nozzles are formed with a gap, and the header tube is premixed. The oxygen-containing gas and the fuel gas thus produced may be supplied. With such a configuration, the oxygen-containing gas and the fuel gas can be dispersed and released into the first reaction zone in a premixed state. In the apparatus for producing fullerenes according to the second aspect of the present invention, the first burner includes a first header tube in which a large number of small-diameter jet nozzles for jetting the oxygen-containing gas are formed with a gap, A plurality of small-diameter jet nozzles for jetting the fuel gas, which are arranged with a gap from the first header pipe and have a second header pipe formed with gaps between the first header pipe and the first header pipe; The second header pipe may be configured such that the oxygen-containing gas and the fuel gas are independently supplied by separate pipes. With such a configuration, the oxygen-containing gas that has been dispersed and released and the fuel gas are diffusively mixed and become a uniform mixed state.
It can be present in the reaction zone.

In the apparatus for producing fullerenes according to the second aspect of the invention, an oxygen-containing gas can be mixed with the raw material hydrocarbon supplied from the second burner. Since the thermal decomposition of the raw material hydrocarbon is an endothermic reaction, the temperature of the combustion gas decreases due to the thermal decomposition of the raw material hydrocarbon. Therefore, by mixing an oxygen-containing gas with the raw material hydrocarbon, a part of the raw material hydrocarbon is burned in the second reaction zone to generate heat energy, and the heat energy consumed when the raw material hydrocarbon is thermally decomposed is generated. It is possible to prevent the temperature of the combustion gas from decreasing due to the compensation.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Next, referring to the attached drawings, an embodiment in which the present invention is embodied will be described to provide an understanding of the present invention. 1 (A) and 1 (B) are explanatory views of a fullerene production apparatus to which the method for producing fullerenes according to the first embodiment of the present invention is applied, a plan sectional view, FIG. 2 (A), (B) is an explanatory view of a manufacturing apparatus for fullerenes according to the second embodiment of the present invention, a plan sectional view, and FIGS. 3 (A) and 3 (B) are respectively related to the third embodiment of the present invention. Explanatory drawing of the manufacturing apparatus for such fullerenes, a plane cross-sectional view, FIG. 4 is a partial explanatory view of the manufacturing apparatus for fullerenes according to a fourth embodiment of the present invention, and FIGS. Explanatory drawing of a manufacturing apparatus for fullerenes according to a fifth embodiment of the invention, a plan sectional view, and FIGS. 6A and 6B are respectively manufacturing apparatus for fullerenes according to a sixth embodiment of the present invention. FIG. 3 is an explanatory view and a plan sectional view.

A method for manufacturing fullerenes according to the first embodiment of the present invention will be described with reference to FIG. First
In the method for producing fullerenes according to the embodiment of the present invention, a raw material hydrocarbon is introduced into a fullerene production apparatus 3 configured by providing a first reaction zone 1 and a second reaction zone 2 in a reaction furnace 3a, The present invention relates to a method for producing fullerenes by burning.

The apparatus 3 for producing fullerenes comprises a first reaction zone 1 for forming a combustion gas stream, and a second reaction zone 2 for supplying a raw material hydrocarbon to the combustion gas stream formed therein and reacting it to produce fullerenes. Have. Second reaction zone 2
May be in substantially the same region as the first reaction zone 1 (outside or inside), and in the combustion gas flow direction formed in the first reaction zone 1 (hereinafter sometimes referred to as “axial direction”). It may be on the downstream side.

In FIG. 1, the second reaction zone 2 is the first reaction zone 1
It shows the case of being downstream. [Regarding the First Reaction Zone] In the first reaction zone 1, generally, the fuel and the oxygen-containing gas are supplied from the fuel supply port and the oxygen-containing gas supply port, respectively, and burned to generate a high-temperature combustion gas flow in the second reaction zone 2. That is, it is generated toward the downstream of the reaction furnace 3a.

The fuel and the oxygen-containing gas are supplied to the reactor 3
A so-called pre-mixing method of mixing before entering into a, or a so-called diffusion-mixing method of supplying to the reaction furnace 3a from independent nozzles may be used. In the case of the diffusion mixing method, in FIG. 1, for example, the fuel is supplied from the central fuel supply port 7 and the oxygen-containing gas is supplied from the oxygen-containing gas supply ports 5 and 6 around it. Further, the premixing method and the diffusion mixing method may be combined. For example, in FIG. 1, the oxygen-containing gas supply port 5 supplies a mixture of the fuel and the oxygen-containing gas in advance to supply the oxygen-containing gas supply port. The oxygen-containing gas may be supplied from 6 and the fuel may be supplied from the fuel supply port 7 independently.

The purpose of the first reaction zone 1 is to generate high-temperature combustion gas, and the combustion method is premixed combustion, diffusion combustion, laminar flow combustion, turbulent flow combustion, high temperature air combustion, etc.
Any known combustion method may be used. Further, if the temperature at which fullerene can be produced in the second reaction zone 2 is obtained, even if the combustion in the first reaction zone 1 is complete combustion,
Although it may be incomplete combustion, it is preferably complete combustion, which generates a large amount of heat relative to the amount of fuel used. When the first reaction zone 1 is a so-called excess fuel incomplete combustion, soot-like substances containing fullerenes may be produced also in the first reaction zone 1.

However, it is preferable that the combustion in the first reaction zone 1 be performed in a lean air-fuel mixture in which the oxygen required for combustion is at least a stoichiometric amount of oxygen. As the oxygen-containing gas, it is possible to use air, oxygen gas, or a gas in which an incombustible gas such as argon gas or nitrogen gas is mixed at an arbitrary ratio. In particular, pure oxygen may be used to suppress the generation of NO _X in high temperature combustion. In order to increase the yield of fullerene, it is preferable to dilute it with a rare gas or the like in the combustion process. The rare gas may be supplied from a dedicated nozzle for supply, or may be mixed in advance with the fuel, the raw material hydrocarbon, and the oxygen-containing gas.

As the fuel, hydrogen, carbon monoxide, fuel gas such as natural gas and petroleum gas, petroleum-based liquid fuel such as heavy oil, benzene and toluene, and coal-based liquid fuel such as creosote oil can be used. . Among them, fuel gas is preferable as the fuel used in the present embodiment. The average temperature in the first reaction zone 1 during the production of fullerenes may be appropriately adjusted depending on the desired fullerene to be obtained, but is preferably 1300 ° C. or higher, more preferably 16
It is set to 00 ° C or higher. This is because the higher the temperature of the combustion gas, the higher the productivity of fullerenes. If the upper limit is too high, the productivity of fullerenes may decrease. Further, it may be determined in consideration of the problem of heat resistance due to the material of the reaction furnace.

Fuel supply port 7, oxygen-containing gas supply ports 5, 6
Arrangement is arbitrary as long as it is open to the reaction furnace 3a. In FIG. 1, a fuel supply port 7, an oxygen-containing gas supply port 5,
6 is open to the same side of the reaction furnace 3a. Reactor 3a
The shape of each of the supply ports 5, 6, and 7 opened inside is arbitrary, and may be a polygonal shape such as a substantially circular shape, an elliptical shape, a triangular shape or a square shape, or an irregular shape such as a gourd shape.

The pressure in the reaction furnace 3a is preferably less than atmospheric pressure, more preferably in the range of 10 to 300 torr.
Is. [Regarding Second Reaction Zone] In the second reaction zone 2, the raw material hydrocarbons are supplied to the combustion gas stream formed in the first reaction zone 1 from the raw material hydrocarbon supply port 4, and the raw material hydrocarbons are partially burned. To produce fullerenes.
For partial combustion, the combustion in the first reaction zone 1 may be made to be oxygen excess so that oxygen remains. Further, a nozzle may be arranged in the second reaction region 2 to supply the oxygen-containing gas from the oxygen-containing gas supply nozzle.

At this time, it is preferable that the above-mentioned raw material hydrocarbon and oxygen-containing gas supplied into the combustion gas are supplied into the reaction furnace 3a as uniformly as possible. Therefore, the second reaction zone 2
The larger the number of the raw material hydrocarbon supply ports 4 and the number of oxygen-containing gas supply nozzles installed in the reactor, the better, and it is desirable that they are evenly arranged in the reactor 3a.

The length of the second reaction zone may be appropriately selected depending on the size of the reaction furnace 3a, the type of fullerene to be produced, and the like. The position and shape of the second reaction zone are arbitrary and may be inside or outside the first reaction zone, and as shown in FIG. Good. The shape of the second reaction zone is also arbitrary, but it is preferable that the sectional shape of the second reaction zone does not change. The reason is that when the influence of the turbulence of the flow due to the change in the cross-sectional shape of the second reaction zone in the process of forming fullerenes has an unfavorable influence on the fullerenes formed.

The average temperature of the second reaction zone 2 may be appropriately selected depending on the fullerene to be produced, but it is preferably a sufficiently high temperature atmosphere so that the raw material hydrocarbons are uniformly vaporized and reacted. Specifically, it is preferably 1000 ° C. or higher, and particularly 1000 to 1900 ° C., especially 1700
It is preferably ˜1900 ° C. Further, in the second reaction zone 2, it is preferable to suppress the oxygen concentration in the combustion gas as much as possible. When a large amount of oxygen is present in the combustion gas, the partial combustion of the raw material hydrocarbons in the reaction zone for producing fullerenes, that is, the second reaction zone 2, actively occurs, so that the temperature in the second reaction zone 2 is not uniform. This may occur. The oxygen concentration in the combustion gas is preferably 3 vol% or less, more preferably 0.05 to 1 vol.
%.

In the present embodiment, the position where the raw material hydrocarbon is supplied is arbitrary, and the raw material hydrocarbon supply port can be provided according to the shape of the reaction furnace. For example, the raw material hydrocarbon supply port may be provided in a portion where the diameter of the reaction furnace 3a is maximum, or the raw material hydrocarbon supply port may be provided in a reduced portion where the diameter is reduced. Further, as shown in FIG. 1, the raw material hydrocarbon supply port 4 may be provided in a portion where the diameter of the reaction furnace 3a is maximum and a reduction portion where the diameter is reduced. Depending on the position of the feedstock hydrocarbon supply port 4,
The flow velocity of gas at the position where the raw material hydrocarbon is introduced, the strength of turbulence, etc. can be controlled.

As the raw material hydrocarbon, any conventionally known one can be used, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene and anthracene, creosote oil, carboxylic acid oil and the like. Petroleum heavy oil such as coal-based hydrocarbon, ethylene heavy-end oil, FCC oil (fluid catalytic cracking residual oil), acetylene-based unsaturated hydrocarbon, ethylene-based hydrocarbon, saturated aliphatic hydrocarbon such as pentane and hexane, etc. These may be used alone or in combination at any ratio. Above all, it is preferable to use a purified aromatic hydrocarbon,
Aromatic hydrocarbons such as benzene and toluene are particularly preferable. The higher the purity of the raw material is, the more preferable the purity is, when the aromatic hydrocarbon is used, the closer the purity is to 100%.

A plurality of raw material hydrocarbon supply ports may be provided in the reaction furnace on the circumference of the cross section in the flow direction of the combustion gas. Further, a plurality of raw material hydrocarbon supply ports may be provided on the same circumference. The place to have may be provided in multiple stages in the flow direction of the combustion gas. In order to make the fullerene formation reaction time uniform and to obtain fullerenes with uniform physical properties, it is preferable to install as many raw material hydrocarbon supply ports as possible on the same circumference.

The type of nozzle used for the feedstock hydrocarbon feed port 4 can be selected as appropriate, but when a feedstock hydrocarbon in liquid form is used, in order to spray it more uniformly and finely, It is preferable that the initial droplet diameter of the raw material hydrocarbon immediately after being sprayed from the nozzle be as small as possible, such as a two-fluid nozzle that injects with another liquid. The opening diameter and shape of the raw material hydrocarbon supply port 4, the degree of protrusion into the furnace, the supply angle to the combustion gas flow, the raw material hydrocarbon supply method such as the gas-liquid ratio, the flow velocity, the flow rate, the temperature, etc. can be selected as appropriate. Good but
It is preferable that the raw material hydrocarbon sprayed in the second reaction zone 2 is sprayed under a condition such that it does not adhere to the furnace wall of the second reaction zone 2 before being evaporated. By spraying that way,
It is possible to reduce foreign substances in the obtained soot-like substance.

As the furnace material forming the first reaction zone 1 and the second reaction zone 2, any material can be used as long as it has heat resistance such as metal and refractory. When a metal is used, the temperature of the internal combustion gas becomes higher than the heat resistant temperature of the metal, so it is necessary to cool it from the outside by adopting a structure such as a water cooling jacket structure or a water cooling tube. Examples of materials other than metals include SiC, diamond,
Examples include aluminum nitride, silicon nitride, and ceramic-based refractory materials.

From the downstream side of the second reaction zone 2, the combustion gas stream containing the soot-like substances containing fullerenes (including those in the middle of the reaction) is cooled to 1000 ° C. or lower, preferably 800 ° C. or lower. . Specifically, water or the like may be sprayed from the reaction-stopping fluid supply port, or cooling may be performed by passing the water through a channel whose outside is cooled by a water cooling structure or the like. In particular, when the diameter of the flow path is small, it may be sufficiently cooled by natural heat dissipation to the atmosphere without a water cooling structure.

The cooled fullerenes and soot-like substances are
It is separated from the gas and collected by a collection bag filter or the like (not shown) provided at the end of the flow path. As a method for collecting fullerenes, a known general process such as adhering to the bag filter or the inner wall of the flow channel can be used.

As shown in FIG. 2, the apparatus 10 for producing fullerenes according to the second embodiment of the present invention comprises a reaction furnace 11
A first reaction zone 13 in which the oxygen-containing gas and the fuel gas supplied through the first burner 12 burn to form a high-temperature combustion gas stream; and a downstream side of the first reaction zone 13, A second reaction zone having a discharge port 15 of a second burner 14 for supplying a raw material hydrocarbon to a combustion gas stream, and reacting the gasified and supplied raw material hydrocarbon in a combustion gas stream to generate fullerenes. Have 16. Hereinafter, these will be described in detail. The reaction furnace 11 is provided with, for example, a cylindrical side wall portion 17 and an end wall 19 that is connected to one end of the side wall portion 17 and has an outer diameter that is gradually reduced to form a discharge port 18. . The side wall 17 and the end wall 19 are made of heat resistant steel such as stainless steel. Furthermore, the side wall 1
A refractory material (not shown) is lined on the inner peripheral surface on the other end side of 7. As the refractory, for example, an alumina refractory brick or an alumina amorphous refractory can be used. Further, one end of an exhaust pipe (not shown) is connected to the discharge port 18, and the other end of the exhaust pipe is connected to an exhaust pump. Therefore, the pressure inside the reaction furnace 11 can be reduced to less than atmospheric pressure, and the combustion gas containing the soot-like substances generated in the reaction furnace 11 can be discharged from the reaction furnace 11 to the outside.

The first burner 12 attached to the base plate 17a on the other end of the side wall portion 17 is provided with the oxygen-containing gas supply pipe 2
A plurality of oxygen-containing gas nozzles 21 connected to 0 and a fuel gas nozzle 23 connected to a fuel gas supply pipe 22;
These gas nozzles 21 and 23 are mixedly arranged on the base 17a. The oxygen-containing gas nozzle 21 and the fuel gas nozzle 23 are made of heat resistant steel such as stainless steel. Therefore, the oxygen-containing gas supplied from the oxygen-containing gas nozzle 21 and the fuel gas supplied from the fuel gas nozzle 23 are diffused and mixed after being released into a uniform mixed state in the first reaction zone 13. To burn. The formed high temperature combustion gas flow then flows into the second reaction zone 16 on the downstream side. The second burner 14 attached to the other end of the side wall portion 17 is formed of a large number of small-diameter discharge pipes 24 (for example, heat-resistant steel such as stainless steel) arranged so as to penetrate the first reaction zone 13. ). As a result, the discharge port 15 provided on the tip side of the small diameter discharge pipe 24.
Are arranged on the upstream side of the second reaction zone 16 with a gap. The base end side of each small diameter discharge pipe 24 is connected to the raw material hydrocarbon supply pipe 25. Therefore, the raw material hydrocarbons can be uniformly supplied directly into the high temperature combustion gas stream flowing from the first reaction zone 13, and the raw material hydrocarbons can be thermally decomposed uniformly in a short time.

Next, a method for producing fullerenes using the apparatus 10 for producing fullerenes according to the second embodiment of the present invention will be described in detail. Oxygen-containing gas nozzle 2
The oxygen-containing gas is supplied from No. 1 and the fuel gas is supplied from the fuel gas nozzle 23, and these are combusted to form a high-temperature combustion gas flow, which is made to flow toward the downstream of the reaction furnace 11.
The oxygen-containing gas is a gas obtained by mixing an oxygen gas, which is an oxygen source, with an inert gas such as argon gas at an arbitrary ratio (for example, the concentration of the inert gas is 0, or more than 0 and within a range of 90 mol% or less. Can be adjusted in).
As the oxygen source, oxygen gas is preferable from the viewpoint of fullerene yield, and air is preferable from the viewpoint of availability of the oxygen source. In particular, in order to raise the combustion temperature, it is preferable to preheat these oxygen-containing gases before they are supplied into the reaction furnace 11. As a preheating method, any known method such as heat exchange with combustion gas using a heat exchanger, a so-called regeneration burner, or the like may be used. The temperature of this preheating may be any temperature as long as it is room temperature or higher, but it is preferably as high as possible in order to increase the yield of fullerene. More preferably, it is higher than the self-ignition temperature of the combustion gas.

As the fuel gas, carbon monoxide, natural gas, fuel gas such as petroleum gas, gasified petroleum liquid fuel such as heavy oil, gasified coal-based liquid fuel such as creosote oil, etc. Can be used. Among them, fuel gas such as natural gas and petroleum gas is preferable. Further, in order to increase the yield of fullerene, it is preferable that the fuel gas is also diluted with an inert gas or the like.

Next, the combustion gas flow formed by burning the fuel gas under the oxygen-containing gas will be described. The amount of fuel gas supplied from the fuel gas nozzle 23 and the amount of oxygen gas supplied from the oxygen-containing gas nozzle 21 were adjusted and supplied to the first reaction zone 13 under the condition that the fuel gas was completely combusted, and connected to the exhaust port 18. The inside of the reaction furnace 11 is maintained at a pressure lower than atmospheric pressure, more preferably 10 to 300 torr through an exhaust pipe (not shown), and combustion of fuel gas is started by an ignition means (not shown). Here, the fuel gas and the oxygen-containing gas are discharged into the first reaction zone 13 from the oxygen-containing gas nozzle 21 and the fuel gas nozzle 23, which are independent of each other and are dispersed at a distance.
The combustion state in can be made uniform. In addition to the fact that the oxygen gas concentration in the oxygen-containing gas is reduced by being diluted with an inert gas such as argon gas, and the pressure inside the reaction furnace 11 is less than atmospheric pressure, the first reaction The combustion state in the zone 13 can be made similar to the high temperature air combustion state. As a result, the combustion of the fuel gas proceeds uniformly, so that the temperature of the first reaction zone 13 is uniform and high (for example, 1000 to 1900 ° C., preferably 170).
0-1900 ° C.).

In the second reaction zone 16, the first reaction zone 13
The temperature of the upstream side of the second reaction zone 16 is, for example, 1000 to 190 because the high temperature combustion gas formed in 1 flows in.
It reaches a high temperature of 0 ° C. The raw material hydrocarbon is the first reaction zone 13
Is discharged from each of the discharge ports 15 of a large number of small-diameter discharge pipes 24, which are dispersed into the combustion gas flow upstream of the second reaction zone 16. Here, since the small-diameter discharge pipe 24 is arranged so as to penetrate the first reaction zone 13, the raw material hydrocarbons are preheated while passing through the small-diameter discharge pipe 24, so that the high-temperature combustion gas is discharged from the discharge port 15. Pyrolyzes immediately upon release into the stream. As a result, thermal decomposition products having high reaction activity are present in the combustion gas, and these are combined to form a fullerene precursor. Then, the fullerene precursor grows into a fullerene while moving with the combustion gas flow. Since the thermal decomposition of the raw material hydrocarbon is an endothermic reaction, heat energy is taken from the combustion gas and the temperature of the combustion gas is lowered. Therefore, the source hydrocarbon may be mixed with an oxygen-containing gas, and a part of the source carbon hydrogen may be burned to supply heat energy. However, when the partial combustion of the raw material carbon hydrogen actively occurs, the temperature in the second reaction zone 16 becomes non-uniform and the production efficiency of fullerenes decreases, so the oxygen concentration in the combustion gas is preferably 3 vol%. Hereafter, it is more preferably 0.05 to 1 vol%.

As the raw material carbon hydrogen, any conventionally known one can be used, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene and anthracene, creosote oil, carboxylic acid oil and the like. Petroleum heavy oil such as coal-based hydrocarbon, ethylene heavy-end oil, FCC oil (fluid catalytic cracking residual oil), acetylene-based unsaturated hydrocarbon, ethylene-based hydrocarbon, saturated aliphatic hydrocarbon such as pentane and hexane, etc. These may be used alone or in combination at any ratio. Above all, it is preferable to use a purified aromatic hydrocarbon,
Aromatic hydrocarbons such as benzene and toluene are particularly preferable. It is preferable that the purity of the raw material carbon hydrogen, which is the main raw material, is higher, and that the purity is 1 when the aromatic hydrocarbon is used.
The closer to 00%, the better.

As shown in FIG. 3, in the apparatus 26 for producing fullerenes according to the third embodiment of the present invention, the oxygen-containing gas and the fuel gas are premixed and supplied to the first burner 27. Is a feature. Therefore, the first with a different structure
The burner 27 will be described, and the same components as those of the fullerene manufacturing facility 10 according to the second embodiment will be denoted by the same reference numerals and detailed description thereof will be omitted. The first burner 27 is made of, for example, a heat-resistant metal, and has a head 28 whose one surface is exposed in the first reaction zone 13 of the reaction furnace 11, and a pressure accumulating chamber 29 provided below the head 28. ing. Then, the small-diameter discharge pipes 24 of the second burner 14 are opened from the lower side of the pressure accumulating chamber 29 through the pressure accumulating chamber 29 and the head 28 and project into the reaction furnace 11 with a predetermined gap therebetween.

Here, the head 28 is composed of, for example, a porous member made of sintered metal. The porous member has a structure having a large number of communication holes communicating from one surface side to the other surface side, and a mixed gas obtained by premixing an oxygen-containing gas and a fuel gas in a pressure accumulating chamber 29 provided at a lower portion of the head 28. When the mixed gas is supplied from the mixed gas supply pipe 30, the mixed gas is supplied to the head 28.
It is possible to move from the surface on the side of the pressure accumulating chamber 29 to the surface exposed on the side of the first reaction zone 13 through the communication hole in the inside, and to jet it into the first reaction zone 13. Therefore, by burning the mixed gas ejected into the first reaction zone 13, high temperature combustion gas can be formed in the first reaction zone 13. Then, the raw material hydrocarbons supplied through the raw material hydrocarbon supply pipe 25 are supplied from the discharge ports 15 of the small-diameter discharge pipes 24 into the high temperature combustion gas flow flowing from the first reaction zone 13.
The raw material hydrocarbon can be uniformly thermally decomposed in a short time. The fullerene production method using the fullerene production facility 26 according to the third embodiment of the present invention is the fullerene production apparatus 1 according to the second embodiment.
Since it is substantially the same as the method for producing fullerenes using 0, detailed description thereof is omitted.

In the fullerene manufacturing apparatus 31 according to the fourth embodiment of the present invention, the oxygen-containing gas and the fuel gas are independently supplied to the first burner 32 through separate pipes, so
Fullerene manufacturing apparatus 26 and first according to the embodiment of
The burner 32 has a different structure. Therefore, only the first burner 32 having a different structure will be described, the same components as those of the fullerene manufacturing facility 10 according to the second embodiment will be denoted by the same reference numerals, and detailed description thereof will be omitted. That is, as shown in FIG.
The first burner 32 is made of a heat-resistant metal, and has a head 33 made of a sintered metal porous member having a communication hole,
Accumulation chamber 34 provided under the head 33, and the accumulation chamber 3
4 has a plurality of gas mixers 35 each having a jet port. Then, each small diameter discharge pipe 24 of the second burner 14
Extend through the pressure accumulating chamber 34 and the head 33 from below the pressure accumulating chamber 34 with a predetermined gap therebetween and project into the reaction furnace 11. As the gas mixer 35, an aspirator-type mixer that sucks and mixes the oxygen-containing gas with the flow of the fuel gas can be used.

With this structure, when the oxygen-containing gas and the fuel gas are independently supplied to the gas mixers 35 through the oxygen-containing gas supply pipe 36 and the fuel gas supply pipe 37, respectively, the oxygen-containing gas and the fuel gas are supplied. While being mixed, the accumulator 34 is mixed as a mixed gas from the ejection port of the gas mixer 35.
Flows in. Then, the mixed gas flowing into the pressure accumulating chamber 34 moves from the surface on the pressure accumulating chamber 34 side to the surface exposed on the first reaction zone 13 side through the communication hole in the head 33, and is ejected into the first reaction zone 13. can do. Therefore, by burning the mixed gas ejected into the first reaction zone 13, a high temperature combustion gas flow can be formed in the first reaction zone 13. Then, the raw material hydrocarbons supplied through the raw material hydrocarbon supply pipe 25 into the high temperature combustion gas flow flowing in from the first reaction zone 13 are discharged through the discharge ports 1 of the small diameter discharge pipes 24.
5, the raw material hydrocarbons can be uniformly pyrolyzed in a short time.

The fullerene manufacturing method using the fullerene manufacturing facility 31 according to the fourth embodiment of the present invention is the same as the fullerene manufacturing apparatus 26 according to the third embodiment. Since it is substantially the same as the manufacturing method of the class, detailed description thereof will be omitted.

As shown in FIG. 5, the apparatus for producing fullerenes 38 according to the fifth embodiment of the present invention is provided with a side wall 17
Having a header pipe 40 attached to the base plate 17a on the other end side and having a large number of small-diameter jet nozzles 39 for jetting a mixed gas in which an oxygen-containing gas and a fuel gas are premixed are formed with a gap therebetween. It is characterized in that it is supplied to the burner 41 of. Therefore, the first burner 4 having a different structure
1 will be described, and the same components as those of the fullerene manufacturing facility 10 according to the second embodiment will be denoted by the same reference numerals and detailed description thereof will be omitted.

The header pipe 40 has a plurality of annular pipes 40a arranged concentrically with the axis of the reaction furnace 11 with a gap therebetween, and each annular pipe 40a is connected to the mixed gas supply pipe 30a. ing. The small-diameter discharge pipes 24 of the second burner 14 are arranged so as to pass through the first reaction zone 13 through the gaps between the annular pipes 40a. Therefore, when the mixed gas in which the oxygen-containing gas and the fuel gas are premixed is supplied to each annular pipe 40a through the mixed gas supply pipe 30a,
The mixed gas is ejected from each jet nozzle 39 of each annular pipe 40a.
Is jetted out into the first reaction zone 13. Therefore, by burning the mixed gas ejected in the first reaction zone 13, a high temperature combustion gas flow can be formed in the first reaction zone 13. Then, the raw material hydrocarbons supplied through the raw material hydrocarbon supply pipe 25 into the high temperature combustion gas flow flowing in from the first reaction zone 13 are discharged through the discharge ports 1 of the small diameter discharge pipes 24.
5, the raw material hydrocarbons can be uniformly pyrolyzed in a short time. The fullerene manufacturing method using the fullerene manufacturing apparatus 38 according to the fifth embodiment of the present invention is the same as the fullerene manufacturing apparatus 10 according to the second embodiment. Since the method is substantially the same, detailed description is omitted.

The fullerene producing apparatus 42 according to the sixth embodiment of the present invention is different from the fullerene producing apparatus 10 according to the second embodiment of the present invention in that of the first burner 43. The feature is that the structure is different. Therefore, only the first burner 43 having a different structure will be described, the same components as those of the fullerene manufacturing apparatus 10 according to the second embodiment will be denoted by the same reference numerals, and detailed description thereof will be omitted. That is, as shown in FIG.
The first burner 43 attached to the base plate 17a on the other end side of 7 is made of a heat-resistant metal, and a large number of small-diameter jet nozzles 44 for jetting an oxygen-containing gas are formed in the first header. The pipe 45 and the first header pipe 45 have a second header pipe 47 which is arranged with a gap and in which a large number of small-diameter jet nozzles 46 for jetting the fuel gas are formed with a gap. Further, the first header pipe 45 and the second header pipe 47 individually supply the oxygen-containing gas and the fuel gas to the oxygen-containing gas supply pipe 20,
The fuel gas supply pipe 22 is connected. Further, each small-diameter discharge pipe 24 of the second burner 14 passes through the gap between the first header pipe 45 and the second header pipe 47, and then the base 17a.
And penetrates into the reactor 11.

With this structure, the oxygen-containing gas can be supplied to the first header 45 through the oxygen-containing gas supply pipe 20 and ejected from the ejection nozzle 44 into the reaction furnace 11. Further, the fuel gas can be supplied to the second header 47 via the fuel gas supply pipe 22 and ejected from the ejection nozzle 46 into the reaction furnace 11. The oxygen-containing gas and the fuel gas ejected from the ejection nozzles 44 and 46 are diffused and mixed after being released, and become a uniform mixed state and burned in the first reaction zone 13. Then, the formed high temperature combustion gas flows into the second reaction zone 16 on the downstream side. Then, the raw material hydrocarbons supplied through the raw material hydrocarbon supply pipe 25 are supplied from the discharge ports 15 of the small-diameter discharge pipes 24 into the high temperature combustion gas flow flowing in from the first reaction zone 13, and the raw material hydrocarbons are supplied. Can be thermally decomposed uniformly in a short time. The fullerene manufacturing method using the fullerene manufacturing apparatus 42 according to the sixth embodiment of the present invention is the same as the fullerene manufacturing apparatus 10 according to the second embodiment. Since the method is substantially the same, detailed description is omitted.

The embodiment of the present invention has been described above.
The present invention is not limited to this embodiment,
Modifications are possible without changing the gist of the invention, and the present invention is also applicable to the case where the fullerene manufacturing method and the apparatus thereof of the present invention are configured by combining some or all of the above-described respective embodiments and modifications. This is the scope of invention rights. For example, in the fifth embodiment, the header pipe 40 is composed of a plurality of annular pipes 40a arranged concentrically with respect to the axis of the reaction furnace 11. However, a plurality of straight pipes are provided in a grid pattern with gaps. You may line up. Further, in the sixth embodiment, a plurality of first header pipes 45 and second header pipes 47 are arranged concentrically with respect to the axis of the reactor 11 with a gap therebetween. The two header tubes may be arranged in a grid pattern with gaps. Furthermore, the small-diameter discharge pipe 24 of the second burner 14 is made of heat-resistant steel such as stainless steel, and the porous member is made of heat-resistant sintered metal in the third and fourth embodiments. It can also be made of ceramics.

[0059]

According to the method for producing fullerenes according to claims 1 to 3, the oxygen-containing gas and the fuel are supplied into the reaction furnace and burned to form a high temperature combustion gas stream.
Characterized by having a reaction zone, a raw material hydrocarbon supply port for supplying a gasified raw material hydrocarbon in the middle of the combustion gas flow, and a second reaction zone for reacting the raw material hydrocarbon to produce fullerenes Since the apparatus for producing fullerenes is used and the pressure in the second reaction zone is less than atmospheric pressure, the thermal decomposition of the raw material hydrocarbons proceeds uniformly and the production efficiency of fullerenes can be improved. Fullerenes can be easily produced in large quantities at low cost.

On the other hand, in the above-described method for producing fullerenes by the known combustion method, the fuel for the combustion reaction and the raw material for producing the fullerene are usually the same, which is necessary for the hydrocarbon fuel combustion reaction. Fuel cannot be selected arbitrarily. On the other hand, according to the present invention, the fuel for the combustion reaction and the raw material for the production of fullerenes can be selected separately. Thus, it is possible to freely select a raw fuel with a low cost.

Particularly, in the method for producing fullerenes according to claim 2, since the second reaction zone is on the downstream side of the first reaction zone, the conditions of the second reaction zone should be kept constant over the entire cross section of the furnace. By adjusting the conditions in this zone to the conditions that maximize the yield of fullerenes, the region where fullerenes are generated can be expanded to the maximum, so fullerenes can be obtained compared to ordinary combustion methods. Higher yield of class. On the other hand, in the conventional combustion method, fullerenes are mainly generated in the flame, but it is generally known that the flame has a temperature distribution and the fullerenes are generated in a specific region of the flame. .

In the method for producing fullerenes according to claim 3, since the temperature of the second reaction zone is 1000 ° C. or higher, the supplied raw material hydrocarbon can be reliably pyrolyzed in a short time, and the fullerene Large quantities can be produced.

In the apparatus for producing fullerenes according to claims 4 to 13, the oxygen-containing gas and the fuel gas are supplied into the reaction furnace through the first burner, and these are burned to generate a high-temperature combustion gas. A first reaction zone for forming a stream, and a first reaction zone
It has a discharge port of a second burner located downstream of the reaction zone for supplying the raw material hydrocarbon to the combustion gas stream, and reacts the gasified and supplied raw material hydrocarbon in the combustion gas stream to produce fullerenes. Since it has the second reaction zone for producing, it becomes easy to control the combustion state of the fuel and the thermal decomposition of the raw material hydrocarbon, and it is possible to easily produce a large amount of fullerenes at a low cost. Becomes

Particularly, in the apparatus for producing fullerenes according to claim 5, a large number of discharge ports of the second burner are formed with a gap on the upstream side of the second reaction zone, and the raw material hydrocarbons are burned with combustion gas. Since it is dispersed and released into the flow, it is possible to uniformly pyrolyze the raw material hydrocarbon in the combustion gas in a short time, and it is possible to increase the yield of fullerenes generated from the pyrolyzed product of the raw material hydrocarbon. Become.

In the apparatus for producing fullerenes according to the sixth aspect, the second burner is composed of a large number of small-diameter discharge pipes arranged so as to penetrate the first reaction zone.
To increase the yield of fullerenes produced from the pyrolysis products of the raw hydrocarbons by uniformly disperse and release the preheated raw hydrocarbons into the high temperature combustion gas stream in the reaction zone. Is possible.

In the fullerene producing apparatus according to the seventh aspect, the first burner has a plurality of oxygen-containing gas nozzles and fuel gas nozzles that emit the oxygen-containing gas and the fuel gas independently and are mixedly arranged. The supplied oxygen-containing gas and fuel gas can be diffusively mixed to be present in the first reaction zone in a uniform mixed state, and the fuel gas can be easily completely burned in the first reaction zone. As a result, a high-temperature combustion gas stream can be formed, and the yield of fullerenes generated from the thermal decomposition product of the raw material hydrocarbon can be increased.

In the apparatus for producing fullerenes according to claim 8, since the head of the first burner is made of a porous member and is jetted from the surface in a state where the oxygen-containing gas and the fuel gas are mixed, The contained gas and the fuel gas can be supplied to the first reaction zone in a premixed state, and the fuel gas can be easily completely burned in the first reaction zone. As a result, a high-temperature combustion gas stream can be formed, and the yield of fullerenes generated from the thermal decomposition product of the raw material hydrocarbon can be increased.

In the apparatus for producing fullerenes according to claim 9, the oxygen-containing gas and the fuel gas are mixed in the first burner, and the oxygen-containing gas and the fuel gas are separately separated in the first burner. Since it is supplied through a pipe, it is not necessary to provide a premixing means for the oxygen-containing gas and the fuel gas, and the structure of the fullerene production apparatus can be simplified.

In the fullerene producing apparatus according to the tenth aspect of the present invention, the oxygen-containing gas and the fuel gas are premixed and supplied to the pressure accumulating chamber provided in the lower portion of the head. Can be simplified and the cost of the first burner can be reduced.

In the apparatus for producing fullerenes according to claim 11, the first burner has a header tube in which a large number of small-diameter jet nozzles are formed at intervals, and the header tube has premixed oxygen. Since the contained gas and the fuel gas are supplied, the oxygen-containing gas and the fuel gas can be pre-mixed and dispersedly released into the first reaction zone, and the fuel gas can be easily completely burned in the first reaction zone. It becomes possible. As a result, a high-temperature combustion gas stream can be formed, and the yield of fullerenes generated from the thermal decomposition product of the raw material hydrocarbon can be increased.

In the fullerene producing apparatus according to the twelfth aspect of the present invention, the first burner includes a first header tube in which a large number of small-diameter jet nozzles for jetting an oxygen-containing gas are formed with gaps, and The first header pipe and the second header have a second header pipe in which a large number of small-diameter jet nozzles for jetting fuel gas are formed with a gap between the first header pipe and the first header pipe. Since the oxygen-containing gas and the fuel gas are independently supplied to the pipe by separate pipes, the oxygen-containing gas and the fuel gas that have been dispersed and released are diffusively mixed and become a uniform mixed state, so that the first reaction zone It can be present, and the fuel gas can be easily completely burned in the first reaction zone. As a result, a high-temperature combustion gas stream can be formed, and the yield of fullerenes generated from the thermal decomposition product of the raw material hydrocarbon can be increased.

In the apparatus for producing fullerenes according to the thirteenth aspect, since the oxygen-containing gas is mixed with the raw material hydrocarbon supplied from the second burner, the thermal energy consumed when the raw material hydrocarbon is thermally decomposed. It is possible to prevent the temperature of the combustion gas from being lowered due to the supplementation, and it is possible to increase the yield of fullerenes generated from the thermal decomposition product of the raw material hydrocarbon.

[Brief description of drawings]

1A and 1B are an explanatory view and a plan sectional view of a fullerene manufacturing apparatus to which a method for manufacturing fullerenes according to a first embodiment of the present invention is applied, respectively.

2 (A) and 2 (B) are respectively an explanatory view and a plan sectional view of a fullerene manufacturing apparatus according to a second embodiment of the present invention.

3 (A) and 3 (B) are respectively an explanatory view and a plan sectional view of a fullerene manufacturing apparatus according to a third embodiment of the present invention.

FIG. 4 is a partial explanatory view of an apparatus for producing fullerenes according to a fourth embodiment of the present invention.

5 (A) and 5 (B) are respectively an explanatory view and a plan sectional view of a fullerene manufacturing apparatus according to a fifth embodiment of the present invention.

6 (A) and 6 (B) are respectively an explanatory view and a plan sectional view of a fullerene manufacturing apparatus according to a sixth embodiment of the present invention.

[Explanation of symbols]

1: 1st reaction zone, 2: 2nd reaction zone, 3: Fullerene production apparatus, 3a: Reactor, 4: Raw material hydrocarbon supply port, 5, 6: Oxygen-containing gas supply port, 7: Fuel supply port 1
0: Fullerene production apparatus, 11: Reactor, 12: First burner, 13: First reaction zone, 14: Second burner, 15: Discharge port, 16: Second reaction zone, 17: Side wall part , 17a: base, 18: outlet, 19: end wall, 2
0: oxygen-containing gas supply pipe, 21: oxygen-containing gas nozzle, 22: fuel gas supply pipe, 23: fuel gas nozzle,
24: small diameter discharge pipe, 25: raw material hydrocarbon supply pipe, 2
6: fullerene production apparatus, 27: first burner,
28: head, 29: accumulator, 30, 30a: mixed gas supply pipe, 31: fullerene production apparatus, 32: first
Burner, 33: head, 34: accumulator, 35: gas mixer, 36: oxygen-containing gas supply pipe, 37: fuel gas supply pipe, 38: fullerene production device, 39: jet nozzle, 40: header pipe , 40a: annular tube, 41: first burner, 42: fullerene production apparatus, 43:
1st burner, 44: ejection nozzle, 45: 1st header pipe, 46: ejection nozzle, 47: 2nd header pipe

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shoji Kazuki             5-5-602 Shimizu-cho, Nishinomiya-shi, Hyogo Prefecture F-term (reference) 4G146 AA07 BA12 BC03 BC07 BC08                       BC27 BC34A BC34B BC35A                       BC35B BC36A BC38A BC38B                       DA03 DA23 DA25 DA35

Claims (13)

[Claims] 1. A first reaction zone in which an oxygen-containing gas and a fuel are supplied and burned in a reaction furnace to form a high temperature combustion gas stream, and a raw material hydrocarbon is supplied in the middle of this combustion gas stream. A fullerene production apparatus characterized by having a raw material hydrocarbon supply port and having a second reaction zone for reacting the raw material hydrocarbon to produce fullerenes,
A method for producing fullerenes, characterized in that the pressure in the second reaction zone is less than atmospheric pressure. 2. The method for producing fullerenes according to claim 1, wherein the second reaction zone is on the downstream side of the first reaction zone. 3. The method for producing fullerenes according to claim 1, wherein the temperature of the second reaction zone is 1000 ° C. or higher. 4. A first reaction zone in which an oxygen-containing gas and a fuel gas are supplied into a reaction furnace through a first burner and burned to form a high temperature combustion gas flow, and the first reaction zone.
A discharge port of a second burner is provided downstream of the reaction zone for supplying the raw material hydrocarbon to the combustion gas stream, and the raw material hydrocarbon gasified and supplied is reacted in the combustion gas stream. An apparatus for producing fullerenes, comprising a second reaction zone for producing fullerenes by heating. 5. The fullerene producing apparatus according to claim 4, wherein a large number of discharge ports of the second burner are formed upstream of the second reaction zone with a gap, and An apparatus for producing fullerenes, characterized in that they are dispersed and released into the combustion gas flow. 6. The apparatus for producing fullerenes according to claim 5, wherein the second burner comprises a large number of small-diameter discharge pipes arranged so as to penetrate the first reaction zone. Fullerene manufacturing equipment. 7. The fullerene production apparatus according to claim 4, wherein the first burner independently discharges the oxygen-containing gas and the fuel gas. An apparatus for producing fullerenes, characterized in that a containing gas nozzle and a fuel gas nozzle are arranged in a mixed manner. 8. The apparatus for producing fullerenes according to claim 4, wherein the head of the first burner is made of a porous member, and the oxygen-containing gas and the fuel gas are introduced from the surface. An apparatus for producing fullerenes, which is characterized by being jetted in a mixed state. 9. The apparatus for producing fullerenes according to claim 8, wherein the oxygen-containing gas and the fuel gas are mixed in the first burner, and the oxygen-containing gas is added to the first burner. An apparatus for producing fullerenes, wherein the fuel gas is independently supplied through a separate pipe. 10. The apparatus for producing fullerenes according to claim 8, wherein the oxygen-containing gas and the fuel gas are premixed and supplied to a pressure accumulating chamber provided under the head. Fullerene manufacturing equipment. 11. The fullerene producing apparatus according to claim 4, wherein the first burner has a header tube in which a large number of small-diameter jet nozzles are formed with gaps. An apparatus for producing fullerenes, wherein the header tube is supplied with the oxygen-containing gas and the fuel gas that have been premixed. 12. The fullerene producing apparatus according to claim 4, wherein the first burner has a large number of small-diameter jet nozzles for jetting the oxygen-containing gas with gaps therebetween. A formed first header pipe and a second header pipe in which a large number of small-diameter jet nozzles for jetting the fuel gas are arranged with a gap between the first header pipe and the first header pipe. An apparatus for manufacturing fullerenes, characterized in that the oxygen-containing gas and the fuel gas are independently supplied to the first header pipe and the second header pipe by separate pipes. 13. The fullerene producing apparatus according to any one of claims 4 to 12, wherein the raw hydrocarbon supplied from the second burner is mixed with an oxygen-containing gas. Manufacturing equipment.