WO2002070406A1

WO2002070406A1 - Device and method for manufacture of carbonaceous material

Info

Publication number: WO2002070406A1
Application number: PCT/JP2002/001648
Authority: WO
Inventors: Hisashi Kajiura; Mitsuaki Miyakoshi; Shigemitsu Tsutsui; Yoshiyuki Hirano
Original assignee: Sony Corporation
Priority date: 2001-03-01
Filing date: 2002-02-25
Publication date: 2002-09-12
Also published as: JP4724929B2; JP2002255521A

Abstract

A device and a method for manufacture of a carbonaceous material; the device, comprising a reaction tube and a gas feed part, the reaction tube further comprising an anode and a cathode for defining an arc discharge part installed therein, wherein the anode and the cathode are pure carbon electrodes formed of carbon only and the gas feed part is so formed that can selectively feed organic gas and catalyst gas into the reaction tube; the method, comprising the steps of forming a carbon lump in the forms of the anode and the cathode, producing an arc discharge at the arc discharge part in the reaction tube, feeding the mixed gas of the organic gas and the catalyst gas to the arc discharge part to produce the carbonaceous material, using the organic gas as the material, at the arc discharge part by a catalyst action, whereby, when the carbonaceous material such as a monolayer carbon nanotube is produced by arc discharge, a labor and a cost for manufacture of the anode can be reduced remarkably.

Description

Method and apparatus for producing carbonaceous material

The present invention relates to a method and an apparatus for producing a carbonaceous material, and more particularly to a method and an apparatus for producing a carbonaceous material for producing a carbonaceous material such as a single-walled carbon nanotube using arc discharge.

Thread

Background art

Carbon nanotubes are a new material first reported by Iijima in 1991 in S. Iijima, Nature, Vol. 354 (1991) 56. In particular, single-walled carbon nanotubes (SWNTs) have been theoretically found to have electronic properties that change from metallic to semiconducting properties due to the spiraling of the so-called chiraity. It is promising as a next-generation electronic material, and is considered to be applied to nanoelectronics materials, field emission emitters, highly directional radiation sources, soft X-ray sources, one-dimensional conductive materials, high thermal conductive materials, hydrogen storage materials, etc. It has been. In addition, functionalization of the surface, metal coating, and inclusion of foreign substances are expected to further expand the application range of carbon nanotubes.

As an apparatus for producing carbonaceous materials such as single-walled carbon nanotubes, an apparatus as shown in FIG. 1 has been conventionally known. This device is provided with a power source 114 and an anode 113, and by generating an arc discharge between the anode 113 and the cathode 114, the carbonaceous material is generated. The production of the material takes place.

Specifically, a reaction tube 1 11 is provided in the carbonaceous material production apparatus 101. An anode 113 and a force sword 114 are arranged inside the reaction tube 111 with a slight gap therebetween. The anode 113 is electrically connected to the current introduction terminal 1442 on the positive electrode side, and the power source 114 is electrically connected to the current introduction terminal 141 on the negative electrode side. These two current introduction terminals 14 1 and 14 2 are electrically connected to a current supply unit (not shown) provided outside the reaction tube 11 1, and It is configured so that a voltage can be applied to the force sword 114. An arc discharge part is defined between the tips of the anodes 113 and the force sword 114 facing each other. The arc discharge section is located substantially at the center of the reaction tube 111 in the axial direction.

The anode 113 is constituted by a carbon containing a catalyst. The catalyst is, specifically, Fe, Ni, or the like, and is used when producing a carbonaceous material such as a single-walled carbon nanotube by generating an arc discharge. The force sword 114 consists of a pure carbon rod containing no catalyst. The anode 113 is consumed because it is used as a raw material when producing a carbonaceous material such as single-walled carbon nanotubes in the arc discharge part. In order to prevent the gap between anode 113 and force sword 114 from expanding due to this wear and prevent arc discharge from occurring, the gap between cathode 114 and anode 113 is prevented. Is designed to be kept constant at all times. That is, the other end opposite to one end of the anode 113 facing the force sword 114 is a linear motion introducing mechanism 111 that enables the anode 113 to move in the longitudinal direction of the anode 113. Supported by 6.

A through-hole (not shown) is formed in the reaction tube 111, and an inert gas injector (not shown) is connected to the through-hole (not shown). The inside of the reaction tube 111 can be filled with an inert gas such as He or Ar by an inert gas injector (not shown). The through holes (not shown) are configured to be openable and closable. After the inert gas is supplied into the reaction tube 111, it is closed during arc discharge.

The anode 1 13 is made by pulverizing carbon powder into powder, mixing powdered carbon with powder of catalytic metal such as Fe, Ni, etc., forming it into a rod shape, and then firing and processing. Manufactured by The force sword 114 is manufactured by forming a force-bon lump as it is into a rod shape. Next, the anode 113 and the force sword 114 are set inside the carbonaceous material manufacturing apparatus 101, and the inside of the reaction tube 111 is evacuated once. Thereafter, the inside of the reaction tube 111 is filled with an inert gas by an inert gas injector (not shown), a through hole (not shown) is closed, and the inside of the reaction tube 111 is isolated from the atmosphere. Then, arc discharge is performed. Carbonaceous materials such as single-walled carbon nanotubes are produced from the carbon constituting the anode 113 by the catalytic action of the catalytic metal.

However, in the conventional method and apparatus 101 for producing a carbonaceous material, as described above, a great deal of labor and cost were required to produce the anode 113 containing the catalytic metal. That is, when the anode 113 is composed of a carbon rod, as described above, first, carbon is pulverized into a powder, and a powder obtained by mixing a powder of a catalyst metal with a powdered carbon is used as the anode. It had to be formed into a shape, then fired and processed. For this reason, there is a serious problem that hinders efficient production and cost reduction of the carbonaceous material production apparatus 101, and as a result, the efficient production of carbonaceous materials such as single-walled carbon nanotubes Production and cost reduction were hindered.

Therefore, an object of the present invention is to provide a method and an apparatus for producing a carbonaceous material that can produce a carbonaceous material at low cost. Disclosure of the invention

In order to achieve the above object, the present invention defines a carbonaceous material production chamber. An anode made of a carbon-based material and a force source made of a carbon-based material facing the anode and defining an arc discharge part are arranged in the reaction tube, and the anode and the cathode are arranged. A method of producing a carbonaceous material in which arc is discharged by supplying a voltage between the electrodes and a carbonaceous material is generated in the arc discharge portion, wherein a catalyst is contained toward the arc discharge portion during the arc discharge. A method for producing a carbonaceous material for supplying gas is provided.

Here, the gas containing the catalyst is preferably a mixed gas of an organic gas and a catalyst gas.

Further, the gas containing the catalyst is preferably a mixed gas of an inert gas and a catalyst gas.

Further, the gas containing the catalyst is preferably a mixed gas of an inert gas, an organic gas, and a catalyst gas.

The anode is preferably made of a carbon-based material that does not contain a catalyst.

Further, it is preferable that the gas containing the catalyst in the reaction tube is flowed in a predetermined direction.

The present invention further provides a reaction tube defining a carbonaceous material generation chamber, an anode disposed in the reaction tube and made of a carbon-based material, and provided in the reaction tube to face the anode. A power source made of a carbon-based material defining an arc discharge portion between the anode and the anode; and an anode and the cathode for generating an arc discharge between the anode and the power source. In the apparatus for producing a carbonaceous material having a connected current supply section, a catalyst-containing gas supply section for supplying a gas containing a catalyst toward the arc discharge section is provided in the reaction tube. And an apparatus for producing a carbonaceous material.

Here, the anode is preferably made of a carbon-based material that does not contain a catalyst. Further, the gas containing the catalyst is preferably a mixed gas of an organic gas and a catalyst gas.

Further, flow rate control means for flowing the gas containing the catalyst in the reaction tube in a predetermined direction is provided so as to be connected to the reaction tube, and the catalyst-containing gas supply unit is provided at least upstream of the arc discharge unit. bRIEF dESCRIPTION oF is preferably _c drawings which are located on the side

FIG. 1 is a schematic diagram showing a conventional apparatus for producing a carbonaceous material, FIG. 2 is a schematic view showing an apparatus for producing a carbonaceous material according to an embodiment of the present invention, and FIG. FIG. 4 is a schematic view showing a portion of a reaction tube of a carbonaceous material manufacturing apparatus according to the embodiment, in which a supply pipe is provided. FIG. FIG. 5 is a schematic view showing a diameter portion, FIG. 5 is a TEM photograph of the carbonaceous material obtained by the method and apparatus for manufacturing a carbonaceous material according to the present invention, and FIG. 6 is a modification of the embodiment of the present invention. FIG. 7 is a schematic diagram showing a portion of a reaction tube according to a modification of the embodiment of the present invention, in which a supply tube is provided. BEST MODE FOR CARRYING OUT THE INVENTION

A method and an apparatus for manufacturing a carbonaceous material according to an embodiment of the present invention will be described with reference to FIGS.

The carbonaceous material production apparatus 1 mainly produces single-walled carbon nanotubes. As shown in FIG. 2, the carbonaceous material manufacturing apparatus 1 has a substantially cylindrical shape. The reaction tube 11 has a substantially tubular left reaction tube 11A and a right reaction tube 11B. Therefore, the reaction tube 11 is configured to be separable into the left reaction tube 11A and the right reaction tube 11B, and has a structure that makes it easy to take out the single-walled carbon nanotube from the trap 23 described later. Has become. The reaction tube 11 is made of quartz, has excellent heat resistance, and has chemically stable properties.

Inside the left reaction tube 11 A, a rod-shaped anode 13 and a cathode 14 are provided. The anode 13 and the cathode 14 are made of pure carbon. The diameters of the anode 13 and the force sword 14 are 10 mm and 15 mm, respectively. The anode 13 and the force sword 14 are arranged on the same line, and one end 13 A of the anode 13 and one end 14 A of the force sword 14 are arranged to face each other with a slight gap therebetween. I have. The other end 13 B of the anode 13 is electrically connected to the positive electrode of the current supply unit 12, and the other end 14 B of the cathode 14 is electrically connected to the negative electrode of the current supply unit 12. To supply current to the anode 13 and the force sword 14 to generate an arc discharge between the end 13 A of the anode 13 and the end 14 A of the force sword 14 It is configured to be possible. The polarity of the electrode can be reversed by a switching switch (not shown), and arc discharge can be generated by reversing the position of the anode 13 and the position of the force source 14. It is configured to be able to. An arc discharge portion is defined between the tips of the anode 13 and the force sword 14 facing each other. The arc discharge part is located at approximately the center of the left reaction tube 11A in the axial direction.

The anode 13 is consumed because it is used as a raw material of the carbonaceous material when producing a carbonaceous material such as a single-walled carbon nanotube. In order to prevent the gap from being widened between the anode 13 and the force sword 14 due to this consumption, arc discharge does not occur. The gap between the sword 14 and the sword 14 is configured to be always kept constant. That is, the other end 13 B of the anode 13 is supported by a linear motion introducing mechanism 16 and the anode 1 3 is movable in the longitudinal direction of the anode 13. The other end 14 B of the force sword 14 is supported by a support member 15 that supports the force sword 14 immovably.

At both ends of the reaction tube 11, lids 11 C and 1 ID are provided to cover the end of the reaction tube 11, respectively, and the inside of the reaction tube 11 is shut off from the atmosphere. Since both ends of the reaction tube 11 are circular, the lids 11 C and 11 D covering both ends of the reaction tube 11 are also circular. A supply pipe 17 for supplying gas into the reaction tube, which is a part of the reaction tube 11 and is slightly shifted from the lid 11 C toward the arc discharge section, is provided. The inside of the tube 17 communicates with the inside of the reaction tube 11.

As shown in FIG. 3, the supply pipe 17 is provided to extend tangentially to the peripheral surface of the left reaction pipe 11A. Therefore, the gas supplied into the left reaction tube 11 A is also supplied from the tangential direction of the reaction tube 11. For this reason, the supplied gas becomes a spiral flow in the reaction tube 11 as shown by an arrow in FIG. 3, and is supplied to the arc discharge portion as the spiral flow. .

A part of the supply pipe 17 is provided with a supply pipe flow meter 18 (FIG. 2) as a flow control means, and is provided at one end of the supply pipe 17 connected to the reaction pipe 11 with respect to the other end. Is provided with a gas supply unit (not shown). The gas supply unit (not shown) is configured to selectively supply an inert gas or a mixed gas of a catalyst gas and an organic gas. As the catalyst gas, specifically, a sublimated Hue Sen is used. Helium gas is used as the inert gas. The organic gas forms a raw material for the carbonaceous material such as single-walled carbon nanotubes that are generated, together with the gas that forms the anode. Gas alone is used. The supply pipe flow meter 18 is configured so that the flow rate of the mixed gas flowing through the supply pipe 17 and supplied into the reaction pipe 11 can be adjusted. The maximum flow rate of the gas in the reaction tube 11 is 5 L / min.

Since the organic gas, which is the raw material of the carbonaceous material to be generated, is supplied to the arc discharge part in the left reaction tube 11A, the ratio of the anode used as the raw material for the carbonaceous material is reduced, and the consumption of the anode is reduced. Since the catalyst gas is supplied to the arc discharge section in the reaction tube 11, there is no need to mix the catalyst and carbon to form the anode, which reduces the time and cost of anode production. And carbonaceous materials such as single-walled carbon nanotubes can be easily manufactured at low cost.

In addition, since the gas is supplied to the arc discharge part in a spiral flow, the catalyst gas and the organic gas are uniformly supplied in the arc discharge part, so that a uniform discharge can be obtained, and a stable quality carbonaceous material can be obtained. Generation can be ensured. A discharge pipe 19 for discharging gas from the inside of the reaction tube is provided at a position that is a part of the right reaction tube 11B and slightly away from the lid 11D toward the arc discharge part. The inside of the discharge pipe 19 communicates with the inside of the reaction pipe 11 .A part of the discharge pipe 19 is provided with a discharge pipe flowmeter 20, which is connected to the reaction pipe 11. A pump 21 is provided at the other end of the discharge pipe 19 with respect to one end. The pump 21 is configured so that the gas inside the reaction tube 11 can be discharged from the inside of the reaction tube 11 by sucking the gas inside the reaction tube 11 by negative pressure. The discharge pipe flow meter 20 is configured so that the suction force by the pump 21 can be adjusted.

At the center of the circular lid 11D, a rod-shaped catcher support member 22 extending in the axial direction of the reaction tube 11, that is, toward the arc discharge portion is provided. The other end of one end of the capturer support member 22 connected to the lid 1 1D includes a single-walled carbon nanotube or the like generated in the arc discharge part. A capture device 23 for capturing the carbonaceous material is provided. The trap 23 is made of a graphite rod, has a cylindrical shape, and has one end in the longitudinal direction connected to the trap support member 22. The trap 23 is located inside the right reaction tube 11B and at a position from the substantially center in the axial direction of the right reaction tube 11B to a predetermined position near the arc discharge part. This position is located downstream of the arc discharge part when focusing on the flow of the gas supplied from the supply pipe 17, whereas the position where the supply pipe 17 is provided is the arc discharge part More upstream. The carbonaceous material generated in the arc discharge section includes a web-like sample, amorphous carbon, graphite, and a catalyst, and the density increases in this order. Focusing on this difference in density, by setting the gas flow rate to an appropriate value, it is configured so that only the web-like sample can be selectively obtained by the trap 23 provided on the downstream side. I have. When the single-walled carbon nanotubes captured by the capture device 23 are taken out, the left reaction tube 11A and the right reaction tube 11B are configured to be separated and taken out.

In order to heat the carbonaceous material captured by the trap 23 inside the right reaction tube 1 IB, the outer periphery of the right reaction tube 11 B is wound around the position where the trap 23 is provided. An RF heater 24 is provided to perform the operation. Since the captured carbonaceous material can be heated by the RF heater 24 while being captured by the trap 23, the resulting carbonaceous material can be purified without being exposed to the atmosphere. be able to. Therefore, it is possible to remove without oxidizing impurities such as F _e contained in the catalyst, and a rearranging bad SWNTs crystallinity good crystallinity monolayer force Ichipo nanotubes The ratio of the single-walled carbon nanotubes in the carbonaceous material can be efficiently increased.

As shown in FIGS. 2 and 4, the diameter of the reaction tube 11 In this case, it is not uniform, and has a reduced diameter portion 11E having a small diameter in part. In other words, from the left end of the reaction tube 11 toward the arc discharge portion, past the position where the supply tube 17 is provided, a large-diameter portion 11F having a large diameter continues with the same diameter. From this position, the reduced diameter portion 11E becomes a small diameter portion, reaches the arc discharge portion, and the reduced diameter portion 11E continues until immediately before the trap 23 on the downstream side in the gas flow direction is provided. The reduced diameter portion 11E has the same diameter in that section. Immediately before the trap 23, the large-diameter portion 11G, which is the same as the left end of the reaction tube 11 again, reaches the right end of the reaction tube 11 past the position where the discharge tube 19 is provided. . This large diameter portion 11G also has the same diameter in the section. The diameter of the reduced diameter portion 11E is 30 mm, and the diameter of the large diameter portion 11F11G is 50 mm. As described above, the large-diameter portions 11F and 11G and the reduced-diameter portion 11E are configured to be small enough to prevent convection of the atmospheric gas in the reaction tube.

Also, at the position of the arc discharge part, the diameter of the reaction tube 11 is a small diameter part 11 E, and the cross-sectional area of the diameter reduction part 11 E is the large diameter part where the supply pipe 17 is provided. Since the cross-sectional area is smaller than 11 F, the organic gas, which is the source gas, can be efficiently converged to the arc discharge section as shown by the arrow in Fig. 4, and the source gas can be supplied stably. Can be. For this reason, it is possible to prevent the organic gas from being diluted in the arc discharge part, and it is possible to perform stable discharge and to stably generate a carbonaceous material.

In addition, the diameter of the reduced diameter portion 11E extends from the arc discharge portion to just before the trap 23, so that the gas flow rate flowing in the reaction tube 11 can be increased, and the arc discharge portion and the trap The generated carbonaceous material can be prevented from adhering to the inner peripheral surface of the reaction tube 1 1 between 2 and 3 as much as possible, and the capture device 2 3 can efficiently capture the carbonaceous material. Can be.

In addition, the large diameter portion 11 G at the position immediately before the trap 23 is Since the flow velocity of the gas flowing around the trap 23 can be reduced, the generated carbonaceous material can be prevented from passing through the trap 23 without being captured.

Next, a method for producing a carbonaceous material such as a single-walled carbon nanotube will be described. Prior to the production of the carbonaceous material, first, the anode 13 is produced. That is, the lump is cut into a rod shape, and the shapes of the anode 13 and the force sword 14 are respectively obtained.

Next, the anode 1 3, Kazodo 1 4 linear movement introducing mechanism 1 6, set respectively in the supporting member (1) 5, once to vacuum pulling the reaction tube 1 1 below 1 0 ¹ P a. Then, an inert gas is supplied into the reaction tube 11 from a gas supply unit (not shown) via a supply tube to make the inside of the reaction tube 11 approximately 66.7 kPa (5 OOT orr). Thereafter, the supply of the inert gas is stopped, an arc discharge is generated in the arc discharge section, a mixed gas of the catalyst gas and the organic gas is supplied from a gas supply section (not shown), and at the same time, the pump 21 is operated. Then, the gas in the reaction tube 11 is discharged to generate a gas flow in the reaction tube 11. The ratio of the catalyst gas in the mixed gas is 50 wt% for the catalyst gas. During this time, the pressure inside the reaction tube 11 is maintained at about 66.7 kPa, and the arc discharge time is 30 minutes. At this time, the gas is supplied from the supply pipe 17 in a tangential direction to the inner peripheral surface of the left reaction tube 11A, and thus, the gas forms a helical flow inside the reaction tube 11 and particularly in the arc discharge portion. At the position of the arc discharge part, the diameter of the reaction tube 11 is a small diameter part 11E, so that the mixed gas of the organic gas and the catalyst gas, which is the raw material gas, is efficiently discharged by the arc discharge. Section. In this state, a carbonaceous material including single-walled carbon nanotubes and the like is generated in the arc discharge section, and is conveyed to the trap 23 by the flow of the mixed gas of the organic gas and the catalyst gas.

After the arc discharge is completed, vacuum pull the reaction tube 1 1 below 1 0- ¹ P a In this state, the carbonaceous material captured by the trap 23 is heated by the RF heater 24. The heating temperature and time were 110 ° C for 30 minutes. Through the above manufacturing process, high-purity single-walled carbon nanotubes can be manufactured with high efficiency.

Next, an experiment was conducted on a method and an apparatus for producing a carbonaceous material according to the present invention. In the experiment, using the carbonaceous material manufacturing apparatus 1 according to the present embodiment, the amount of the carbonaceous material recovered with respect to the change in the ratio of the catalyst gas (Hueguchisen) in the mixed gas supplied into the reaction tube 11 And the content of Fe contained in the recovered carbonaceous material. This Fe is Fe contained in the catalyst gas Hue Mouth Sen, and is an impurity contained in the generated single-walled carbon nanotube. In this experiment, the carbonaceous material captured by the trap 23 was not heated by the RF heater 24 in order to clarify the amount of the impurity Fe relative to the ratio of the catalyst gas.

As shown in Table 1, when the catalyst ratio is as low as 2%, the recovered amount of the carbonaceous material is as low as 0.9 g. As the ratio of the catalyst is increased to 4% and 20%, the recovery amount of the carbonaceous material increases to 1.8 g and 2.0 g. Only However, even if the catalyst ratio was increased to 50% or 55%, the recovered amount did not increase more than 2.lg. On the other hand, the content of the impurity Fe in the recovered carbonaceous material increases as the ratio of the catalyst increases. Therefore, when the ratio of the catalyst increases to 50% or 55%, the ratio of the single-walled carbon nanotubes in the collected carbonaceous material decreases. From the above, it can be seen that the appropriate ratio of the catalyst gas in the mixed gas is 4 to 50%. The carbonaceous material was manufactured within this range, and the collected carbonaceous material was observed by TEM.As shown in Fig. 5, it was observed that a large amount of high-purity single-walled carbon nanotubes was contained in the carbonaceous material. Was done.

The method and apparatus for producing a carbonaceous material according to the present invention are not limited to the above-described embodiments, and various modifications and improvements can be made within the scope described in the claims. For example, in the present embodiment, a mixed gas of a catalyst gas and an organic gas is used. However, a mixed gas of an inert gas such as He and Ar and a catalyst gas is used. However, instead of Hue sen, other meta sens other than Hue sen, i.e., Nikkerocene having Ni instead of Fe in Hue sen or Fe Cono riretocene having Bi (Bis (eyelopentadienylcoba 1 t)) or the like may be used, or a mixture of these, for example, a mixture of fue mouth and Ecke mouth may be used. Good.

Although the anode 13 and the power sword 14 are made of pure carbon, the anode 13 is manufactured using a material containing a catalyst such as Fe, Ni, and Co in advance. It is not necessary to remove these catalysts from the carbon rod, and they may be used as they are.

As the organic gas supplied into the reaction tube, methane gas alone was used, but alkane gas such as methane, ethane, butane, etc. was used alone or mixed. It may be a thing. These are particularly preferred, but instead of these, simple substances or mixtures of organic gases such as alkenes, alkynes and aromatics can be used.

Further, as the inert gas, argon gas, neon gas or the like may be used instead of helium gas.

The ratio of the mixed gas is set at 50 wt% for the catalyst gas, but may be within the range of 4 to 50%.

Although the reaction tube 11 is made of quartz, it may be made of SUS304, SUS316, tantalum, molybdenum, or the like. That is, any material that can be welded, has high heat resistance, is chemically stable, and is not affected by high frequency may be used. Further, only a part of the reaction tube 11 and around the arc discharge part may be made of these substances.

In addition, an electric furnace or an infrared furnace may be provided instead of the RF heater 24 to heat the carbonaceous material including the single-walled carbon nanotubes captured by the capture device 23.

In addition, although the heating by the RF heater 24 was performed after the arc discharge was completed, the heating may be performed simultaneously with the arc discharge. By doing so, a carbonaceous material such as a single-walled carbon nanotube can be manufactured in a short time.

The pressure in the reaction tube 11 during arc discharge was set to 66.7 kPa (500 Torr), but about 13.3 to 33.3 kPa ( It should be within the range of 100 to 250 0 To rr).

Although only one supply pipe 17 for supplying gas is provided in the reaction pipe 11, it may be provided in a plurality of tangential directions as shown in FIG. Even in this case, the supply pipe is provided at a position upstream of the arc discharge part in the gas flow direction. In addition, multiple types of different gases can be separately and independently Alternatively, a plurality of gases may be mixed in the reaction tube. If a flow meter is provided in each supply pipe and the flow rates of the gases supplied from the supply pipes are made different as velocity V 1 and velocity V 2 respectively, the spiral of the mixed gas generated in the reaction pipe Since the flow can be strengthened and the first gas can flow through the first pipe and the second gas can flow through the second pipe, not only is it easy to control the blending of both, The trouble of mixing the first gas and the second gas before introducing the gas into the reaction tube can be omitted. Further, the first gas and the second gas are easily mixed, and the homogeneity of the mixed gas can be improved.

Further, the supply pipe 17 for supplying gas is provided to extend in a tangential direction on the peripheral surface of the reaction pipe 17. In addition to this, in addition to the direction from the arc discharge part to the trap, the supply pipe 17 is provided. It may be configured to extend at an acute angle to be connected to the reaction tube. In this way, the flow velocity of the spiral flow of the mixed gas generated in the reaction tube in the downstream direction can be increased.

Further, in order to form the above-mentioned spiral flow of the mixed gas better, an inner tube having a smaller diameter than the reaction tube may be arranged coaxially with the reaction tube in the reaction tube. The inner pipe is provided at least at a position where the supply pipe is provided.

Further, although the reduced diameter portion 11E of the reaction tube 11 is set to the position from the position of the arc discharge portion to immediately before the trap 23, only the position of the arc discharge portion may be set to the reduced diameter portion.

The large-diameter portion 11 G is a part of the reaction tube 11 and around the trap 23, but this portion is also a reduced-diameter portion, and the reduced-diameter portion 11 E is used as the right-side reaction tube 11 B. The shape may be extended to the whole.

In addition, the heating of the carbonaceous material captured by the capturing device 23 was performed under vacuum, but it may be performed under reduced pressure, or may be performed under vacuum or in a state other than under reduced pressure. Further, a window for monitoring the state of the arc discharge may be provided near the arc discharge part of the reaction tube 11.

Further, the supply pipe 17 for supplying gas is provided to extend in a tangential direction on the peripheral surface of the reaction pipe 17, but may extend in any direction. Although the reduced diameter portion 11E is provided in the reaction tube 11, the reduced diameter portion may not be provided.

Further, the apparatus for manufacturing a carbonaceous material according to the present embodiment has the RF heater 24, but the cooling mechanism may be provided in the trap and the trap supporting member without the RF heater 24. Good. By providing the cooling mechanism, the carbonaceous material captured by the trap can be cooled in a short time, so that the carbonaceous material can be taken out of the reaction tube immediately after the carbonaceous material is generated. Specifically, as shown in FIG. 6, a through-hole penetrating the reaction tube 11 in the axial direction is formed in the lid 11 D ′ provided at the other end of the reaction tube 11. In the through hole, a catcher support member 25 forming a double tube is provided in a state penetrating therethrough. Therefore, a part of the trap support member 25 is located inside the reaction tube 11. A capture device 26 is provided at one end of the capture device support member 25 on the side located inside the reaction tube 11. The inside of the catcher 26 has a space communicating with a space defined by the inner periphery of the outer tube and the outer periphery of the inner tube of the catcher support member 25, and the inner periphery of the inner tube of the catcher support member 25. And a space communicating with the space defined by. These two spaces communicate with each other. With this configuration, when the cooling water is injected into the space defined by the inner circumference of the inner pipe from the end of the capturing device supporting member 25 on the side where the capturing device 26 is not provided, the cooling water Passes through the space defined by the inner circumference of the inner tube, reaches the trap 26, cools the trap, cools the trap, supports the inner circumference of the outer pipe of the trap support member 25, and the outer circumference of the inner pipe. It is configured to flow into the space defined by, and to be discharged from the other end of the trap support member 25. According to the method for producing a carbonaceous material according to claim 1, since a gas containing a catalyst is supplied toward an arc discharge portion during arc discharge, the anode can be produced without containing a catalyst. . Therefore, the labor of mixing, molding, calcining, and processing the powdered catalyst and the powdered catalyst as in the conventional method to produce the anode is greatly reduced, and the production thereof is simplified. According to the method for producing a carbonaceous material according to claim 2, since the gas containing the catalyst is a mixed gas of the organic gas and the catalyst gas, the consumption of carbon by arc discharge is supplemented by the organic gas. Therefore, the arc discharge can be performed for a long period of time, and the anode can be manufactured without containing a catalyst.

According to the method for producing a carbonaceous material according to claim 3, since the gas containing the catalyst is a mixed gas of the inert gas and the catalyst gas, the anode can be produced without containing the catalyst.

According to the method for producing a carbonaceous material according to claim 4, since the gas containing the catalyst is a mixed gas of an inert gas, an organic gas, and a catalyst gas, carbon consumption by arc discharge is reduced by the organic gas. Thus, the consumption of the anode is reduced, the arc discharge can be performed for a long time, and the anode can be produced without containing a catalyst.

According to the method for producing a carbonaceous material according to claim 5, since the anode is made of a carbon-based material that does not contain a catalyst, the anode is made of only a carbonaceous material that does not contain a catalyst, for example, a graphite rod or the like. can do.

According to the method for producing a carbonaceous material according to claim 6, the gas containing the catalyst in the reaction tube flows in a predetermined direction, so that a positive gas flow is generated in the reaction tube. Therefore, the carbonaceous material generated by the arc discharge flows in a predetermined direction without adhering to the inner wall surface of any reaction tube, It can be gathered or aggregated at a predetermined location in the tube, which facilitates collection. According to the apparatus for producing a carbonaceous material according to claim 7, since the anode is configured without containing a catalyst, a pulverizing force is mixed with a powdery metal catalyst as in a conventional apparatus, The labor of forming, firing, and processing the anode to produce is greatly reduced, and the production is simplified.

According to the apparatus for producing a carbonaceous material described in claim 8, since the anode is made of a carbon-based material that does not contain a catalyst, the anode is made of only a carbonaceous material that does not contain a catalyst, such as a graphite rod. can do.

According to the apparatus for manufacturing a carbonaceous material according to claim 9, since the gas containing the catalyst is a mixed gas of the organic gas and the catalyst gas, the carbon consumption by the arc discharge is supplemented by the organic gas. Therefore, the arc discharge can be performed for a long period of time, and the anode can be manufactured without containing a catalyst.

According to the apparatus for manufacturing a carbonaceous material described in claim 10, since the gas containing the catalyst is a mixed gas of the inert gas and the catalyst gas, the anode can be manufactured without containing the catalyst. Can be.

According to the apparatus for manufacturing a carbonaceous material described in claim 11, since the gas containing the catalyst is a mixed gas of an inert gas, an organic gas, and a catalyst gas, consumption of carbon by arc discharge is reduced. Since the gas is supplemented by the organic gas, the consumption of the anode is reduced, a long-term arc discharge is possible, and

-Can be produced without containing a catalyst.

According to the apparatus for producing a carbonaceous material according to claim 12, since the gas containing the catalyst is caused to flow in the predetermined direction by the flow control means, an aggressive gas flow is generated in the reaction tube. Therefore, the carbonaceous material generated by the arc discharge flows in a predetermined direction without adhering to the inner wall surface of any reaction tube. Thus, it can be collected or aggregated at a predetermined location in the reaction tube, and the collection thereof can be facilitated. In addition, since the catalyst-containing gas supply section is located at least on the upstream side of the arc discharge section, it always passes through the arc discharge section and can efficiently generate a carbonaceous material.

Claims

The scope of the claims

1. An anode made of a carbon-based material and a carbon-based material that opposes the anode and defines an arc discharge part between the anode and a reaction tube that defines a carbonaceous material generation chamber. Place the cathode and

In a method for producing a carbonaceous material, a voltage is supplied between the anode and the cathode to cause arc discharge, and a carbonaceous material is generated in the arc discharge part. A method for producing a carbonaceous material, comprising supplying a gas containing a catalyst by heating.

2. The method for producing a carbonaceous material according to claim 1, wherein the gas containing the catalyst is a mixed gas of an organic gas and a catalyst gas.

3. The method for producing a carbonaceous material according to claim 1, wherein the gas containing the catalyst is a mixed gas of an inert gas and a catalyst gas.

4. The method for producing a carbonaceous material according to claim 1, wherein the gas containing the catalyst is a mixed gas of an inert gas, an organic gas, and a catalyst gas.

5. The method for producing a carbonaceous material according to claim 1, wherein the anode is made of a carbon-based material that does not contain a catalyst.

6. The method for producing a carbonaceous material according to claim 1, wherein the gas containing the catalyst in the reaction tube is flowed in a predetermined direction.

7. A reaction tube defining a carbonaceous material production chamber;

An anode arranged in the reaction tube and made of a carbon-based material;

A force sword provided in the reaction tube so as to face the anode, the force sword being made of a carbon-based material defining an arc discharge portion with the anode;

To generate an arc discharge between the anode and the cathode, a carbonaceous material provided with the anode and a current supply connected to the cathode. Manufacturing equipment,

An apparatus for producing a carbonaceous material, characterized in that the reaction tube is provided with a catalyst-containing gas supply unit for supplying a gas containing a catalyst toward the arc discharge unit.

8. The apparatus for producing a carbonaceous material according to claim 7, wherein the anode is made of a carbon-based material containing no catalyst.

9. The apparatus for producing a carbonaceous material according to claim 7, wherein the gas containing the catalyst is a mixed gas of an organic gas and a catalyst gas.

10. The apparatus for producing a carbonaceous material according to claim 7, wherein the gas containing the catalyst is a mixed gas of an inert gas and a catalyst gas.

11. The production of a carbonaceous material according to claim 7, wherein the gas containing the catalyst is a mixed gas of an inert gas, an organic gas, and a catalyst gas.

12. A flow rate control means for flowing the gas containing the catalyst in the reaction tube in a predetermined direction is provided in connection with the reaction tube, and the catalyst-containing gas supply unit is at least one of the arc discharge unit. 8. The apparatus for producing a carbonaceous material according to claim 7, wherein the apparatus is located on an upstream side.