JP4940190B2 - Carbon nanotube production equipment - Google Patents

Description

  The present invention relates to a nanocarbon production apparatus for efficiently producing highly useful fibrous nanocarbon such as carbon nanotubes.

Examples of the method for producing the carbon nanotube include an arc discharge method, a laser vapor deposition method, and a chemical vapor deposition method (CVD method).
The arc discharge method is a method in which graphite is evaporated by causing an arc discharge between positive and negative graphite electrodes, and carbon nanotubes are generated in a carbon deposit condensed at the tip of the cathode (see, for example, Patent Document 1). ). The laser vapor deposition method is a method of generating a carbon nanotube by putting a graphite sample mixed with a metal catalyst in an inert gas heated to a high temperature and irradiating it with a laser (see, for example, Patent Document 2).

In general, the arc discharge method or the laser evaporation method can produce carbon nanotubes with good crystallinity, but it is said that the amount of carbon nanotubes to be produced is small and difficult to produce in large quantities.
In the CVD method, a vapor phase growth substrate method (for example, refer to Patent Document 3) in which carbon nanotubes are generated on a substrate disposed in a reaction furnace, and a catalyst metal and a carbon source are flowed together in a high-temperature furnace. There are two methods such as a fluidized gas phase method (see, for example, Patent Document 4).

  However, since the vapor phase growth substrate method is a badge process, mass production is difficult. Further, the fluidized gas phase method is said to be difficult to produce carbon nanotubes with low temperature uniformity and good crystallinity. Further, as a development type of the fluidized gas phase method, a method of forming a fibrous nanocarbon by forming a fluidized bed with a fluid material also serving as a catalyst in a high-temperature furnace and supplying a carbon raw material has been proposed. However, it is considered difficult to produce carbon nanotubes with low temperature uniformity in the furnace and good crystallinity.

If carbon nanotubes with high purity and stability can be mass-produced efficiently at low cost, it will be possible to supply large quantities of nanotechnology products that make use of the characteristics of carbon nanotubes at low cost. .
JP 2000-95509 A Japanese Patent Laid-Open No. 10-273308 JP 2000-86217 A JP 2003-342840 A

  The present invention has been made in consideration of such circumstances, and an object of the present invention is to provide a nanocarbon production apparatus capable of efficiently mass-producing highly functional nanocarbon having high purity and stability at low cost.

The carbon nanotube production apparatus according to the present invention includes a reaction vessel capable of maintaining the inside in a reducing atmosphere, an endless strip-shaped iron plate that is provided in the reaction vessel and is driven by a roller and on the surface of which carbon nanotubes are generated, A heating means for heating the strip iron plate, a carbon raw material supply means for supplying a carbon raw material into the reaction vessel, an inert gas supply means for supplying an inert gas into the reaction vessel, and a carbon nanotube generated on the strip iron plate Scraping and collecting means for collecting, gas exhaust means for exhausting the gas in the reaction vessel, an acid solution applying brush for applying an acid solution to the surface of the strip-shaped iron plate, and a strip-shaped iron plate by supplying an acid solution to the strip-shaped iron plate An iron plate activating means for activating the acid plate, wherein the iron plate activating means has an acid solution supply nozzle having one end extending to the acid solution application brush, and an acid solution container for containing the acid solution. A tank, the acid liquid in the acid solution contained in the tank, characterized in that it comprises a pump for sending to the acid solution application brush through acid solution supply nozzle.

  According to the present invention, highly functional nanocarbon having high purity and stability can be mass-produced efficiently at low cost.

Hereinafter, the nanocarbon production apparatus of the present invention will be described in more detail.
In the first and second inventions of the present application, as the strip-shaped iron plate, an iron plate having high iron purity or an iron plate made of carbon steel containing iron can be used. Here, the iron plate having a high iron purity means that the purity is 90% or more.
In the second invention of the present application, “surface-treated” means that the band-shaped iron plate is polished with sandpaper or the like and then treated with hydrochloric acid or the like.
In the present invention, examples of the inert gas include nitrogen gas and argon gas. Examples of the hydrocarbon include ethanol (including bioethanol).

  In the present invention, the hydrocarbon supply means generally includes a hydrocarbon supply nozzle for supplying hydrocarbons such as ethanol, a hydrocarbon storage tank for storing hydrocarbons, and for sending the hydrocarbons in the tank onto the iron plate. And the pump. The inert gas supply means includes, for example, an inert gas supply nozzle for supplying an inert gas such as nitrogen, an inert gas storage tank for storing the inert gas, and the inert gas in the tank in the reaction vessel. And a pump for sending to. The iron plate activation means includes, for example, an acid solution supply nozzle for supplying an acid solution such as hydrochloric acid, an acid solution storage tank that stores the acid solution, and a nanocarbon that has generated the acid solution in the tank. And a pump for sending to the iron plate. The gas exhaust means includes an exhaust nozzle provided in the reaction vessel, a liquid seal tank for storing a liquid such as water, a pipe connecting the exhaust nozzle and the liquid seal tank, and a pump for exhausting the gas in the reaction vessel It is comprised by. The reason why the liquid is stored in the liquid seal tank is to prevent the backflow of gas generated in the nanocarbon manufacturing apparatus.

Next, embodiments of the present invention will be described with reference to the drawings. Note that the present embodiment is not limited to the following description.
(First embodiment)
FIG. 1 is a schematic view of a carbon nanotube (CNT) manufacturing apparatus according to the first embodiment of the present invention.
The manufacturing apparatus includes a reaction vessel 1 capable of maintaining the inside in a reducing atmosphere, an endless strip-shaped iron plate 3 on which nanocarbon (for example, carbon nanotubes) 2 is generated, a heater 4 as a heating means, a hydrocarbon, A supply means 5, an inert gas supply means 6, a carbon nanotube scraping and collecting means (hereinafter referred to as CNT scraping and collecting means) 7, an iron plate activating means 8, and a gas exhaust means 9 are provided.

  The strip-shaped iron plate 3 is, for example, an iron plate having high iron purity (purity: 99.5%), and is rotated and moved as indicated by an arrow A by a driving roller 10 and a driven roller 11. The strip-shaped iron plate 3 is surrounded by a heater 4, a heat-resistant material 12 that fixes and keeps the heater 4 warm, and a heat-insulating material 13 that blocks heat. A heater control means 14 is electrically connected to the heater 4. A hydrocarbon raw material such as ethanol B is supplied from the hydrocarbon supply means 5 to the space between the heater 4 and the strip-shaped iron plate 3.

  The hydrocarbon supply means 5 includes, for example, a hydrocarbon supply nozzle 16 that supplies ethanol B to the space between the heater 4 and the belt-shaped iron plate 3, a hydrocarbon storage tank 17 connected to the nozzle 16, a liquid feed pump (not shown), It has. The belt-like iron plate 3, the driving roller 10, the driven roller 11, the heater 4, the heat-resistant material 12, the heat insulating material 13, a scraping plate, a polishing brush, and an acid solution application brush described later are surrounded by a casing 18. A heat insulating material 19 made of rock wool, for example, is provided on the outer periphery of the housing 18. The inert gas supply means 6 includes an inert gas supply nozzle 20 for supplying an inert gas such as nitrogen gas C into the reaction vessel 1, an inert gas storage tank 21 connected to the nozzle 20, a pump (not shown), It has.

  The CNT scraping and collecting means 7 includes a carbon nanotube scraping plate (hereinafter referred to as a CNT scraping plate) 22 disposed immediately below the driven roller 11 and in the vicinity of the strip-shaped iron plate 3, and a scraping plate 22 for scraping. And a carbon nanotube recovery can (hereinafter referred to as a CNT recovery can) 23 that accommodates carbon nanotubes (hereinafter referred to as a CNT) 2. The gas exhaust means 8 connects an exhaust nozzle 24 provided on the downstream side (right side in the drawing) of the reaction vessel 1, a water seal tank 26 for storing water 25, and the exhaust nozzle 24 and the water seal tank 26. The pipe 27 and a gas suction pump (not shown) are included.

  On the lower side of the reaction vessel 1 and further downstream of the scraping plate 22, a polishing brush 29 for polishing the surface of the strip-shaped iron plate 2 and an acid solution for applying an acid solution to the surface of the strip-shaped iron plate 2 that has been polished. A coating brush 30 is provided for each. Immediately below the polishing brush 29, a polishing powder recovery can 32 for recovering the polishing powder 31 obtained by polishing the belt-like iron plate 3 is disposed. An acid solution recovery can 34 for recovering an acid solution 33 obtained by acid-treating the surface of the belt-shaped iron plate 3 is disposed directly below the acid solution application brush 30. The acid solution application brush 30 is supplied with hydrochloric acid D by an iron plate activating means 8 comprising an acid solution supply nozzle 35 and an acid solution storage tank 37 for storing an acid solution such as hydrochloric acid D. The reaction vessel 1 near the driven roller 10 is provided with a viewing window 38 for directly observing the CNT 2 generated on the belt-like iron plate 3.

Next, the test verified about the method of producing CNTs will be described with reference to the schematic process diagram of FIG.
1) First, the surface treatment of the surface _{S 2} with hydrochloric acid as after polished surface _{S 1} of a purity of 99.5% iron plate 41 as in shown in FIG. 2 (A) with sandpaper, shown in FIG. 2 (B) To do. Subsequently, the surface-treated iron plate 41 is placed in a reaction vessel 46 having a raw material supply means 42, an inert gas supply means 43, an exhaust gas recovery means 44, and a heating means 45, and is heated to about 500 to 1000 ° C. (Refer to FIG. 2C).

2) Next, when the iron plate 41 was cooled and taken out, CNTs 47 were generated on the surface of the iron plate 41 (see FIG. 2D). Subsequently, the CNT 47 on the iron plate 41 as shown in FIG. 2E is scraped off by the cutter 48 (see FIG. 2F). As a result, CNT 47 was recovered as shown in FIG.
FIG. 3 shows the outline of a photograph in which the CNT 47 is generated by the above-described generation method. That is, FIG. 3 shows that the steel plate 41 is heated while being suspended from the top plate 50 by the stainless steel wire 49 to generate the CNT 47.

Next, a manufacturing method using the CNT manufacturing apparatus of FIG. 1 will be described.
First, in order to make the inside of the apparatus an inert atmosphere, for example, nitrogen gas is supplied using the inert supply means 6 and the inside is replaced with a nitrogen atmosphere. Then, the strip-shaped iron plate 3 is rotated and moved, the heater control means 14 is turned on, and the temperature is raised until the carbon nanotube generation atmosphere reaches a generation temperature of 500 to 1000 ° C. When the generation temperature is reached, the supply of nitrogen is stopped, and at the same time, the carbon raw material supply means 5 is started. It becomes gas. The gas reacts with a sufficiently heated iron catalyst on the surface of the iron plate to produce CNT2 in a reducing atmosphere and grow. The CNTs 2 grown on the surface of the belt-like iron plate 3 are scraped off by a CNT scraping plate 22 provided at the lower portion of the driven roller 11 and collected in a lower CNT collection can 23. The belt-like iron plate 3 is cooled by the driven roller 11 and then moved to the right, the polished metal surface is exposed by the polishing brush 29, and the surface is activated by the acid solution coating brush 30 to improve the catalytic effect. In this state, the carbon nanotubes are returned to the carbon nanotube generator between the iron plate 3 and the heater 4 to generate carbon again.

  As shown in FIG. 1, the nanocarbon production apparatus according to the first embodiment includes a reaction vessel 1 capable of maintaining the inside in a reducing atmosphere, an endless strip-shaped iron plate 3 on which CNT2 is generated, and a heater 4. And a hydrocarbon supplying means 5, an inert gas supplying means 6, a CNT scraping and collecting means 7, an iron plate activating means 8, and a gas exhausting means 9, so that there is little catalyst and purity. Can be obtained. Further, according to the present invention, the inert atmosphere in the reaction vessel 1, the temperature rise, the CNT generation on the surface of the strip iron plate 3, the CNT 2 scraping off, and the activation of the strip iron plate 3 can be automatically performed in sequence. Therefore, it is possible to efficiently mass-produce highly functional CNT2 having high purity and stability at low cost.

(Second Embodiment)
FIG. 4 is a schematic view of a CNT manufacturing apparatus according to the second embodiment of the present invention. However, the same members as those in FIG. 1 are denoted by the same reference numerals and the description thereof will be omitted, and only the main parts will be described.
Compared with the case of FIG. 1, the nanocarbon manufacturing apparatus which concerns on 2nd Embodiment is a point which excluded the polishing brush, the acid solution application brush, the abrasive powder collection can, the acid solution recovery can, and the iron plate activation means, and CNT It is characterized in that a part of the iron catalyst remains when scraping off with a scraping plate.

Next, a method for manufacturing CNTs in the CNT manufacturing apparatus of FIG. 4 will be described.
First, in order to make the inside of the apparatus an inert atmosphere, for example, nitrogen is supplied using the inert supply means 6, and the inside is replaced with a nitrogen atmosphere. Thereafter, the strip-shaped iron plate 3 is rotated and moved, the heater control means 14 is turned on, and the temperature is raised until the CNT generation atmosphere reaches a generation temperature of 500 to 1000 ° C. When the generation temperature is reached, the supply of nitrogen is stopped, and at the same time, the carbon raw material supply means 5 is started. It becomes gas. The gas reacts with a sufficiently heated iron catalyst on the surface of the iron plate to produce CNT2 in a reducing atmosphere and grow. The CNTs 3 grown on the surface of the belt-like iron plate 3 are scraped off by a CNT scraping plate 22 provided at the lower part of the driven roller 10 and collected in a lower CNT collection can 23. Most of the iron catalyst that functions as a catalyst is left during the scraping. Based on this, CNT2 is generated again.

  As shown in FIG. 4, the CNT manufacturing apparatus according to the second embodiment includes a reaction vessel 1 that can maintain the inside in a reducing atmosphere, an endless strip-shaped iron plate 3 on which CNT 2 is generated, and a heater 4. The hydrocarbon supply means 5, the inert gas supply means 6, the CNT scraping and collecting means 7 and the gas exhaust means 9 are provided, so that a CNT having a small amount of catalyst and extremely high purity can be obtained. In addition, according to the present invention, when scraping with the CNT scraping plate 22, most of the iron catalyst remains, so that the remaining iron catalyst can be used as a base, and the CNT generating unit can generate CNT3 again. Furthermore, since an inert atmosphere in the reaction vessel 1, temperature rise, CNT generation on the surface of the strip-shaped iron plate 3, and scraping off of the CNT 2 can be automatically performed in sequence, a highly functional CNT 2 with high purity and stability can be obtained. It can be mass-produced efficiently at low cost.

(Third embodiment)
FIG. 5 is a schematic view of a CNT manufacturing apparatus according to the third embodiment of the present invention. However, the same members as those in FIG. 1 are denoted by the same reference numerals and the description thereof will be omitted, and only the main parts will be described.
Reference numeral 51 in FIG. 5 denotes a drive take-up roller that generates CNTs and takes up the strip-shaped iron plate 3a after scraping off the CNTs. Reference numeral 52 is a driven roller around which a belt-like iron plate 3 surface-treated with hydrochloric acid or the like is wound. The surface-treated strip-shaped iron plate 3a generates CNT from the driven roller 52 through the first support roller 53a at the CNT generation unit, scrapes the CNT, and then winds up with the take-up roller 51 through the second support roller 53b. It has become.

Next, a method for producing CNTs in the nanocarbon production apparatus of FIG. 5 will be described.
First, in order to make the inside of the apparatus an inert atmosphere, for example, nitrogen is supplied using the inert gas supply means 6, and the inside is replaced with a nitrogen atmosphere. Next, the heater control means 14 is turned on and heated up until the carbon nanotube generation atmosphere reaches a generation temperature of 500 to 1000 ° C. When the generation temperature is reached, the supply of nitrogen is stopped, and at the same time, the surface-treated strip-shaped iron plate 3a is rotated and moved, the carbon raw material supply means 5 is activated, and, for example, ethanol B is supplied from the carbon raw material supply luz 16 and the temperature of the atmosphere It instantly evaporates and becomes a gas containing hydrocarbons. The gas reacts with a sufficiently heated iron catalyst on the surface of the iron plate to produce CNT2 in a reducing atmosphere and grow. The CNTs 2 grown on the surface of the strip-shaped iron plate 3a are scraped off by the CNT scraping plate 22 provided at the lower part of the drive take-up roller 51 and are collected in the lower CNT collecting can 23.

  As shown in FIG. 5, the CNT manufacturing apparatus according to the third embodiment includes a reaction vessel 1 capable of maintaining the inside in a reducing atmosphere, a surface-treated strip-shaped iron plate 3 a on which CNT 2 is generated, and a heater 4. A hydrocarbon supply means 5, an inert gas supply means 6, a CNT scraping and collecting means 7, a gas exhaust means 9, a driven roller 52 around which the surface-treated strip-shaped iron plate 3 is wound, and a CNT is generated. Since the drive take-up roller 51 is provided to take up the strip-shaped iron plate 3 after scraping off, CNTs with little catalyst and extremely high purity can be obtained. In addition, according to the present invention, the inert atmosphere in the reaction vessel 1, the temperature rise, the CNT generation on the surface of the strip-shaped iron plate 3, and the scraping off of the CNT 2 can be automatically performed sequentially, so that purity and stability can be improved. High-function CNT2 can be mass-produced efficiently at low cost.

(Fourth embodiment)
FIG. 6 is a schematic view showing only main parts of a CNT manufacturing apparatus according to the fourth embodiment of the present invention. However, the same members as those in FIG. 1 are denoted by the same reference numerals and the description thereof will be omitted, and only the main parts will be described.
The manufacturing apparatus includes a reaction vessel (not shown) capable of maintaining the inside in a reducing atmosphere, a disk-shaped iron plate 60 on the surface of which CNT2 is generated, a heater 4 as a heating unit, and a hydrocarbon supply unit 5. The carbon raw material supply nozzle 16 constituting the above, the inert gas supply means (not shown), the CNT scraping plate 22 constituting the CNT scraping recovery means, and the acid solution supply nozzle 35 constituting the iron plate activation means 8. And a gas exhaust means (not shown) and a rotating means 61 for slowly rotating the iron plate 60.

The rotating means 61 includes a main shaft 63 whose one end is connected to the inner end of the iron plate 3b via a plurality of spokes 62, and a drive motor 64 that rotates the main shaft 63 as indicated by an arrow F. Reference numerals 65a and 65b in the figure are partition plates to which a heat insulating material (not shown) is attached, and the upper part of the iron plate 60 is divided into regions A ₁ and A ₂ . The one area A ₁ is arranged a carbon raw material supply nozzle 16, such as ethanol is fed onto the iron plate 60. Abrasive brush 66 is provided in an upper portion of the other region A ₂ of the iron plate 60. Further, in the region A _2, is arranged acid solution supply nozzle 35 to supply the surface, for example, hydrochloric acid D of the iron plate 60 after polishing, is thereby iron surface becomes activated surface S. Note that reference numeral 67 in the figure indicates a CNT generator. Further, the peripheral parts such as the polishing brush 66, the acid solution supply nozzle 35, the carbon raw material supply nozzle 16, the CNT scraping plate 22 and the like are all surrounded by the casing 18 so that the reducing atmosphere can be maintained by blocking the outside air. Has been.

Next, a manufacturing method using the CNT manufacturing apparatus of FIG. 6 will be described.
First, in order to make the inside of the apparatus an inert atmosphere, for example, nitrogen is supplied into the housing 18 using a nitrogen supply means, and the inside is replaced with a nitrogen atmosphere. Next, the drive motor 64 is rotated in the direction of arrow F. Next, the heater 4 is turned on, and the temperature of the iron plate 60 is increased until the carbon nanotube generation atmosphere reaches a generation temperature of 500 to 1000 ° C. When the generation temperature is reached, the supply of nitrogen is stopped, and at the same time, the carbon raw material supply means is started, and, for example, ethanol B is supplied from the carbon raw material supply luz 16. The ethanol 16 is instantly evaporated at the temperature of the atmosphere and becomes a gas containing hydrocarbons. The gas reacts with the iron catalyst on the surface of the sufficiently heated iron plate 60 to generate and grow CNT2 in a reducing atmosphere. The CNT 2 grown on the surface of the iron plate 60 is scraped off by the CNT scraping plate 22 and collected in the lower CNT collection can 24. The iron plate 60 passes through the partition plate 65a, and after being cooled, is polished with a polishing brush 66, and further, for example, hydrochloric acid D is sprayed onto the surface of the iron plate 50 with the acid solution coating nozzle 35 to activate the surface (activation surface S). , Improve the catalytic effect. Thereafter, the iron plate 60 passes through the partition plate 65b and repeats the generation of CNT2 again.

  As shown in FIG. 6, the nanocarbon production apparatus according to the fourth embodiment includes a reaction vessel capable of maintaining the inside in a reducing atmosphere, a circular iron plate 60 in which CNT2 is generated on the surface, the heater 4, Since it is configured to include a hydrocarbon supply means, an inert gas supply means, a CNT scraping and recovery means, a gas exhaust means, and a rotating means 61 that rotationally drives the iron plate 60, the purity is low with little catalyst. Very high CNTs are obtained. Further, according to the present invention, the inert atmosphere in the reaction vessel 1, the temperature rise, the CNT generation on the surface of the iron plate 60, and the CNT 2 scraping can be automatically performed in sequence, so that the purity and stability are high. High-performance CNT2 can be mass-produced efficiently at low cost.

  In the fourth embodiment, the case where CNT is generated using one circular iron plate has been described. However, the present invention is not limited to this. For example, a plurality of circular iron plates are arranged parallel to the axial direction of the main shaft at regular intervals so as to be rotatable by the main shaft, and for each iron plate, a polishing brush, an acid solution supply means, a carbon raw material supply means, By arranging the heating means and the like, it is possible to mass-produce CNTs more than when using a single iron plate.

(Fifth embodiment)
FIG. 7 is a schematic view showing only main parts of a CNT manufacturing apparatus according to the fifth embodiment of the present invention. However, the same members as those in FIGS. 1 and 6 are denoted by the same reference numerals and the description thereof will be omitted, and only the main parts will be described. Compared with the case of FIG. 6, the nanocarbon manufacturing apparatus which concerns on 5th Embodiment made the circular iron plate 60 vertical, and sprayed hydrochloric acid D from the acid solution supply nozzle 35 to the iron plate 60 from the horizontal direction. Are the same as in the case of FIG. The method of manufacturing CNT2 is also as described in the fourth embodiment.

  According to the CNT manufacturing apparatus according to the fifth embodiment, the same effect as in the fourth embodiment can be obtained. Also in the case of the fifth embodiment, as in the fourth embodiment, a plurality of circular iron plates are arranged in parallel to the axial direction of the main shaft at regular intervals so as to be rotatable by the main shaft. By arranging a polishing brush, an acid solution supply means, a carbon raw material supply means, a heating means, etc. for each iron plate, it becomes possible to mass-produce CNT as compared with the case of using a single iron plate.

(Sixth embodiment)
FIG. 8 is a schematic view of a CNT manufacturing apparatus according to the sixth embodiment of the present invention. However, the same members as those in FIG. 1 are denoted by the same reference numerals and the description thereof will be omitted, and only the main parts will be described.

  Reference numeral 71 in the figure is a non-rotating stainless steel cylindrical vertical reaction vessel. Inside the reaction vessel 71, an iron cylinder 72 is arranged coaxially with the reaction vessel 71. Inside the cylinder 72, a scraping blade 74 rotated by a rotating shaft 73 is provided. This scraping blade 74 is arranged to rotate in the direction of arrow F by a driving motor 75 as a driving source connected to the rotating shaft 73 and scrape off the CNT 2 generated on the inner wall of the cylinder 72. An opening hole for passing the rotation shaft 73 is provided in the upper part of the reaction vessel 71. Between the rotation shaft 73 and the reaction vessel 71 at the opening hole portion, the inside of the reaction vessel is blocked from the outside air to maintain a reducing atmosphere. The ring-shaped sealing material 76 is provided.

Next, a manufacturing method using the CNT manufacturing apparatus in FIG. 8 will be described.
First, in order to make the inside of the apparatus an inert atmosphere, for example, nitrogen is supplied using an inert supply means, and the inside is replaced with a nitrogen atmosphere. Next, the heater 4 is turned on and the temperature is raised until the cylinder 72 reaches a carbon nanotube generation temperature of 500 to 1000 ° C. When the production temperature is reached, the supply of nitrogen is stopped, and at the same time, the carbon raw material supply means is started to supply, for example, ethanol from the carbon raw material supply luz. Ethanol is instantly evaporated at ambient temperature to become a hydrocarbon-containing gas. The gas reacts with the iron catalyst on the inner surface of the sufficiently heated cylinder 72 to generate and grow CNT2 in a reducing atmosphere.
When the CNT2 is sufficiently grown, the drive motor 75 is rotated in the direction of arrow F, and the CNT2 grown on the inner surface of the cylinder 72 is scraped off by the blades 74 and collected in the lower CNT collection can 24. The gas generated in the carbon production apparatus is exhausted by the gas exhaust means 8 so that the gas does not flow back through the water seal.

  As shown in FIG. 8, the CNT manufacturing apparatus according to the sixth embodiment includes a cylindrical vertical reaction vessel 71 capable of maintaining the inside in a reducing atmosphere, and an iron cylinder 72 disposed in the reaction vessel 71. The scraper blade 74 disposed in the cylinder 72 and scraping off the CNT 2 produced on the inner wall of the cylinder 72, the drive motor 75 for driving the scraper blade 74, the heater 4, the hydrocarbon supply means, the inert Since it has a configuration including the gas supply means and the gas exhaust means 8, it is possible to efficiently mass-produce high-performance CNT2 having high purity and stability at low cost. Further, according to the present invention, the inert atmosphere in the reaction vessel 71, the temperature rise, the CNT generation on the inner wall of the cylinder 72, and the scraping off of the CNT2 can be automatically performed sequentially, so that the purity and stability are high. High-performance CNT2 can be mass-produced efficiently at low cost. Furthermore, when the production capacity decreases due to a decrease in the production amount of CNT2, it is possible to newly produce CNT2 by replacing only the cylinder 72 in the reaction vessel 71, and to keep the maintenance of the apparatus at low cost. Can do.

  By the way, in the sixth embodiment, the case where the cylinder has a cylindrical shape has been described. However, the present invention is not limited to this. A cylinder may be used.

(Seventh embodiment)
FIG. 9 is a schematic view of a CNT manufacturing apparatus according to the seventh embodiment of the present invention. However, the same members as those in FIGS. 1 and 8 are denoted by the same reference numerals and the description thereof will be omitted, and only the main parts will be described.
The CNT manufacturing apparatus of FIG. 9 differs from that of FIG. 8 in that only an iron cylinder 81 capable of maintaining the inside in a reducing atmosphere is used, and CNTs are generated on the inner wall of the cylinder 81. Other components and manufacturing methods are the same as in FIG.

  As shown in FIG. 9, the CNT manufacturing apparatus according to the seventh embodiment scrapes the iron cylinder 81 capable of maintaining the inside in a reducing atmosphere and the CNT 2 disposed in the cylinder 81 and generated on the inner wall of the cylinder. The scraper blade 74 to be removed, the drive motor 75 for driving the scraper blade 74, the heater 4, the hydrocarbon supply means, the inert gas supply means, and the gas exhaust means 8 are provided. Therefore, it is possible to efficiently mass-produce highly functional CNT2 having high purity and stability at low cost. Further, according to the present invention, the inert atmosphere in the reaction vessel 71, the temperature rise, the CNT generation on the inner wall of the cylinder 72, and the scraping off of the CNT2 can be automatically performed sequentially, so that the purity and stability are high. High-performance CNT2 can be mass-produced efficiently at low cost.

Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage. Further, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, you may combine suitably the component covering different embodiment. Specifically, in the above embodiment, a large amount of CNT can be generated when the substrate material or cylinder for generating CNT is iron and the hydrocarbon raw material is ethanol. However, the substrate or cylinder is not limited to iron, the carbon raw material is not limited to ethanol, and an optimum carbon nanotube production apparatus can be obtained by using the structure of the present invention with the optimal combination of the substrate or cylinder and the carbon raw material. Can be configured.
Hereinafter, the invention described in the scope of claims of the present application will be appended.
[1] A reaction vessel capable of maintaining the inside in a reducing atmosphere, an endless belt-like iron plate provided in the reaction vessel, driven by a roller and generating nanocarbon on the surface, and heating means for heating the belt-like iron plate A hydrocarbon supply means for supplying hydrocarbons into the reaction vessel, an inert gas supply means for supplying an inert gas into the reaction vessel, and a scraping and recovery means for recovering the nanocarbon produced in the belt-like iron plate An apparatus for producing nanocarbon, comprising: a gas exhaust means for exhausting the gas in the reaction vessel.
[2] The nanocarbon production apparatus according to [1], further comprising iron plate activation means for activating the belt-like iron plate.
[3] A reaction vessel capable of maintaining the inside in a reducing atmosphere, a surface-treated strip-like iron plate provided in the reaction vessel, driven by a roller and generating nanocarbon on the surface, and heating for heating the strip-like iron plate Means, hydrocarbon supply means for supplying hydrocarbons into the reaction vessel, inert gas supply means for supplying inert gas into the reaction vessel, and scraping and recovery means for recovering nanocarbon generated in the strip-shaped iron plate And a gas exhaust means for exhausting the gas in the reaction vessel.
[4] The nanocarbon production apparatus according to [1] or [2], wherein the iron plate is an iron plate having high iron purity or an iron plate made of carbon steel containing iron.
[5] A reaction vessel capable of maintaining the inside in a reducing atmosphere, a disk-shaped iron plate provided in the reaction vessel, on which nanocarbon is generated, driving means for driving the iron plate, and the iron plate A heating means for heating, a hydrocarbon supply means for supplying hydrocarbons into the reaction vessel, an inert gas supply means for supplying an inert gas into the reaction vessel, and a scraper for recovering the nanocarbon produced on the iron plate An apparatus for producing nanocarbon, comprising: a collecting and collecting means; an iron plate activating means for activating the iron plate; and a gas exhausting means for exhausting the gas in the reaction vessel.
[6] A cylindrical vertical reaction vessel that can keep the inside in a reducing atmosphere and can be shut off from the outside air, a cylinder made of iron-based material placed in the vertical reaction vessel, and formed on the inner wall of this cylinder A spiral scraping blade for scraping off the nanocarbon, a driving source for driving the scraping blade, a heating means for heating the cylinder, and a hydrocarbon supply means for supplying hydrocarbons into the vertical reaction vessel, , An inert gas supply means for supplying an inert gas into the vertical reaction container, a recovery means for recovering nanocarbon generated on a cylindrical iron plate made of an iron-based material, and an exhaust gas in the vertical reaction container A nanocarbon production apparatus comprising a gas exhaust means.
[7] The nanocarbon production apparatus according to any one of [1] to [6], wherein the hydrocarbon supplied into the reaction vessel from the hydrocarbon supply means is ethanol (including bioethanol). .

It is the schematic of the CNT manufacturing apparatus which concerns on the 1st Embodiment of this invention. It is a schematic process drawing of the test verified about the method of producing | generating CNT in the CNT manufacturing apparatus which concerns on the 1st Embodiment of this invention. It is the figure on which the external shape of the photograph which produced | generated CNT with the production | generation method of FIG. 2 was drawn. It is the schematic of the CNT manufacturing apparatus which concerns on the 2nd Embodiment of this invention. It is the schematic of the CNT manufacturing apparatus which concerns on the 3rd Embodiment of this invention. It is the schematic of the CNT manufacturing apparatus which concerns on the 4th Embodiment of this invention. It is the schematic of the CNT manufacturing apparatus which concerns on the 5th Embodiment of this invention. It is the schematic of the CNT manufacturing apparatus which concerns on the 6th Embodiment of this invention. It is the schematic of the CNT manufacturing apparatus which concerns on the 7th Embodiment of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Reaction container, 2,47 ... Carbon nanotube (CNT), 3,41 ... Iron plate, 4 ... Heater (heating means), 5 ... Carbon raw material supply means, 6 ... Inert gas supply means, 7 ... CNT scraping collection Means 8: Iron plate activating means 9 ... Gas exhaust means 10 ... Driving roller 11, 52 ... Driven roller, 12 ... Heat resistant material, 13 ... Heat insulating material, 14 ... Heater control means, 16 ... Hydrocarbon supply nozzle, 17 DESCRIPTION OF SYMBOLS ... Carbon raw material accommodation tank, 18 ... Housing | casing, 19 ... Insulation material, 20 ... Inert gas supply nozzle, 21 ... Inert gas accommodation tank, 22 ... CNT scraping plate, 23 ... CNT collection can, 24 ... Exhaust nozzle, DESCRIPTION OF SYMBOLS 29 ... Polishing brush, 30 ... Acid solution supply nozzle, 35 ... Acid solution supply nozzle, 37 ... Acid solution supply means, 38 ... Viewing window, 51 ... Drive-up roller, 53a, 53b ... Support roller, 61 ... Drive means, 62 ... Pork, 63 ... main shaft, 64, 75 ... drive motor, 65a, 65b ... partition plate, 66 ... polishing brush, 67 ... CNT generator, 71 ... cylindrical vertical reaction vessel, 72, 81 ... cylinder, 73 ... rotating shaft 74 ... scraping blades, 76 ... sealing material.

Claims (3)

A reaction vessel capable of maintaining the inside in a reducing atmosphere, an endless strip-shaped iron plate which is provided in the reaction vessel and is driven by a roller and on which carbon nanotubes are generated, heating means for heating the strip-shaped iron plate, and reaction A carbon raw material supply means for supplying a carbon raw material into the container, an inert gas supply means for supplying an inert gas into the reaction container, a scraping recovery means for recovering the carbon nanotubes produced on the strip-shaped iron plate, and a reaction container Gas exhausting means for exhausting the gas inside, an acid solution applying brush for applying an acid solution to the surface of the strip-shaped iron plate, and an iron plate activating means for activating the strip-shaped iron plate by supplying an acid solution to the strip-shaped iron plate The iron plate activating means includes an acid solution supply nozzle having one end extending to the acid solution application brush, an acid solution storage tank that stores the acid solution, and an acid solution in the acid solution storage tank. Carbon nanotube production apparatus characterized by comprising a pump for sending to the acid solution application brush through feed nozzles. 2. The carbon nanotube production apparatus according to claim 1 , wherein the iron plate is an iron plate having high iron purity or an iron plate made of carbon steel containing iron. The carbon raw material supplied into the reaction vessel from the carbon source means, ethanol carbon nanotube production apparatus according to claim 1 or 2, wherein the a (including bioethanol).

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