WO2005033007A1 - カーボンナノチューブの製法方法および製造装置 - Google Patents
カーボンナノチューブの製法方法および製造装置 Download PDFInfo
- Publication number
- WO2005033007A1 WO2005033007A1 PCT/JP2004/014094 JP2004014094W WO2005033007A1 WO 2005033007 A1 WO2005033007 A1 WO 2005033007A1 JP 2004014094 W JP2004014094 W JP 2004014094W WO 2005033007 A1 WO2005033007 A1 WO 2005033007A1
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- WIPO (PCT)
- Prior art keywords
- carbon nanotubes
- producing
- irradiating
- carbon nanotube
- mixed solution
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/166—Preparation in liquid phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Definitions
- the present invention relates to an apparatus and a method for decomposing and recombining organic substances to form carbon nanotubes.
- Carbon nanotubes are substances that have applications as electrode materials for fuel cells or as next-generation nanodevice materials. Depending on its structure, such as single-phase or multi-layer, thickness and twist, it can be used as metal or semiconductor, and its application range is wide. In addition, it is a substance composed only of carbon atoms and is environmentally friendly.
- a conventional method for producing carbon nanotubes there is a technique in which an Fe-based metal catalyst supported on zeolite is used to thermally synthesize a carbon compound gas while flowing it in an appropriate amount in a vacuum vessel while synthesizing (CCVD method). Further, as a technique for mass-producing carbon nanotubes, a method using a gas such as a pressurized fluidized bed process, a gas phase fluidization method, and a C02 laser method has been proposed (Non-Patent Document 1).
- WO 02Z038827 pamphlet uses a source of a material to be deposited in an electrolytic solution containing a pair of spaced electrodes.
- An invention is described in which a stream of foam containing bubbles is generated, a plasma glow discharge is formed in the bubble area, and a material is plasma-deposited on the electrode.
- this is an invention relating to electroplating and does not apply to the production of carbon nanotubes.
- the principle is based on DC glow discharge, and the reaction speed is low.
- microwave and electromagnetic waves are used to assist in the generation of glow discharge, it does not mention any specific content, and it does not provide any technical details.
- the technique described in the literature is considered to be pure DC glow discharge. Therefore, only an electrolytic solution can be used, it cannot be applied to many organic solvents which are non-electrolytic solutions, and it is not suitable for the production of carbon nanotubes.
- Patent document 1 International Publication No. 02Z038827 pamphlet
- Non-Patent Document 1 -You Diamond Vol. 13, No. 3, page 2, New Diamond Forum Edited, issued on July 25, 2003
- Non-Patent Document 1 uses gas as a raw material and performs synthesis in a gas phase, so that production efficiency is limited.
- An object of the present invention is to provide a manufacturing method and a manufacturing apparatus for manufacturing carbon nanotubes at high speed and at low cost.
- the method for producing carbon nanotubes of the present invention generates bubbles in a mixed solution containing an organic solvent and an organometallic complex and irradiates electromagnetic waves to generate plasma in the mixed solution. This is to produce carbon nanotubes.
- Zeolite supporting a metal may be added to the mixed solution, and the mixed solution may particularly support iron.
- the organic solvent may include benzene.
- the organometallic complex may contain at least one of fluorene or metacene. Further, the mixture may be irradiated with ultrasonic waves together with electromagnetic waves.
- the apparatus for producing carbon nanotubes of the present invention includes a container for containing a mixed solution containing an organic solvent and an organometallic complex, a bubble generating means for generating bubbles in the mixed solution, and a plasma for irradiating the bubbles with electromagnetic waves. And a recovery means for recovering the synthesized carbon nanotubes.
- the method and apparatus for producing carbon nanotubes of the present invention have an effect that carbon nanotubes can be produced at a high speed by generating high-energy plasma in an organic solvent to cause a high-speed reaction. .
- FIG. 1 is an explanatory view showing one example of a carbon nanotube manufacturing apparatus.
- FIG. 2 is an explanatory view showing another example of a carbon nanotube manufacturing apparatus.
- FIG. 3 is a transmission electron micrograph of a synthesized carbon nanotube.
- FIG. 4 is a graph showing a Raman spectrum.
- FIG. 1 is an explanatory view showing one example of a carbon nanotube production apparatus according to the present invention.
- the container 2 of the carbon nanotube manufacturing apparatus 1 contains a mixed solution 3 containing an organic solvent and an organometallic complex.
- the size of the container 2 can be appropriately selected according to the required processing capacity, and may be as small as a beaker or a large processing tank for implementing as a large plant. .
- the carbon nanotube manufacturing apparatus 1 further includes bubble generating means, but in this example, the ultrasonic wave irradiating means 4 is the bubble generating means.
- the bubble generation means bubbles can be generated by covering the container 2 with another container and reducing the pressure with a vacuum pump or the like, or providing a heating means in the mixed solution 3 or supplying gas from the outside. Even if they are introduced, a combination of these may be used.
- the carbon nanotube manufacturing apparatus 1 has an electromagnetic wave irradiation unit 5 for irradiating the mixed solution 3 with an electromagnetic wave.
- the tip of the electromagnetic wave irradiating means 5 is provided in the container 2, so that the electromagnetic wave can be intensively irradiated toward the bubbles from the tip in the liquid.
- a mixed solution 3 containing an organic solvent and an organometallic complex is placed in the container 2, and as the organic solvent, for example, a hydrocarbon such as benzene-dodecane can be used.
- the organic metal complex include, for example, Hue sen (CH Fe) and Fe
- the mixed solution 3 ⁇ may also contain zeolite powder!
- the carbon nanotube manufacturing apparatus of this example is of a batch processing type. After synthesizing a predetermined amount of carbon nanotubes, the reaction is terminated, and the carbon nanotubes contained in the mixed solution 3 are separated and recovered.
- FIG. 2 is an explanatory view showing another example of a carbon nanotube manufacturing apparatus. Descriptions of items common to the example shown in FIG. 1 are omitted.
- This example is a manufacturing apparatus for continuous processing.
- the carbon nanotube production apparatus 1 includes a pipe 7 and a pump 8 for allowing the mixed solution 3 to flow out of the container 2 and flow into the container 2 again. Further, in the middle of the pipe 7, a carbon nanotube separation / collection tank 9 is provided as a collecting means for separating and collecting the carbon nanotubes. Is provided.
- the pump 8 By operating the pump 8, a predetermined amount of the mixed liquid is constantly circulated. If the mixed liquid is not circulated, the synthesized carbon nanotubes will float near the electrodes of the electromagnetic wave generating means 5 and try to hinder the continuity of the plasma. By quickly bringing the nanotubes to the outside, the sustaining of the plasma is facilitated, and a large amount of carbon nanotubes can be produced continuously.
- the mixture 3 circulates clockwise in the pipe 7.
- the mixed liquid containing the synthesized carbon nanotubes is discharged from the right side of the container 2 and carried to the carbon nanotube separation / recovery tank 9. In the carbon nanotube separation / recovery tank 9, the carbon nanotubes are separated from the mixed solution and recovered.
- the mixed solution from which the carbon nanotubes have been removed flows through the pipe 7 from the left side of the container 2.
- the zeolite used here will be described in detail. This zeolite has an average pore size of 0.5 nm (M / 0-A1 O-xSiO-yH0
- n is the valence of the cation M
- x is an integer of 2 or more
- y is an integer of 0 or more, commonly known as molecular sieves 5A) impregnated with Fe ions.
- FeCl 2 ferrous iron
- HONH CI hydroxylamine hydrochloride
- This solution and molecular sieve 5A are placed in an appropriate container and stirred well, and then the container is evacuated to impregnate Fe 2+ into the molecular sieve.
- stirring was performed in a vacuum for 5 hours.
- the solution after stirring is filtered, and the solid matter remaining on the filter paper is dried at 70 ° C for 5 hours in a nitrogen atmosphere.
- the solid after drying was polished well in a mortar and used as Fe-supported zeolite. Benzene mixed with this Fe-supported zeolite exhibits electrical conductivity, but does not hinder plasma generation!
- the mixed solution thus prepared is placed in the container 2, and irradiated with ultrasonic waves at an output of 30W.
- the mixture was irradiated with 2.45 GHz electromagnetic waves at a power of 300 W for 10 seconds while dispersing and diffusing zeolite and Hue-Sen Sen. White plasma was generated, and black powder was instantaneously formed in the mixture.
- FIG. 3 is a transmission electron micrograph of the formed black powder. It can be confirmed that carbon nanotubes having a zeolite particle surface force of about 0.5 m were formed.
- Figure 4 is a graph showing the Raman spectrum of the black powder. A radial breathing mode of so-called carbon nanotubes was observed at 200 to 300 cm-1 and it can be confirmed that carbon nanotubes were also formed.
- the method and apparatus for producing carbon nanotubes of the present invention synthesize a large amount of carbon nanotubes at a high speed using a liquid containing an organic solvent as a material, and can be applied as a means for industrially producing carbon nanotubes.
- the structure of the device is simple, it can be made small, and it can be applied as a test device.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2005514423A JP4674304B2 (ja) | 2003-09-30 | 2004-09-27 | カーボンナノチューブの製法方法および製造装置 |
Applications Claiming Priority (2)
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JP2003-339642 | 2003-09-30 | ||
JP2003339642 | 2003-09-30 |
Publications (1)
Publication Number | Publication Date |
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WO2005033007A1 true WO2005033007A1 (ja) | 2005-04-14 |
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PCT/JP2004/014094 WO2005033007A1 (ja) | 2003-09-30 | 2004-09-27 | カーボンナノチューブの製法方法および製造装置 |
Country Status (2)
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WO (1) | WO2005033007A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004306029A (ja) * | 2003-03-27 | 2004-11-04 | Techno Network Shikoku Co Ltd | 化学反応装置および有害物質分解方法 |
JP2008247627A (ja) * | 2007-03-29 | 2008-10-16 | Nippon Steel Chem Co Ltd | 炭素材料の製造方法および炭素材料ならびに電気二重層キャパシタ |
JP2008254985A (ja) * | 2007-04-09 | 2008-10-23 | Toyama Prefecture | ナノカーボン材料の製造方法 |
WO2009119059A1 (ja) * | 2008-03-26 | 2009-10-01 | Nuエコ・エンジニアリング株式会社 | グラフェンの製造方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1143316A (ja) * | 1997-07-23 | 1999-02-16 | Agency Of Ind Science & Technol | カーボンナノチューブの製造方法 |
JP2004244283A (ja) * | 2003-02-14 | 2004-09-02 | Kanegafuchi Chem Ind Co Ltd | カーボンナノチューブの製造方法 |
JP2004299987A (ja) * | 2003-03-31 | 2004-10-28 | National Institute Of Advanced Industrial & Technology | カーボンナノチューブの製造方法 |
-
2004
- 2004-09-27 WO PCT/JP2004/014094 patent/WO2005033007A1/ja active Application Filing
- 2004-09-27 JP JP2005514423A patent/JP4674304B2/ja not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1143316A (ja) * | 1997-07-23 | 1999-02-16 | Agency Of Ind Science & Technol | カーボンナノチューブの製造方法 |
JP2004244283A (ja) * | 2003-02-14 | 2004-09-02 | Kanegafuchi Chem Ind Co Ltd | カーボンナノチューブの製造方法 |
JP2004299987A (ja) * | 2003-03-31 | 2004-10-28 | National Institute Of Advanced Industrial & Technology | カーボンナノチューブの製造方法 |
Non-Patent Citations (1)
Title |
---|
ZHANG Y. ET AL.: "Synthesis of aligned carbon nanotubes in organic liquids", J. MATER. RES., vol. 17, no. 9, 2002, pages 2457 - 2464, XP002982511 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004306029A (ja) * | 2003-03-27 | 2004-11-04 | Techno Network Shikoku Co Ltd | 化学反応装置および有害物質分解方法 |
JP2008247627A (ja) * | 2007-03-29 | 2008-10-16 | Nippon Steel Chem Co Ltd | 炭素材料の製造方法および炭素材料ならびに電気二重層キャパシタ |
JP2008254985A (ja) * | 2007-04-09 | 2008-10-23 | Toyama Prefecture | ナノカーボン材料の製造方法 |
WO2009119059A1 (ja) * | 2008-03-26 | 2009-10-01 | Nuエコ・エンジニアリング株式会社 | グラフェンの製造方法 |
US8349142B2 (en) | 2008-03-26 | 2013-01-08 | Masaru Hori | Method for producing graphene |
JP5463282B2 (ja) * | 2008-03-26 | 2014-04-09 | 勝 堀 | グラフェンの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2005033007A1 (ja) | 2007-11-15 |
JP4674304B2 (ja) | 2011-04-20 |
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