WO2010084721A1 - Procédé de fabrication d'un complexe de nanocarbone - Google Patents

Procédé de fabrication d'un complexe de nanocarbone Download PDF

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Publication number
WO2010084721A1
WO2010084721A1 PCT/JP2010/000203 JP2010000203W WO2010084721A1 WO 2010084721 A1 WO2010084721 A1 WO 2010084721A1 JP 2010000203 W JP2010000203 W JP 2010000203W WO 2010084721 A1 WO2010084721 A1 WO 2010084721A1
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Prior art keywords
carbon
catalyst
core tube
nanocarbon composite
carrier gas
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PCT/JP2010/000203
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English (en)
Japanese (ja)
Inventor
弓削亮太
湯田坂雅子
飯島澄男
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日本電気株式会社
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Priority to JP2010547428A priority Critical patent/JP5672008B2/ja
Publication of WO2010084721A1 publication Critical patent/WO2010084721A1/fr

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    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30

Definitions

  • Patent Document 2 describes a method of forming fine metal particles used as a catalyst for producing single-walled carbon nanotubes on a substrate.
  • a solution in which an inorganic metal salt or an organic metal salt of a catalyst metal is dispersed or dissolved in an organic solvent is prepared, this solution is applied to the substrate, dried, and then heated in an oxidizing atmosphere.
  • the solvent component remaining on the substrate is removed by oxidative decomposition, and metal oxide fine particles are formed on the substrate.
  • the catalyst metal oxide is removed in an atmosphere of an inert gas or a gas having a reducing action.
  • the catalyst metal fine particles are fixed to the substrate by reduction. According to this document, it is said that metal catalyst particles suitable for producing single-walled carbon nanotubes can be uniformly and reliably fixed to a solid surface of a substrate by a simple method.
  • Patent Document 1 describes a carbon fiber material manufacturing apparatus.
  • the catalytic metal used in this carbon fiber material production apparatus has a risk of causing sintering (aggregation) by heating, coalescing of metal particles, and an increase in the particle size.
  • the particle diameter of the catalyst metal varies, and it is difficult to control the diameter of the carbon nanotube formed from the catalyst metal.
  • Patent Document 2 describes a method for producing single-walled carbon nanotubes by fixing metal catalyst particles to a solid surface of a substrate. Also in this method, when the substrate is heated, the metal elements constituting the metal catalyst particles fixed to the substrate move, and there is a possibility that sintering occurs as in the above-mentioned Patent Document 1, and the diameter of the carbon nanotube is increased. It was difficult to control. In addition, when carbon nanotubes are synthesized using this method, it is necessary to exchange the substrate on which the metal catalyst particles are fixed each time, and it is difficult to synthesize a large number of carbon nanotubes by continuous production.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a nanocarbon composite capable of synthesizing a large amount of carbon nanotubes and obtaining carbon nanotubes as designed. is there.
  • a vertical core tube Heating means for heating the vertical core tube, Raw material supply means for using carbon nanohorn as a catalyst carrier, and supplying the catalyst carrier and a carbon source to the vertical furnace core tube, Carrier gas supply means for supplying a carrier gas to the vertical furnace core tube, In the state where the vertical furnace core tube is heated using the heating means, the catalyst carrier, the carbon source and the carrier gas are transferred to the vertical core tube using the raw material supply means and the carrier gas supply means.
  • An apparatus for producing a nanocarbon composite is provided in which the carbon nanotubes are vapor-phased and grown from the catalyst support to obtain a nanocarbon composite by circulating inside.
  • a large amount of carbon nanotubes can be synthesized and carbon nanotubes can be obtained as designed.
  • FIG. 1 It is a cross-sectional schematic diagram which shows the structure of the nanocarbon composite manufacturing apparatus of embodiment of this invention. It is a schematic diagram of a carbon nanohorn aggregate. It is a schematic diagram of a catalyst-supporting carbon nanohorn aggregate. It is a schematic diagram which shows the catalyst carrying
  • the nanocarbon composite manufacturing apparatus 100 includes the control unit 122, the discharge unit 130, the first flow rate control unit 142, the raw material supply path 144, the first nozzle 146, the second flow rate control unit 152, and the like shown in FIG.
  • a carrier gas supply path 154 and a second nozzle 156 are provided.
  • the vertical furnace core tube 110 includes an electric furnace 120 (heating means) on the outer periphery thereof.
  • the vertical core tube 110 has a function as a reaction tube for growing a nanotube from a catalyst particle on a catalyst-supporting carbon nanohorn aggregate in a gas phase flow growth in the core tube.
  • the electric furnace 120 heats the vertical core tube 110 and raises the temperature inside the vertical core tube 110.
  • the electric furnace 120 is provided with a control unit 122 for controlling the heat generation temperature of the electric furnace 120.
  • the catalyst particles 4 supported and encapsulated in the carbon nanohorn aggregate 2 according to the present embodiment may be of various types including known ones that are conventionally known to have nanotube-forming ability. Then, Fe, Ni, Co, Pt, Au, Cu, Mo, W, Mg, or a compound thereof, or an alloy thereof is exemplified.
  • the compound may be in the form of a conventionally known inorganic acid salt or organic acid salt, complex, organometallic compound, or the like.
  • an oxide of the above metal is preferable, and a metal complex such as ferrocene, phthalocyanine, or cisplatin is preferably used.
  • the pressure is preferably 1 atm (1013 Pa) or less in the gas phase, and the size and amount of the catalyst particles 4 to be introduced can be controlled by changing the introduction amount, temperature, time, and the like.
  • the introduction amount is preferably up to about 80% by weight with respect to the amount of nanocarbon.
  • the temperature at the time of introduction is preferably about room temperature or higher and about 1800 ° C. or lower.
  • the introduction time can be about 0 hour to 48 hours or less.
  • the carbon nanohorn 1 has a tubular structure in which one end of a carbon nanotube obtained by rounding a graphite sheet into a cylindrical shape has a conical shape, and usually van der Waals force acting between the conical portions.
  • the conical portions are aggregated so as to protrude from the surface like horns around the carbon nanotubes.
  • the lower end portion of the conical portion of the carbon nanohorn 1 is provided around the tube.
  • the horn vicinity of a cone part be the front-end
  • the catalyst-carrying carbon nanohorn aggregate 5 obtained through the above steps and the carbon source 6 are dispersed in a solvent to prepare a dispersion.
  • a solvent for example, dimethylformamide (DMF), toluene, ethanol used for the carbon source 6 and the like can be used, and these can be used alone or in admixture of two or more. Further, if necessary, the dispersion is stirred so as to be uniform. Further, the catalyst-supporting carbon nanohorn aggregate 5 may be dispersed in the carbon source 6.
  • the temperature in the vertical furnace core tube 110 is raised to the nanotube growth temperature by the electric furnace 120 (heating means).
  • Carrier gas is supplied from the carrier gas supply unit 150 to the upper part of the vertical core tube 110 and is circulated from the upper part of the vertical core tube 110 toward the lower part. At this time, the carrier gas is lowered at a constant flow rate.
  • the catalyst particles 4 of the catalyst-supporting carbon nanohorn aggregate 5 are heated in the heating region of the vertical core tube 110.
  • the catalyst particles 4 and the carbon source 6 react with each other, and the carbon nanotubes 9 are vapor-grown and grown from the catalyst particles 4.
  • the nanocarbon composite 10 in which the carbon nanotubes 9 are grown from the catalyst of the catalyst-supporting carbon nanohorn aggregate 5 can be synthesized in the vertical furnace core tube 110 (S102, FIG. 5).
  • the carrier gas is discharged from the discharge unit 130, and the synthesized nanocarbon composite 10 is recovered by a recovery device provided in the discharge unit 130 (S104). This completes the synthesis of the nanocarbon composite.
  • the vapor phase flow growth method of the present embodiment is a kind of CVD (Chemical Vapor Deposition) method, in which a carbon raw material containing a catalyst and a reaction accelerator is atomized by a spray or the like and introduced into a heating furnace.
  • CVD Chemical Vapor Deposition
  • Carbon nanotubes 9 such as single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes can be selectively produced by using the above metals or compounds as a catalyst and changing the gas phase flow growth conditions. . Furthermore, it is possible to control the diameter of the carbon nanotube 9 by changing the vapor-phase flow growth conditions. For example, in a simple substance of Fe, Ni, Co or an alloy thereof, it is possible to mainly grow double-walled carbon nanotubes by controlling the catalyst size to 3 nm or more and 6 nm or less. Further, by controlling the catalyst size to 1 nm or more and 3 nm or less, single-walled carbon nanotubes can mainly be grown. When the catalyst size is 6 nm or more, many multi-walled carbon nanotubes are included.
  • the carrier gas, the catalyst-supporting carbon nanohorn aggregate 5, and the carbon source 6 are lowered from the upper part of the vertical core tube 110 toward the vertical core tube 110, and the electric furnace 120 region of the vertical core tube 110 is formed.
  • the carbon nanotubes 9 can be synthesized from the catalyst of the catalyst-supporting carbon nanohorn aggregate 5 by the vapor phase growth method.
  • the catalyst-supporting carbon nanohorn aggregate 5 and the carbon source 6 are composed of a hydrocarbon compound such as methane, ethane, ethylene, acetylene, benzene, and toluene, or an alcohol such as methanol and ethanol.
  • a carrier gas such as an organic compound or a carbon source-containing compound such as Co as an atmosphere gas, a rare gas such as argon, an inert gas such as nitrogen, or a mixed gas of an inert gas and hydrogen, It is heated at a temperature of 350 ° C. or higher and 1500 ° C. or higher.
  • the obtained carbon nanotubes produced single-walled or double-walled carbon nanotubes, and many single-walled carbon nanotubes were observed under the above conditions. It was done. Further, the carbon nanotubes grown from the catalyst had few carbon nanotube bundles, and the carbon nanotubes were uniformly dispersed and grown. The diameter of the carbon nanotube is about 0.7 nm to 2.5 nm in the case of a single wall, 1.5 nm to 3 nm in the case of a double wall, and the length is about 10 ⁇ m to 100 ⁇ m in many cases. .
  • carbon nanotube growth was attempted using the CVD method. As a result, similar results were obtained with Co and Ni. As a result of continuous operation for 1 hour under the above conditions, 2 g of the nanocarbon composite could be easily synthesized.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)

Abstract

Ce procédé de fabrication d'un complexe de nanocarbone, qui utilise des nanocornets de carbone en tant que support de catalyseur, est tel que, grâce à une méthode de croissance en lit fluidisé en phase gazeuse, l'on obtient un complexe de nanocarbone en faisant croître des nanotubes de carbone à partir dudit support de catalyseur.
PCT/JP2010/000203 2009-01-20 2010-01-15 Procédé de fabrication d'un complexe de nanocarbone WO2010084721A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010547428A JP5672008B2 (ja) 2009-01-20 2010-01-15 ナノカーボン複合体の製造方法および製造装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-010401 2009-01-20
JP2009010401 2009-01-20

Publications (1)

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WO2010084721A1 true WO2010084721A1 (fr) 2010-07-29

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012079683A (ja) * 2010-09-09 2012-04-19 Nec Corp 導電性ペーストおよびこれを用いた回路基板
JP2012079682A (ja) * 2010-09-09 2012-04-19 Nec Corp 導電性ペーストおよびこれを用いた回路基板
US20120202060A1 (en) * 2009-10-16 2012-08-09 Nec Corporation Nanotube-nanohorn complex and method of manufacturing the same
WO2017154529A1 (fr) * 2016-03-08 2017-09-14 学校法人早稲田大学 Appareil de fabrication de nanostructure de carbone fibreux et procédé de fabrication de nanostructure de carbone fibreux
JP2022545305A (ja) * 2019-08-21 2022-10-27 ヒンドスタン ペテローリアム コーポレーション リミテッド 触媒組成物およびその用途

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113490638B (zh) * 2019-02-22 2024-03-29 住友电气工业株式会社 碳纳米管及其集合线、集合线集束的制法、它们的制造装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001073231A (ja) * 1999-09-01 2001-03-21 Nikkiso Co Ltd 炭素繊維質物製造装置、炭素繊維質物の製造方法及び炭素繊維質物付着防止装置
WO2007088829A1 (fr) * 2006-01-31 2007-08-09 Japan Science And Technology Agency Materiau portant un nanohorn de carbone et procede de synthese de nanotube de carbone
WO2008090728A1 (fr) * 2007-01-25 2008-07-31 Nec Corporation Composite de nanocornet de carbone de support de catalyseur et procédé permettant de le produire
WO2008093661A1 (fr) * 2007-01-31 2008-08-07 Nec Corporation Agrégat de nanocarbone et son procédé de production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001073231A (ja) * 1999-09-01 2001-03-21 Nikkiso Co Ltd 炭素繊維質物製造装置、炭素繊維質物の製造方法及び炭素繊維質物付着防止装置
WO2007088829A1 (fr) * 2006-01-31 2007-08-09 Japan Science And Technology Agency Materiau portant un nanohorn de carbone et procede de synthese de nanotube de carbone
WO2008090728A1 (fr) * 2007-01-25 2008-07-31 Nec Corporation Composite de nanocornet de carbone de support de catalyseur et procédé permettant de le produire
WO2008093661A1 (fr) * 2007-01-31 2008-08-07 Nec Corporation Agrégat de nanocarbone et son procédé de production

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120202060A1 (en) * 2009-10-16 2012-08-09 Nec Corporation Nanotube-nanohorn complex and method of manufacturing the same
JP2012079683A (ja) * 2010-09-09 2012-04-19 Nec Corp 導電性ペーストおよびこれを用いた回路基板
JP2012079682A (ja) * 2010-09-09 2012-04-19 Nec Corp 導電性ペーストおよびこれを用いた回路基板
WO2017154529A1 (fr) * 2016-03-08 2017-09-14 学校法人早稲田大学 Appareil de fabrication de nanostructure de carbone fibreux et procédé de fabrication de nanostructure de carbone fibreux
JPWO2017154529A1 (ja) * 2016-03-08 2019-01-17 学校法人早稲田大学 繊維状炭素ナノ構造体製造装置及び繊維状炭素ナノ構造体製造方法
JP2022545305A (ja) * 2019-08-21 2022-10-27 ヒンドスタン ペテローリアム コーポレーション リミテッド 触媒組成物およびその用途
JP7311596B2 (ja) 2019-08-21 2023-07-19 ヒンドスタン ペテローリアム コーポレーション リミテッド 触媒組成物およびその用途

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JPWO2010084721A1 (ja) 2012-07-12

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