[go: up one dir, main page]

US20090022651A1 - Process and Apparatus for Producing Carbon Nanotube - Google Patents

Process and Apparatus for Producing Carbon Nanotube Download PDF

Info

Publication number
US20090022651A1
US20090022651A1 US12/223,450 US22345007A US2009022651A1 US 20090022651 A1 US20090022651 A1 US 20090022651A1 US 22345007 A US22345007 A US 22345007A US 2009022651 A1 US2009022651 A1 US 2009022651A1
Authority
US
United States
Prior art keywords
catalyst
porous support
powder
flame
carbon nanotubes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/223,450
Other languages
English (en)
Inventor
Masato Tani
Toshiki Goto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Otsuka Chemical Co Ltd
Original Assignee
Otsuka Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Otsuka Chemical Co Ltd filed Critical Otsuka Chemical Co Ltd
Assigned to OTSUKA CHEMICAL CO., LTD. reassignment OTSUKA CHEMICAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GOTO, TOSHIKI, TANI, MASATO
Publication of US20090022651A1 publication Critical patent/US20090022651A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • C01B32/162—Preparation characterised by catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • 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
    • 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

Definitions

  • the present invention relates to process and apparatus for producing carbon nanotube by a combustion method.
  • Arc discharge, laser irradiation and chemical vapor deposition (CVD) have been conventionally known as methods for synthesis of carbon nanotubes.
  • the arc discharge and laser irradiation methods require expensive and dangerous apparatuses such as an evacuator and a high-voltage large-current power source and produce carbon nanotubes in the low yield, which have been problems.
  • the CVD method achieves production of carbon nanotubes generally under low pressure. This not only requires a vacuum apparatus and the like but also complicates control of process conditions such as temperature and pressure, which problematically increase the production cost.
  • a combustion method utilizing a flame has been noted as a promising industrial production method, because it can obtain both a raw material for carbon nanotubes and a formation energy of carbon nanotubes from a fuel gas.
  • Fullerene known as carbon nanomaterial other than carbon nanotube, can be produced at low prices by this combustion method.
  • Non-patent Literature 1 synthesis of carbon nanotubes is achieved by the combustion method wherein a stainless steel mesh having a catalytic effect is exposed to a flame.
  • this process is low in carbon nanotube productivity and also difficult to recover produced carbon nanotubes, which have been problems.
  • Patent Literature 1 proposes to hold a substrate having a catalyst metal perpendicular to a flame and physically shave off carbon nanotubes formed on the substrate. This case results in the improved yield of carbon nanotubes compared to the case where they are synthesized on the mesh substrate. However, a major portion of the flame that does not come into direct contact with the substrate is wasted because it is unserviceable as a raw material for the carbon nanotubes and only evacuated for diffusion, which raises a problem of low industrial production efficiency.
  • Patent Literature 2 discloses a method for producing carbon nanotubes by allowing a magnesium oxide substrate to support thereon a catalyst metal and a cocatalyst metal, forming carbon nanotubes by a CVD method and then contacting them with an acid or alkaline solution for dissolution of the substrate, catalyst metal and cocatalyst metal so that the carbon nanotubes are separated therefrom.
  • this method utilizes a CVD method in the production of carbon nanotubes, which requires a vacuum apparatus and the like and involves complex control of process conditions such as temperature and pressure. Accordingly, the problem of high production cost arises.
  • Patent Literature 1 Japanese Patent Laid-Open No. 2005-247644
  • Patent Literature 2 Japanese Patent Laid-Open No. 2004-182548
  • Non-patent Literature 1 Randall L. VanderWal, Lee J. Proceedings of the combustion Institute, 29 (2002), PP. 1079-1085
  • the production process of the present invention is a process which produces carbon nanotubes by a combustion method and is characterized as including the steps of preparing a catalyst-supporting powder comprising a base powder and a catalyst supported on a surface of the base powder, allowing a porous support having internal through-pores that permit passage of a flame to hold the catalyst-supporting powder non-adherently within the through-pores, placing the porous support holding the catalyst-supporting powder in a combustion oven having one open end, and generating a carbon-containing flame in a burner portion disposed at the other end of the combustion oven and feeding the flame into the through-pores of the porous support to form carbon nanotubes on the surface of the catalyst-supporting powder within the through-pores.
  • the catalyst-supporting powder comprising a base powder and a catalyst supported on a surface of the base powder is held non-adherently within the through-pores of the porous support and the carbon-containing flame is subsequently fed into the through-pores of the porous support so that carbon nanotubes are formed on the surface of the catalyst-supporting powder within the through-pores. Since the catalyst-supporting powder is held non-adherently within the through-pores, its entire surface can be utilized in the formation of carbon nanotubes thereon. This enables efficient production of carbon nanotubes.
  • the catalyst-supporting powder having a surface on which carbon nanotubes have been formed is not affixed to the through-pores of the porous support. Accordingly, the catalyst-supporting powder subsequent to formation of carbon nanotubes can be easily extracted from the porous support.
  • the use of a combustion method in the production of carbon nanotubes eliminates the necessity of controlling complex production conditions such as temperature and pressure and thus permits production of carbon nanotubes with a simpler apparatus. Therefore, a large quantity of carbon nanotubes can be produced economically at low cost, which makes the present process more suitable for industrial production.
  • a shielding member is preferably provided at one end of the combustion oven for directing a part of a flow of the flame back to the porous support side.
  • the provision of such shielding member allows a flow of the flame to partly return to the porous support side and enables the flame containing unreacted carbon to again contact with the catalyst-supporting powder within the through-pores of the porous support, leading to further formation of carbon nanotubes. Accordingly, carbon nanotubes can be produced further efficiently.
  • the base powder preferably comprises a material which is soluble in an acid or alkali.
  • the use of such base powder eases recovery of carbon nanotubes by the fashion which follows. Subsequent to formation of carbon nanotubes on its surface, the catalyst-supporting powder is extracted from the porous support and then contacted to an acid or alkali that dissolves the base powder and the catalyst.
  • the base powder soluble in an acid or alkali can be illustrated by an oxide or salt of at least one metal selected from Mg, Si, Na, Li, Ca, Al and Zn.
  • Examples of particularly preferred base powders include magnesium hydroxide, magnesium oxide, calcium hydroxide and calcium oxide.
  • the acid that dissolves the base powder can be illustrated by aqueous solutions of hydrochloric acid, nitric acid, sulfuric acid and organic acid.
  • the alkali that dissolves the base powder can be illustrated by aqueous solutions of sodium hydroxide, potassium hydroxide and ammonia.
  • a concentration of the acid or alkali may preferably be at least 0.01% by weight, more preferably 0.5-10% by weight, for example.
  • a temperature of an aqueous solution of the acid or alkali is not particularly specified, so long as it can maintain the state of aqueous solution, but generally preferably within the range of 30-80° C.
  • the catalyst-supporting powder for use in the present invention comprises the base powder and the catalyst supported on the surface of the base powder.
  • a compound containing at least one metal selected from Co, Cr, Fe, Mo, Ni and V is preferably used as the catalyst to be supported.
  • the base powder may be allowed to support the catalyst thereon by a method wherein the base powder is contacted to a solution containing a metal salt of the catalyst dissolved therein.
  • salts of catalyst metal compounds include nitrates, chlorides, sulfates, carboxylates and the like. A concentration of this solution is preferably up to the saturated solubility of the salt, generally 0.005-0.5% by weight, preferably 0.005-0.1% by weight.
  • solvents that dissolve the metal salt of the catalyst include water, organic solvents such as lower alcohols (e.g., methanol and ethanol), and mixed solvents containing water and water-soluble organic solvents. The use of water is particularly preferred.
  • the base powder can be contacted to the solution by various methods such as dipping and spraying.
  • the use of the dipping method is particularly preferred.
  • the base powder is contacted to the solution at a temperature of 0-100° C., preferably 20-80° C., more preferably 40-60° C.
  • the solvent is dried to thereby form the catalyst-supporting powder.
  • the drying temperature may be 50-300° C., for example.
  • the amount of the catalyst supported on the powder is preferably 1-20% by weight, more preferably 5-10% by weight, based on the weight of the catalyst-supporting powder.
  • the porous support in the present invention has the through-pores capable of holding the catalyst-supporting powder.
  • porous supports include (1) a tangled metal or ceramic fibers aggregate, (2) a stack of metal or ceramic meshes and (3) a structure made of a porous metal or ceramic.
  • the material for the porous support is preferably heat-resistant and has a melting point of at least 700° C., more preferably at least 1,000° C.
  • materials include titanium, tungsten, tungsten carbide, molybdenum, stainless steel, aluminum oxide, mullite and quartz. Particularly preferred among them are tungsten, tungsten carbide and stainless steel.
  • the porous support has internal through-pores which permit passage of a carbon-containing flame in the production of carbon nanotubes and preferably has a volumetric porosity of 50-99.9%, more preferably 98-99.9%.
  • volumetric porosity is below 50%, efficient production of carbon nanotubes may fail due to the increasing difficulty of the porous support to hold a large quantity of the catalyst-supporting powder.
  • an upper limit of the volumetric porosity is not particularly specified, it is generally difficult to fabricate or obtain the porous support having a volumetric porosity of exceeding 99.9%.
  • the above-specified volumetric porosity is the one prior to formation of carbon nanotubes. As such carbon nanotubes are formed on the surface of the catalyst-supporting powder, the catalyst-supporting powder within the through-pores increases its volume to reduce the volumetric porosity.
  • the present invention provides a process for producing carbon nanotubes by a combustion method.
  • a carbon-containing flame is generated in the burner portion disposed at the other end of the combustion oven.
  • the flame is generated by burning a carbon-containing gas and an oxygen-containing gas.
  • the burner may be a premixed burner or a diffusion burner. Also, the burner may be provided with a cooling or other heat-dissipation system.
  • useful carbon-containing gases include hydrocarbons that can be gasified at elevated temperatures, such as methane, ethane, propane, butane, ethylene, propylene, acetylene, methanol, ethanol, propanol, benzene, toluene and xylene; and hydrocarbons containing oxygen, sulfur, nitrogen or the like.
  • hydrocarbons that can be gasified at elevated temperatures, such as methane, ethane, propane, butane, ethylene, propylene, acetylene, methanol, ethanol, propanol, benzene, toluene and xylene
  • hydrocarbons containing oxygen, sulfur, nitrogen or the like such as methane, ethane, propane, butane, ethylene, propylene, acetylene, methanol, ethanol, propanol, benzene, toluene and xylene
  • ethylene and propane is particularly preferred.
  • Examples of useful oxygen-containing gases include air and oxygen. Air is preferably used.
  • oxygen in the oxygen-containing gas is preferably present in the amount of 0.1-20 parts by volume, more preferably 1-3 parts by volume, based on 1 part by volume of the carbon-containing gas.
  • the flame in the combustion oven is preferably a laminar flame free of a turbulent flow.
  • a steady, premixed laminar flame preferably constitutes a gas composition.
  • a temperature of the flame is preferably maintained within the range of 500° C.-1,000° C., more preferably within the range of 600° C.-800° C. If the flame temperature falls below 500° C., a combustion reaction of the fuel gas does not proceed to result in the failure to form carbon nanotubes. On the other hand, if the flame temperature goes beyond 1,000° C., this high temperature retards formation of carbon nanotubes (conversion of carbon into solid form) and subjects carbon nanotubes, even if formed in a small quantity, to burning and decomposition.
  • a time period during which the catalyst-supporting powder is kept in contact with the flame may be 3 minutes-30 minutes, more preferably 5 minutes-15 minutes, for example. If the contact time period is less than 3 minutes, a temperature rise of an entire reaction region inside the combustion oven remains insufficient, so that carbon nanotubes are only formed locally.
  • the production apparatus of the present invention is an apparatus for producing carbon nanotubes by a combustion method.
  • the production apparatus has a porous support having internal through-pores for non-adherently holding a catalyst-supporting powder which comprises a base powder and a catalyst supported on a surface of the base powder, a combustion oven having one open end and an interior portion for accommodation of the porous support and a burner portion disposed at the other end of the combustion oven, and is operable to generate a carbon-containing flame in the burner portion and subsequently feed the flame into the through-pores of the porous support so that carbon tubes are formed on the surface of the catalyst-supporting powder within the through-pores.
  • the production apparatus of the present invention also includes a shielding member provided at the one end of the combustion oven for directing a part of a flow of the flame back to the porous support side.
  • a shielding member provided at the one end of the combustion oven for directing a part of a flow of the flame back to the porous support side.
  • the provision of such a shielding member allows a part of a flow of the flame to return to the porous support side and enables the component remaining unreacted in the flame to again contact with the catalyst-supporting powder within the through-pores of the porous support for formation of carbon nanotubes. Accordingly, carbon nanotubes can be produced further efficiently.
  • the shielding member is not particularly specified, so long as it can be disposed at the one end of the combustion oven and direct a part of the flame flow back to the porous support side.
  • the shielding member may have the same material type and structure as the porous support.
  • the shielding member in the present invention is preferably configured such that it directs a part of the flame flow back to the porous support side and discharges the other part of the flame flow to outside from the one end of the combustion oven.
  • carbon nanotubes can be produced more efficiency with a simpler apparatus.
  • FIG. 1 is a schematic view, showing the apparatus used in Examples in accordance with the present invention for producing carbon nanotubes.
  • FIG. 2 is a photomicrograph taken using a scanning electron microscope, showing the catalyst-supporting powder with carbon nanotubes formed on its surface, as obtained in Examples in accordance with the present invention.
  • FIG. 3 is a photomicrograph taken using a scanning electron microscope, showing carbon nanotubes obtained in Examples in accordance with the present invention.
  • the resultant was allowed to stand and then filtered to obtain a precipitate.
  • This precipitate was thrice washed with water and filtered to obtain a precipitate.
  • the resulting precipitate was dried at 20° C. for 12 hours and then ground in a mortar to obtain 21.2 g of a catalyst-supporting powder.
  • This catalyst-supporting powder was subjected to powder X-ray diffraction analysis, differential thermogravimetric analysis and energy dispersive X-ray analysis and, as a result, confirmed as comprising the catalyst-supporting magnesium hydroxide and magnesium oxide each containing magnesium, nickel and molybdenum at the ratio by mol of 78:14:8. Also, the catalyst metal content of the catalyst-supporting powder was approximately 29% by weight.
  • the thus-obtained catalyst-supporting powder was used to produce carbon nanotubes by a combustion method.
  • FIG. 1 is a schematic view, showing a production apparatus. Disposed at a lower end 1 a of a combustion oven 1 is a burner 3 above which a mesh tray 6 is located. A porous support 2 is located above the mesh tray 6 . A shielding member 5 is disposed at an upper end of the combustion oven 1 .
  • the combustion oven 1 is 3 cm in inner diameter and 30 cm in height.
  • the burner 3 is 7 cm in height.
  • the mesh tray 6 is located 5 cm above a top edge of the burner 3 . This mesh tray 6 is designed to prevent the porous support 2 from falling off.
  • a brush-like stainless steel aggregate obtained by randomly entangling 0.5 mm wide, 0.1 mm thick and 10-100 mm long stainless steel fibers is used as the porous support 2 .
  • This porous support 2 has a volumetric porosity of 98% and is inserted from the upper end 1 a of the combustion oven 1 for placement in the position.
  • the porous support 2 is about 6 cm in height and placed in a region 15-21 cm away from a bottom of the combustion oven 1 .
  • porous support 2 comprising the stainless steel fibers aggregate was placed inside the combustion oven 1 in the preceding fashion, 1.0 g of the catalyst-supporting powder was allowed to fall dispersingly so that the catalyst-supporting powder particles were held within the porous support 2 .
  • a shielding member 5 made by randomly entangling the same stainless steel fibers as used in obtaining the porous support 2 and having a volumetric porosity of 90% was inserted through the upper end 1 b of the combustion oven 1 .
  • a premixed combustion gas containing ethylene and air at the ratio (ethylene:air) by volume of 1.5:10 was supplied to the burner 3 to generate a flame 4 .
  • the flame 4 was passed through the mesh tray 6 and the porous support 2 , and discharged outside from the shielding member 5 . A part of a flow of the flame 4 was directed back to the porous support 2 side by the shielding member 5 .
  • the flame was generated for about 10 minutes to form carbon nanotubes on a surface of the catalyst-supporting powder within the porous support 2 .
  • a temperature near the porous support 2 was 700-900° C.
  • a differential pressure with respect to an atmosphere was 0.25-0.4 Pa and a velocity of an exhaust gas was 0.31-0.5 m/second.
  • porous support 2 was removed from the combustion oven 1 .
  • the porous support 2 comprising stainless steel fibers was in the form of a cocoon that caught black powder particles therein. These black powder particles were shaken off from the porous support 2 and collected. The collected black powder particles were then added to a 1-N nitric acid at 50° C., followed by an hour of stirring. This was then filtered through a 5C filter paper to obtain a precipitate which was subsequently dried at 120° C. for 10 hours.
  • the thus-obtained black substance was observed with a scanning electron microscope and a transmission electron microscope, and further analyzed and measured using a Raman spectroscope and a thermal analyzer. From the results, the obtained black substance was identified as multi-wall carbon nanotube (MWCNT).
  • MWCNT multi-wall carbon nanotube
  • FIG. 2 is a photomicrograph taken using a scanning electron microscope, showing the black powder subsequent to removal from the porous support but prior to addition to the nitric acid solution.
  • FIG. 3 is a photomicrograph taken using a scanning electron microscope, showing the carbon nanotubes (CNT) obtained subsequent to treatment of the black powder with the nitric acid solution that removed the base powder and the catalyst.
  • CNT carbon nanotubes
  • the thus-obtained carbon nanotubes weighed 2.3 g. Accordingly, the process was confirmed to enable efficient production of a large amount of carbon nanotubes.
  • Example 1 The procedure of Example 1 was followed, except that the burner 3 was changed from a premixed burner to a diffusion burner and a premixed combustion gas containing ethylene and air at the ratio (ethylene:air) by volume of 1.75:10 was supplied to the diffusion burner, to produce carbon nanotubes.
  • Ethylene and air were separately supplied to the diffusion burner. They were mixed just before a burner port and burned.
  • the thus-obtained carbon nanotubes weighed 3.5 g. Accordingly, the process was confirmed to enable efficient production of a large amount of carbon nanotubes.
  • Example 1 The procedure of Example 1 was followed, except that a metal porous support (product of Sumitomo Electric Toyama Co., Ltd., product name CELMET; nickel-based) was used as the porous support 2 , to produce carbon nanotubes.
  • a metal porous support product of Sumitomo Electric Toyama Co., Ltd., product name CELMET; nickel-based
  • the metal porous support has a volumetric porosity of 98%, a height of about 7 cm and a diameter of about 3 cm.
  • the catalyst-supporting powder was held within the metal porous support in the following fashion. After the metal porous support was placed inside the combustion oven 1 , 0.2 g of the catalyst-supporting powder was allowed to fall dispersingly from the upper end 1 b of the combustion oven 1 . Vibration was applied to the metal porous support so that the catalyst-supporting powder particles were shaken off to enter an interior portion of the metal porous support and held therein. This operation was repeated 5 times, so that 1.0 g of the catalyst-supporting powder particles was held dispersedly throughout the interior portion of the metal porous support.
  • the thus-obtained carbon nanotubes weighed 2.1 g. Accordingly, the process was confirmed to enable efficient production of a large amount of carbon nanotubes.
  • Example 2 The procedure of Example 2 was followed, except that a stack of stainless steel meshes was used as the porous support 2 , to produce carbon nanotubes.
  • the stainless steel mesh was used in the form of a stainless steel mesh cage (3 cm in diameter and 1 cm in height) having a 40-mesh size (40 openings per square inch) with an opening diameter of 0.2 mm. 5 of these stainless steel meshes were arranged above each other to provide a stack thereof for use as the porous support. A volumetric porosity of this porous support was 98.5%.
  • the thus-obtained carbon nanotubes weighed 2.2 g. Accordingly, the process was confirmed to enable efficient production of a large amount of carbon nanotubes.
  • porous support in the present invention is not limited to those embodied in the above Examples. Any other porous support can be used, so long as it can hold the catalyst-supporting powder non-adherently and has sufficient heat resistance to withstand combustion in the combustion oven.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)
  • Inorganic Fibers (AREA)
US12/223,450 2006-02-01 2007-01-31 Process and Apparatus for Producing Carbon Nanotube Abandoned US20090022651A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2006024553 2006-02-01
JP2006-024553 2006-02-01
PCT/JP2007/051544 WO2007088867A1 (ja) 2006-02-01 2007-01-31 カーボンナノチューブの製造方法及び製造装置

Publications (1)

Publication Number Publication Date
US20090022651A1 true US20090022651A1 (en) 2009-01-22

Family

ID=38327438

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/223,450 Abandoned US20090022651A1 (en) 2006-02-01 2007-01-31 Process and Apparatus for Producing Carbon Nanotube

Country Status (7)

Country Link
US (1) US20090022651A1 (zh)
EP (1) EP1980529A1 (zh)
JP (1) JP5173440B2 (zh)
KR (1) KR20080092934A (zh)
CN (1) CN101378988B (zh)
TW (1) TWI341295B (zh)
WO (1) WO2007088867A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8608989B2 (en) * 2011-03-03 2013-12-17 Florida State University Research Foundation, Inc. Fire retardant materials and methods

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8951632B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US9005755B2 (en) 2007-01-03 2015-04-14 Applied Nanostructured Solutions, Llc CNS-infused carbon nanomaterials and process therefor
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US20110038785A1 (en) * 2008-03-17 2011-02-17 Otsuka Chemical Co., Ltd. Method for manufacturing carbon nanotube
JP5473306B2 (ja) * 2008-12-03 2014-04-16 関西電力株式会社 カーボンナノチューブ製造用触媒、それを用いたカーボンナノチューブの製造方法及び該触媒の製造方法
DE102008060560A1 (de) * 2008-12-04 2010-06-10 Linde Aktiengesellschaft Vorrichtung und Verfahren zum Herstellen von Kohlenstoff-Nanoröhrchen (Carbon nanotubes (CNTs))
US20100266478A1 (en) * 2008-12-10 2010-10-21 Cheil Industries Inc. Metal Nano Catalyst, Method for Preparing the Same and Method for Controlling the Growth Types of Carbon Nanotubes Using the Same
WO2010076885A1 (ja) * 2008-12-30 2010-07-08 独立行政法人産業技術総合研究所 単層カーボンナノチューブ配向集合体、バルク状単層カーボンナノチューブ配向集合体、粉体状単層カーボンナノチューブ配向集合体、およびその製造方法
CA2752525C (en) 2009-02-27 2017-05-16 Applied Nanostructured Solutions, Llc Low temperature cnt growth using gas-preheat method
US20100224129A1 (en) 2009-03-03 2010-09-09 Lockheed Martin Corporation System and method for surface treatment and barrier coating of fibers for in situ cnt growth
KR101696212B1 (ko) * 2009-04-10 2017-01-13 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. 연속하여 이동하는 기질에서 탄소 나노튜브를 제조하는 장치 및 방법
US8969225B2 (en) 2009-08-03 2015-03-03 Applied Nano Structured Soultions, LLC Incorporation of nanoparticles in composite fibers
KR101870844B1 (ko) 2010-09-14 2018-06-25 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. 표면 상에 성장된 탄소 나노튜브를 가진 유리 기판 및 그의 제조 방법
BR112013005529A2 (pt) 2010-09-22 2016-05-03 Applied Nanostructured Sols substratos de fibras de carbono que têm nanotubos de carbono desenvolvidos nos mesmos, e processos para a produção dos mesmos
RU2480398C1 (ru) * 2011-09-29 2013-04-27 Учреждение Российской академии наук Институт прикладной механики (ИПРИМ РАН) Способ получения углеродных нанотрубок и устройство для его осуществления
US20150093322A1 (en) * 2012-04-27 2015-04-02 Showa Denko K.K. Method for purifying multi-walled carbon nanotubes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5985232A (en) * 1994-03-30 1999-11-16 Massachusetts Institute Of Technology Production of fullerenic nanostructures in flames
US20030044342A1 (en) * 2001-08-30 2003-03-06 Alford J. Michael Burners and combustion apparatus for carbon nanomaterial production
US20030119920A1 (en) * 2001-12-21 2003-06-26 Yong Wang Carbon nanotube-containing catalysts, methods of making, and reactions catalyzed over nanotube catalysts

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003221216A (ja) * 2001-11-22 2003-08-05 Mitsubishi Chemicals Corp フラーレン類の製造方法及びその装置
US7250148B2 (en) * 2002-07-31 2007-07-31 Carbon Nanotechnologies, Inc. Method for making single-wall carbon nanotubes using supported catalysts
US7335344B2 (en) * 2003-03-14 2008-02-26 Massachusetts Institute Of Technology Method and apparatus for synthesizing filamentary structures
CN1673073A (zh) * 2005-03-11 2005-09-28 北京大学 一种合成单壁碳纳米管的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5985232A (en) * 1994-03-30 1999-11-16 Massachusetts Institute Of Technology Production of fullerenic nanostructures in flames
US20030044342A1 (en) * 2001-08-30 2003-03-06 Alford J. Michael Burners and combustion apparatus for carbon nanomaterial production
US20030119920A1 (en) * 2001-12-21 2003-06-26 Yong Wang Carbon nanotube-containing catalysts, methods of making, and reactions catalyzed over nanotube catalysts

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8608989B2 (en) * 2011-03-03 2013-12-17 Florida State University Research Foundation, Inc. Fire retardant materials and methods
US8608990B1 (en) * 2011-03-03 2013-12-17 Florida State University Research Foundation, Inc. Fire retardant materials and methods
US8728359B2 (en) 2011-03-03 2014-05-20 Florida State University Research Foundation, Inc. Fire retardant materials and methods

Also Published As

Publication number Publication date
EP1980529A1 (en) 2008-10-15
TWI341295B (en) 2011-05-01
TW200734271A (en) 2007-09-16
KR20080092934A (ko) 2008-10-16
JPWO2007088867A1 (ja) 2009-06-25
CN101378988B (zh) 2012-04-18
JP5173440B2 (ja) 2013-04-03
WO2007088867A1 (ja) 2007-08-09
CN101378988A (zh) 2009-03-04

Similar Documents

Publication Publication Date Title
US20090022651A1 (en) Process and Apparatus for Producing Carbon Nanotube
JP5550833B2 (ja) 高品質単層カーボンナノチューブ成長の方法および装置
JP5065898B2 (ja) 狭小な直径分布のカーボン単層ナノチューブの合成
JP5156383B2 (ja) 単層カーボンナノチューブ合成用触媒
US9796591B2 (en) Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products
JP5102633B2 (ja) 長いカーボン単層ナノチューブを成長させるための方法
AU2010236807B2 (en) Method for producing solid carbon by reducing carbon oxides
US9409779B2 (en) Catalyst for producing carbon nanotubes by means of the decomposition of gaseous carbon compounds on a heterogeneous catalyst
JP5594961B2 (ja) 狭小な直径のカーボン単層ナノチューブの合成
JP4777518B2 (ja) カーボンナノチューブを生産するための方法および触媒
CN1297474C (zh) 生产碳纳米管的方法和装置
US9783421B2 (en) Carbon oxide reduction with intermetallic and carbide catalysts
JP2015518461A (ja) 固体カーボンナノチューブ、固体炭素クラスタ、およびフォレストを生成するための方法および反応器
JP2009530214A (ja) カーボン単層ナノチューブの成長のための触媒
JPWO2007088829A1 (ja) カーボンナノホーン担持体とカーボンナノチューブの合成方法
WO2021054897A1 (en) Waste treatment system
Kingston et al. Recent advances in laser synthesis of single-walled carbon nanotubes
Somanathan et al. Helical multiwalled carbon nanotubes (h-MWCNTs) synthesized by catalytic chemical vapor deposition
Hu et al. The structural effect of Ni/ZrO2 on the formation and the reactivity of the carbon formed from methane decomposition
JP2009508797A (ja) 高品質単層カーボンナノチューブの合成方法
KR20070110739A (ko) 탄소나노튜브 합성용 촉매의 제조 방법 및 이의 제조 장치
KR20230083719A (ko) 활성화 전처리된 촉매를 포함하는 유동화 반응기를 이용하는 수소 및 탄소체 제조방법 및 제조장치
JP2009041151A (ja) 燃焼法による炭素繊維の製造方法
Shajahan et al. Growth Phenomena of Carbon Nanotubes Over Co-Mo/MgO Catalyst from the Decomposition of Acetylene

Legal Events

Date Code Title Description
AS Assignment

Owner name: OTSUKA CHEMICAL CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TANI, MASATO;GOTO, TOSHIKI;REEL/FRAME:021359/0057;SIGNING DATES FROM 20080704 TO 20080707

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION