WO2002094713A1 - Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed and the reactor - Google Patents

Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed and the reactor Download PDF

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Publication number
WO2002094713A1
WO2002094713A1 PCT/CN2002/000044 CN0200044W WO02094713A1 WO 2002094713 A1 WO2002094713 A1 WO 2002094713A1 CN 0200044 W CN0200044 W CN 0200044W WO 02094713 A1 WO02094713 A1 WO 02094713A1
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Prior art keywords
reactor
gas
catalyst
carbon
nano
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Ceased
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PCT/CN2002/000044
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English (en)
French (fr)
Chinese (zh)
Inventor
Fei Wei
Yao Wang
Guohua Luo
Hao Yu
Zhifei Li
Weizhong Qian
Zhanwen Wang
Yong Jin
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Tsinghua University
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Tsinghua University
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Application filed by Tsinghua University filed Critical Tsinghua University
Priority to AT02700107T priority Critical patent/ATE478031T1/de
Priority to JP2002591391A priority patent/JP3878555B2/ja
Priority to EP02700107A priority patent/EP1391425B1/en
Priority to US10/478,512 priority patent/US7563427B2/en
Priority to DE60237361T priority patent/DE60237361D1/de
Publication of WO2002094713A1 publication Critical patent/WO2002094713A1/zh
Anticipated expiration legal-status Critical
Priority to US12/400,713 priority patent/US20090286675A1/en
Ceased legal-status Critical Current

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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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836—Heating and cooling the reactor
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/22—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • 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
    • C01B32/164—Preparation involving continuous processes
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00132—Tubes
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/84—Manufacture, treatment, or detection of nanostructure
    • Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
    • Y10S977/843—Gas phase catalytic growth, i.e. chemical vapor deposition

Definitions

  • the invention relates to a method for continuously preparing carbon nanotubes by a gas-solid nano-agglomerated fluidized bed and a reaction device thereof, and belongs to the technical field of new materials and chemical equipment.
  • BACKGROUND-Carbon nanotubes have been reported as a new material for a decade. Although their excellent mechanical and electrical properties have attracted much attention from many physicists, chemists and materials scientists in the world, Without industrial application, the high price and difficulty of batch preparation are two important reasons that are interrelated. For example, the international market
  • the main technology of batch production of carbon nanotubes is a new process route and corresponding reactor technology.
  • the main methods for preparing carbon nanotubes are: graphite arc method, arc catalysis method and catalytic cracking method.
  • the catalytic cracking method is the mainstream method for preparing carbon nanotubes at present, and the generally favored technology is a low-carbon hydrocarbon catalytic cracking method.
  • the production of carbon nanotubes by catalytic cracking of low-carbon hydrocarbons is a typical chemical process, but it also involves the preparation of nanomaterials. The key issue is how to maximize the properties and characteristics of nanomaterials while meeting the reactions in the chemical process, Passing requirements.
  • Gas-solid fluidization technology as an effective means to strengthen gas-solid contact, has been widely used in many industrial and scientific research fields, especially suitable for powder production, processing and various use processes. It has the advantages of strong heat / heat supply capacity, easy to move in / out of powder products or catalysts.
  • the traditional gas-solid fluidized bed can only be used for the fluidization process of non-C particles with a diameter greater than 30 microns (Geldart D. Powder Technology, 1973, 7: 285).
  • the process because one-dimensional nano-materials will appear and easily bond, it will easily cause fluidization difficulties in the production process, which will cause agglomeration, local temperature, uneven concentration in the bed, or abnormality due to carbon deposition between particles. operating. Therefore, there have been no reports on the continuous mass production of carbon nanomaterials using fluidized beds.
  • the purpose of the present invention is to propose a method for continuously preparing carbon nanotubes in a nano-agglomerated fluidized bed and a reaction device thereof.
  • a nano-agglomerate fluidization technology full consideration is given to the aggregation and bonding behavior of the nanoparticles.
  • the method for continuously preparing carbon nanotubes by the nano-agglomerated fluidized bed reactor provided by the present invention includes the following steps:
  • the above-mentioned supported catalyst is placed in a catalyst activation reactor, and a flowing hydrogen or a mixture of carbon monoxide and nitrogen is passed through a reduction reaction at 500-90 ° C to reduce the transition metal oxide nanoparticles to elemental metals.
  • Nanoparticles in which hydrogen and nitrogen are mixed in a volume ratio of 1: 0 to 3 ⁇ 1, and the reduction space velocity is 0.3 to 3 hours.
  • the catalyst is a nano-agglomerate, and the agglomerate size is 1 to 1000 microns;
  • the above process can realize continuous production.
  • the second method for preparing carbon nanotubes of the present invention is:
  • the aggregate size of the catalyst is 1-1000 microns, and the bed density in the reactor is 20-1500 kg / m3, so that the catalyst support can be fluidized;
  • the nano-agglomerated fluidized bed reaction device designed by the present invention comprises a main reactor, a catalyst activator, a gas distributor, a gas-solid separator and a product degassing section.
  • the catalyst activator is in communication with the main reactor
  • the gas distributor is placed in the lower part of the main reactor, and the gas-solid separator is placed on the top of the main reactor.
  • the main reactor is provided with a heat exchange tube.
  • the bottom of the main reactor is provided with a gas inlet.
  • the product degassing section and the main reaction The lower part of the device is connected.
  • the catalyst activator can be omitted, and the metallocene compound can be directly passed into the main reactor containing the catalyst carrier, thereby achieving integration of catalyst preparation and reaction.
  • the key to this process is to maintain good flow / fluidization characteristics of the catalyst and the resulting carbon nanotube products in the form of agglomerates by selecting the appropriate catalyst and controlling appropriate operating conditions.
  • As the catalyst support fine fluid glass beads, silica, alumina, and carbon nanotubes can be used.
  • a carbon nanotube agglomerate with a loose agglomerate structure, an agglomerate size of 1 to 1000 microns, and a bulk density of 20 to 800 kg / m3 can be produced. Flow / fluidization performance.
  • the reactor designed by the invention has the following obvious features:
  • the bed density of the material in the reactor is moderate, and the material maintains the flow / fluidization state under the action of the airflow, which can provide sufficient growth space for the carbon nanotube and obtain a sufficiently high reaction intensity.
  • the heat transfer / heating of the reactor can be realized on a large-scale device, which is suitable for the exothermic or endothermic catalytic cracking process.
  • the reactor system has strong adjustability and great operation flexibility.
  • the feed and discharge positions of the reactor can be adjusted according to the requirements of the reaction residence time and the requirements of the product structure.
  • FIG. 1 is a schematic structural diagram of a device of a reaction device designed by the present invention.
  • 1 is the main reactor
  • 2 is a gas distributor
  • 3 is a heat transfer / heater
  • 4 is a catalyst inlet
  • 5 is a product outlet
  • 6 is a catalyst activator
  • 7 is a gas-solid separator
  • 8 is Air intake device
  • 9 is the product degassing section.
  • FIG. 2 is a typical scanning electron microscope photograph of carbon nanotube aggregates prepared by the method and the reaction device of the present invention.
  • FIG. 3 is a typical transmission electron micrograph of a carbon nanotube prepared by the method and the reaction device of the present invention.
  • FIG. 4 is a typical high-resolution transmission electron microscope photograph of carbon nanotubes prepared by the method and the reaction device of the present invention. detailed description
  • the nano-agglomerated fluidized bed reaction device designed by the present invention for continuous production of carbon nanotubes includes a main reactor 1, a catalyst activator 6, a gas distributor 2, a gas-solid separator 7 and product desorption. ⁇ ⁇ 9 ⁇ Gas section 9.
  • the catalyst activator 6 is in communication with the main reactor 1, the gas distributor 2 is placed at the lower part of the main reactor 1, the gas-solid separator 7 is placed at the top of the main reactor 1, and the heat exchanger tube 3 is provided in the main reactor.
  • a gas inlet is provided at the bottom of the main reactor, and a product degassing section 9 is connected to the lower part of the main reactor 1 through a product outlet 5.
  • the product outlet 5 can be used to adjust the height of the material in the reactor.
  • a degassing section 9 is provided at the discharge port to remove organic matter adsorbed by the product. Gas-solid separation at the top of the reactor ⁇ 7 ⁇ Seven.
  • the space velocity of the gas is 10,000 hours, and the flow velocity of the gas tower is 0.5 m / s.
  • FIG. 2 is a scanning electron microscope photograph of a carbon nanotube sample prepared in this embodiment.
  • the sample was obtained directly from the reactor without any purification and comminution. It can be seen from the figure that the sample exists in the form of agglomerates, the agglomerates vary in size, most of the agglomerates are less than 100 microns, and the shape is nearly spherical.
  • Figure 3 is a transmission electron micrograph of the above sample.
  • a small amount of unpurified sample was first ultrasonically dispersed in ethanol, and then dropped on a copper grid microgrid for observation under an electron microscope. It can be seen from the figure that the carbon tube in the sample has high purity, the diameter of the carbon tube is less than 10 nm, the thickness is uniform, and the tube length is very long.
  • Figure 4 is a high-resolution transmission electron micrograph of the above sample.
  • the sample preparation method is the same as that shown in Figure 3.
  • the carbon atom layer of multi-walled carbon nanotubes can be observed from the figure.
  • the catalyst is sent to a fluidized bed at a temperature of 520 ° C.
  • the catalyst is sent to the fluidized bed at a temperature of 870 ° C.
  • the reaction process The space velocity is 5000 hours-the air velocity of the gas tower is 0.8 m / s.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • the space velocity of the reaction process is 8000 hours— '
  • the tower flow rate was 1.3 m / s.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • the catalyst is sent to a fluidized bed at a temperature of 870 ° C.
  • the space velocity of the reaction process is 9000 hours, and the air flow velocity of the gas is 1.7 m / s.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)
  • Inorganic Fibers (AREA)
PCT/CN2002/000044 2001-05-25 2002-01-29 Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed and the reactor Ceased WO2002094713A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AT02700107T ATE478031T1 (de) 2001-05-25 2002-01-29 Kontinuierliche massenproduktion von kohlenstoffnanoröhren in einer nanoagglomerat- wirbelschicht
JP2002591391A JP3878555B2 (ja) 2001-05-25 2002-01-29 ナノ凝集体流動層を用いたカーボンナノチューブの連続製造方法及びその反応装置
EP02700107A EP1391425B1 (en) 2001-05-25 2002-01-29 Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed
US10/478,512 US7563427B2 (en) 2001-05-25 2002-01-29 Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed and the reactor
DE60237361T DE60237361D1 (de) 2001-05-25 2002-01-29 Kontinuierliche massenproduktion von kohlenstoffnanoröhren in einer nanoagglomerat-wirbelschicht
US12/400,713 US20090286675A1 (en) 2001-05-25 2009-03-09 Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed and the reactor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN01118349.7 2001-05-25
CNB011183497A CN1141250C (zh) 2001-05-25 2001-05-25 一种流化床连续化制备碳纳米管的方法及其反应装置

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/400,713 Continuation-In-Part US20090286675A1 (en) 2001-05-25 2009-03-09 Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed and the reactor

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WO2002094713A1 true WO2002094713A1 (en) 2002-11-28

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US (1) US7563427B2 (https=)
EP (1) EP1391425B1 (https=)
JP (1) JP3878555B2 (https=)
CN (1) CN1141250C (https=)
AT (1) ATE478031T1 (https=)
DE (1) DE60237361D1 (https=)
WO (1) WO2002094713A1 (https=)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005239531A (ja) * 2004-01-27 2005-09-08 Shimizu Corp 球状カーボンナノチューブ集合体およびその製造方法並びに複合体の製造方法
EP1428573A3 (de) * 2002-12-03 2009-07-29 FutureCarbon GmbH Vorrichtung und Verfahren zum Herstellen von Kohlenstoff-Nanomaterial
WO2011020970A2 (fr) 2009-08-17 2011-02-24 Arkema France Catalyseur fe/mo supporté, son procédé de préparation et utilisation pour la fabrication de nanotubes
WO2011020971A2 (fr) 2009-08-17 2011-02-24 Arkema France Catalyseur bi-couche, son procédé de préparation et son utilisation pour la fabrication de nanotubes
KR101155057B1 (ko) * 2003-04-09 2012-06-11 삼성코닝정밀소재 주식회사 탄소나노튜브의 제조방법
CN113135562A (zh) * 2020-01-20 2021-07-20 山东晶石大展纳米科技有限公司 一种制备碳纳米管和氢气的方法和装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090286675A1 (en) * 2001-05-25 2009-11-19 Tsinghua University Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed and the reactor
JP4160781B2 (ja) * 2002-05-27 2008-10-08 三菱重工業株式会社 繊維状ナノ炭素の製造方法及び装置
US6905544B2 (en) 2002-06-26 2005-06-14 Mitsubishi Heavy Industries, Ltd. Manufacturing method for a carbon nanomaterial, a manufacturing apparatus for a carbon nanomaterial, and manufacturing facility for a carbon nanomaterial
AU2003291133A1 (en) * 2002-11-26 2004-06-18 Carbon Nanotechnologies, Inc. Carbon nanotube particulates, compositions and use thereof
EP1445236A1 (fr) * 2003-02-05 2004-08-11 Université de Liège Procédé et installation pour la fabrication de nanotubes de carbone
GB0327169D0 (en) * 2003-11-21 2003-12-24 Statoil Asa Method
KR100626016B1 (ko) * 2004-09-20 2006-09-20 삼성에스디아이 주식회사 탄소나노케이지 제조 방법
DE102004054959A1 (de) * 2004-11-13 2006-05-18 Bayer Technology Services Gmbh Katalysator zur Herstellung von Kohlenstoffnanoröhrchen durch Zersetzung von gas-förmigen Kohlenverbindungen an einem heterogenen Katalysator
CN100371241C (zh) * 2004-11-24 2008-02-27 中国科学院金属研究所 一种制备大尺寸机械密封用各向同性热解炭材料的设备
CN1323029C (zh) * 2004-12-10 2007-06-27 中国科学院长春应用化学研究所 燃烧聚烯烃合成碳纳米管的方法
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