WO2008065121A1 - Procédé de synthèse et utilisation de nanotubes, en particulier de nanotubes de carbone - Google Patents

Procédé de synthèse et utilisation de nanotubes, en particulier de nanotubes de carbone Download PDF

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Publication number
WO2008065121A1
WO2008065121A1 PCT/EP2007/062900 EP2007062900W WO2008065121A1 WO 2008065121 A1 WO2008065121 A1 WO 2008065121A1 EP 2007062900 W EP2007062900 W EP 2007062900W WO 2008065121 A1 WO2008065121 A1 WO 2008065121A1
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WIPO (PCT)
Prior art keywords
nanotubes
process according
catalyst
support
alumina
Prior art date
Application number
PCT/EP2007/062900
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English (en)
Inventor
Dominique Plee
Jean-Luc Dubois
Anne Pigamo
Original Assignee
Arkema France
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
Priority claimed from FR0655226A external-priority patent/FR2909369B1/fr
Application filed by Arkema France filed Critical Arkema France
Priority to EP07847425A priority Critical patent/EP2086878A1/fr
Publication of WO2008065121A1 publication Critical patent/WO2008065121A1/fr

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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
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B1/008—Nanostructures not provided for in groups B82B1/001 - B82B1/007
    • 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
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/06—Multi-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/22—Electronic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/24—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/26—Mechanical properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter

Definitions

  • the subject of the present invention is a process for synthesizing nanotubes, especially carbon nanotubes, by chemical vapour deposition employing a fluidized catalyst bed.
  • the subject of the invention is also the nanotubes synthesized and their use for improving the mechanical and/or electrical and/or thermal properties of materials, especially polymeric materials.
  • Inorganic or carbon nanotubes are recognized at the present time as being materials having great advantages because of their mechanical properties, their very high aspect ratio (length/diameter ratio) and their electrical and thermal conduction properties.
  • Nanotubes based on boron, nitrogen and/or carbon are composed of graphite sheets that are wound up and terminated by hemispheres consisting of pentagons and hexagons with a structure similar to fullerenes.
  • Nanotubes are known to be composed of either a single sheet - they are then referred to as single-walled nanotubes or SWNTs - or several concentric sheets - called multi-walled nanotubes or MWNTs.
  • Boron, nitrogen and/or carbon nanotubes may be produced by various processes, such as electrical discharge, laser ablation or chemical vapour deposition (CVD).
  • CVD chemical vapour deposition
  • metal-based nanotubes sol-gel processes are used.
  • CVD seems to be the only one capable of manufacturing boron, nitrogen and/or carbon nanotubes in large quantity, an essential condition for achieving a cost price allowing them to be used industrially in bulk in materials based on polymers and/or resins, used in various industries, such as the automobile, electronics, optoelectronics, aeronautical and thermal or electrical protection industries.
  • a source of nitrogen-containing, boron-containing and/or carbon-containing gas is injected at a relatively high temperature high temperature onto a catalyst, said catalyst possibly consisting of a metal supported on an inorganic solid.
  • catalyst metals mention may preferably be made of iron, cobalt, nickel, molybdenum, and among supports, alumina, silica and magnesia, or even carbon, are found.
  • Carbon sources that may be envisaged are methane, ethane, ethylene, acetylene, benzene, ethanol, methanol, acetone or even CO/H 2 synthesis gas (the HIPCO process).
  • the gaseous source of boron is for example borane (B 2 H 6 ), and the gaseous source of nitrogen is especially pyridine, ammonia or ethylenediamine.
  • the reader may refer to the doctoral thesis of Marie Castignolles: "Etudes de Ia synthese et de Ia structure par microscopie et spectroscopie electroniques de nanotubes de carbone purs et dopes a I'azote [Studies on the synthesis and structure, using electron microscopy and spectroscopy, of pure and nitrogen-doped carbon nanotubes]", University of affiliated II, defended on 15 June 2006.
  • CNTs carbon nanotubes
  • a catalyst containing iron for example Fe 3 O 4 , iron on a carbon support, iron on an alumina support or iron on a carbon-containing fibril support
  • a carbon-containing gaseous compound preferably CO or one or more hydrocarbons
  • the catalysts are prepared by dry impregnation, by precipitation or by wet impregnation of a support.
  • this article mentions that the CNTs synthesized using a Co/AI 2 O 3 or Fe/AI 2 O 3 catalyst in the presence of acetylene have a diameter ranging from 20 to 40 nm, whereas they are finer (8 to 12 nm diameter) if an Fe-Co/ AI 2 O 3 catalyst is used.
  • the object of the present invention is to provide a novel process that is effective for manufacturing nanotubes, especially carbon nanotubes, having good weight productivity and good reproducibility. This process also makes it easier to purify the nanotubes, should this step be necessary for their application.
  • the subject of the present invention is a process for synthesizing nanotubes, especially carbon nanotubes, by decomposition of a gas source, at a temperature ranging from 400 to 1200 0 C in a reactor, by bringing it into contact with at least one (one or more) multivalent transition metals, the transition metal or metals being supported on a support having a specific surface area determined by the BET method of greater than 50 m 2 /g.
  • the BET method is based on the molecular multilayer adsorption of gas at low temperature, well known to those skilled in the art.
  • the catalyst is brought into contact with the gases in a fluidized bed.
  • the specific surface area of the support is chosen to be in the range from 70 m 2 /g to 400 m 2 /g.
  • inorganic supports for example a support consisting of at least one alumina, the intraparticle porosity of which is multimodal, as determined by the mercury porosimetry method.
  • the support is a multimodal alumina (having 2 or more than 2 porosity peaks), the total mercury pore volume of which is greater than 0.9 cm 3 /g, said alumina having at least one porosity peak in the range from 50 to 3000 nm.
  • the supports can be impregnated with an amount of transition metal(s) ranging up to 50% by weight of the final catalyst and especially in a range from 10 to 50% by weight of the final catalyst.
  • the size of the support particles is chosen so as to allow good fluidization of the catalyst during the CNT synthesis reaction.
  • the support particles preferably have a mean diameter D 50 ranging from 20 to 500 ⁇ m.
  • the catalyst is prepared by impregnating the support particles, especially in a stream of dry gas, with an impregnation solution containing at least one transition metal salt, especially an iron and/or cobalt and/or molybdenum salt, at a temperature lying within the range from room temperature to the boiling point of the solution.
  • the amount of impregnation solution is chosen so that the support particles are, at all times, in contact with a sufficient amount of solution to ensure formation of a film of the impregnation solution on the surface of the support particles.
  • the iron impregnation solution may be an aqueous iron nitrate solution.
  • the catalyst is calcined in a furnace, especially at a temperature between 300 and 750 0 C, for the purpose of purifying them and, for example, denitrifying them.
  • aqueous discharges for example aqueous nitrate discharges when the impregnation solution contains iron nitrate; after impregnation, the product obtained is heated to between 300 0 C and 400 0 C in a gas, whether inert or not, in order to remove the nitrates.
  • the catalyst is reduced in situ in the synthesis reactor and the catalyst does not see air again before the synthesis of the nanotubes. The iron thus remains in metallic form.
  • the carbon source may be chosen from any type of carbon-containing material, such as methane, ethane, propane, butane or any other aliphatic alkane containing more than 4 carbon atoms, cyclohexane, ethylene, propylene, butane, isobutene or any other aliphatic alkane containing more than 4 carbon atoms, benzene, toluene, xylene, cymene, ethyl benzene, naphthalene, phenanthrene, anthracene, acetylene or any other alkyne containing more than 4 carbon atoms, formaldehyde, acetaldehyde, acetone, methanol, ethanol, carbon monoxide, by themselves or as a mixture.
  • carbon-containing material such as methane, ethane, propane, butane or any other aliphatic alkane containing more than 4 carbon atoms, cyclohexan
  • the boron source is for example borane (B 2 H 6 ).
  • the nitrogen source is for example pyridine, ammonia or ethylenediamine.
  • the gas source and its composition fixes the composition of the nanotubes.
  • a carbon source allows carbon nanotubes to be manufactured.
  • the subject of the present invention is also nanotubes, especially carbon nanotubes, obtained by the above process.
  • the nanotubes thus obtained are multi-walled nanotubes having an external diameter lying within the range from 10 to 30 nm.
  • These nanotubes may be used as agents for improving the mechanical and/or electrical and/or thermal conductivity properties, especially in compositions based on polymers and/or resins. These nanotubes may be used in many fields, especially in electronics (depending on the use temperature and their structure, they may be conductors, semiconductors or insulators); in the mechanical field, for example for the reinforcement of composites, for example in the automotive field, aeronautical field (CNTs are one hundred times stronger and six times lighter than steel) and in the electromechanical field (they can elongate or contract by charge injection).
  • CNTs in macromolecular compositions intended for example for the packaging of electronic components, for the manufacture of fuel (petrol or diesel) lines, antistatic coatings, in thermistors, in electrodes for the energy sector, especially for supercapacitors, as agents dispersed in aqueous media, such as electromagnetic screening, etc.
  • the method of purifying the nanotubes, in order to remove the catalyst residues, for example using an acid solution is made easier owing to greater accessibility to the support.
  • the instrument used for carrying out the BET specific surface area measurements was a Micromeritics ASAP ® 2000 machine.
  • a catalyst containing 35% iron by weight was prepared by impregnation of
  • the particles of this alumina had a median diameter of about 85 ⁇ m and the surface area and porosity characteristics indicated below: BET surface area (m 2 /g) 148
  • An alumina was prepared by spray drying, without prior micronization, a suspension consisting of water, a calcined alumina (Sasol Puralox ® UF 5/230) and a pseudoboehmite (Sasol Dispersal ® 40). After calcination to convert the pseudoboehmite into ⁇ -alumina, the catalyst was prepared as explained in the counter-example.
  • An alumina was prepared by milling a bimodal alumina from Norton, supplied in the form of extrudates 5 mm in length having a BET surface area of 252 m 2 /g.
  • An alumina was prepared by spray drying, with prior micronization, a suspension consisting of water, a calcined alumina (Sasol Puralox ® UF 5/230) and a pseudoboehmite (Eurosupport Versal ® 250). The solids content was 21.3% by weight. After calcination to convert the pseudoboehmite into ⁇ -alumina, the catalyst was prepared as explained in the counter-example.
  • An alumina was prepared by spray drying, with prior micronization, a suspension consisting of water, a calcined alumina (Sasol Puralox ® UF 5/230) and a pseudoboehmite (Sasol Pural ® 400). The solids content was 42.5% by weight. After calcination to convert the pseudoboehmite into ⁇ -alumina, the catalyst was prepared as explained in the counter-example.
  • An alumina was prepared by spray drying, without prior micronization, a suspension consisting of water and a pseudoboehmite (Sasol Versal ® 250). The solids content was 26% by weight. After calcination to convert the pseudoboehmite into ⁇ -alumina, the catalyst was prepared as explained in the counter-example.
  • Example 6 (Ref: 2017 C93) (according to the invention) (according to the invention) (according to the invention) An alumina was prepared by spray drying, without prior micronization, a suspension consisting of water and a pseudoboehmite (Sasol Versal ® 250). The solids content was 15% by weight. After calcination to convert the pseudoboehmite into ⁇ -alumina, the catalyst was prepared as explained in the counter-example.
  • An alumina was prepared by milling a bimodal alumina in the form of extrudates 1.2 mm in length from Norton.
  • D 50 Apparent mean diameter of 50% of the particle population.
  • Example 9 (according to the invention) The denitrification operations, corresponding to the step of purifying the catalysts obtained according to the counter-example and examples 1 to 8, were carried out at 350 0 C in an oven under a stream of air for 2 h. About 2.5 g of catalyst thus denitrified was introduced, as a layer, into a reactor having a diameter of 5 cm and an effective height of 1 m, fitted with a separator intended to prevent fine particles from being entrained towards the top of the reactor. The reactor was heated for about 30 minutes up to 650 0 C and then the catalysts were reduced under 25 vol% H 2 /75 vol% N 2 for 30 minutes. The nitrogen was then replaced with ethylene, the reaction was left to continue for 1 hour and then the nanotubes formed were collected. In all cases, the total N 2 , H 2 /N 2 or C 2 H 2 /H 2 flow rates were constant at 160 Sl/min.
  • the productivity was determined by loss of ignition of the CNTs and the quality of the CNTs determined by electron microscopy.
  • MWNT multi-walled nanotubes
  • 0 diameter of the nanotubes.
  • Table 2 shows that the best productivity is obtained with catalysts having a multimodal porosity.
  • Table 2 also shows that the combination of iron and cobalt results in better CNT productivity and smaller CNTs. It may also be seen that the amount of catalyst has no influence on the productivity nor on the reproducibility of the CNTs in terms of diameter and structure.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un procédé de synthèse de nanotubes et en particulier de nanotubes de carbone, par décomposition d'une source gazeuse dans un réacteur, à une température allant de 400 à 1200 °C. Le procédé consiste à mettre en contact ladite source gazeuse avec au moins un métal de transition multivalent, le ou lesdits métaux de transition étant portés par un support ayant une surface spécifique, telle que déterminée par méthode BET, supérieure ou égale à 50 m2/g, spécialement comprise dans la plage allant de 70 m2/g à 400 m²/g. Le support selon l'invention est en particulier un support inorganique, par exemple de l'alumine ayant une porosité multimodale. L'invention concerne également les nanotubes ainsi produits et leur utilisation dans le but d'améliorer les propriétés mécaniques et/ou électriques et/ou thermiques de matériaux, en particulier de matériaux polymères.
PCT/EP2007/062900 2006-11-30 2007-11-27 Procédé de synthèse et utilisation de nanotubes, en particulier de nanotubes de carbone WO2008065121A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07847425A EP2086878A1 (fr) 2006-11-30 2007-11-27 Procédé de synthèse et utilisation de nanotubes, en particulier de nanotubes de carbone

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR0655226A FR2909369B1 (fr) 2006-11-30 2006-11-30 Procede de synthese de nanotubes, notamment de carbone, et leurs utilisations.
FR06/55226 2006-11-30
US87882707P 2007-01-05 2007-01-05
US60/878,827 2007-01-05

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2337631A1 (fr) * 2008-10-17 2011-06-29 Cheil Industries INC. Catalyseur sur support pour la synthèse de nanotubes de carbone, son procédé de préparation et nanotube de carbone l'utilisant
EP2340114A1 (fr) * 2008-10-23 2011-07-06 Cheil Industries Inc. Catalyseur supporté pour la synthèse de nanotubes de carbone, procédé d'élaboration et nanotube de carbone utilisant ce catalyseur
WO2013125689A1 (fr) * 2012-02-22 2013-08-29 三菱重工業株式会社 Catalyseur pour la production de nanotubes de carbone
US9506194B2 (en) 2012-09-04 2016-11-29 Ocv Intellectual Capital, Llc Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101785773B1 (ko) * 2015-02-06 2017-10-17 주식회사 엘지화학 구 형상의 알파-알루미나를 함유하는 카본나노튜브 합성용 담지촉매 및 그의 제조방법

Citations (6)

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EP0353129A1 (fr) * 1988-07-29 1990-01-31 Rhone-Poulenc Chimie Procédé de fabrication d'agglomérés d'alumine
WO2003002456A2 (fr) * 2001-06-28 2003-01-09 Institut National Polytechnique De Toulouse Procede de fabrication selective de nanotubes de carbone ordonne en lit fluidise
EP1449885A1 (fr) * 2003-02-18 2004-08-25 Atofina Mélanges de polyamide et de polyoléfine contenant des nanotubes de carbone
WO2005037745A1 (fr) * 2003-10-16 2005-04-28 Conocophillips Company Support de catalyseur de silice-alumine a distribution de pore bimodale, catalyseurs, procedes de fabrication et d'utilisation
WO2006008385A1 (fr) * 2004-06-23 2006-01-26 Institut National Polytechnique De Toulouse Procede de fabrication selective de nanotubes de carbone ordonne
EP1640065A2 (fr) * 2004-09-28 2006-03-29 Institut Français du Pétrole Nouveaux supports composites alumine sur alumine et méthode de préparation

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
EP0353129A1 (fr) * 1988-07-29 1990-01-31 Rhone-Poulenc Chimie Procédé de fabrication d'agglomérés d'alumine
WO2003002456A2 (fr) * 2001-06-28 2003-01-09 Institut National Polytechnique De Toulouse Procede de fabrication selective de nanotubes de carbone ordonne en lit fluidise
EP1449885A1 (fr) * 2003-02-18 2004-08-25 Atofina Mélanges de polyamide et de polyoléfine contenant des nanotubes de carbone
WO2005037745A1 (fr) * 2003-10-16 2005-04-28 Conocophillips Company Support de catalyseur de silice-alumine a distribution de pore bimodale, catalyseurs, procedes de fabrication et d'utilisation
WO2006008385A1 (fr) * 2004-06-23 2006-01-26 Institut National Polytechnique De Toulouse Procede de fabrication selective de nanotubes de carbone ordonne
EP1640065A2 (fr) * 2004-09-28 2006-03-29 Institut Français du Pétrole Nouveaux supports composites alumine sur alumine et méthode de préparation

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2337631A1 (fr) * 2008-10-17 2011-06-29 Cheil Industries INC. Catalyseur sur support pour la synthèse de nanotubes de carbone, son procédé de préparation et nanotube de carbone l'utilisant
CN102186583A (zh) * 2008-10-17 2011-09-14 第一毛织株式会社 用于合成碳纳米管的载体催化剂、其制备方法以及使用其的碳纳米管
EP2337631A4 (fr) * 2008-10-17 2014-07-09 Cheil Ind Inc Catalyseur sur support pour la synthèse de nanotubes de carbone, son procédé de préparation et nanotube de carbone l'utilisant
EP2340114A1 (fr) * 2008-10-23 2011-07-06 Cheil Industries Inc. Catalyseur supporté pour la synthèse de nanotubes de carbone, procédé d'élaboration et nanotube de carbone utilisant ce catalyseur
EP2340114A4 (fr) * 2008-10-23 2014-07-09 Cheil Ind Inc Catalyseur supporté pour la synthèse de nanotubes de carbone, procédé d'élaboration et nanotube de carbone utilisant ce catalyseur
WO2013125689A1 (fr) * 2012-02-22 2013-08-29 三菱重工業株式会社 Catalyseur pour la production de nanotubes de carbone
US20150011380A1 (en) * 2012-02-22 2015-01-08 Mitsubishi Heavy Industries, Ltd. Catalyst for carbon nanotube production
JPWO2013125689A1 (ja) * 2012-02-22 2015-07-30 三菱重工業株式会社 カーボンナノチューブ生成用触媒
US9506194B2 (en) 2012-09-04 2016-11-29 Ocv Intellectual Capital, Llc Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media

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EP2086878A1 (fr) 2009-08-12
KR20090087454A (ko) 2009-08-17

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