WO2007069267A2 - Procede et appareil pour la synthese de nanotubes de carbone - Google Patents

Procede et appareil pour la synthese de nanotubes de carbone Download PDF

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Publication number
WO2007069267A2
WO2007069267A2 PCT/IN2006/000403 IN2006000403W WO2007069267A2 WO 2007069267 A2 WO2007069267 A2 WO 2007069267A2 IN 2006000403 W IN2006000403 W IN 2006000403W WO 2007069267 A2 WO2007069267 A2 WO 2007069267A2
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WIPO (PCT)
Prior art keywords
precursor material
growth reactor
group
inorganic precursor
growth
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PCT/IN2006/000403
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English (en)
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WO2007069267A3 (fr
Inventor
Gaurav Namdhar
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Gaurav Namdhar
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Application filed by Gaurav Namdhar filed Critical Gaurav Namdhar
Publication of WO2007069267A2 publication Critical patent/WO2007069267A2/fr
Publication of WO2007069267A3 publication Critical patent/WO2007069267A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts

Definitions

  • the present Invention relates generally to the large scale production of Carbon Nanotubes (CNT). Specifically it relates to a method and apparatus for single step continuous or semi-continuous synthesis of CNT, utilizing inorganic precursors for availability of required catalyst in situ in the nanotube growth environment.
  • CNT Carbon Nanotubes
  • CNT are long and thin hollow cylinders, made of carbon atoms.
  • CNT are rolled tubes of graphite in appearance having a hexagonal network of carbon atoms forming seamless tubes which may or may not be capped with fullerene like structure having pentagons at ends.
  • CNT are known for their remarkable mechanical, electronic, thermal and other properties.
  • CNT are mainly of two types, Single Wall Carbon Nano-tube (SWCNT) and Multi Walled Carbon Nano-tube (MWCNT), depending on number of concentric tubes involved in forming the structure. CNT were first discovered and reported in 1991 by Sumio Ijima, in an arc discharge.
  • CNT Various processes for producing CNT exist such as arc discharge, laser ablation, CVD, gas phase and plasma torch etc.
  • arc discharge process arc evaporates graphitic or composite anode (graphitic electrode doped with transition metals like Fe, Ni, Co etc.), which further yield CNT upon condensation on cathode and / or chamber walls.
  • Arc discharge process can be performed in various environments including air, inert gases and even liquids. These processes have high power requirement and provide lower yield. Further, the product from the arc discharge process is difficult to purify.
  • a graphitic or composite (graphite doped with transition metals like Fe, Ni, Co etc.) target is evaporated using pulsed or continuous laser in various environments.
  • CNT are obtained by condensation of evaporated graphitic or composite target on the walls of laser ablation chamber.
  • gaseous carbon precursors like hydrocarbon and organo-metallic catalyst precursors like metallocenes, metal carbonyls are subjected to plasma generated either by arc or microwave, which further yield CNT.
  • organo-metallic catalyst precursors like metallocenes
  • metal carbonyls are subjected to plasma generated either by arc or microwave, which further yield CNT.
  • Chemical Vapor deposition (CVD) and gas phase processes are essentially dependent on catalytic growth of nanotubes from carbon feeds like hydrocarbons and CO upon nanometer size transition metals acting as catalyst.
  • CVD processes use prior fabricated solid state catalyst, which is further fed in to a
  • CNT growth reactor or furnace for CNT growth gas phase processes utilize organo- metallic precursors to generate required catalyst in-situ in the CNT growth reactor itself.
  • CVD methods are essentially multi-step process because of involvement of at least two process blocks; one for the fabrication of catalyst and other for the growth of CNT.
  • Gas phase methods can be considered as single-step process where a single process block is responsible for generation of catalyst as well as nanotubes unlike CVD.
  • inorganic precursors like transition metal compounds and salts are used to prepare solid state catalyst to feed in to CVD processes for large scale synthesis.
  • the decomposition of inorganic precursors results in highly oxidative decomposition product which can be detrimental to CNT growth, especially in large scale production where significant amount of catalyst is needed for sizeable production. Therefore an inorganic precursor based system is essentially multi-step, where precursors are decomposed first out side CNT growth reactor and then solid state catalyst having very low or zero oxidation potential are fed into CNT growth reactor.
  • single-step process like gas phase methods essentially utilizes organo metallic precursors which don't complicate CNT growth because of their oxidation potential.
  • An object of the present invention is synthesis of carbon nanotubes.
  • Another object of the present invention is to provide a method and an apparatus for single-step, low cost and large scale synthesis of carbon nanotubes.
  • Yet another object of the present invention is to provide a solid-gas phase synthesis of carbon nanotubes, where catalyst is generated in-situ utilizing inorganic precursor.
  • Yet another object of the present invention is synthesis of carbon nanotubes which is easy in purification and its use in various applications.
  • FIG. 1 is a block diagram illustrating a system for the production of carbon nanotubes in accordance with an embodiment of the present invention.
  • FlG. 2 is a flow chart illustrating a method for production of carbon nanotubes in accordance with an embodiment of the present invention.
  • FIG. 4 is a Scanning Electron Microscopy (SEM) image of carbon nanotube material produced in accordance to an embodiment of the present invention.
  • FIG. 5 is a Raman spectra plot of carbon nanotube material produced in accordance to an embodiment of the present invention.
  • FIG. 1 is a block diagram illustrating an apparatus 100 for the production of carbon nanotubes in accordance with an embodiment of the present invention.
  • Apparatus 100 is a growth reactor capable of growing carbon nanotubes.
  • Apparatus 100 is attached with an inorganic precursor input module 101 and a support material input module 103.
  • Inorganic precursor input module 101 helps in introducing inorganic precursor.
  • examples of inorganic precursor are iron nitrate, iron acetate and the like in accordance with an embodiment of the present invention.
  • the inorganic precursor may be a mixture of two or more inorganic precursors along with water.
  • Support material input module 103 is used to introduce the support material into the growth reactor.
  • the support material is selected from a group comprising TiO 2 , MgO, AI 2 O 3 , SiO 2 and the like.
  • Support material provides required surface area for heterogeneous stabilization of liquid phase precursor and it further provides nucleation sites for decomposing inorganic precursor material. Use of support is not a necessary condition for nanotube growth but helps in achieving higher production by significantly improving available surface area for heterogeneous catalyst nucleation.
  • Apparatus 100 is further attached with a reactant gas inlet module 105.
  • Reactant gas input module 105 is utilized to introduce reactant gas flowing in counter to inorganic precursor and support.
  • the reactant gas is selected from the group comprising methane, ethane, propane, ethylene, propylene, butane, liquefied petroleum gas, natural gas and the like.
  • Apparatus 100 is a concentric tubular in shape, comprising an inner tube and an outer tube.
  • Inner tube allows decomposition and partial reduction of inorganic precursor material in a counter flow of gases. Nanotube growth takes place in a reducing atmosphere provided by the reactant gas in annular space. The decomposition products of inorganic precursor material have significant oxidation potential which can prove to be detrimental for nanotubes growth.
  • the annular nature of apparatus 100 allows the decomposition and partial reduction of inorganic precursor material to take place without mixing with the reducing atmosphere required for nanotube growth.
  • G1 in apparatus 100 is exhaust containing highly oxidative gaseous product resulting from the decomposition of inorganic precursor material.
  • G2 in apparatus 100 is exhaust containing unused hydrocarbon and gaseous products resulting due to dehydrogenation of hydrocarbons.
  • Annular space could support growth of nanotubes on catalyst clusters generated in inner tube in plug flow, fluidized bed or moving bed designs.
  • FIG. 2 is a flow chart illustrating a method for production of carbon nanotubes in accordance with an embodiment of the present invention.
  • support material is introduced into apparatus 100.
  • support material is selected from the group comprising Magnesium Oxide (MgO), Aluminum Oxide (AI 2 O 3 ), Titanium-di-oxide (TiO 2 ), Silicon-di-oxide (SiO 2 ) and the like.
  • inorganic precursor material is introduced into apparatus 100.
  • inorganic precursor material comprises one or more compound selected from a group comprising transition metal nitrate, transition metal acetate transition metal sulphates, transition metal chlorides, and the like in accordance with an embodiment of the present invention.
  • the inorganic precursor material further comprises one or more compounds selected from a group comprising nitrates, sulphates, chlorides and acetates of magnesium, titanium and aluminum.
  • the inorganic precursor material may further comprise additives selected from a group comprising urea, citric acid, glucose, glycerol, ammonia, ammonium nitrate, toluene, benzene and xylene.
  • the inorganic precursor material is selected from the group comprising ferric nitrate (Fe(NO 3 ) 3 ), ferric acetate (Fe(CH 3 COO) 3 ), and the like.
  • the inorganic precursor may be a mixture of two or more inorganic precursors along with water.
  • reactant gas is introduced into growth reactor 100.
  • the reactant gas comprises one or more gases selected from the group comprising methane, ethane, propane, butane, ethylene, propylene, acetylene, carbon monoxide and the like.
  • reactant gas comprises commercial fuel gases such as liquefied petroleum gas, natural gas and the like.
  • reactant gas may additionally comprise gases such as argon, neon, nitrogen and hydrogen.
  • the inorganic precursor material is decomposed to metal oxide in fine clusters. The particle size of the fine clusters ranges from few nanometers to few microns.
  • the decomposed inorganic precursor material is partially reduced to metallic clusters.
  • the metallic clusters help in initiating the growth of carbon nanotubes.
  • the catalytic reaction of reactant gas over metallic clusters leads to growth of carbon nanotubes at step 211.
  • FIG. 3 is a flow chart illustrating a method for production of carbon nanotubes in accordance with an embodiment of the present invention.
  • inorganic precursor material is introduced into apparatus 100.
  • inorganic precursor material comprises one or more compound selected from a group comprising transition metal nitrate, transition metal acetate transition metal sulphates, transition metal chlorides, and the like in accordance with an embodiment of the present invention.
  • the inorganic precursor material further comprises one or more compounds selected from a group comprising nitrates, sulphates, chlorides and acetates of magnesium, titanium and aluminum.
  • the inorganic precursor material may further comprise additives selected from a group comprising urea, citric acid, glucose, glycerol, ammonia, ammonium nitrate, toluene, benzene and xylene.
  • the inorganic precursor material is selected from the group comprising ferric nitrate (Fe(NO 3 ) 3 ), ferric acetate (Fe(CH 3 COO) 3 ), and the like.
  • the inorganic precursor may be a mixture of two or more inorganic precursors along with water.
  • reactant gas is introduced into growth reactor 100.
  • the reactant gas comprises one or more gases selected from the group comprising methane, ethane, propane, butane, ethylene, propylene, acetylene, carbon monoxide and the like.
  • reactant gas comprises commercial fuel gases such as liquefied petroleum gas, natural gas and the like.
  • reactant gas may additionally comprise gases such as argon, neon, nitrogen and hydrogen.
  • the inorganic precursor material is decomposed to metal oxide in fine clusters. The particle size of the fine clusters ranges from few nanometers to few microns.
  • the decomposed inorganic precursor material is partially reduced to metallic clusters. The metallic clusters help in initiating the growth of carbon nanotubes.
  • the catalytic reaction of reactant gas over metallic clusters leads to growth of carbon nanotubes at step 309.
  • FIG. 4 is an SEM image showing bundle of carbon nanotubes.
  • FIG. 5 is a Raman spectra plot of carbon nanotube material produced in accordance to an embodiment of the present invention.
  • the peaks at 1584 cm “1 and 2707 cm “1 in FIG. 6 clearly confirms the presence of carbon nanotubes. Further, the side peak at 1349 cm “1 indicates the existence defects and impurities.

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

Abstract

LA présente invention décrit un procédé et un appareil pour la synthèse en une étape, à faible coût et à grande échelle de nanotubes de carbone. Le procédé décrit la synthèse de nanotubes de carbone en utilisant des précurseurs inorganiques pour la disponibilité de catalyseur requis in situ dans un environnement de croissance de nanotube.
PCT/IN2006/000403 2005-10-07 2006-10-06 Procede et appareil pour la synthese de nanotubes de carbone WO2007069267A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN126MU2005 2005-10-07
IN126/MUM/2005 2005-10-07

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WO2007069267A2 true WO2007069267A2 (fr) 2007-06-21
WO2007069267A3 WO2007069267A3 (fr) 2007-09-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9987608B2 (en) 2014-09-19 2018-06-05 NanoSynthesis Plus, Ltd. Methods and apparatuses for producing dispersed nanostructures

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040234445A1 (en) * 2001-06-28 2004-11-25 Serp Philippe Gilles Method for the selective production of ordered carbon nanotubes in a fluidised bed
WO2005085130A2 (fr) * 2004-03-09 2005-09-15 Canatu Oy Nanotubes de carbone monoparoi, multiparois, fonctionnalises, dopes et composites de ces derniers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040234445A1 (en) * 2001-06-28 2004-11-25 Serp Philippe Gilles Method for the selective production of ordered carbon nanotubes in a fluidised bed
WO2005085130A2 (fr) * 2004-03-09 2005-09-15 Canatu Oy Nanotubes de carbone monoparoi, multiparois, fonctionnalises, dopes et composites de ces derniers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9987608B2 (en) 2014-09-19 2018-06-05 NanoSynthesis Plus, Ltd. Methods and apparatuses for producing dispersed nanostructures

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