AbstractA method and apparatus for catalytic production of carbon nanotubes. Catalytic particles are exposed to different process conditions at successive stages wherein the catalytic particles do not come in contact with reactive (catalytic) gases until preferred process conditions have been attained, thereby controlling the quantity and form of carbon nanotubes produced. The method also contemplates methods and apparatus which recycle and reuse the gases and catalytic particulate materials, thereby maximizing cost efficiency, reducing wastes, reducing the need for additional raw materials, and producing the carbon nanotubes, especially SWNTs, in greater quantities and for lower costs. Other References- Bethune et al.; “Cobalt-Catalyzed Growth of Carbon Nanotubes with Single-Atomic-Layer Walls,” Nature, 363:605-607, Jun. 1993.
- V. Brotons et al., “Catalytic influence of bimetallic phases for the synthesis of single-walled carbon nanotubes”, Journal of Molecular Catalysis, A: Chemical 116 (1997) 397-403.
- Cassell et al., “Large Scale CVC Synthesis of Single-Walled Carbon Nanotubes”, American Chemical Society, pp. 6483-6492, 1999.
- Che et al., “Chemical Vapor Deposition Based Synthesis of Carbon Nanotubes and Nanofibers Using a Template Method”, Chemical Mater. 1998, 10, PP. 260-267.
- Chen et al., “Growth of carbon nanotubes by catalytic decomposition of CH4 or CO on a Ni-MgO catalyst”, Carbon vol. 35, No. 10-11, pp. 1495-1501, 1997.
- Cheng et al.; “Bulk Morphology and Diameter Distribution of Single-Walled Carbon Nanotubes Synthesized by Catalytic Decompositon of Hydrocarbons,” Chemical Physics Letters, 289:602-610, 1998.
- Cheng et al.; “Large-Scale and Low-Cost Synthesis of Single-Walled Carbon Nanotubes by the Catalytic Pyrolysis of Hydrocarbons,” Applied Physics Letters, 72(25):3282-3284, Jun. 25, 1998.
- Dai et al.; “Single-Wall Nanotubes Produced By Metal-Catalyzed Disproportionation of Carbon Monoxide,” Chemical Physics Letters, 260:471-475, 1996.
- Database, Accession No. 1999-366878, Cano, “Canno KK”, XP-002149235, May 25, 1999.
- Fonseca et al., “Synthesis of single-and multi-wall carbon nanotubes over supported catalysts”, Applied Physics A, 67, PP. 11-22, 1998.
- Govindaraj et al., “Carbon structures obtained by the disproportionation of carbon monoxide over nickel catalysts”, Materials Research Bulletin, vol. 33, No. 4, pp. 663-667, 1998.
- Hafner et al., “Catalytic growth of single-wall carbon nanotubes from metal particles”, Chemical Physics Letters, 296, PP 195-202, 1998.
- Hernadi et al., “Catalytic synthesis of carbon nanotubes using zeolite support”, Elsevier Science Inc. 1996.
- Iijima, Sumio; “Helical Microtubules of Graphitic Carbon,” Nature, 354:56-59, Nov. 1991.
- Iijima et al.; “Single-Shell Carbon Nanotubes of 1-nm Diameter”, Nature 363:603-605, Jun. 1993.
- Ivanov et al.; “The Study of Carbon Nanotubes Produced by Catalytic Method,” Chemical Physics Lettersm 223:329-335, 1994.
- Journet et al.; “Large-Scale Production of Single-Walled Carbon Nanotubes by the Electric-Arc Technique,” Nature, 338:756-758, Aug. 1997.
- B. Kitiyanan et al., “Controlled production of single-wall carbon nanotubes by catalytic decomposition of CO on bimetallic Co-Mo catlaysts”, Chemical Physics Letters, 317 (2000), pp. 497-503, Feb. 4, 2000.
- Krishnankutty et al.; “The Effect of Copper on the Structural Characteristics of Carbon Filaments Produced from Iron Catalyzed Decomposition of Ethylene,” Catalysts Today, 37:295-307, 1997.
- Li et al., “Large-Scale Synthesis of Aligned Carbon Nanotubes”, Science, vol. 274, pp. 1701-1703.
- Rinzler et al.; “Large-Scale Purification of Single-Wall Carbon Nanotubes: Process, Product, and Characterization,” Applied Physics A, 67:29-37, 1998.
- Thess et al., Crystalline Ropes of Metallic Carbon Nanotubes, Science, vol. 273, pp. 483-487.
- I. Willems et al., “Control of the outer diameter of thin carbon nanotubes synthesized by catalytic decomposition of hydrocarbons”, Chemical Physics Letters, 317 (2000) pp. 71-76.
- Yakobson et al.; “Fullerene Nanotubes: C1,000,000 and Beyond,” American Scientist, 85:324-337, Jul.-Aug. 1997.
- Patent Abstracts of Japan, vol. 1996, No. 12, Dec. 26, 1995, & JP 08 198611 A (NEC Corp), Aug. 6, 1996, Abstract.
- U.S. Appl. No. 60/101,093, filed Sep. 18, 1998, Smalley et al.
- Alvarez, et al., “Synergism of Co and Mo in the catalytic production of single-wall carbon nanotubes by decomposition of CO”, Elsevier Science Ltd., Carbon 39 (2001), pp. 547-558.
- Anderson et al., “50 nm Polystyrene Particles via Miniemulsion Polymerization”, Macromolecules, American Chemical Society, vol. 35, pp. 574-576, 2002.
- Bandow et al., “Effect of the Growth Temperature on the Diameter Distribution and Chirality of Single-Wall Carbon Nanotubes”, The American Physical Society, Physical Review Letters, vol. 80, No. 17, (1998), pp. 3779-3782.
- Bower et al., “Deformation of Carbon Nanotubes in Nanotube-Polymer Composites”, Applied Physics Letters, vol. 74, No. 22, pp. 3317-3319, May 31, 1999.
- Cadek et al., “Mechanical and Thermal Properties of CNT and CNF Reinforced Polymer Composites”, Structural and Electronic Properties of Molecular Nanostructures, American Institute of Physics, pp. 562-565, 2002.
- Chattopadhyay, et al., “A Route for Bulk Separation of Semiconducting from Metallic Singel-Wall Carbon Nanotubes”, Journal of American Chemical Society, vol. 125, No. 11, pp. 3370-3375, 2003.
- Chaturvedi et al., “Properties of pure and sulfided NiMo04 and CoMo04 catalysts: TPR, XANES and time-resolved XRD studies”, Database Accession No. EIX99044490981 XP002246342, Proceedings of the 1997 Mrs Fall Symposium, Boston, MA, USA, Dec. 2-4, 1997; Mater Res Soc Symp Proc, Materials Research Society Symposium-Proceedings, Recent Advances in Catalytic Materials, 1998, Mrs. Warrendale, PA, USA.
- Chen et al., “Bulk, Separative Enrichment in Metallic or Semiconducting Single-Walled Carbon Nanotubes”, Nano Letters, xxxx vol. 0, No. 0, p. est: 4.9 A-E.
- Chen et al., “Dissolution of Full-Length Single-Walled Carbon Nanotubes”, J. Phys. Chem. B, vol. 105, pp. 2525-2528, 2001.
- De Boer et al., “The cobalt-molybdenum interaction in CoMo/SiO2 catalysts: A CO-oxidation study”, Elsevier Science Ltd., Solid State Ionics 63-65 (1993), pp. 736-742.
- Deng et al., “Hybrid Composite of Polyaniline Containing Carbon Nanotube”, Chinese Chemical Letters, vol. 12, pp. 1037-1040, 2001.
- Franco et al., “Electric and magnetic properties of polymer electrolyte/carbon black composites”, Solid State Ionics 113-115, pp. 149-160, 1998.
- Gaspar et al., “The Influence of Cr precursors in the ethylene polymerization on Cr/SiO2 catalysts”, Applied Catalysis A: General, vol. 227, pp. 240-254, 2002.
- Gong et al., “Surfactant-Assisted Processing of Carbon Nanotube/Polymer Composites”, Chemical Material, vol. 12, pp. 1049-1052, 2000.
- Hamon et al., “End-group and defect analysis of soluble single-walled carbon nanotubes”, Chemical Physics Letters, vol. 347 pp. 8-12, 2001.
- Hwang et al., “Carbon nanotube reinforced ceramics”, Journal of Materials Chemistry, vol. 11, pp. 1722-1725, 2001.
- Jin et al., “Alignment of Carbon nanotubes in a polymer matrix by mechanical stretching”, Applied Physics Letters, vol. 73, No. 9, pp. 1197-1199, Aug. 31, 1998.
- Journet et al., “Large-Scale Production of Single-Walled Carbon Nanotubes by the Electric-Arc Technique”, Letters to Nature, vol. 338, pp. 756-758, Aug. 21, 1997.
- Landfester et al., “Miniemulsion polymerization”, Jun. 4, 2003, http://www.mpikg-golm.mpg.de/kc/landfester/, 1-22.
- Landfester, “Polyreactions in Miniemulsions”, Macromol. Rapid Commun., vol. 22, No. 12, pp. 896-936, 2001.
- Landfester, “The Generation of Nanoparticles in Miniemulsions”, Advanced Materials, vol. 13, No. 10, pp. 765-768, May 17, 2001.
- McCarthy et al., “A Microscopic and Spectroscopic Study of Interactions between Carbon Nanotubes and a Conjugated Polymer”, J. Phys. Chem. B, vol. 106, pp. 2210-2216, 2001.
- Niyogi et al., Communications to the Editor, “Chromatographic Purification of Soluble Single-walled Carbon Nanotubes (s-SWNTs)”, J. Am. Chem. Soc., vol. 123, pp. 733-734, 2001.
- Pompeo et al., “Water Solubilization of Single-Walled Carbon Nanotubes by Functionalization with Glucosamine”, Nano Letters, American Chemical Society, vol. 2, No. 4, pp. 369-373, 2002.
- Qian et al., “Load transfer and deformation mechanisms in carbon nanotube-polystyrene composites”,Applied Physics Letters, American Institute of Physics, vol. 76, No. 20, pp. 2868-2870, May 15, 2000.
- Razavi, “Metallocene catalysts technology and environment”, Chemistry 3, pp. 615-625, 2000.
- Sears et al., “Raman scattering from polymerizing styrene. I. Vibrational mode analysis a)”, J. Chem. Phys., vol. 75, No. 4, pp. 1589-1598.
- Shaffer et al., “Fabrication and Characterization of Carbon Nanotube/Poly (vinyl alcohol) Composites**”, Advanced Materials, vol. II, No. 11, pp. 937-941, 1999.
- Tahji et al., “Purification Procedure for Single-Wall Nanotubes”, J. Phys. Chem. B, vol. 101, pp. 1974-1978 (1997).
- Tiarks et al., “Encapsulation of Carbon Black by Miniemulsion Polymerization”, Macromol. Chem. Phys., vol. 202, pp. 51-60, 2001.
- Tiarks et al., “Silica Nanoparticles as Surfactants and Fillers for Latexes Made by Miniemulsion Polymerization”, Langmuir, American Chemical Society, vol. 17, pp. 5775-5780, 2001.
- Zhao, et al., “Chromatographic Purification and Properties of Soluble Single-Walled Carbon Nanotubes”, American Chemical Society, p. Est: 4.1, pp. A-E, Feb. 22, 2001.
- Zhu et al., “Direct Synthesis of Long Single-Walled Carbon Nanotube Strands”, Science, vol. 296, pp. 884-886, May 13, 2002.
| InventorsAssigneeApplication No. 10145193 filed on 05/13/2002 US Classes:423/447.3, From gaseous reactants428/367, Including free carbon or carbide or therewith (not as steel)204/173, Carbon502/174, Inorganic carbon containing423/461, Recovery or purification502/180, Elemental carbon423/210, MODIFYING OR REMOVING COMPONENT OF NORMALLY GASEOUS MIXTURE502/416, Free carbon containing428/364, Rod, strand, filament or fiber427/216, Metal base423/344, Binary compound (e.g., silicide, etc.)428/408, SELF-SUSTAINING CARBON MASS OR LAYER WITH IMPREGNANT OR OTHER LAYER423/249RADIOACTIVE (AT. NO. 84+ OR RADIOACTIVE ISOTOPE OF ANOTHER ELEMENT)Field of Search423/447.3From gaseous reactantsExaminers Primary: Hendrickson, Stuart L.Attorney, Agent or FirmUS Patent References 3746657, 4456694, Catalysts for producing alcohols from olefins and synthesis gas Issued on: 06/26/1984 Inventor: Blaskie , et al.4574120, Method for preparing high activity silica supported hydrotreating catalysts Issued on: 03/04/1986 Inventor: Thompson4663230, Carbon fibrils, method for producing same and compositions containing same Issued on: 05/05/1987 Inventor: Tennent5165909, Carbon fibrils and method for producing same Issued on: 11/24/1992 Inventor: Tennent, et al.5227038, Electric arc process for making fullerenes Issued on: 07/13/1993 Inventor: Smalley, et al.5300203, Process for making fullerenes by the laser evaporation of carbon Issued on: 04/05/1994 Inventor: Smalley5405996, Process for producing acetic acid Issued on: 04/11/1995 Inventor: Suzuki, et al.5424054, Carbon fibers and method for their production Issued on: 06/13/1995 Inventor: Bethune, et al.5482601, Method and device for the production of carbon nanotubes Issued on: 01/09/1996 Inventor: Ohshima, et al.5500200, Fibrils Issued on: 03/19/1996 Inventor: Mandeville, et al.5543378, Carbon nanostructures encapsulating palladium Issued on: 08/06/1996 Inventor: Wang5556517, Solar process for making fullerenes Issued on: 09/17/1996 Inventor: Smalley5560898, Process of isolating carbon nanotubes from a mixture containing carbon nanotubes and graphite particles Issued on: 10/01/1996 Inventor: Uchida, et al.5578543, Carbon fibrils, method for producing same and adhesive compositions containing same Issued on: 11/26/1996 Inventor: Tennent, et al.5587141, Method and device for the production of fullerenes Issued on: 12/24/1996 Inventor: Ohshima, et al.5591312, Process for making fullerene fibers Issued on: 01/07/1997 Inventor: Smalley5603907, Process and device for treating fluids by means of a pourable solid by the countercurrent method Issued on: 02/18/1997 Inventor: Grochowski5641466, Method of purifying carbon nanotubes Issued on: 06/24/1997 Inventor: Ebbesen, et al.5648056, Fullerene composite Issued on: 07/15/1997 Inventor: Tanaka5695734, Process for the separation of carbon nanotubes from graphite Issued on: 12/09/1997 Inventor: Ikazaki, et al.5698175, Process for purifying, uncapping and chemically modifying carbon nanotubes Issued on: 12/16/1997 Inventor: Hiura, et al.5707916, Carbon fibrils Issued on: 01/13/1998 Inventor: Snyder, et al.5744235, Process for preparing composite structures Issued on: 04/28/1998 Inventor: Creehan5747161, Graphite filaments having tubular structure and method of forming the same Issued on: 05/05/1998 Inventor: Iijima5753088, Method for making carbon nanotubes Issued on: 05/19/1998 Inventor: Olk5773834, Method of forming carbon nanotubes on a carbonaceous body, composite material obtained thereby and electron beam source element using same Issued on: 06/30/1998 Inventor: Yamamoto, et al.5780101, Method for producing encapsulated nanoparticles and carbon nanotubes using catalytic disproportionation of carbon monoxide Issued on: 07/14/1998 Inventor: Nolan, et al.5814290, Silicon nitride nanowhiskers and method of making same Issued on: 09/29/1998 Inventor: Niu, et al.5877110, Carbon fibrils Issued on: 03/02/1999 Inventor: Snyder, et al.5965267, Method for producing encapsulated nanoparticles and carbon nanotubes using catalytic disproportionation of carbon monoxide and the nanoencapsulates and nanotubes formed thereby Issued on: 10/12/1999 Inventor: Nolan, et al.5985232, Production of fullerenic nanostructures in flames Issued on: 11/16/1999 Inventor: Howard, et al.5997832, Preparation of carbide nanorods Issued on: 12/07/1999 Inventor: Lieber, et al.6221330, Process for producing single wall nanotubes using unsupported metal catalysts Issued on: 04/24/2001 Inventor: Moy, et al.6312303, Alignment of carbon nanotubes Issued on: 11/06/2001 Inventor: Yaniv, et al.6333016, Method of producing carbon nanotubes Issued on: 12/25/2001 Inventor: Resasco, et al.6346189, Carbon nanotube structures made using catalyst islands Issued on: 02/12/2002 Inventor: Dai, et al.6401526, Carbon nanotubes and methods of fabrication thereof using a liquid phase catalyst precursor Issued on: 06/11/2002 Inventor: Dai, et al.6413487, Method and apparatus for producing carbon nanotubes Issued on: 07/02/2002 Inventor: Resasco, et al.6426134, Single-wall carbon nanotube-polymer composites Issued on: 07/30/2002 Inventor: Lavin, et al.6432866, Rigid porous carbon structures, methods of making, methods of using and products containing same Issued on: 08/13/2002 Inventor: Tennent, et al.6479939, Emitter material having a plurlarity of grains with interfaces in between Issued on: 11/12/2002 Inventor: Yaniv, et al.6573643, Field emission light source Issued on: 06/03/2003 Inventor: Kumar, et al.6580225, Cold cathode Issued on: 06/17/2003 Inventor: Yaniv, et al.6596187, Method of forming a nano-supported sponge catalyst on a substrate for nanotube growth Issued on: 07/22/2003 Inventor: Coll, et al.6599961, Polymethylmethacrylate augmented with carbon nanotubes Issued on: 07/29/2003 Inventor: Pienkowski, et al.6656339, Method of forming a nano-supported catalyst on a substrate for nanotube growth Issued on: 12/02/2003 Inventor: Talin , et al.6664722, Field emission material Issued on: 12/16/2003 Inventor: Yaniv , et al.6699457, Low-temperature hydrogen production from oxygenated hydrocarbons Issued on: 03/02/2004 Inventor: Cortright , et al.6761870Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure CO Issued on: 07/13/2004 Inventor: Smalley, et al.Foreign Patent References- 0 945 402 EP 09/01/1999
- 01 93 9821 EP 06/01/2004
- WO 97/09272 WO 03/01/1997
- WO 98/39250 WO 09/01/1998
- WO 98/42620 WO 10/01/1998
- WO 00/17102 WO 03/01/2000
- PCT/US00/15362 WO 10/01/2000
- WO 00/73205 WO 12/01/2000
- WO 03/048038 WO 06/01/2003
- PCT/US02/23155 WO 07/01/2003
- WO 04/001107 WO 12/01/2003
- PCT/US03/19664 WO 03/01/2004
International Class D01F009/12
|