US20050025695A1 - Catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures - Google Patents

Catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures Download PDF

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US20050025695A1
US20050025695A1 US10/628,842 US62884203A US2005025695A1 US 20050025695 A1 US20050025695 A1 US 20050025695A1 US 62884203 A US62884203 A US 62884203A US 2005025695 A1 US2005025695 A1 US 2005025695A1
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Bhabendra Pradhan
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COLUMBIAN CHEMICALS COMPANY A CORP OF DELAWARE
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/745Iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/755Nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/023Catalysts characterised by dimensions, e.g. grain size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/10Solids characterised by their surface properties or porosity
    • B01J35/1004Surface area
    • B01J35/101410-100 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0072Preparation of particles, e.g. dispersion of droplets in an oil bath
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/082Decomposition and pyrolysis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/16Preparation
    • C01B32/162Preparation characterised by catalysts
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols

Abstract

A carbon nanofiber system is synthesized with very high purity (above 95%), selectivity of the carbon morphology, and exceptionally high yield. A custom made catalyst with a particle size of ≦10 nm and a high surface area (>50 m2/g), provides a higher morphological selectivity and higher yield. The reactivity of these catalyst particles is maintained even after 24 hours reaction such that yield exceeds 200 g carbon per gram of catalyst. The catalysts which are key to the products and yields achieved are prepared to specific parameters (size distribution, composition and crystallinity) specified and via a flame synthesis process as taught in U.S. Pat. No. 6,132,653.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • None
  • STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
  • Not applicable
  • REFERENCE TO A “MICROFICHE APPENDIX”
  • Not applicable
  • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention relates to the production of Nanocarbon materials. More particularly, the present invention relates to an improved catalyst and process to produce Nanocarbon materials in high yield and high selectivity and at reduced reaction temperatures.
  • 2. General Background of the Invention
  • Nano-structured materials, more particular carbon nano structure materials, are gaining importance for various commercial applications. Such applications include their use to store molecular hydrogen, to serve as catalyst supports, as reinforcing components of polymeric composites, for use in electromagnetic shielding and for use in various types of batteries and other energy storage devices. Carbon nano-structure materials are generally prepared from the decomposition of carbon containing gases over selected catalytic metal surfaces at temperatures ranging from about 500° C. to about 1200° C.
  • For example, carbon nanofibers can be used in lithium ion batteries, wherein the anode would be comprised of graphitic nanofibers. The graphite sheets are substantially perpendicular or parallel to the longitudinal axis of the carbon nanofiber. Example of such a use can be found in U.S. Pat. No. 6,503,660 which is contained in the information disclosure statement submitted herewith. Furthermore U.S. Pat. No. 5,879,836 teaches the use of fibrils as a material for the lithium ion battery anode. Fibrils are described as being composed of parallel layers of carbon in the form of a series of concentric tubes disposed about a longitudinal axis rather than as multi-layers of flat graphite sheets.
  • Furthermore in U.S. Pat. No. 6,485,858 the graphite nanofibers possess structures in which the graphite sheets are aligned in the direction either substantially perpendicular or substantially parallel to the fiber axis and designated as platelet and ribbon respectively. In addition, the exposed surfaces of the nanofibers are comprised of at least 95% edge regions in contrast to conventional graphites that are comprised almost entirely of basal plane regions and very little edge sites.
  • Other references include “Catalytic Growth of Carbon Filaments,” which is an article from the Chemical Engineering Department of Auburn University dated 1989, wherein it discusses the formation of filamentous carbon. Another source of information is an article entitled “A Review of Catalytic Grown Carbon Nanofibers,” published by the Material Research Society, in 1993. In that article, carbon nanofibers are discussed as being produced in a relatively large scale through a catalytic decomposition of certain hydrocarbons on small metal particles.
  • In all cases, as was discussed above, synthesizing a pure carbon nanomaterial is challenging. Most of the applications of these materials require pure carbon nanomaterials systems. Therefore, it would be beneficial to provide a system of producing pure carbon nanomaterials where the carbon system can be synthesized with very high purity (greater than 95%), high crystallinity, selectivity of the carbon morphology, and exceptionally high yield. Furthermore, a custom made catalyst with a particular particle size and high surface area would give a higher selectivity and higher reactivity.
  • BRIEF SUMMARY OF THE INVENTION
  • In the present invention, a carbon nanofiber system is synthesized with very high purity (above 95%), high crystallinity, selectivity of the carbon morphology, and exceptionally high yield. A custom made catalyst with an average single crystal-particle size of <10 nm and a high surface area (>50 m2/g), provides a higher morphological selectivity and higher reactivity than heretofore attainable. The reactivity of these catalyst particles is maintained even after 24 hours reaction such that yield exceeds 200 g carbon per gram of catalyst. The catalysts which are key to the products and yield achieved are prepared to specific parameters (size distribution, composition and crystallinity) specified and via a flame synthesis process as taught in U.S. Pat. No. 6,132,653. The disclosure of U.S. Pat. No. 6,132,653, is totally incorporated herein by reference thereto.
  • For purposes of this application the terms used herein will have the following definitions: “Purity” is defined as carbon content with the impurity understood to comprise the catalyst.
  • “Selectivity” is defined as fraction of the carbonaceous product possessing the intended morphology (orientation of graphene layers); and “yield” is defined as weight carbon produced divided by weight of catalysts; in such catalytic processes, this is also sometimes expressed as turnover.
  • Therefore, it is a principal object of the present invention to synthesize a pure carbon nanomaterial with extremely high purity, high selectivity, of the carbon morphology and exceptionally high yield.
  • It is a further object of the present invention to synthesize a pure carbon nanomaterial in the presence of a custom made catalyst having a particular particle size, surface area, and chemical composition to provide the high morphological selectivity, yield, and purity.
  • It is a further object of the present invention to produce a carbon nanomaterial in the presence of a custom made catalyst so that over a given amount of time the yield exceeds 200 g carbon/g of catalyst.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • For a further understanding of the nature, objects, and advantages of the present invention, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein:
  • FIG. 1 is a graph of the Effect of Time on Growth of the carbon nanofiber in the presence of the Iron oxide catalyst over a 24 hour period;
  • FIG. 2 is a graph of the Effect of Time on Growth of the carbon nanofiber in the presence of an Iron:Nickel catalyst over a 24 hour period;
  • FIG. 3 illustrates the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron oxide catalyst as described in relation to FIG. 1;
  • FIG. 4 is a high resolution view of the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron oxide catalyst as described in relation to FIG. 1.
  • FIG. 5 illustrates the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron:Nickel catalyst as described in relation to FIG. 2;
  • FIG. 6 is a high resolution view of the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron:Nickel catalyst as described in relation to FIG. 2;
  • FIG. 7 is a graph of the production of nanocarbon fibers having platelet morphology prepared with Iron oxide catalyst compared with a conventional catalyst; and
  • FIG. 8 is a graph of the production of nanocarbon fibers having tubular morphology prepared with Iron:Nickel catalyst compared with a conventional catalyst.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS PROCESS FOR PRODUCING THE CATALYSTS
  • The production of the catalyst utilized in the production of the nanofibers disclosed herein is similar to that disclosed in U.S. Pat. No. 6,132,653, referenced and incorporated earlier herein.
  • List of metals that can be used as part of the catalyst are as follows:
    • Fe, Ni, Co, Mo, Cu, La, Ag, Au and alloys.
  • The Nanocarbon Materials Produced with the Catalysts
  • Reference is now made to the table and information below which discusses the properties of the material as produced with the new catalyst as described above (flame synthesized) and a conventional catalyst (co-precipitated)
    TABLE 2
    New Catalyst Conventional or
    (flame Commercial Catalyst
    Properties synthesized) (co-precipitation)
    Chemical form Metal Oxide Pre-reduced Metal with
    thin cover of oxide
    Size (nm) ˜10 500-2000
    Morphology Single Crystal Polycrystalline
    Surface area ˜130 <20
    (m2/g)
    Packing density Lower than bulk Same as bulk

    Experimental Detail to Achieve Results Above:
  • a. Conventional or Commercial Catalyst:
  • A known amount of pre-reduced catalyst (0.1 g) was placed in a ceramic boat or a quartz cylinder. The boat was then transferred into a quartz reactor (ø=47 mm). The reactor was flushed for 30 min with nitrogen gas with a flow rate of 200 sccm. The reactor was heated up to 450° C. with a heating rate of 5° C./min under 10-20% H2 (balanced with N2). This was held for 1 h at this temperature. The temperature was then increased to reaction temperature 600° C. for iron or 650° C. for iron-nickel catalyst in 30 min under N2 flow. Once the set temperature was stabilized, the reaction gas (CO/H2 or C2H4/H2) was introduced into the reactor for different periods of time (1, 2, 4, 6, 8 and 24 h).
  • b. New Catalyst:
  • A known amount of oxide catalyst (0.1 g) was placed in ceramic boat or a quartz cylinder. The boat was then transferred into the quartz reactor (ø=47 mm). The reactor was flushed for 30 min with nitrogen gas with a flow rate of 200 sccm. The reactor was heated up to 450° C. with a heating rate of 5° C./min under 10-20% H2 (balanced with N2). This was held for 1 h at this temperature than the temperature was increased to reaction temperature 550° C. for iron oxide and iron-nickel oxide catalyst in 30 min under N2 flow. Once the set temperature was stabilized, the reaction gas (CO/H2 or C2H4/H2) was introduced into the reactor for different periods of time (1, 2, 4, 6, 8 and 24 h).
  • The Iron oxide catalyst utilized with CO:H2::4::1 at 550° C. produces a specific morphology of the carbon micro structure where the graphite planes are perpendicular to the carbon growth axis as seen in FIGS. 3 and 4. In comparison to the commercial catalyst, this trial shows a better carbon yield (2 to 3 time higher) and at 50° C. lower synthesis temperature (550° vs 600° C.). There is a greater than 99.6% purity of the carbon product which can be reached in the system. Morphological selectivity is 100%.
  • In the second example, an Iron:Nickel catalyst was used, with C2H2:H2::1:4 at 550° C. to produce a specific morphology of the carbon micro structure, i.e., where the graphite planes are parallel and/or at an angle to the carbon growth axis, as seen in FIGS. 5 and 6. In comparison to other conventional or commercial catalyst, this trial shows a better carbon yield (2 to 3 times higher) and at 100° C. lower synthesis temperature (5500 vs 650° C.). A greater than 99.2% purity of the carbon product can be reached in this system. Morphological selectivity is >95%. In the two examples used above, the catalyst can be a metal oxide catalyst selected from the metals including iron, nickel, cobalt, lanthanum, gold, silver, molybdenum, iron-nickel, iron-copper and their alloys.
  • c. Fluid Bed Process Option:
  • A known amount of oxide catalyst (0.1-1.2 g) was placed in a ebullated fluid-bed reactor with Al2O3 (14.9-13.8 g) The reactor was flushed for 30 min with nitrogen gas with a flow rate of 1000 sccm. The reactor was heated up to 450° C. with a heating rate of 5° C./min under 10-20% H2 (balanced with N2). This was held for 1 h at this temperature then the temperature was increased to a reaction temperature 550° C. for iron-nickel oxide catalyst in 30 min under N2 flow. Once the set temperature was stabilized, the reaction gas (C2H4/H2) was introduced into the reactor for a known period of time (2 h). The yield can reach to 140 g carbon/g catalyst.
  • Reference is now made to FIG. 1 which shows the graph of the effect of time on growth of carbon nanofibers utilizing an iron oxide catalyst with CO:H2::4:1 at 550° C. In this graph, the carbon nanofibers produced comprise the carbon platelet morphology as seen in FIGS. 3 and 4. With reference to FIG. 1: As the process continues over some 24 hour period, the metal content as a percentage weight of the product decreases to 0.3% and the yield of carbon per gram of catalyst was >300 g/g. It also shows that the catalytic particle was still active even after the 24 hours reaction time. In this particular example, the iron oxide catalyst, with CO:H2::4:1 at 550° C. produced a specific morphology of the carbon micro structure, i.e., where the graphite planes are perpendicular to the carbon growth axis, again as depicted in FIGS. 3 and 4. Furthermore, in comparison to the commercial catalyst, as stated earlier this trial shows a better carbon yield (2-3 times higher) and at 50° C. lower synthesis temperature. This provides a 99.7 pure carbon product and with a morphological selectivity of 100%. As seen in FIGS. 3 and 4, the specific morphology of the carbon microstructure shows the graphite planes perpendicular to the carbon growth axis.
  • Turning now to FIG. 2, the graph depicts utilizing the iron-nickel catalyst with C2H2:H2::1:4 at 550° C. The carbon nanofibers which were produced as shown in this graph resulted in a specific morphology of the carbon micro structure, i.e., where the graphite planes are parallel or at an angle to the growth axis as seen in FIGS. 5 and 6. In comparison to the conventional catalyst, this shows a better carbon yield and at a 100° C. lower synthesis temperature. Again there is a 99.6% purity of the carbon product and morphological selectivity is >95%. At the end of a 24 hour reaction period, the metal content of the product was 0.4% while the yield of carbon was between 200 and 250 g/g catalyst.
  • In both of these systems, as shown in FIGS. 1 and 2, there can be reached a 99% carbon in an 8 hour reaction time. These results are shown in the following tables.
  • In each of these tables and as depicted in FIGS. 7 and 8 respectively, both the Iron catalyst and the Iron:Nickel catalyst respectively produced a carbon nanomaterial platelet or tubular morphology at lower temperature, >95% morphological selectivity, higher yield and lower impurity of metal than the commercial or conventional catalysts.
  • For Platelet Morphology, Catalyst Iron, CO:H2::4:1.
    Temperature Selectivity Yield Impurity
    Catalyst (° C.) (visual) (g/6 h) (metal)
    Flame 550 100 77 1.3
    Commercial 600 90 50 2
    (J. T. Baker)
  • For Tubular Morphology, Catalyst Iron:Nickel::8:2, C2H4:H2::1:4
    Temperature Selectivity Yield Impurity
    Catalyst (° C.) (visual) (g/6 h) (metal)
    Flame 550 >95 81 1.25
    CCC 650 60 26.33 3.8
    Produced
    Conventional

    The “CCC Produced Conventional” catalyst was prepared utilizing a liquid precipitation process. Iron, nickel, and copper metal nitrates were utilized. The metal nitrates were stoichimetrically mixed in H2O and rapidly stirred at room temperature. Ammonium bicarbonate is added to a pH ˜9, and stirred ˜5 minutes. A precipitate forms overnight; the precipitate is washed and dried. Metal carbonate is dried at 110° C. for 24 hrs. and then calcinated in air for 4 hrs. at 400° C. Metal oxides are ball milled for 6 hrs. and reduced in 10% H2 in N2 at 500° C. for 20 hrs. in 200 sccm flow. Metal powder is passivated in 2% O2 in N2 at room temperature for 1 hour. This technique and the reaction taking place, as shown below, are referenced in R. J. Best and W. W. Russel, J. Am. Chem. Soc. 76, 8383 (1954). M ( NO 3 ) × NH 4 HCO 3 H 2 O > M ( CO 3 ) × air 400 ° C . > M 2 O × 10 % H 2 500 ° C . > M
    Powder Catalyst Synthesis by Flame/Plasma Process:
  • A mixture of nitrate/sulfate salt of metal (Fe, Ni and Cu) ethanolic solution were prepared and vaporized/atomized into either flame or plasma torch and powder of pure oxide or mixed metal oxide were obtained by this process. U.S. Pat. No. 6,123,653 (Oct. 17, 2000).
  • In general, the process for producing nanocarbon materials, is undertaken by providing a catalyst with an average particle size of ≦10 nm and a surface area greater than 50 m2/g, although this may vary. Next, carbonaceous reactants are reacted in the presence of the catalyst over a given period of time to produce carbon nanofibers with over 99% purity and a morphological selectivity approaching 100% with higher reactivity.
  • The catalyst, produced by the method described in U.S. Pat. No. 6,123,653, incorporated herein by reference, is a metal oxide catalyst selected from the metals including iron, nickel, cobalt, lanthanum, gold, silver, molybdenum, iron-nickel, iron-copper and their alloys. There may be other suitable metal oxides which may be found as experimentation continues. The catalyst, itself, is prepared to specific parameters (size distribution, composition and crystallinity) specified and via a flame synthesis process; and it possesses a single crystal morphology. By utilizing the catalyst from the group identified, the resulting yield of carbon nanomaterial is ≧140 g carbon per g catalyst, but it may be more, while the morphology of the carbon micro structure comprises graphite planes of controllable orientation (depending on catalyst composition and carbonaceous feedstock) perpendicular or parallel to the carbon growth axis resulting in the 99.6% purity of the carbon product.
  • The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims.

Claims (19)

1. A process for producing nanocarbon materials, comprising the following steps:
a. providing a catalyst with a particle size of ≦10 nm and a surface area greater than 50 m2/g;
b. reacting carbonaceous feedstocks in the presence of the catalyst over a given period of time to produce carbon nanofibers with over 99% purity and a morphological selectivity approaching 100% in yields ≧140 g carbon/g catalyst with higher reactivity.
2. The process in claim 1, wherein the catalyst is a metal oxide catalyst selected from the metals including iron, nickel, cobalt, lanthanum, gold, silver, molybdenum, iron-nickel, iron-copper and their alloys.
3. The process in claim 1, wherein the catalyst is prepared to specific parameters (size distribution, composition and crystallinity) specified and via a flame synthesis process.
4. The catalyst in claim 1, wherein the catalyst possesses a single crystal morphology.
5. The process in claim 1, wherein the yield of carbon nanomaterial resulted in ≧140 g carbon per g/catalyst.
6. The process in claim 1, wherein the morphology of the carbon micro structure can be selectively controlled to achieve various desired orientations in selectivities of ≧90%.
7. A process for producing nanocarbon materials, comprising the following steps:
a. providing a metal oxide catalyst with a particle size of about ≦10 nm and a surface area greater than 50 m2/g;
b. reacting carbonaceous feedstocks in the presence of the catalyst over a given period of time to produce carbon nanofibers with over 99% purity and a morphological selectivity approaching 100% with yield ≧140 g carbon/g catalyst.
8. The process in claim 7, wherein the reaction took place at a temperature not exceeding 550 C.
9. The process in claim 7, wherein the purity of carbon nanofibers was >99% after 8 hours reaction time.
10. The process in claim 7, wherein the metal oxide catalyst is selected from a group of metals including iron, nickel, cobalt, lanthanum, gold, silver, molybdenum, iron-nickel, iron-copper and their alloys.
11. Carbon nanofibers of high purity and high reactivity, produced by the steps of:
a. providing a metal oxide catalyst with a particle size of ≦10 nm and a surface area greater than 50 m2/g;
b. reacting carbonaceous feedstocks in the presence of the catalyst over a given period of time to produce the carbon nanofibers with over 99% purity and a selectivity approaching 100% with higher reactivity.
12. The carbon nanofibers produced by the process in claim 11, wherein the metal oxide catalyst is selected from a group of metals including iron, nickel, cobalt, lanthanum, gold, silver, molybdenum, iron-nickel, iron-copper and their alloys.
13. The carbon nanofibers produced by the process in claim 11, wherein the purity of carbon nanofibers was ≧99% in after 8 hours reaction time.
14. A carbon nanofiber, of the type produced in the presence of an metal oxide catalyst, the carbon nanofiber comprising at least 99% pure carbon, and produced at high yield, and >90% morphological selectivity.
15. The carbon nanofiber in claim 14, wherein the metal oxide catalyst is selected from a group of metals including iron, nickel, cobalt, lanthanum, gold, silver, molybdenum, iron-nickel, iron-copper and their alloys.
16. A carbon nanofiber composition exhibiting 90% Selectivity to a single morphology as produced.
17. The composition in claim 16, wherein the morphology comprises graphene layers oriented parallel to the fiber axis.
18. The composition in claim 16, wherein the morphology comprises graphene layers oriented perpendicular to the fiber axis.
19. The composition of claim 16, wherein the morphology comprises graphene layers oriented at a specific and equal (±10°) angle to the fiber axis.
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US10/628,842 US20050025695A1 (en) 2003-07-28 2003-07-28 Catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures
PCT/US2004/012136 WO2005016853A2 (en) 2003-07-28 2004-04-20 Improved catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures
EP04750358A EP1654406A4 (en) 2003-07-28 2004-04-20 Improved catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures
JP2006521812A JP2007500121A (en) 2003-07-28 2004-04-20 In reduced reaction temperature, improved catalyst and method for producing nano-carbon material with high selectivity in high yield
KR1020067001924A KR20060052923A (en) 2003-07-28 2004-04-20 Improved catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures
CNA2004800219719A CN1833055A (en) 2003-07-28 2004-04-20 Improved catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures
BRPI0413069-3A BRPI0413069A (en) 2003-07-28 2004-04-20 improved catalyst and process for producing nanocarbono materials with high selectivity and low reaction temperatures
TW093112404A TW200505788A (en) 2003-07-28 2004-05-03 Improved catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures
ARP040101720A AR044387A1 (en) 2003-07-28 2004-05-18 Process for producing nanocarbon materials of high yield and high selectivity at low reaction temperatures

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090324897A1 (en) * 2007-09-18 2009-12-31 Samsung Electronics Co., Ltd. Graphene pattern and process of preparing the same
WO2013081302A1 (en) * 2011-11-29 2013-06-06 Samsung Techwin Co., Ltd Thin metal film for synthesizinggraphene and graphene manufacturing method using the same
US8679444B2 (en) 2009-04-17 2014-03-25 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
US9090472B2 (en) 2012-04-16 2015-07-28 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
US9221685B2 (en) 2012-04-16 2015-12-29 Seerstone Llc Methods of capturing and sequestering carbon
US9475699B2 (en) 2012-04-16 2016-10-25 Seerstone Llc. Methods for treating an offgas containing carbon oxides
US9506194B2 (en) 2012-09-04 2016-11-29 Ocv Intellectual Capital, Llc Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media
US9586823B2 (en) 2013-03-15 2017-03-07 Seerstone Llc Systems for producing solid carbon by reducing carbon oxides
US9598286B2 (en) 2012-07-13 2017-03-21 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US9604848B2 (en) 2012-07-12 2017-03-28 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
US9650251B2 (en) 2012-11-29 2017-05-16 Seerstone Llc Reactors and methods for producing solid carbon materials
US9731970B2 (en) 2012-04-16 2017-08-15 Seerstone Llc Methods and systems for thermal energy recovery from production of solid carbon materials by reducing carbon oxides
US9779845B2 (en) 2012-07-18 2017-10-03 Seerstone Llc Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same
US9783416B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Methods of producing hydrogen and solid carbon
US9783421B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Carbon oxide reduction with intermetallic and carbide catalysts
US9796591B2 (en) 2012-04-16 2017-10-24 Seerstone Llc Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products
US9896341B2 (en) 2012-04-23 2018-02-20 Seerstone Llc Methods of forming carbon nanotubes having a bimodal size distribution
US10086349B2 (en) 2013-03-15 2018-10-02 Seerstone Llc Reactors, systems, and methods for forming solid products
US10115844B2 (en) 2013-03-15 2018-10-30 Seerstone Llc Electrodes comprising nanostructured carbon

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101426610A (en) * 2005-06-08 2009-05-06 丰田发动机工程及制造北美公司;新墨西哥大学 Metal oxide nanoparticles and process for producing the same
US20160130519A1 (en) * 2014-11-06 2016-05-12 Baker Hughes Incorporated Methods for preparing anti-friction coatings

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US54849A (en) * 1866-05-22 Improvement in trunk-locks
US4881994A (en) * 1987-04-30 1989-11-21 United Technologies Corporation Iron oxide catalyst propellant, and method for making same
US5458784A (en) * 1990-10-23 1995-10-17 Catalytic Materials Limited Removal of contaminants from aqueous and gaseous streams using graphic filaments
US5618875A (en) * 1990-10-23 1997-04-08 Catalytic Materials Limited High performance carbon filament structures
US6132653A (en) * 1995-08-04 2000-10-17 Microcoating Technologies Chemical vapor deposition and powder formation using thermal spray with near supercritical and supercritical fluid solutions
US6159538A (en) * 1999-06-15 2000-12-12 Rodriguez; Nelly M. Method for introducing hydrogen into layered nanostructures
US6221330B1 (en) * 1997-08-04 2001-04-24 Hyperion Catalysis International Inc. Process for producing single wall nanotubes using unsupported metal catalysts
US6485858B1 (en) * 1999-08-23 2002-11-26 Catalytic Materials Graphite nanofiber catalyst systems for use in fuel cell electrodes
US20030004058A1 (en) * 2001-05-21 2003-01-02 Trustees Of Boston College Varied morphology carbon nanotubes and method for their manufacture
US6503660B2 (en) * 2000-12-06 2003-01-07 R. Terry K. Baker Lithium ion battery containing an anode comprised of graphitic carbon nanofibers
US6537515B1 (en) * 2000-09-08 2003-03-25 Catalytic Materials Llc Crystalline graphite nanofibers and a process for producing same
US6596187B2 (en) * 2001-08-29 2003-07-22 Motorola, Inc. Method of forming a nano-supported sponge catalyst on a substrate for nanotube growth
US20030211029A1 (en) * 2002-03-25 2003-11-13 Mitsubishi Gas Chemical Company, Inc. Aligned carbon nanotube films and a process for producing them
US20040005269A1 (en) * 2002-06-06 2004-01-08 Houjin Huang Method for selectively producing carbon nanostructures
US6761870B1 (en) * 1998-11-03 2004-07-13 William Marsh Rice University Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure CO
US6849245B2 (en) * 2001-12-11 2005-02-01 Catalytic Materials Llc Catalysts for producing narrow carbon nanostructures

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020054849A1 (en) * 2000-09-08 2002-05-09 Baker R. Terry K. Crystalline graphite nanofibers and a process for producing same
US6743408B2 (en) * 2000-09-29 2004-06-01 President And Fellows Of Harvard College Direct growth of nanotubes, and their use in nanotweezers
US6752977B2 (en) * 2001-02-12 2004-06-22 William Marsh Rice University Process for purifying single-wall carbon nanotubes and compositions thereof
EP1560791A1 (en) * 2002-11-15 2005-08-10 MGill University Method for producing carbon nanotubes using a dc non-transferred thermal plasma torch

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US54849A (en) * 1866-05-22 Improvement in trunk-locks
US4881994A (en) * 1987-04-30 1989-11-21 United Technologies Corporation Iron oxide catalyst propellant, and method for making same
US5618875A (en) * 1990-10-23 1997-04-08 Catalytic Materials Limited High performance carbon filament structures
US5458784A (en) * 1990-10-23 1995-10-17 Catalytic Materials Limited Removal of contaminants from aqueous and gaseous streams using graphic filaments
US5653951A (en) * 1995-01-17 1997-08-05 Catalytic Materials Limited Storage of hydrogen in layered nanostructures
US6132653A (en) * 1995-08-04 2000-10-17 Microcoating Technologies Chemical vapor deposition and powder formation using thermal spray with near supercritical and supercritical fluid solutions
US6221330B1 (en) * 1997-08-04 2001-04-24 Hyperion Catalysis International Inc. Process for producing single wall nanotubes using unsupported metal catalysts
US6761870B1 (en) * 1998-11-03 2004-07-13 William Marsh Rice University Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure CO
US6159538A (en) * 1999-06-15 2000-12-12 Rodriguez; Nelly M. Method for introducing hydrogen into layered nanostructures
US6485858B1 (en) * 1999-08-23 2002-11-26 Catalytic Materials Graphite nanofiber catalyst systems for use in fuel cell electrodes
US6537515B1 (en) * 2000-09-08 2003-03-25 Catalytic Materials Llc Crystalline graphite nanofibers and a process for producing same
US6503660B2 (en) * 2000-12-06 2003-01-07 R. Terry K. Baker Lithium ion battery containing an anode comprised of graphitic carbon nanofibers
US20030004058A1 (en) * 2001-05-21 2003-01-02 Trustees Of Boston College Varied morphology carbon nanotubes and method for their manufacture
US6596187B2 (en) * 2001-08-29 2003-07-22 Motorola, Inc. Method of forming a nano-supported sponge catalyst on a substrate for nanotube growth
US6849245B2 (en) * 2001-12-11 2005-02-01 Catalytic Materials Llc Catalysts for producing narrow carbon nanostructures
US20030211029A1 (en) * 2002-03-25 2003-11-13 Mitsubishi Gas Chemical Company, Inc. Aligned carbon nanotube films and a process for producing them
US20040005269A1 (en) * 2002-06-06 2004-01-08 Houjin Huang Method for selectively producing carbon nanostructures

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9670590B2 (en) 2007-09-18 2017-06-06 Samsung Electronics Co., Ltd. Graphene pattern and process of preparing the same
US8337949B2 (en) * 2007-09-18 2012-12-25 Samsung Electronics Co., Ltd. Graphene pattern and process of preparing the same
US20090324897A1 (en) * 2007-09-18 2009-12-31 Samsung Electronics Co., Ltd. Graphene pattern and process of preparing the same
US8679444B2 (en) 2009-04-17 2014-03-25 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
US9556031B2 (en) 2009-04-17 2017-01-31 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
WO2013081302A1 (en) * 2011-11-29 2013-06-06 Samsung Techwin Co., Ltd Thin metal film for synthesizinggraphene and graphene manufacturing method using the same
KR20130060005A (en) * 2011-11-29 2013-06-07 삼성테크윈 주식회사 Copper based thin metal layer and manufacturing method of graphene using the same
US9796591B2 (en) 2012-04-16 2017-10-24 Seerstone Llc Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products
US10106416B2 (en) 2012-04-16 2018-10-23 Seerstone Llc Methods for treating an offgas containing carbon oxides
US9475699B2 (en) 2012-04-16 2016-10-25 Seerstone Llc. Methods for treating an offgas containing carbon oxides
US9221685B2 (en) 2012-04-16 2015-12-29 Seerstone Llc Methods of capturing and sequestering carbon
US9090472B2 (en) 2012-04-16 2015-07-28 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
US9637382B2 (en) 2012-04-16 2017-05-02 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
US9731970B2 (en) 2012-04-16 2017-08-15 Seerstone Llc Methods and systems for thermal energy recovery from production of solid carbon materials by reducing carbon oxides
US9896341B2 (en) 2012-04-23 2018-02-20 Seerstone Llc Methods of forming carbon nanotubes having a bimodal size distribution
US9604848B2 (en) 2012-07-12 2017-03-28 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
US9598286B2 (en) 2012-07-13 2017-03-21 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US10358346B2 (en) 2012-07-13 2019-07-23 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US9779845B2 (en) 2012-07-18 2017-10-03 Seerstone Llc Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same
US9506194B2 (en) 2012-09-04 2016-11-29 Ocv Intellectual Capital, Llc Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media
US9650251B2 (en) 2012-11-29 2017-05-16 Seerstone Llc Reactors and methods for producing solid carbon materials
US9993791B2 (en) 2012-11-29 2018-06-12 Seerstone Llc Reactors and methods for producing solid carbon materials
US9783421B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Carbon oxide reduction with intermetallic and carbide catalysts
US10086349B2 (en) 2013-03-15 2018-10-02 Seerstone Llc Reactors, systems, and methods for forming solid products
US9783416B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Methods of producing hydrogen and solid carbon
US10115844B2 (en) 2013-03-15 2018-10-30 Seerstone Llc Electrodes comprising nanostructured carbon
US10322832B2 (en) 2013-03-15 2019-06-18 Seerstone, Llc Systems for producing solid carbon by reducing carbon oxides
US9586823B2 (en) 2013-03-15 2017-03-07 Seerstone Llc Systems for producing solid carbon by reducing carbon oxides

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