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

Info

Publication number
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
Authority
US
United States
Prior art keywords
catalyst
carbon
iron
nickel
morphology
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US10/628,842
Other languages
English (en)
Inventor
Bhabendra Pradhan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Columbian Chemicals Co
Original Assignee
Columbian Chemicals Co
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
Assigned to COLUMBIAN CHEMICALS COMPANY, A CORP. OF DELAWARE reassignment COLUMBIAN CHEMICALS COMPANY, A CORP. OF DELAWARE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PRADHAN, BHABENDRA
Priority to US10/628,842 priority Critical patent/US20050025695A1/en
Application filed by Columbian Chemicals Co filed Critical Columbian Chemicals Co
Priority to EP04750358A priority patent/EP1654406A4/en
Priority to JP2006521812A priority patent/JP2007500121A/ja
Priority to KR1020067001924A priority patent/KR20060052923A/ko
Priority to PCT/US2004/012136 priority patent/WO2005016853A2/en
Priority to CNA2004800219719A priority patent/CN1833055A/zh
Priority to BRPI0413069-3A priority patent/BRPI0413069A/pt
Priority to TW093112404A priority patent/TW200505788A/zh
Priority to ARP040101720A priority patent/AR044387A1/es
Publication of US20050025695A1 publication Critical patent/US20050025695A1/en
Assigned to JPMORGAN CHASE BANK SEOUL BRANCH reassignment JPMORGAN CHASE BANK SEOUL BRANCH SECURITY AGREEMENT Assignors: COLUMBIAN CHEMICALS COMPANY
Assigned to COLUMBIAN CHEMICALS COMPANY reassignment COLUMBIAN CHEMICALS COMPANY RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: JPMORGAN CHASE BANK SEOUL BRANCH
Assigned to COLUMBIAN CHEMICALS COMPANY reassignment COLUMBIAN CHEMICALS COMPANY TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENT RIGHTS Assignors: HSBC BANK, USA, NATIONAL ASSOCIATION
Abandoned legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon 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
    • 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

Definitions

  • 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.
  • Nano-structured 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 m 2 /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.
  • “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.
  • 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.
  • FIG. 8 is a graph of the production of nanocarbon fibers having tubular morphology prepared with Iron:Nickel catalyst compared with a conventional catalyst.
  • the Iron oxide catalyst utilized with CO:H 2 ::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 .
  • this trial shows a better carbon yield (2 to 3 time higher) and at 50° C. lower synthesis temperature (550° vs 600° C.).
  • Morphological selectivity is 100%.
  • an Iron:Nickel catalyst was used, with C 2 H 2 :H 2 ::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 .
  • 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%.
  • 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.
  • a known amount of oxide catalyst (0.1-1.2 g) was placed in a ebullated fluid-bed reactor with Al 2 O 3 (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% H 2 (balanced with N 2 ). 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 N 2 flow. Once the set temperature was stabilized, the reaction gas (C 2 H 4 /H 2 ) was introduced into the reactor for a known period of time (2 h). The yield can reach to 140 g carbon/g catalyst.
  • FIG. 1 shows the graph of the effect of time on growth of carbon nanofibers utilizing an iron oxide catalyst with CO:H 2 ::4:1 at 550° C.
  • the carbon nanofibers produced comprise the carbon platelet morphology as seen in FIGS. 3 and 4 .
  • FIG. 1 shows 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.
  • FIG. 2 the graph depicts utilizing the iron-nickel catalyst with C 2 H 2 :H 2 ::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 .
  • this shows a better carbon yield and at a 100° C. lower synthesis temperature.
  • 99.6% purity of the carbon product and morphological selectivity is >95%.
  • the metal content of the product was 0.4% while the yield of carbon was between 200 and 250 g/g catalyst.
  • 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.
  • 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 H 2 O 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% O 2 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).
  • 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.
  • 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)
US10/628,842 2003-07-28 2003-07-28 Catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures Abandoned US20050025695A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
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
EP04750358A EP1654406A4 (en) 2003-07-28 2004-04-20 IMPROVED CATALYST AND PROCESS FOR PRODUCING NANOCARBON MATERIALS AT HIGH YIELD AND SELECTIVITY AT REDUCED REACTION TEMPERATURES
JP2006521812A JP2007500121A (ja) 2003-07-28 2004-04-20 低下した反応温度において、高収量で高選択性でナノカーボン材料を製造するための改良型の触媒および方法
KR1020067001924A KR20060052923A (ko) 2003-07-28 2004-04-20 나노탄소 물질을 감소된 반응 온도에서 높은 수율 및 높은선택도로 제조하기 위한, 개선된 촉매 및 방법
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
CNA2004800219719A CN1833055A (zh) 2003-07-28 2004-04-20 在降低的反应温度下以高产率和高选择性制备纳米碳材料的改进的催化剂和方法
BRPI0413069-3A BRPI0413069A (pt) 2003-07-28 2004-04-20 processo e catalisador aperfeiçoados para produzir materiais de nanocarbono com alta seletividade e reduzidas temperaturas de reação
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 (es) 2003-07-28 2004-05-18 Procedimiento para producir materiales nanocarbono de alto rendimiento y alta selectividad a temperaturas de reaccion reducidas

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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

Publications (1)

Publication Number Publication Date
US20050025695A1 true US20050025695A1 (en) 2005-02-03

Family

ID=34103461

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/628,842 Abandoned 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

Country Status (9)

Country Link
US (1) US20050025695A1 (ja)
EP (1) EP1654406A4 (ja)
JP (1) JP2007500121A (ja)
KR (1) KR20060052923A (ja)
CN (1) CN1833055A (ja)
AR (1) AR044387A1 (ja)
BR (1) BRPI0413069A (ja)
TW (1) TW200505788A (ja)
WO (1) WO2005016853A2 (ja)

Cited By (21)

* 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
US9783421B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Carbon oxide reduction with intermetallic and carbide catalysts
US9783416B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Methods of producing hydrogen and solid carbon
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
US10815124B2 (en) 2012-07-12 2020-10-27 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
US11752459B2 (en) 2016-07-28 2023-09-12 Seerstone Llc Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5620059B2 (ja) * 2005-06-08 2014-11-05 トヨタ モーター エンジニアリング アンド マニュファクチャリング ノース アメリカ，インコーポレイティド 金属酸化物ナノ粒子及びその製造方法
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
AU2001294876A1 (en) * 2000-09-29 2002-04-08 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
WO2004046030A1 (en) * 2002-11-15 2004-06-03 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
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
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

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US9670590B2 (en) 2007-09-18 2017-06-06 Samsung Electronics Co., Ltd. Graphene pattern and process of preparing the same
US9556031B2 (en) 2009-04-17 2017-01-31 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
US8679444B2 (en) 2009-04-17 2014-03-25 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
US10500582B2 (en) 2009-04-17 2019-12-10 Seerstone Llc Compositions of matter including solid carbon formed 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 (ko) * 2011-11-29 2013-06-07 삼성테크윈 주식회사 그래핀 합성용 금속 박막 및 이를 이용한 그래핀 제조 방법
US10106416B2 (en) 2012-04-16 2018-10-23 Seerstone Llc Methods for treating an offgas containing carbon oxides
US9090472B2 (en) 2012-04-16 2015-07-28 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
US9796591B2 (en) 2012-04-16 2017-10-24 Seerstone Llc Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products
US9221685B2 (en) 2012-04-16 2015-12-29 Seerstone Llc Methods of capturing and sequestering carbon
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
US9637382B2 (en) 2012-04-16 2017-05-02 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
US9475699B2 (en) 2012-04-16 2016-10-25 Seerstone Llc. Methods for treating an offgas containing 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
US10815124B2 (en) 2012-07-12 2020-10-27 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
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
US10322832B2 (en) 2013-03-15 2019-06-18 Seerstone, Llc Systems for producing solid carbon by reducing carbon oxides
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
US9586823B2 (en) 2013-03-15 2017-03-07 Seerstone Llc Systems for producing solid carbon by reducing carbon oxides
US11752459B2 (en) 2016-07-28 2023-09-12 Seerstone Llc Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same
US11951428B2 (en) 2016-07-28 2024-04-09 Seerstone, Llc Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same

Also Published As

Publication number Publication date
AR044387A1 (es) 2005-09-07
CN1833055A (zh) 2006-09-13
BRPI0413069A (pt) 2006-10-17
KR20060052923A (ko) 2006-05-19
WO2005016853A2 (en) 2005-02-24
WO2005016853A3 (en) 2005-09-29
EP1654406A2 (en) 2006-05-10
JP2007500121A (ja) 2007-01-11
TW200505788A (en) 2005-02-16
EP1654406A4 (en) 2007-08-22

Similar Documents

Publication Publication Date Title
US20050025695A1 (en) Catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures
US9006132B2 (en) Process for preparing catalyst composition for the synthesis of carbon nanotube with high yields using the spray pyrolysis method
US7700068B2 (en) Method of making NiO and Ni nanostructures
EP1456439B1 (en) Method for producing multifaceted graphitic nanotubes
JP5250535B2 (ja) 薄型多層カーボンナノチューブ製造用触媒組成物
US9409779B2 (en) Catalyst for producing carbon nanotubes by means of the decomposition of gaseous carbon compounds on a heterogeneous catalyst
EP1797950A1 (en) Catalyst for a multi-walled carbon nanotube production process
US6537515B1 (en) Crystalline graphite nanofibers and a process for producing same
US20070087470A1 (en) Vapor phase synthesis of metal and metal oxide nanowires
CN1199727C (zh) 用于制备碳纳米管的催化剂
US10584032B2 (en) Method for preparing boron nitride nanotubes
KR101018660B1 (ko) 다중벽 탄소나노튜브 제조용 촉매조성물
Jin et al. Controllable preparation of helical carbon nanofibers by CCVD method and their characterization
Saita et al. Hydriding chemical vapor deposition of metal hydride nano-fibers
KR101241035B1 (ko) 높은 겉보기밀도를 지닌 탄소나노튜브 합성용 촉매조성물의 제조 방법
CN107074548A (zh) 具有改善结晶性的碳纳米管
CN1113990C (zh) 高弹性螺旋状碳纤维及其制备方法
EP3915676A1 (en) Improved catalyst for mwcnt production
CN113101981B (zh) 碳纳米管制备用催化剂的制备方法
Agboola Development and model formulation of scalable carbon nanotube processes: HiPCO and CoMoCAT process models
JP2004277925A (ja) コイン積層型ナノグラファイト、その製造方法及びその製造用触媒
KR101265979B1 (ko) 고순도 탄소나노튜브 대량 합성방법 및 이에 의하여 제조되는 탄소나노튜브
US20050255034A1 (en) Process for producing narrow platelet graphite nanofibers
Buhari et al. Synthesis of carbon nanotubes using catalytic chemical vapour decomposition of acetylene over Co-Mo bimetallic catalyst supported on magnesia
JP3826283B2 (ja) アモルファスナノスケールカーボンチューブの製造方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: COLUMBIAN CHEMICALS COMPANY, A CORP. OF DELAWARE,

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:PRADHAN, BHABENDRA;REEL/FRAME:014361/0605

Effective date: 20030723

AS Assignment

Owner name: JPMORGAN CHASE BANK SEOUL BRANCH, KOREA, REPUBLIC

Free format text: SECURITY AGREEMENT;ASSIGNOR:COLUMBIAN CHEMICALS COMPANY;REEL/FRAME:017344/0361

Effective date: 20060316

AS Assignment

Owner name: COLUMBIAN CHEMICALS COMPANY, GEORGIA

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK SEOUL BRANCH;REEL/FRAME:019341/0120

Effective date: 20070326

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: COLUMBIAN CHEMICALS COMPANY, GEORGIA

Free format text: TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENT RIGHTS;ASSIGNOR:HSBC BANK, USA, NATIONAL ASSOCIATION;REEL/FRAME:025408/0645

Effective date: 20101117