EP1654406A4 - Catalyseur et procede ameliores permettant de produire des materiaux de nanocarbone a un rendement et a une selectivite eleves a des temperatures de reaction reduites - Google Patents

Catalyseur et procede ameliores permettant de produire des materiaux de nanocarbone a un rendement et a une selectivite eleves a des temperatures de reaction reduites

Info

Publication number
EP1654406A4
EP1654406A4 EP04750358A EP04750358A EP1654406A4 EP 1654406 A4 EP1654406 A4 EP 1654406A4 EP 04750358 A EP04750358 A EP 04750358A EP 04750358 A EP04750358 A EP 04750358A EP 1654406 A4 EP1654406 A4 EP 1654406A4
Authority
EP
European Patent Office
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.)
Withdrawn
Application number
EP04750358A
Other languages
German (de)
English (en)
Other versions
EP1654406A2 (fr
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
Application filed by Columbian Chemicals Co filed Critical Columbian Chemicals Co
Publication of EP1654406A2 publication Critical patent/EP1654406A2/fr
Publication of EP1654406A4 publication Critical patent/EP1654406A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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 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.
  • 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.
  • a carbon nanofiber system is synthesized with very high purity (above 95 percent), 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 200g 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 US Patent No.
  • Figure 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
  • Figure 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
  • Figure 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 Figure 1
  • Figure 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 Figure 1.
  • Figure 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 Figure 2
  • Figure 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 Figure 2
  • Figure 7 is a graph of the production of nanocarbon fibers having platelet morphology prepared with Iron oxide catalyst compared with a conventional catalyst
  • Figure 8 is a graph of the production of nanocarbon fibers having tubular morphology prepared with Iron:Nickel catalyst compared with a conventional catalyst.
  • reaction gas CO/H or C 2 H 4 /H 2
  • reaction gas CO/H or C 2 H 4 /H 2
  • the reaction gas (CO/H 2 or C 2 H 4 /H 2 ) was introduced into the reactor for different periods of time (1, 2, 4, 6, 8 and 24 hours).
  • the Iron oxide catalyst utilized with CO:H 2 ::4::l 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 Figures 3 and 4.
  • this trial shows a better carbon yield (2 to 3 times higher) and at 50°C lower synthesis temperature (550°C versus 600°C).
  • Morphological selectivity is 100 percent.
  • 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 microstructure, that is where the graphite planes are parallel and/or at an angle to the carbon growth axis, as seen in Figures 5 and 6.
  • this trial shows a better carbon yield(2 to 3 times higher) and at 100°C lower synthesis temperature (550°C versus 650°C). A greater than 99.2 percent purity of the carbon product can be reached in this system. Morphological selectivity is greater than 95 percent.
  • 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 (0.1-1.2g) was placed in a ebullated fluid-bed reactor with A1 2 0 3 (14.9-13.8 g). The reactor was flushed for 30 minutes with nitrogen gas with a flow rate of 1 OOOsccm. The reactor was heated up to 450°C with a heating rate of 5°C per minute under 10-20% H 2 (balanced withN 2 ).
  • 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 Figures 3 and 4.
  • Plot 10 tracks g carbon g catalyst.
  • Plot 20 tracks metal content (weight percent).
  • both the Iron catalyst and the Iron:Nickel catalyst respectively produced a carbon nanomaterial platelet or tubular morphology at lower temperature greater than 95 percent morphological selectivity, higher yield and lower impurity of metal than the commercial or conventional catalysts.
  • Plot 50 tracks g carbon/g MCT catalyst at 550°C.
  • Plot 60 tracks metal content (weight percent).
  • Plot 70 tracks g carbon/g JT Baker catalyst at 600°C.
  • Plot 80 tracks metal content (weight percent).
  • Plot 90 tracks g carbon/g MCT catalyst at 550°C.
  • Plot 100 tracks metal content (weight percent).
  • Plot 110 tracks g carbon/g CCC catalyst at 600°C.
  • Plot 120 tracks metal content (weight percent).
  • 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 of approximately 9, and stirred approximately 5 minutes. A precipitate forms overnight; the precipitate is washed and dried. Metal carbonate is dried at 110°C for 24 hours and then calcinated in air for 4 hours at 400°C. Metal oxides are ball milled for 6 hours and reduced in 10% H 2 in N 2 at 500°C for 20 hours in 200 seem flow. Metal powder is passivated in 2% O 2 in N 2 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).
  • 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 using the method described in US patent 6,123,653.
  • 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 m 2 /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 percent purity and a morphological selectivity approaching 100 percent with higher reactivity.
  • the catalyst produced by the method described in US Patent No. 6,123,653, 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 ⁇ 140g 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 percent purity of the carbon product.

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  • 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)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un système de nanofibres de carbone qui est synthétisé avec une pureté (plus de 95%) et une sélectivité morphologique du carbone très élevées et un rendement exceptionnellement élevé. Un catalyseur fait sur mesure présentant une taille de particules = 10 nm et une grande surface (>50 m2/g) apporte une sélectivité morphologique et un rendement supérieurs. La réactivité des particules de catalyseur est conservée, y compris après une réaction de 24 heures, de façon que le rendement dépasse 200g de carbone par gramme de catalyseur. Ces catalyseurs, qui sont essentiels aux produits et rendements atteints, sont préparés selon des paramètres spécifiques (distribution granulométrique, composition et cristallinité) et à l'aide d'un processus de synthèse de flamme développé dans le brevet US No. 6.132.653.
EP04750358A 2003-07-28 2004-04-20 Catalyseur et procede ameliores permettant de produire des materiaux de nanocarbone a un rendement et a une selectivite eleves a des temperatures de reaction reduites Withdrawn EP1654406A4 (fr)

Applications Claiming Priority (2)

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
PCT/US2004/012136 WO2005016853A2 (fr) 2003-07-28 2004-04-20 Catalyseur et procede ameliores permettant de produire des materiaux de nanocarbone a un rendement et a une selectivite eleves a des temperatures de reaction reduites

Publications (2)

Publication Number Publication Date
EP1654406A2 EP1654406A2 (fr) 2006-05-10
EP1654406A4 true EP1654406A4 (fr) 2007-08-22

Family

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Family Applications (1)

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EP04750358A Withdrawn EP1654406A4 (fr) 2003-07-28 2004-04-20 Catalyseur et procede ameliores permettant de produire des materiaux de nanocarbone a un rendement et a une selectivite eleves a des temperatures de reaction reduites

Country Status (9)

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

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CA2758694C (fr) 2009-04-17 2017-05-23 Seerstone Llc Procede de fabrication de carbone solide par reduction d'oxydes de carbone
KR101900758B1 (ko) * 2011-11-29 2018-09-20 한화에어로스페이스 주식회사 그래핀 합성용 금속 박막 및 이를 이용한 그래핀 제조 방법
US9221685B2 (en) 2012-04-16 2015-12-29 Seerstone Llc Methods of capturing and sequestering carbon
WO2013158158A1 (fr) 2012-04-16 2013-10-24 Seerstone Llc Procédé de traitement d'un dégagement gazeux contenant des oxydes de carbone
MX354529B (es) 2012-04-16 2018-03-07 Seerstone Llc Métodos para producir carbono sólido mediante la reducción de dióxido de carbono.
NO2749379T3 (fr) 2012-04-16 2018-07-28
MX2014012548A (es) 2012-04-16 2015-04-10 Seerstone Llc Metodos y estructuras para reducir oxidos de carbono con catalizadores no ferrosos.
US9896341B2 (en) 2012-04-23 2018-02-20 Seerstone Llc Methods of forming carbon nanotubes having a bimodal size distribution
US10815124B2 (en) 2012-07-12 2020-10-27 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
CN107651667A (zh) 2012-07-12 2018-02-02 赛尔斯通股份有限公司 包含碳纳米管的固体碳产物以及其形成方法
MX2015000580A (es) 2012-07-13 2015-08-20 Seerstone Llc Metodos y sistemas para formar productos de carbono solido y amoniaco.
US9779845B2 (en) 2012-07-18 2017-10-03 Seerstone Llc Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same
WO2014039509A2 (fr) 2012-09-04 2014-03-13 Ocv Intellectual Capital, Llc Dispersion de fibres de renforcement améliorées par du carbone dans des milieux aqueux ou non aqueux
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US10115844B2 (en) 2013-03-15 2018-10-30 Seerstone Llc Electrodes comprising nanostructured carbon
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WO2014151138A1 (fr) 2013-03-15 2014-09-25 Seerstone Llc Réacteurs, systèmes et procédés de formation de produits solides
EP3129133A4 (fr) 2013-03-15 2018-01-10 Seerstone LLC Systèmes de production de carbone solide par réduction d'oxydes de carbone
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Also Published As

Publication number Publication date
WO2005016853A3 (fr) 2005-09-29
KR20060052923A (ko) 2006-05-19
EP1654406A2 (fr) 2006-05-10
AR044387A1 (es) 2005-09-07
JP2007500121A (ja) 2007-01-11
BRPI0413069A (pt) 2006-10-17
WO2005016853A2 (fr) 2005-02-24
US20050025695A1 (en) 2005-02-03
TW200505788A (en) 2005-02-16
CN1833055A (zh) 2006-09-13

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