WO1999043609A1 - Production de filaments de carbone par le craquage direct d'hydrocarbures - Google Patents

Production de filaments de carbone par le craquage direct d'hydrocarbures Download PDF

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Publication number
WO1999043609A1
WO1999043609A1 PCT/US1999/003572 US9903572W WO9943609A1 WO 1999043609 A1 WO1999043609 A1 WO 1999043609A1 US 9903572 W US9903572 W US 9903572W WO 9943609 A1 WO9943609 A1 WO 9943609A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
carbon
nickel
fibers
hydrogen
Prior art date
Application number
PCT/US1999/003572
Other languages
English (en)
Inventor
Michael D. Amiridis
Cicero A. Bernales
Original Assignee
Niagara Mohawk Power Corporation
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 Niagara Mohawk Power Corporation filed Critical Niagara Mohawk Power Corporation
Priority to AU27737/99A priority Critical patent/AU2773799A/en
Publication of WO1999043609A1 publication Critical patent/WO1999043609A1/fr

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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
    • 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
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane

Definitions

  • This invention relates generally to the production of carbon and hydrogen, and more specifically to carbon filament production by the direct cracking of hydrocarbons such as methane and natural gas.
  • the current proton-exchange membrane (PEM) fuel cells utilize hydrogen as the energy source and require essential elimination (ideally below 20 ppmv) of carbon monoxide from the hydrogen stream to prevent poisoning of the electrocatalyst.
  • Hydrogen is typically produced through steam reforming, partial oxidation or autothermal reforming of natural gas. In all these cases, however, carbon monoxide is a co-product, which has to be converted into carbon dioxide in subsequent steps which adds to the cost of the produced hydrogen.
  • An alternative route is to directly crack the hydrocarbon fuel into hydrogen and carbon.
  • the formation of carbon oxides is avoided and the need for downstream reactions such as water-gas shift and selective oxidation for the conversion of carbon monoxide to carbon dioxide is eliminated.
  • this approach has not been extensively studied. While commercial processes exist that utilize thermal cracking of methane at extremely high temperatures for the -2- production of acetylene and carbon black, hydrogen production via the catalytic cracking of methane has been only briefly considered in the past.
  • the carbon black material produced from these existing commercial processes is not filamentous or fibrous in nature. As such, it contains no added value other than the marginal value for typical end-uses or applications of carbon black.
  • the carbon produced in this invention is of high value. In a commercial operation using this invention, the high value carbon produced can be continuously removed using fluid bed or moving bed reactors before regenerating the catalyst bed, if necessary.
  • the rates of methane conversion and hydrogen formation were found to be in ratio of 1 :2, thus, verifying the reaction stoichiometry for methane cracking.
  • the amounts of carbon deposited on the spent catalyst and methane reacted indicated a good closure of the carbon balance (100 ⁇ 5%).
  • the process of the invention may be -4- applicable to any other suitable hydrocarbon such as ethane, ethylene, propane, propylene, butane, pentane, hexane and mixtures thereof, and hydrocarbons with molecular weights in the gasoline and diesel range. Nevertheless, it is anticipated that the preferred hydrocarbons will be methane and natural gas. During the catalytic cracking of higher molecular weight hydrocarbons, it is expected that several other undesirable products will be formed in addition to hydrogen and carbon fibers and filaments.
  • activity measurements for the methane cracking reaction were conducted over a set of 9 Ni-Cu/SIO 2 catalysts in which the total metal amount (on a molar basis) was maintained constant at 2.6 mmole of metal/g of support while the ratio of Ni:Cu was varied from approximately 8:1 to approximately 1:8.
  • the reaction was carried out in a pure methane stream, at 650 and 800 °C and at a gas hourly space velocity of 6000 hr' 1- The results indicate that the presence of small amounts of Cu enhanced significantly the Ni activity at 800 °C.
  • the promoting effect is also more pronounced when small amounts of Cu are added (i.e., Ni:Cu ratios greater than 1).
  • the highest initial methane conversion observed with this set of catalysts is at the 8:1 Ni:Cu ratio. Even higher initial methane conversions are expected with higher Ni:Cu ratios up to about 20:1.
  • FIG. 2 represents a plot of initial methane conversion as a function of catalyst composition at two different temperatures over a series of Ni-Cu/SiO 2 catalysts (O at 650 °C and D at 800°C).
  • FIG. 3 is a SEM micrograph at 25,000X illustrating the structure of the carbon fibers of the present invention.
  • FIG. 4 is a SEM micrograph at 50,000X illustrating the structure of the carbon fibers of the present invention.
  • FIG. 5 is a TEM micrograph at 100,000X illustrating the structure of the carbon fibers of the present invention.
  • the catalyst used in the first embodiment of this invention was prepared by incipient wetness impregnation of an aqueous solution of nickel nitrate onto the silica support, followed by calcination in air and in-situ reduction in flowing hydrogen.
  • This is a standard method of preparation of supported metal catalysts and several different nickel salts can be used instead of nickel nitrate as the nickel precursor.
  • other standard methods for the preparation of supported metal catalysts could be used without having a detrimental effect on the properties of the catalyst.
  • silica we investigated other inorganic supports such as alumina and titania.
  • nickel supported on these supports was also found to be effective for the catalytic cracking of methane, the performance of nickel supported on silica was superior to those of the other catalysts and therefore, this system was chosen to demonstrate the invention in this application.
  • other transition metals such as Co and Fe, supported on silica for this reaction.
  • these catalysts were also found to be effective for the reaction, at 550°C the performance of nickel was again superior to the other catalysts.
  • Ni/SiO 2 catalysts of variable Ni content it was determined that optimum performance for the catalytic cracking of methane can be obtained with a nickel content in excess of 5 wt.%, and, in particular a content of -6- approximately 16 wt.%. As a result, a 16 wt.% Ni/SiO 2 catalyst was chosen to demonstrate the invention in this application.
  • Carbon may deposit on the surface to cover the active sites (site-blocking) or accumulate at the entrance of the pores to block further access of the reactants to the interior (pore-mouth plugging). It has been estimated that in both cases catalyst deactivation would occur within a short period of time. Even if 10 carbon atoms are needed to block each surface ⁇ i atom, for example, 11 mg of carbon deposition would be enough to completely deactivate one gram of the 16.4% ⁇ i/SiO 2 catalyst. Furthermore, if pore-mouth plugging was the main deactivation mechanism, approximately 250 mg of carbon would be sufficient to clog the external 10% of the pores, in one gram of the Ni/SiO 2 catalyst sample.
  • Spent catalyst samples were further studied by the use of X-Ray Diffraction (XRD).
  • XRD patterns suggest that graphitic carbon constituents with different degrees of defect or distortion are present in the deactivated samples.
  • TEM micrographs of the fully deactivated sample show that the growth of the carbon is terminated as a result of spatial limitations.
  • the modes of filament termination include the nickel particle's restriction by the silica surface, the arm and the tip of another carbon filament.
  • the formation of carbon filaments as a result of hydrocarbon cracking has been extensively reported in the literature with higher molecular weight hydrocarbons over supported nickel, iron, cobalt and several alloy catalysts.
  • carbon fibers or filaments are produced preferably from the catalytic cracking of either pure methane or commercial natural gas.
  • the type of carbon produced in the present invention is highly desirable and has added value in certain applications such as electrochemical and adsorption storage of fuel gases.
  • the enhanced value of the carbon material from the present invention is due to its filamentous or fibrous nature, since the properties of the carbon filaments are superior to those of the ordinary carbon black.
  • the morphology of the carbon fibers is more clearly shown in SEM and TEM micrographs, (See Figs. 3, 4 and 5).
  • the set of Ni-Cu/SiO 2 catalysts used in the second embodiment of this invention had the total metal amount (on a molar basis) maintained constant at 2.6 mmole of metal/g of support while the ratio of Ni:Cu was varied from approximately -8-
  • the catalysts were prepared by incipient wetness impregnation of nickel and copper nitrates (Ni(NO 3 ) 2 x6H 2 O and Cu(NO 3 ) 2 x2.5H 2 O) obtained from Aldrich Chem. Co. Inc. (with a purity of 99.999%) onto commercially available SiO 2 (Grace Davison-Syloid 74). Prior to impregnation the silica support was dried, pressed into pellets under a pressure of 15,000 psig, crushed and sieved to obtain a granulometric fraction in the 20-35 mesh size.
  • the impregnated samples were dried in a vacuum oven at 120 °C overnight and subsequently calcined in a muffler furnace at 700 °C for 6 hours.
  • the Ni and Cu loadings were estimated by the weight difference between the blank support and the catalyst reduced overnight in a 1 :2 H 2 /N 2 mixture (total flow rate of 120 ml/min) at 650 °C .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

Le procédé faisant l'objet de cette invention, qui sert à produire des filaments ou des fibres de carbone et de l'hydrogène sensiblement pur, consiste à mettre en contact un flux d'hydrocarbure gazeux avec un catalyseur à teneur en nickel ou en cuivre-nickel à une température comprise entre environ 400 et 900 °C. On obtient ainsi la conversion de l'hydrocarbure gazeux en carbone et en hydrogène sensiblement pur. Les filaments ou les fibres de carbone qui se sont déposés sur le catalyseur constituent un matériau d'une grande valeur ayant une utilisation séparée pour des utilisations électrochimiques et de stockage de carburant, et ces filaments ou fibres sont récupérés pour un usage ultérieur.
PCT/US1999/003572 1998-02-24 1999-02-19 Production de filaments de carbone par le craquage direct d'hydrocarbures WO1999043609A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU27737/99A AU2773799A (en) 1998-02-24 1999-02-19 Carbon filament production via the direct cracking of hydrocarbons

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US7581998P 1998-02-24 1998-02-24
US60/075,819 1998-02-24
US23186199A 1999-01-14 1999-01-14
US09/231,861 1999-01-14

Publications (1)

Publication Number Publication Date
WO1999043609A1 true WO1999043609A1 (fr) 1999-09-02

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WO (1) WO1999043609A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100457602C (zh) * 2003-11-21 2009-02-04 斯塔托伊尔公司 烃的转化方法
US20120045572A1 (en) * 2009-04-09 2012-02-23 Toyota Jidosha Kabushiki Kaisha Carbon nanotube production process and carbon nanotube production apparatus
US20210122629A1 (en) * 2019-10-25 2021-04-29 Mark Kevin Robertson Catalytic Decomposition of Hydrocarbons for the Production of Hydrogen and Carbon
US11434132B2 (en) 2019-09-12 2022-09-06 Saudi Arabian Oil Company Process and means for decomposition of sour gas and hydrogen generation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2946164A1 (de) * 1978-11-15 1980-07-03 Stamicarbon Verfahren zum verarbeiten von stickstoffhaltigem erdgas
US4435376A (en) * 1982-03-26 1984-03-06 Phillips Petroleum Company Fibrous carbon production
DD287015A5 (de) * 1989-08-11 1991-02-14 Leipzig Chemieanlagen Verfahren zur herstellung von reinwasserstoff und russ aus methan

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2946164A1 (de) * 1978-11-15 1980-07-03 Stamicarbon Verfahren zum verarbeiten von stickstoffhaltigem erdgas
US4435376A (en) * 1982-03-26 1984-03-06 Phillips Petroleum Company Fibrous carbon production
DD287015A5 (de) * 1989-08-11 1991-02-14 Leipzig Chemieanlagen Verfahren zur herstellung von reinwasserstoff und russ aus methan

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ABSTRACTS OF PAPERS. ACS NATIONAL MEETING., XX, XX, no. PART 02., 24 March 1996 (1996-03-24), XX, pages COMPLETE 02., XP002104030 *
FENELONOV V B ET AL: "Structure and texture of filamentous carbons produced by methane decomposition on Ni and Ni-Cu catalysts", CARBON, vol. 35, no. 8, 1 January 1997 (1997-01-01), pages 1129-1140, XP004086485 *
MATSUKATA M ET AL: "Novel hydrogen/syngas production process: Catalytic activity and stability of Ni/SiO2", PROCEEDINGS OF THE 1996 14TH INTERNATIONAL SYMPOSIUM ON CHEMICAL REACTION ENGINEERING. PART B;BRUGGE, BELG MAY 5-8 1996, vol. 51, no. 11 part B, 5 May 1996 (1996-05-05), Chem Eng Sci;Chemical Engineering Science; Chemical Reaction Engineering: From Fundamentals to Commercial Plants and Products Jun 1996 Pergamon Press Inc, Tarrytown, NY, USA, pages 2769 - 2774, XP002103798 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100457602C (zh) * 2003-11-21 2009-02-04 斯塔托伊尔公司 烃的转化方法
US20120045572A1 (en) * 2009-04-09 2012-02-23 Toyota Jidosha Kabushiki Kaisha Carbon nanotube production process and carbon nanotube production apparatus
US8784562B2 (en) * 2009-04-09 2014-07-22 Toyota Jidosha Kabushiki Kaisha Carbon nanotube production process and carbon nanotube production apparatus
US11434132B2 (en) 2019-09-12 2022-09-06 Saudi Arabian Oil Company Process and means for decomposition of sour gas and hydrogen generation
US20210122629A1 (en) * 2019-10-25 2021-04-29 Mark Kevin Robertson Catalytic Decomposition of Hydrocarbons for the Production of Hydrogen and Carbon
US11685651B2 (en) * 2019-10-25 2023-06-27 Mark Kevin Robertson Catalytic decomposition of hydrocarbons for the production of hydrogen and carbon

Also Published As

Publication number Publication date
AU2773799A (en) 1999-09-15

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