EP1351881A4 - Materiau a base de carbure de tungstene - Google Patents

Materiau a base de carbure de tungstene

Info

Publication number
EP1351881A4
EP1351881A4 EP01964498A EP01964498A EP1351881A4 EP 1351881 A4 EP1351881 A4 EP 1351881A4 EP 01964498 A EP01964498 A EP 01964498A EP 01964498 A EP01964498 A EP 01964498A EP 1351881 A4 EP1351881 A4 EP 1351881A4
Authority
EP
European Patent Office
Prior art keywords
peak
ray diffraction
tungsten
tungsten carbide
carbide material
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Withdrawn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
EP01964498A
Other languages
German (de)
English (en)
Other versions
EP1351881A1 (fr
Inventor
Joel B Christian
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.)
Osram Sylvania Inc
Original Assignee
Osram Sylvania Inc
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 Osram Sylvania Inc filed Critical Osram Sylvania Inc
Publication of EP1351881A1 publication Critical patent/EP1351881A1/fr
Publication of EP1351881A4 publication Critical patent/EP1351881A4/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Withdrawn legal-status Critical Current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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • This invention relates to tungsten carbides and methods of making same. More particularly, this invention relates to tungsten carbide catalysts .
  • High-surface-area tungsten and molybdenum carbide materials are known to possess catalytic properties similar to ruthenium, iridium, palladium and platinum.
  • high-surface-area tungsten and molybdenum carbides have been described as highly efficient catalysts for the conversion of methane to synthesis gas via steam reforming and dry reforming, and for water-gas shift reactions.
  • platinum, palladium and ruthenium tungsten carbide is also known to catalyze the oxidation of hydrogen gas at room temperature which makes it a potential catalyst for low- temperature fuel cell applications such as the PEM (polymer electrolyte membrane) , sulfuric acid, and direct methanol types of fuel cells.
  • PEM polymer electrolyte membrane
  • sulfuric acid sulfuric acid
  • direct methanol types of fuel cells The 2 C form has been reported as being more catalytically active than the WC form in some applications .
  • a tungsten carbide material comprising tungsten and carbon.
  • the material has an x-ray diffraction pattern containing a primary x-ray diffraction peak and first and second secondary x-ray diffraction peaks; the primary x-ray diffraction peak having a reflection angle corresponding to a d-spacing of 2.39 ⁇ 0.02 A; the first secondary x-ray diffraction peak has a reflection angle corresponding to a d-spacing of 1.496 + 0.007 A and a relative peak height of 25% to 40% of the peak height of the primary x-ray diffraction peak; and the second secondary x-ray diffraction peak has a reflection angle corresponding to a d-spacing of 1.268 ⁇ 0.005 A and a relative peak height of 35% to 55% of the peak height of the primary x-ray diffraction ' peak.
  • a method for forming a high-surface-area tungsten carbide material comprising heating a tungsten precursor to a temperature from about 500 °C to about 800°C in an atmosphere containing a hydrocarbon gas and, optionally, hydrogen gas for a time sufficient to convert the tungsten precursor to the tungsten carbide material .
  • Fig. 1 is an x-ray diffraction pattern of the tungsten carbide material of this invention.
  • Fig. 2 is the x-ray diffraction pattern of Fig. 1 overlaid with x-ray diffraction lines associated with W 2 (C,0) .
  • Fig. 3 is the x-ray diffraction pattern of Fig. 1 overlaid with x-ray diffraction lines associated with WC ⁇ .
  • the tungsten carbide material of this invention achieves a high surface area desirable for catalysis and features substoichiometric levels of carbon in the active crystal matrix which are known to make the active surfaces less prone to coking.
  • the composition of the material may be represented by the general formula WC- ⁇ .. where x is from 0 to 0.5
  • the x-ray diffraction (XRD) pattern of the tungsten carbide material is exemplified in Fig. 1 (Cu Ka radiation, 1.5405 A).
  • the XRD pattern indicates that the tungsten carbide material has a face centered cubic lattice.
  • the broad diffraction peaks are consistent with the presence of extremely small crystallites. According to the Scherrer relationship, the peak widths correspond to crystallite sizes in the range of about 15 A to about 30 A. This is a major improvement over previously reported crystallite sizes of 275 to 385 A.
  • the peak positions in the XRD pattern indicate a similarity with W 2 (C,0) and WC X _ X .
  • Figs. 2 and 3 respectively show the XRD line positions and relative intensities for W 2 (C,0) and WC X _ X superimposed on the diffraction pattern shown in Fig. 1.
  • the data for the W 2 (C,0) and WC ⁇ XRD patterns were obtained from the powder diffraction files maintained by the International Centre for Diffraction Data (PDF#22-0959 and PDF#20-1316) . Referring to Fig. 2, it can be seen that the W 2 (C,0) line positions while arising near the major peak positions for the tungsten carbide material do not exactly correspond. .
  • the XRD pattern of the tungsten carbide material of this invention is characterized by three peaks: a primary peak P and two secondary peaks SI and S2.
  • the primary peak P occurs at a 2-theta (20) angle of 37.6 + 0.3 degrees. Applying the Bragg equation, this reflection angle corresponds to a d-spacing of about 2.39 ⁇ 0.02 A.
  • the two secondary peaks SI and S2 occur at 20 angles of 62.0 ⁇ 0.3° and 74.8 ⁇ 0.3°. These angles correspond to d-spacings of 1.496 ⁇ 0.007 A and 1.268 ⁇ 0.005 A, respectively.
  • the relative peak height of the first secondary peak SI varies from 25% to 40% of the peak height of the primary peak.
  • the relative peak height of the second secondary peak S2 varies from 35% to 55% of the peak height of the primary peak.
  • the peak height ratio of the first secondary peak SI to the second secondary peak S2 ranges from 0.65 to 0.80, and preferably from 0.69 to 0.75.
  • peak height refers to the maximum intensity of a peak after applying a simple background subtraction.
  • the tungsten carbide material is formed by the reaction of a tungsten precursor in flowing hydrocarbon and, optionally, hydrogen gases at a temperature from about 500°C to about 800 °C.
  • the tungsten precursor material may be ammonium metatungstate, ammonium paratungstate, tungsten metal powder, tungsten oxides, tungsten halides, absorbed tungsten species, or dissolved tungstates .
  • the tungsten precursor is ammonium paratungstate decahydrate .
  • Suitable hydrocarbon gases include propane, ethane, natural gas, ethylene, acetylene, or combinations thereof.
  • the hydrocarbon gas is propane or ethane.
  • the tungsten precursor is loaded into a ceramic boat which is placed into a tube furnace.
  • An inert atmosphere is established in the tube furnace using flowing argon gas.
  • the furnace is then heated to the reaction temperature and the gas flow is changed to a combination of hydrocarbon and, optionally, hydrogen gases. Once sufficiently reacted, the gas flow is changed back to solely argon gas and the furnace is allowed to cool to room temperature.
  • the tungsten carbide material is then passivated by flowing nitrogen gas through the tube furnace. Passivation is achieved by impurity oxygen adsorption on the surface of the material .
  • Preferred flow rates in standard liters per minute (slm) for these gases include: 0.05 slm to 9.5 slm for the hydrocarbon gases, 0 to 2.4 slm for the hydrogen gas, and 0 to 14.2 slm for the argon gas.
  • the tungsten carbide material formed from these methods has a high surface area.
  • the surface area is at least about 6 m 2 /g and preferably ranges from about 10 m 2 /g to about 60 m 2 /g.
  • XRD analyses were performed with a Rigaku D/Max X-ray Diffractometer using Cu Kc. radiation (40keV, 30ma) .
  • the Cu Koi 2 contribution in the Cu Kc. radiation was removed mathematically from the diffraction patterns.
  • the diffractometer was measured to be accurate to +0.04° (20) .
  • a 5 g amount of reagent/catalyst grade ammonium metatungstate (AMT) , (NH 4 ) s H 2 W 12 O 40 *5H 2 O, (OSRAM SYLVANIA Products Inc., Towanda, PA) was placed evenly in a ceramic boat .
  • the ceramic boat was then loaded into a Lindberg/Blue M Model HTF55000 hinged tube furnace utilizing a 2.5 inch diameter quartz tube.
  • An inert atmosphere was established in the tube by flowing argon gas through the tube at 0.5 slm.
  • the furnace temperature was then raised to 650°C and the gas flow was switched to a propane flow of 0.2 slm and a hydrogen flow of 1 slm.
  • the gas flow was switched back to only argon at 0.5 slm and the furnace turned off.
  • the material was passivated by passing flowing nitrogen gas (cryogenic grade, 99 . 998% from liquid nitrogen or generated to 0.9 ppm oxygen max., Air Liquide) through the tube at 1.0 slm for 6 hours.
  • nitrogen gas cryogenic grade, 99 . 998% from liquid nitrogen or generated to 0.9 ppm oxygen max., Air Liquide
  • Ammonium paratungstate decahydrate (APT) (NH 4 ) 10 H 2 W 12 O 42 «10H 2 O, was generated from ammonium metatungsate by dissolving 0.5 kg of AMT in 1.5 1 of deionized water. The pH of the solution was adjusted to between 9 and 11 using concentrated ammonium hydroxide. The solution was allowed to set for 48 to 72 hours. Needle-like crystals of APT appeared along the walls of the beaker and at the solution surface. The APT crystals were harvested and allowed to dry. The highly pure APT needles were measured to have a surface area of 0.11 m 2 /g.
  • a 5 g amount of the APT needles was placed evenly in a ceramic boat which was then loaded into a Lindberg/Blue M model HTF55-000 hinged tube furnace utilizing a 2.5 inch diameter quartz tube.
  • An inert atmosphere was established by flowing argon gas through the tube at 0.5 slm.
  • the furnace temperature was raised to 650°C and the gas flow was changed to a propane flow of 0.2 slm and a hydrogen flow of 1 slm. After 2.5 hours, the gas flow was changed back to only argon at 0.5 slm and the furnace turned off. After allowing the material to cool in the furnace under the flowing argon, the material was passivated by passing flowing nitrogen gas through the tube at 1.0 slm for 6 hours. XRD analysis confirmed the presence of the tungsten carbide material .
  • Example 3 A 25 g amount of a used tungsten carbide tool was leached in 6N hydrochloric acid at 97°C for 6 hours. The resulting solid was dried and fired in air at 750 °C to an expanded yellow tungsten oxide. The yellow oxide was placed evenly in a ceramic boat which was then loaded into a Lindberg/Blue M model HTF55000 hinged tube furnace utilizing a 2.5 inch diameter quartz tube. An inert atmosphere was established by flowing argon gas through the tube at 0.5 slm. The furnace temperature was raised to 700°C and the gas flow was changed to a propane flow of 0.2 slm and a hydrogen flow of 1 slm.
  • Example 2 Same as Example 1 except that ethane was used instead of propane. XRD analysis confirmed the presence of the tungsten carbide material .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un matériau à base de carbure de tungstène de surface active étendue. Le matériau présente une structure unique définie par le diagramme de diffraction des rayons X et consiste en des cristallites extrêmement petites de l'ordre d'environ 15 à environ 30 angströms. Selon l'invention, la surface active étendue d'au moins environ 6 m2/g est souhaitable dans des applications catalytiques.
EP01964498A 2000-09-29 2001-08-30 Materiau a base de carbure de tungstene Withdrawn EP1351881A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US67551000A 2000-09-29 2000-09-29
US675510 2000-09-29
PCT/US2001/026875 WO2002028773A1 (fr) 2000-09-29 2001-08-30 Materiau a base de carbure de tungstene

Publications (2)

Publication Number Publication Date
EP1351881A1 EP1351881A1 (fr) 2003-10-15
EP1351881A4 true EP1351881A4 (fr) 2005-09-14

Family

ID=24710815

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01964498A Withdrawn EP1351881A4 (fr) 2000-09-29 2001-08-30 Materiau a base de carbure de tungstene

Country Status (7)

Country Link
EP (1) EP1351881A4 (fr)
JP (1) JP2004510668A (fr)
AU (1) AU2001285343A1 (fr)
CA (1) CA2421626A1 (fr)
DE (1) DE10196680T1 (fr)
GB (1) GB2383998A (fr)
WO (1) WO2002028773A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6696184B1 (en) * 2000-09-29 2004-02-24 Osram Sylvania Inc. Supported tungsten carbide material
JP4815823B2 (ja) * 2004-03-31 2011-11-16 三菱化学株式会社 燃料電池用触媒及びその製造方法、並びにそれを用いた燃料電池用電極及び燃料電池
JP2006107987A (ja) * 2004-10-07 2006-04-20 Hitachi Maxell Ltd 燃料電池用触媒、該触媒を用いた燃料電池及び膜電極接合体
KR100825688B1 (ko) * 2006-04-04 2008-04-29 학교법인 포항공과대학교 나노다공성 텅스텐 카바이드 촉매 및 그의 제조방법
KR101688524B1 (ko) * 2010-07-30 2016-12-22 삼성전자주식회사 연료전지용 전극촉매, 이 전극촉매를 포함하는 막 전극 접합체와 연료전지, 및 연료전지용 전극촉매의 제조방법
CN107428618A (zh) * 2015-03-31 2017-12-01 捷客斯金属株式会社 碳化钨的制造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325843A (en) * 1980-12-08 1982-04-20 Shell Oil Company Process for preparing a supported tungsten carbide composition
US4702784A (en) * 1982-06-15 1987-10-27 Kernforschungsanlage Julich Gesellschaft Mit Beschrnakter Haftung Process for production of a tungsten carbide-activated electrode
US4990372A (en) * 1987-09-03 1991-02-05 Air Products And Chemicals, Inc. Method for producing wear resistant internal surfaces of structures
US5200060A (en) * 1991-04-26 1993-04-06 Amoco Corporation Hydrotreating process using carbides and nitrides of group VIB metals
US5277987A (en) * 1991-02-01 1994-01-11 Air Products And Chemicals, Inc. High hardness fine grained beta tungsten carbide
US6090992A (en) * 1998-12-08 2000-07-18 Phillips Petroleum Company Isomerization catalyst system, method of making and method of using such catalyst system in the isomerization of saturated hydrocarbons
WO2000041808A1 (fr) * 1999-01-12 2000-07-20 Hyperion Catalysis International, Inc. Compositions et nanotubes a base de carbure et d'oxycarbure
WO2002028544A1 (fr) * 2000-09-29 2002-04-11 Osram Sylvania Inc. Materiau supporte a base de carbure de tungstene

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3077385A (en) * 1959-01-06 1963-02-12 Gen Electric Process for producing carbides
DE2063350A1 (de) * 1970-06-04 1972-06-29 Bosch Gmbh Robert Verfahren zur Herstellung von Brennstoffelektroden für elektrochemische Systeme, insbesondere für Brennstoffzellen
US3848062A (en) * 1972-02-17 1974-11-12 Ppg Industries Inc Preparation of monotungsten carbide

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325843A (en) * 1980-12-08 1982-04-20 Shell Oil Company Process for preparing a supported tungsten carbide composition
US4702784A (en) * 1982-06-15 1987-10-27 Kernforschungsanlage Julich Gesellschaft Mit Beschrnakter Haftung Process for production of a tungsten carbide-activated electrode
US4990372A (en) * 1987-09-03 1991-02-05 Air Products And Chemicals, Inc. Method for producing wear resistant internal surfaces of structures
US5277987A (en) * 1991-02-01 1994-01-11 Air Products And Chemicals, Inc. High hardness fine grained beta tungsten carbide
US5200060A (en) * 1991-04-26 1993-04-06 Amoco Corporation Hydrotreating process using carbides and nitrides of group VIB metals
US6090992A (en) * 1998-12-08 2000-07-18 Phillips Petroleum Company Isomerization catalyst system, method of making and method of using such catalyst system in the isomerization of saturated hydrocarbons
WO2000041808A1 (fr) * 1999-01-12 2000-07-20 Hyperion Catalysis International, Inc. Compositions et nanotubes a base de carbure et d'oxycarbure
WO2002028544A1 (fr) * 2000-09-29 2002-04-11 Osram Sylvania Inc. Materiau supporte a base de carbure de tungstene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO0228773A1 *

Also Published As

Publication number Publication date
GB0306436D0 (en) 2003-04-23
JP2004510668A (ja) 2004-04-08
GB2383998A (en) 2003-07-16
AU2001285343A1 (en) 2002-04-15
CA2421626A1 (fr) 2002-04-11
EP1351881A1 (fr) 2003-10-15
DE10196680T1 (de) 2003-08-28
WO2002028773A1 (fr) 2002-04-11

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