WO2002028773A1 - Tungsten carbide material - Google Patents
Tungsten carbide material Download PDFInfo
- Publication number
- WO2002028773A1 WO2002028773A1 PCT/US2001/026875 US0126875W WO0228773A1 WO 2002028773 A1 WO2002028773 A1 WO 2002028773A1 US 0126875 W US0126875 W US 0126875W WO 0228773 A1 WO0228773 A1 WO 0228773A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- peak
- ray diffraction
- tungsten
- tungsten carbide
- carbide material
- Prior art date
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Classifications
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- 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
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0306436A GB2383998A (en) | 2000-09-29 | 2001-08-30 | Tungsten carbide material |
EP01964498A EP1351881A4 (en) | 2000-09-29 | 2001-08-30 | Tungsten carbide material |
DE10196680T DE10196680T1 (en) | 2000-09-29 | 2001-08-30 | tungsten carbide |
JP2002532164A JP2004510668A (en) | 2000-09-29 | 2001-08-30 | Tungsten carbide material |
AU2001285343A AU2001285343A1 (en) | 2000-09-29 | 2001-08-30 | Tungsten carbide material |
CA002421626A CA2421626A1 (en) | 2000-09-29 | 2001-08-30 | Tungsten carbide material |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US67551000A | 2000-09-29 | 2000-09-29 | |
US09/675,510 | 2000-09-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002028773A1 true WO2002028773A1 (en) | 2002-04-11 |
Family
ID=24710815
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/026875 WO2002028773A1 (en) | 2000-09-29 | 2001-08-30 | Tungsten carbide material |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1351881A4 (en) |
JP (1) | JP2004510668A (en) |
AU (1) | AU2001285343A1 (en) |
CA (1) | CA2421626A1 (en) |
DE (1) | DE10196680T1 (en) |
GB (1) | GB2383998A (en) |
WO (1) | WO2002028773A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1383611A1 (en) * | 2000-09-29 | 2004-01-28 | Osram Sylvania, Inc. | Supported tungsten carbide material |
EP2413407A1 (en) * | 2010-07-30 | 2012-02-01 | Samsung Electronics Co., Ltd. | Electrode catalyst and method of preparing electrode catalyst for fuel cell, and membrane electrode assembly and fuel cell including same |
US10227235B2 (en) | 2015-03-31 | 2019-03-12 | Jx Nippon Mining & Metals Corporation | Method for producing tungsten carbide |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4815823B2 (en) * | 2004-03-31 | 2011-11-16 | 三菱化学株式会社 | Fuel cell catalyst and method for producing the same, fuel cell electrode and fuel cell using the same |
JP2006107987A (en) * | 2004-10-07 | 2006-04-20 | Hitachi Maxell Ltd | Catalyst for fuel cell, fuel cell and membrane electrode junction using catalyst |
KR100825688B1 (en) * | 2006-04-04 | 2008-04-29 | 학교법인 포항공과대학교 | Nanoporous tungsten carbide catalyst and preparation method of the same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3077385A (en) * | 1959-01-06 | 1963-02-12 | Gen Electric | Process for producing carbides |
US3848062A (en) * | 1972-02-17 | 1974-11-12 | Ppg Industries Inc | Preparation of monotungsten carbide |
US3902917A (en) * | 1970-06-04 | 1975-09-02 | Bosch Gmbh Robert | Process for the production of tungsten carbide catalyst adapted for use in fuel cells |
Family Cites Families (8)
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 |
DE3222436A1 (en) * | 1982-06-15 | 1983-12-15 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | METHOD FOR PRODUCING A TUNGSTEN CARBID-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 |
KR100907214B1 (en) * | 1999-01-12 | 2009-07-10 | 하이페리온 커탤리시스 인터내셔널 인코포레이티드 | Carbide and oxycarbide based compositions and nanorods |
US6696184B1 (en) * | 2000-09-29 | 2004-02-24 | Osram Sylvania Inc. | Supported tungsten carbide material |
-
2001
- 2001-08-30 JP JP2002532164A patent/JP2004510668A/en not_active Withdrawn
- 2001-08-30 EP EP01964498A patent/EP1351881A4/en not_active Withdrawn
- 2001-08-30 CA CA002421626A patent/CA2421626A1/en not_active Abandoned
- 2001-08-30 WO PCT/US2001/026875 patent/WO2002028773A1/en not_active Application Discontinuation
- 2001-08-30 AU AU2001285343A patent/AU2001285343A1/en not_active Abandoned
- 2001-08-30 GB GB0306436A patent/GB2383998A/en not_active Withdrawn
- 2001-08-30 DE DE10196680T patent/DE10196680T1/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3077385A (en) * | 1959-01-06 | 1963-02-12 | Gen Electric | Process for producing carbides |
US3902917A (en) * | 1970-06-04 | 1975-09-02 | Bosch Gmbh Robert | Process for the production of tungsten carbide catalyst adapted for use in fuel cells |
US3848062A (en) * | 1972-02-17 | 1974-11-12 | Ppg Industries Inc | Preparation of monotungsten carbide |
Non-Patent Citations (1)
Title |
---|
See also references of EP1351881A4 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1383611A1 (en) * | 2000-09-29 | 2004-01-28 | Osram Sylvania, Inc. | Supported tungsten carbide material |
EP1383611A4 (en) * | 2000-09-29 | 2005-09-14 | Osram Sylvania Inc | Supported tungsten carbide material |
EP2413407A1 (en) * | 2010-07-30 | 2012-02-01 | Samsung Electronics Co., Ltd. | Electrode catalyst and method of preparing electrode catalyst for fuel cell, and membrane electrode assembly and fuel cell including same |
US9466843B2 (en) | 2010-07-30 | 2016-10-11 | Samsung Electronics Co., Ltd. | Electrode catalyst and method of preparing electrode catalyst for fuel cell, and membrane electrode assembly and fuel cell including same |
US10227235B2 (en) | 2015-03-31 | 2019-03-12 | Jx Nippon Mining & Metals Corporation | Method for producing tungsten carbide |
Also Published As
Publication number | Publication date |
---|---|
AU2001285343A1 (en) | 2002-04-15 |
JP2004510668A (en) | 2004-04-08 |
CA2421626A1 (en) | 2002-04-11 |
DE10196680T1 (en) | 2003-08-28 |
GB2383998A (en) | 2003-07-16 |
GB0306436D0 (en) | 2003-04-23 |
EP1351881A1 (en) | 2003-10-15 |
EP1351881A4 (en) | 2005-09-14 |
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