WO1997043042A1 - Catalyst compositions of nanoparticulate metal on a refractory support - Google Patents
Catalyst compositions of nanoparticulate metal on a refractory support Download PDFInfo
- Publication number
- WO1997043042A1 WO1997043042A1 PCT/US1997/007793 US9707793W WO9743042A1 WO 1997043042 A1 WO1997043042 A1 WO 1997043042A1 US 9707793 W US9707793 W US 9707793W WO 9743042 A1 WO9743042 A1 WO 9743042A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- refractory support
- active metal
- palladium
- catalyst composition
- catalyst
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 54
- 229910052763 palladium Inorganic materials 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 150000004056 anthraquinones Chemical class 0.000 claims description 6
- 238000005240 physical vapour deposition Methods 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 230000006872 improvement Effects 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- -1 alkyl anthrahydroquinone Chemical compound 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- B01J35/23—
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/40—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
Definitions
- the invention generally relates to catalyst compositions of nanoparticulate metal deposited on a refractory support material, processes for manufacturing said catalyst compositions and the use of said catalyst compositions.
- the catalyst compositions are useful in hydrogenation processes.
- U. S. Patent No. 4,046,712 discloses a catalyst comprising a hard, substantially non-porous paniculate substrate and a sputtered deposit of catalytic metal on the substrate, said deposit existing as an atomic dispersion and derived from a target of material subjected to ion beam bombardment. Specific utility of these catalysts is for high temperature, gas phase catalytic reactions.
- 1086710 discloses a process for preparing supported palladium catalysts comprising the vapor deposition of a compound of palladium onto a porous support while the support is at a temperature above the decomposition temperature of the compound of palladium. Deposition of palladium occurs on the surface of the support and as well as into pores having diameters greater than 50 Angstrom units (A).
- U. S. Patent No. 4,536,482 discloses a catalyst wherein a paniculate catalyst support has co-sputtered on its surface a mixture of a catalytically active metal and a co-sputtered support material. The use of RF sputtering is disclosed.
- U. S. Patent No. 5,077,258 discloses a metal catalytic film comprising a flexible substrate, a catalytic metal layer adherent thereto, said layer having a thickness of 200 to 10,000 Angstroms (A). The process for preparing this film material involves the use of an electron beam gun or a magnetron sputtering device. Sputtering is carried out under reduced pressure of 0.1 Torr or less.
- the process of the present invention provides catalysts comprising catalytic metals in the form of nanoparticles on a refractory support.
- the metal nanoparticles are neither atomic dispersions nor thin films. They are particles ranging in size from between about 10 and 100 nanometers (nm).
- the catalysts of the present invention are prepared by magnetron sputtering, as opposed to ion beam sputtering, which is a different and a much simpler process compared to the process disclosed by Cairns.
- the present invention provides a composition having utility as a catalyst comprising a nanoparticulate catalytically active metal on a refractory support.
- the invention further provides a process for the preparation of a composition having utility as a catalyst comprising a nanoparticulate catalytically active metal on a refractory support, said process comprising the physical vapor deposition of a catalytically active metal by sputtering, at a preferred pressure of > 10 mTorr, onto a refractory support cooled, preferably by liquid nitrogen, during deposition to ensure limited mobility of the incoming sputtered catalytically active metal atoms.
- sputtering takes place using a magnetron gun.
- the invention further provides for an improved process for the reduction of anthraquinones to anthrahydroquinones as an integral part of a process to prepare hydrogen peroxide, said improvement comprising the use of the composition of the present invention as a hydrogenation catalyst.
- the present invention provides a composition having utility as a catalyst comprising a nanoparticulate catalytically active metal on a refractory support.
- the nanoparticulate catalytically active metal can be a single active metal or can be a combination of one or more selected active metals.
- the catalytically active metal, or combination of active metals is selected from the group consisting of platinum, palladium, rhodium, iridium, ruthenium, silver, gold, copper, mercury and rhenium.
- the most preferred catalytically active metal is palladium, including combinations therewith.
- the refractory support is preferably selected from the group consisting of alumina, (various forms), silica, titania, carbon (various forms), zirconia, silica- alumina and magnesia.
- a specifically preferred refractory support is alumina, most preferred being ⁇ -alumina.
- the size of the catalyst support is not critical to the practice of the invention but may be important in the subsequent use of the catalyst. In gas phase reactions and in fixed bed reactors, a suitable support size would generally be about 2-3 mm in diameter as spherical or cylindrical shapes (L/D - 1). For slurry liquid phase reactions, a suitable support size would generally have a mean particle diameter of about 40 to about 150 microns depending on substrate density.
- nanoparticulate is meant that the particles of the catalytically active metal have particle sizes in the range of about 10 nanometers to about 100 nanometers.
- Pressures usable in the sputtering process of the present invention range from greater than about 10 up to about 200 mTorr. Most preferred is a pressure of approximately 30 mTorr.
- the refractory support is cooled during deposition to ensure limited mobility of the incoming sputtered catalytically active metal atoms. Temperatures usable are from between about 20 C C to about minus 180°C. Liquid nitrogen is the preferred and most convenient means of providing such an environment.
- catalytically active metals dispersed on refractory supports are common in the chemical process industry.
- a major group of processes included in this category are catalytic hydrogenations.
- Several important catalytic hydrogenations include, for example, the conversion of benzene to cyclohexane, the hydrogenation of edible oils to yield margerine-type products and the conversion of unsaturated oxygen-containing compounds, aldehydes and ketones, to alcohols.
- Palladium supported on ⁇ -Al2 ⁇ 3 is a catalyst that may be used, for example, in the process for the production of hydrogen peroxide.
- An integral part of this process involves the catalytic hydrogenation of various substituted anthraquinones to the corresponding anthrahydroquinones.
- a catalyst currently employed in this hydrogenation process is palladium either supported or as palladium black.
- One catalyst currently in use is produced by solution precipitation and deposition of palladium on the chosen support.
- a commonly used support material is alumina.
- the present invention provides a new process, physical vapor deposition (PVD) as a process for producing such an alumina supported palladium hydrogenation catalyst.
- PVD physical vapor deposition
- the grain size is apparent in the attached figures wherein a lattice image of nanoparticulate palladium on a copper grid is shown.
- palladium nanocatalyst supported on ⁇ 20 ⁇ m ⁇ -Al 2 O 3 was prepared by high pressure sputtering. Sputtering was carried out using a magnetron gun with a palladium target. High sputtering pressure ( > 10 mTorr) is required to thermalize the sputtered atoms so as to limit their mobility at the surface of the AI 2 O 3 particles. With this limited mobility diffusion of not more than 2-3 atomic distances, cluster or nanoparticle formation occurs rather than the deposition of a continuous film. The particles of the refractory support are cooled in liquid nitrogen during deposition to ensure limited mobility of the incoming sputtered palladium atoms.
- the temperature of AI 2 O 3 can be varied in a controlled fashion in order to produce nanoparticles of varying sizes. Sputtering is a line-of-sight process. Therefore, the Al 2 O 3 must be either agitated while being deposited on or the deposition has to be done several times with mixing in between to expose fresh support surface so that the desired amount of metal loading can be achieved. Moreover, since the total exposed area of the nanoparticle is the determining factor for the enhancement of activity, if multilayers of palladium nanoparticles are formed, the activity per unit weight metal is reduced. Ideally, a monolayer of well dispersed nanoparticles is desired.
- Scanning electron microscopy (SEM) analysis of a palladium/alumina catalyst for anthraquinone reduction prepared by the Applicants' solution precipitation method shows an average grain size of palladium to be about 0.1 ⁇ m.
- the resolution of conventional SEM is not high enough to measure the grain size of the nanoparticulate palladium/alumina prepared by the process of the present invention. Therefore, transmission electron microscopy (TEM) analyses of parallel samples deposited on a copper grid support were used to show the grain size to be less than about 200 angstrom (A), (20 nanometers).
- EXAMPLE 1 Catalyst Preparation Physical Vapor Deposition was carried out in a stainless steel vacuum chamber (Huntington, Santa Clara, CA). The base pressure prior to the deposition was 3.2 x 10( _6 )Torr. A 99.999% pure palladium target was used (Englehard Industries Inc.). Argon gas was introduced in the chamber at 30 seem and a pressure of 30 mTorr was established by throttling the high vacuum gate valve. A commercially available magnetron gun was used for sputtering (US Gun: 2 inch) in a sputter down configuration. A DC power supply (MDX) was used.
- Sputtering was carried out in a constant power mode at 75 Watts with the target voltage being 250 V and the current 0.3 A.
- the alumina powder 0.2 grams, was placed 2 inches away from, and directly underneath, the target in a copper boat.
- the boat was cooled to -150 C C by flowing liquid nitrogen through the copper tubes welded to the bottom of the boat. Once a temperature of -150°C was established, the plasma was ignited.
- the powder was mixed using a wobble stick to coat the powder uniformly. A loading of approximately 1 wt. % was achieved in 20 minutes of deposition. Once the desired loading was achieved, the power to the target, the Argon gas to the chamber and the liquid nitrogen to the powder holder were turned off. The sample was allowed to warm-up to the room temperature in vacuum to avoid any moisture condensation.
- the hydrogenated product was then air sparged to convert the alkyl anthrahydroquinone to quinone and hydrogen peroxide.
- the hydrogen peroxide was extracted and the amount was determined by titration.
- the activity was finally calculated in terms of mL H 2 /min/g Pd.
- Activity measured for the palladium/alumina catalyst of the present invention gave values of 300 mL H 2 /min/g palladium where the best values for the palladium/alumina catalyst prepared by solution precipitation are about 30 mL H 2 /min/g palladium at the same Pd loading.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97933987A EP0902728A1 (en) | 1996-05-14 | 1997-05-07 | Catalyst compositions of nanoparticulate metal on a refractory support |
AU37155/97A AU3715597A (en) | 1996-05-14 | 1997-05-07 | Catalyst compositions of nanoparticulate metal on a refractory support |
JP09540943A JP2000510042A (en) | 1996-05-14 | 1997-05-07 | Catalyst composition having nanoparticulate metal on refractory support |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6264196P | 1996-05-14 | 1996-05-14 | |
US60/062,641 | 1996-05-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997043042A1 true WO1997043042A1 (en) | 1997-11-20 |
Family
ID=22043846
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/007793 WO1997043042A1 (en) | 1996-05-14 | 1997-05-07 | Catalyst compositions of nanoparticulate metal on a refractory support |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0902728A1 (en) |
JP (1) | JP2000510042A (en) |
AU (1) | AU3715597A (en) |
WO (1) | WO1997043042A1 (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002055432A1 (en) * | 2001-01-10 | 2002-07-18 | Razmik Malkhasyan | Method of synthesizing of nanosize carbides and active catalysts__________________________________________________________________ ___________________________________________ |
WO2003094195A1 (en) * | 2002-05-02 | 2003-11-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for the production of catalysts |
US6787500B2 (en) | 2001-06-29 | 2004-09-07 | Denso Corporation | Catalyst particles and method of manufacturing the same |
WO2005030382A2 (en) * | 2003-09-26 | 2005-04-07 | 3M Innovative Properties Company | Nanoscale gold catalysts, activating agents, support media, and related methodologies useful for making such catalyst systems especially when the gold is deposited onto the support media using physical vapor deposition |
US7274458B2 (en) | 2005-03-07 | 2007-09-25 | 3M Innovative Properties Company | Thermoplastic film having metallic nanoparticle coating |
WO2008118097A1 (en) * | 2007-03-23 | 2008-10-02 | Agency For Science, Technology And Research | Palladium catalysts |
FR2941878A1 (en) * | 2009-02-10 | 2010-08-13 | Quertech Ingenierie | METHOD FOR TREATING AN ION BEAM WITH A METAL LAYER DEPOSITED ON A SUBSTRATE |
US8058202B2 (en) | 2005-01-04 | 2011-11-15 | 3M Innovative Properties Company | Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold |
US8137750B2 (en) | 2006-02-15 | 2012-03-20 | 3M Innovative Properties Company | Catalytically active gold supported on thermally treated nanoporous supports |
WO2013160163A1 (en) | 2012-04-27 | 2013-10-31 | Solvay Sa | Hydrogenation catalysts, method for making same and use thereof for preparing hydrogen peroxide |
WO2014001133A1 (en) | 2012-06-27 | 2014-01-03 | Solvay Sa | Hydrogenation catalysts, method for making same and process for preparing hydrogen peroxide |
EP2705901A1 (en) | 2012-09-06 | 2014-03-12 | Solvay SA | Hydrogenation catalysts, method for making same and use thereof for preparing hydrogen peroxide |
EP2794105A4 (en) * | 2011-12-21 | 2016-03-09 | 3M Innovative Properties Co | Catalysts systems |
GB2544277A (en) * | 2015-11-10 | 2017-05-17 | Johnson Matthey Plc | Catalysts |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4052517B2 (en) * | 2004-06-25 | 2008-02-27 | 孝之 阿部 | Method for producing supported fine particles |
JP4769783B2 (en) * | 2007-10-30 | 2011-09-07 | 孝之 阿部 | Method for producing supported fine particles |
JP5751484B2 (en) * | 2011-06-10 | 2015-07-22 | 国立大学法人東北大学 | Method for producing nanometal glass particle aggregate thin film |
IN2014DN07057A (en) * | 2012-02-24 | 2015-04-10 | Dsm Ip Assets Bv |
Citations (3)
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---|---|---|---|---|
GB1486108A (en) * | 1975-02-27 | 1977-09-21 | Ici Ltd | Reforming and/or isomerisation of hydrocarbon feedstocks using a sputtered catalyst |
GB1537839A (en) * | 1975-06-10 | 1979-01-04 | Atomic Energy Authority Uk | Catalysts comprising a particulate substrate with a sputtered deposit of catalytic material |
US5077258A (en) * | 1990-06-15 | 1991-12-31 | Flex Products, Inc. | Vapor deposited metal catalytic film, process for making the same and liquid container with the film |
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1997
- 1997-05-07 AU AU37155/97A patent/AU3715597A/en not_active Abandoned
- 1997-05-07 JP JP09540943A patent/JP2000510042A/en active Pending
- 1997-05-07 WO PCT/US1997/007793 patent/WO1997043042A1/en not_active Application Discontinuation
- 1997-05-07 EP EP97933987A patent/EP0902728A1/en not_active Withdrawn
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Also Published As
Publication number | Publication date |
---|---|
EP0902728A1 (en) | 1999-03-24 |
AU3715597A (en) | 1997-12-05 |
JP2000510042A (en) | 2000-08-08 |
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