GB2408956A - Reforming catalyst - Google Patents
Reforming catalyst Download PDFInfo
- Publication number
- GB2408956A GB2408956A GB0328648A GB0328648A GB2408956A GB 2408956 A GB2408956 A GB 2408956A GB 0328648 A GB0328648 A GB 0328648A GB 0328648 A GB0328648 A GB 0328648A GB 2408956 A GB2408956 A GB 2408956A
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- United Kingdom
- Prior art keywords
- catalyst
- metal particles
- reforming
- catalytic metal
- support material
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- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- 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
- B01J37/0201—Impregnation
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- 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
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming 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
-
- 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
- C01B2203/1064—Platinum group metal 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
A reforming catalyst comprising catalytic metal particles dispersed on a support material, wherein the catalytic metal particles comprise rhodium, ruthenium or platinum, and wherein the catalyst further comprises gold is disclosed. Catalysed components and fuel processing systems comprising the catalyst, and reforming processes using the catalyst are also disclosed.
Description
REFORMING CATALYST
The present invention relates to Mel reforming catalysts, catalysed components and fuel processing systems comprising the catalysts, and reforming processes using the catalysts.
Hydrogen is an important industrial gas and is used in a number of applications such as ammonia synthesis, methanol synthesis, chemical hydrogenations, metal manufacture, glass processing and fuel cells. Fuel processors produce hydrogen by reforming fuels such as methane, propane, methanol, ethanol, natural gas, liquefied petroleum gas (LPG), diesel and gasoline, and are used to provide hydrogen for a variety of applications, particularly for fuel cells. The reforming process produces a hydrogenrich reformats stream that also comprises carbon dioxide, carbon monoxide and trace amounts of hydrocarbons or alcohols. Carbon monoxide is a severe poison for the catalysts in the anode of a fuel cell, so fuel processing systems generally comprise a fuel reformer and one or more carbon monoxide clean-up stages.
In a steam reforming process, water and fuel are combined to produce hydrogen and carbon dioxide, e.g. for methanol: CH3OH + H2O CO2 + 3H2 This process is endothermic, so steam reforming requires a continuous input of energy.
In an autothermal reforming process, both water and air are mixed with the fuel.
The process combines steam reforming and partial oxidation, e.g. for methanol: CH3OH + H2O CO2 + 3H2 CH3OH + '/202 CO2 + 2H2 The partial oxidation is exothermic, thus providing the heat for the endothermic steam reforming reaction. Another reaction which may take place within the autothermal reformer is the water gas shift reaction: CO + H2O CO2 + H2 This is a particularly useful reaction because it reduces CO content and increases hydrogen content. Autothermal reforming processes are described in WO 96/00186.
ëe eee ee e e e e e see e e e ee e e e e e ee ee e e e e e PFC1682GB/1 IDec2003 Catalysts are used to promote the various reforming reactions. Generally the catalysts comprise metal particles deposited on ceramic support materials. Promoter materials such as lithium are deposited with the catalytic metals to improve the performance of the catalyst.
The present inventors have sought to provide an improved reforming catalyst.
Desirably the catalyst should promote the reforming reactions over a wide temperature range and for a variety of fuels. The catalyst should be durable, i.e. the performance should not decrease significantly with time.
Accordingly the present invention provides a reforming catalyst comprising catalytic metal particles dispersed on a support material, wherein the catalytic metal particles comprise rhodium, ruthenium or platinum, and characterised in that the catalyst further comprises gold.
The present inventors have found that the catalysts according to the invention have improved performance when compared to state-of-the-art catalysts that do not contain gold.
The gold is suitably not alloyed with the catalytic metal particles, but is present as gold particles that are dispersed, with the catalytic metal particles, on the surface of the support material. Some of the gold particles are likely to be in contact with the catalytic metal particles and this is believed to be important in achieving the improved performance shown by the catalysts of the present invention.
The catalytic metal particles may be rhodium, ruthenium or platinum alone, or may be alloy particles comprising one or more of rhodium, ruthenium and platinum.
Suitable alloying metals include precious metals such as palladium, osmium or iridium, but may also include base metals. In a preferred embodiment the catalytic metal particles are rhodium particles or platinum-rhodium alloy particles. In a particularly preferred embodiment the catalytic metal particles are rhodium particles.
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PFC1682GB/1 IDec2003 The molar ratio of catalytic metal particles to gold is suitably between 20:1 and 1:1, preferably between 15:1 and 3:2.
Suitably the loading of the catalytic metal particles is 0.5-10 weight %, based on the weight of the support material. If the catalytic metal particles are platinum-rhodium alloy particles, a suitable atomic ratio of platinum:rhodium is between 5:1 and 1:5, preferably about 1:1.
The support material suitably comprises ceria and optionally zirconia dispersed on a material such as alumina or silica-alumina. The loading of ceria and zirconia (i.e. the combined mass of the ceria and, if present, the zirconia as a percentage of the total mass of the support material) is suitably 10-60wt%, preferably 25-60wt%. The ceria and zirconia may be present as regions of ceria, regions of zirconia and/or regions of mixed ceria-zirconia oxide. It is preferred that the majority of the ceria and zirconia is present as the mixed oxide. The atomic ratio of ceria:zirconia is suitably in the range from 10:1 to 1:10, preferably from 5:1 to 1:1, most preferably about 3:1. The average particle size of the ceria and/or zirconia particles is suitably below 15nm, preferably below 8nm.
The catalyst may be prepared by any suitable methods known to those skilled in the art. Suitable methods include co-impregnation, deposition precipitation and co-precipitation procedures.
A suitable method for preparing the support material is the deposition of ceria and zirconia onto a material such as alumina or silica-alumina by co-precipitation of cerium oxyhydroxide and zirconium oxyhydroxide. Sols of ceria and zirconia, which are stabilised by counter ions such as nitrate and acetate, are added to a slurry of an alumina or silicaalumina material. A base such as 1M ammonia solution is added to the slurry.
The product is then washed several times, dried, e.g. at 120 C and calcined, e.g. at 800 C.
A suitable method for the deposition of the catalytic metal particles and the gold particles onto the support material is co-impregnation. Suitable metal salts are made up into a solution such that the volume of solution is sufficient to fill the entire pore volume a e . .. e. - . .. ..
. . . . . e...
. - PFCI60 2GB/I IDec2003 of the support material. The solution is added to the support material, the material is mixed thoroughly and then dried and calcined. Alternatively, the catalytic metal particles and gold particles can be impregnated sequentially.
Another suitable method for the deposition of the precious metal particles is co- deposition. The support material is dispersed in a slurry containing suitable metal salts.
A base is added to deposit the metal onto the support material, and the catalyst is dried and calcined.
In a further aspect, the present invention provides a catalysed component comprising the reforming catalyst according to the invention. The catalysed component comprises the reforming catalyst deposited on a suitable substrate. The substrate may be any suitable flow-through substrate such as a monolith, foam, static mixer or heat exchanger unit. Alternatively the substrate may comprise discrete units such as pellets, rings etc. which are enclosed in a container. The substrate may be ceramic, e.g. cordierite, or metallic. The amount of catalyst on the substrate is suitably from 0.5- 5g/in3 (0.03-0.3g/cm3).
The catalyst is deposited on the substrate using any appropriate techniques known to those skilled in the art. Suitably, the catalyst is dispersed in water, possibly with additional binders, thickeners or adhesive agents to form a slurry. It is usually necessary to break down the particle size of the catalyst by milling the slurry, e.g. in a ball mill or a bead mill, or by milling the dry catalyst before it is added to the slurry, e.g. in a jet mill.
The slurry is passed over or through the substrate to coat the surfaces that will be exposed to the reactant gases. This can be done by dip coating, flood coating or waterfall coating. These and other methods, such as vacuum impregnation, are well known in the art. Any excess slurry is removed, and the substrate is subsequently dried and calcified.
In a yet further aspect, the present invention provides a process for reforming fuel using a catalysed component according to the invention. The process comprises the step of supplying fuel, steam and optionally air to the catalysed component. The fuel may be an alkane such as methane, an alcohol such as methanol or a mixture of components, * e . . PFC 1 682GB/1 I Dec2003 such as gasoline. Liquid fuels must be vaporised before they are supplied to the catalysed component. If the process uses steam reforming (and not autotherrnal reforming), heat must be supplied to the reaction or to the catalysed component, e.g. by pre-heating the fuel and/or steam. The reforming process is typically carried out at temperatures above 600 C.
In a yet further aspect, the present invention provides a fuel processing system comprising a catalysed component according to the invention. The system may further comprise carbon monoxide clean-up components (e.g. water gas shift reactors, selective oxidation reactors, hydrogen diffusion membranes), heat exchanger components and catalytic burners.
The invention will now be described by reference to examples which are not meant to be limiting thereof.
Catalyst Manufacture Four catalysts, all comprising 2wt% rhodium on a ceria-zirconia alumina support but with different amounts of gold promoter, were prepared: | Rh: Au ratio l Comparative Example 1 T Rh only l
Example 1 10:1
Example 2 5:1
Example 3 2:1
The alumina was slurried in demineralized water, nitrate-stabilised ceria and zirconia sots were added. Ammonia solution (1M) was added until the pH of the slurry reached 8. The product was filtered and washed several times to remove NH4NO3 and then dried at 120 C for 8 hours and calcined at 800 C for 2 hours. Each of the support materials had a ceria-zirconia loading of 30wt%.
. . e. . . PFC1682GB/1 IDec2003 Rhodium and gold were deposited on each support material by incipient wetness co-impregnation. Rhodium nitrate (Johnson Matthey, UK) and tetrachloroauric acid (HAuCI4, Johnson Matthey, UK) in appropriate proportions were made up into an aqueous solution such that the volume of solution was sufficient to fill the entire pore volume of the support material. The solution was added to the support material, the material was mixed and then the material was dried at 120 C for 8 hours and calcined at 500 C for 2 hours.
Performance Tests Catalyst powder samples were diluted with cordierite (10:1 cordierite:catalyst) and pelletised (250-355pm). lOOmg of the pelletised samples were tested in a continuous flow, fixed-bed microreactor.
Gasoline steam reforming performance of the catalysts was measured at atmospheric pressure and a furnace temperature of 700 C. The fuel flow was 1.9 ml/in and the H2O:C ratio was 4. Nitrogen was used as a diluent at lOOml/min.
Conversion to CO, CO2 and CH4 and the NMHC level (residual non- methane hydrocarbon as C1 equivalents in dry gas flow) were measured. The NMHC level is considered to be a more sensitive indicator of performance than conversion to Cl components. Lower NMHC levels indicate better performance.
% Conversion to NMHC/ppm CO+CO2+CH4 Comparative Example 1 71.9 51150
Example 1 82.2 31340
Example 2 80.1 34185
Example 3 77.0 40740
The catalysts comprising gold had better performance than the catalyst that did not contain gold.
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ë e as a a a a a PFC1682GB/1 IDec2003 l
Claims (7)
1. A reforming catalyst comprising catalytic metal particles dispersed on a support material, wherein the catalytic metal particles comprise rhodium, ruthenium or platinum, and characterized in that the catalyst further comprises gold.
2. A reforming catalyst according to claim 1, wherein the molar ratio of catalytic metal particles to gold is between 15:1 and 3:2.
3. A reforming catalyst according to claim 1 or claim 2, wherein the loading of the catalytic metal particles is 0.5-10 weight %, based on the weight of the support material.
4. A reforming catalyst according to any preceding claim, wherein the support material comprises ceria and zirconia.
5. A catalysed component comprising the reforming catalyst according to any one of claims 1 to 4 deposited on a substrate.
6. A process for reforming fuel using a catalysed component according claim 5.
7. A filet processing system comprising a catalysed component according claim 5.
. .. as . . . . . . . . . . . . . . . . . . - .. . . . PFC1682GB/1 IDec2003
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0328648A GB2408956A (en) | 2003-12-11 | 2003-12-11 | Reforming catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0328648A GB2408956A (en) | 2003-12-11 | 2003-12-11 | Reforming catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0328648D0 GB0328648D0 (en) | 2004-01-14 |
| GB2408956A true GB2408956A (en) | 2005-06-15 |
Family
ID=30129983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0328648A Withdrawn GB2408956A (en) | 2003-12-11 | 2003-12-11 | Reforming catalyst |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2408956A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007017157A1 (en) | 2005-08-05 | 2007-02-15 | Südzucker Aktiengesellschaft Mannheim/Ochsenfurt | Supported gold catalyst |
| WO2012047864A1 (en) * | 2010-10-05 | 2012-04-12 | Pacific Industrial Development Corporation | Sulfur-resistant catalyst support material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3899413A (en) * | 1973-05-17 | 1975-08-12 | Phillips Petroleum Co | Platinum-germanium-gold reforming catalyst and process |
| GB2016510A (en) * | 1978-02-03 | 1979-09-26 | Inst Francais Du Petrole | Process for steam-dealkylating allrylaromatic hydrocarbons |
| US20030012719A1 (en) * | 2001-04-14 | 2003-01-16 | Omg Ag & Co. Kg | Catalyst and process for removing carbon monoxide from a reformate gas |
-
2003
- 2003-12-11 GB GB0328648A patent/GB2408956A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3899413A (en) * | 1973-05-17 | 1975-08-12 | Phillips Petroleum Co | Platinum-germanium-gold reforming catalyst and process |
| GB2016510A (en) * | 1978-02-03 | 1979-09-26 | Inst Francais Du Petrole | Process for steam-dealkylating allrylaromatic hydrocarbons |
| US20030012719A1 (en) * | 2001-04-14 | 2003-01-16 | Omg Ag & Co. Kg | Catalyst and process for removing carbon monoxide from a reformate gas |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007017157A1 (en) | 2005-08-05 | 2007-02-15 | Südzucker Aktiengesellschaft Mannheim/Ochsenfurt | Supported gold catalyst |
| US8329613B2 (en) * | 2005-08-05 | 2012-12-11 | Südzucker Aktiengesellschaft Mannheim/Ochsenfurt | Supported gold catalyst |
| WO2012047864A1 (en) * | 2010-10-05 | 2012-04-12 | Pacific Industrial Development Corporation | Sulfur-resistant catalyst support material |
| JP2013541414A (en) * | 2010-10-05 | 2013-11-14 | パシフィック インダストリアル デベロップメント コーポレイション | Sulfur-resistant catalyst support material |
| US10065177B2 (en) | 2010-10-05 | 2018-09-04 | Pacific Industrial Development Corporation | Sulfur-resistant catalyst support material |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0328648D0 (en) | 2004-01-14 |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |