EP1208062A1 - Catalyseur pour dispositif de traitement de carburant hydrocarbone - Google Patents
Catalyseur pour dispositif de traitement de carburant hydrocarboneInfo
- Publication number
- EP1208062A1 EP1208062A1 EP00948168A EP00948168A EP1208062A1 EP 1208062 A1 EP1208062 A1 EP 1208062A1 EP 00948168 A EP00948168 A EP 00948168A EP 00948168 A EP00948168 A EP 00948168A EP 1208062 A1 EP1208062 A1 EP 1208062A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- oxide
- noble metal
- earth metal
- fuel
- 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- Withdrawn
Links
Classifications
-
- 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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
- B01J2523/00—Constitutive chemical elements of heterogeneous 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
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- 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
Definitions
- This invention relates to a hydrocarbon fuel processor catalyst for converting or reforming a hydrocarbon fuel into a simple fuel and is more especially, although not exclusively, concerned with a catalyst for converting a liquid hydrocarbon fuel to hydrogen for use in a fuel cell.
- Fuel cells offer the promise of smaller and lighter weight power sources that are potentially instantaneous and silent in their operation.
- fuel-cell powered vehicles are currently being developed as a more fuel-efficient and less polluting alternative to the internal combustion engine.
- solid oxide fuel cells can be used for large scale, generally static applications. Due to their high operating temperature, typically around 800 °C, such fuel cells are able to directly utilise fuels such as methanol, methane or natural gas. Whilst suitable for large scale operation, such as combined heat and power facilities for building complexes, these cells are not suited to mobile applications as they are bulky and have a slow start up due to their high operating temperature.
- polymer fuel cells For mobile applications such as vehicles, polymer fuel cells have been proposed. Due to their relatively low operating temperature (typically around 80 °C), such cells offer
- a fuel processor or reformer converts hydrocarbon fuels to hydrogen gas, potentially enabling fuel-cell powered vehicles to run on fuels which are widely available today, such as liquefied petroleum gas (LPG), paraffin, gasoline or diesel.
- LPG liquefied petroleum gas
- Compact fuel processors suitable for use on vehicles have already been developed for lighter hydrocarbon fuels such as methanol.
- these processors are usually specific to one type of fuel and require a high purity feed since impurities such as sulphur are very detrimental to the reforming catalyst and can permanently deactivate it. It is therefore desirable to produce a compact fuel processor that can extract acceptable amounts of hydrogen from a wide range of commercial fuels and function without adjustment as the fuel type changes.
- These new reforming catalysts should be much more resistant to coking or sulphur deactivation than the currently available catalysts.
- a catalyst may optionally be used to increase the reaction rate, though high temperatures and pressures are still required.
- the carbon in the hydrocarbon fuel is converted to carbon monoxide by oxidation using the oxygen provided by the steam whilst the hydrogen in the fuel and steam is released as hydrogen gas.
- the optimum steam to carbon ratio (H 2 O:C) depends on the processor conditions (temperature and pressure), but invariably this ratio increases as the carbon content of the hydrocarbon increases. Large quantities of steam are therefore required for heavy fuels such as diesel and this demands a high energy input to vaporise the water, leading to a poor thermal efficiency, a slow response time and a slow start up from cold.
- the optimum oxygen to carbon ratio depends on the processor conditions and increases as the carbon content of the hydrocarbon increases.
- a catalyst can be used to increase the reaction rate.
- the initial combustion can occur at high temperatures in the absence of a catalyst to break the hydrocarbon fuel down to simpler molecules.
- the gas stream is then passed over a catalyst to further break down the molecules into carbon monoxide and hydrogen.
- Such a processor exhibits a faster response it has relatively lower hydrogen conversion efficiency than a steam reforming system. It has been further proposed to provide fuel processors which use an "autothermal reforming process" to convert the hydrocarbon fuel to hydrogen and carbon monoxide with a combination of the above two processes.
- the heat liberated by the exothermic partial oxidation reaction (Eq. 2) is used to drive the endothermic steam reforming reaction (Eq. 1) thereby improving the overall thermal efficiency of the processor.
- Different specialist catalysts may be used in physically separate partial oxidation and steam reforming reaction volumes within the processor or alternatively the partial oxidation and steam reforming reactions can take place over a common catalyst bed. The latter produces a simpler system design but places great demands on the catalyst material.
- the vaporised fuel is mixed with air and steam and then injected into an enclosure containing the granulated catalyst material.
- the known fuel processors capable of processing heavier hydrocarbons fuels such as diesel are not ideally suited to small scale mobile applications.
- the endothermic nature of the steam generating and steam reforming processes does not readily lend itself to operating efficiently on a small scale.
- the comparatively high carbon content (high carbon to hydrogen ratio C:H) of many hydrocarbon fuels such as diesel clogs the catalyst through the deposition of coke (carbon) on the surface of the catalyst which blocks access to the active surface of the catalyst.
- the high sulphur level in many heavier hydrocarbon fuels poisons, that is reduces the activity of, the known catalysts used in the steam-reforming process thereby degrading the conversion efficiency.
- the known catalysts for fuel conversion, or reforming comprise base metals (such as nickel), noble metals (such as platinum), or a mixture of these, either in powdered form or as a coating on the surface of an inert ceramic substrate.
- the noble metal is generally dispersed in the form of small particles in order to minimise the metal cost and maximise the surface activity.
- These catalysts are, however, adversely affected by sulphur present in the fuels and are vulnerable to coking since there is no mechanism to remove the carbon from the catalyst surface once it has been deposited. There is therefore considerable scope for the development of improved catalyst systems that are cheaper, more efficient and more versatile than the current materials.
- the present invention has arisen in an endeavour to develop a new catalyst formulation which is suitable for use with diesel and other heavy hydrocarbon fuels in an autothermal fuel processing system, and which is in part at least resistant to both sulphur poisoning and clogging with coke deposition.
- a rare earth metal cobalt oxide (MCoO 3 ) having the perovskite crystal structure as a catalyst in a hydrocarbon fuel processor for converting or reforming a hydrocarbon fuel into a simple fuel most especially hydrogen. Due to its high oxygen ion mobility at temperatures at which such fuel processors operate, typically less than 800°C, use of such a catalyst offers a number of advantages over the known catalysts: (i) the presence of the oxygen ions at the catalyst surface coating promotes the fuel breakdown process; (ii) the oxygen ions oxidise any carbon or contaminants which may be deposited on the catalyst surface coating during the fuel breakdown reaction and this reduces the likelihood of the catalyst becoming clogged, especially when using a high C:H fuel such as diesel.
- MoO 3 rare earth metal cobalt oxide
- the oxygen ions prevent contaminants which might otherwise de-activate the catalyst, such as sulphur, becoming bonded to the surface coating.
- the inventors further believe that during the use of the catalyst the surface decomposes and becomes covered with a catalytically active coating of rare earth oxide, hydrated rare- earth oxide and cobalt metal particles which prevents the catalyst's activity becoming rapidly degraded by carbon deposition and/or by the effects of sulphur or other contaminants.
- a catalyst in accordance with the invention can therefore be said to be self cleaning.
- the known catalysts comprise an inert support structure with a catalytically active coating which is vulnerable to the effects of carbon and/or sulphur.
- the catalyst further includes a noble metal or noble metal oxide.
- a noble metal or noble metal oxide offers a high catalytic activity in which the oxygen ions provide a scouring activity which protects the activity of the noble metal or noble metal oxide at the operating temperature of the fuel processor.
- the noble metal or noble metal oxide comprises platinum or platinum oxide.
- the noble metal or noble metal oxide comprises ruthenium or ruthenium oxide which is found to give at least the same activity but which has a cost appreciably less than that of platinum.
- the noble metal or noble metal oxide is present up to 2 mole %.
- the catalyst further comprises a solid solution having the perovskite crystal structure of the rare earth metal cobalt oxide and an alkaline earth metal cobalt oxide, such as for example a solid solution of lanthanum cobalt oxide and strontium cobalt oxide.
- an alkaline earth metal cobalt oxide such as for example a solid solution of lanthanum cobalt oxide and strontium cobalt oxide.
- the substitution of the rare earth ions by alkaline earth ions increases the number of vacant sites for oxygen within the perovskite crystal structure thereby increasing the number and the mobility of oxygen ions within the crystal lattice.
- the alkaline earth metal cobalt oxide is included in a proportion of up to 50%.
- the alkaline earth metal comprises strontium although calcium or barium can be used.
- a hydrocarbon fuel processor catalyst is characterised by comprising a rare earth metal cobalt oxide having the perovskite structure as described above.
- a hydrocarbon fuel processor for converting a hydrocarbon fuel to hydrocarbon incorporates a catalyst as described above.
- the first catalyst composition described is lanthanum cobalt oxide (LaCO 3 ) having the perovskite crystal structure.
- Lanthanum oxide (La 2 O 3 ) powder was heated in air at 1000°C to decompose any Lanthanum Hydroxide La(OH) 3 present in the material to give single phase La 2 O 3 .
- the single phase La 2 O material was mixed with cobalt oxide (CoO) powder in appropriate weights to give the LaCoO 3 and the mixture ball-milled for 4 hours in approximately 40 gramme batches and then calcined (heated in a furnace) in air at 1050°C for 3 hours.
- the ceramic product after calcining was crushed and graded into a desired particle size, approximately 1-1 O ⁇ m, prior to testing.
- the desired particle size will depend on the type of fuel processor and can accordingly be readily optimised for a required application.
- the perovskite crystal structure is that which exists in mineral perovskite CaTiO and which is commonly adopted in compounds having the general formula ABO 3 where A is a relatively large cation (lanthanum in this example) and B is a relatively smaller cation (cobalt in this example).
- A is a relatively large cation (lanthanum in this example)
- B is a relatively smaller cation (cobalt in this example).
- the B cations are each surrounded by a maximum of six oxygen ions to form a three-dimensional network of comer shared octohedra whilst the A cations occupy the interstices between the octohedra.
- Catalysts containing the noble metal and/or noble metal oxide were found to exhibit an enhanced activity compared to LaCoO 3 . This is attributed to the catalytic activity of the noble metal which is protected against clogging and or contamination by the scouring effect of the high mobility oxygen ions from the LaCoO 3 perovskite crystal structure. This being said it will be appreciated that the concentration of noble metal is selected such that there is sufficient LaCoO 3 to provide adequate cleaning of the metal. Test results indicate that ruthenium is at least as effective as platinum but has the substantial advantage of being much lower in cost.
- Table 3 Test results and test conditions for various hydrocarbon fuels using the catalyst composition 3.
- composition of the reformate would therefore be:
- the conversion efficiency for gasoline was lower than that of the other tested fuels, and this is attributed to the higher sulphur content of this fuel.
- the LPG, paraffin and city diesel had a very low sulphur contents (less than lOppm) while the unleaded gasoline had a much higher sulphur content of lOOppm.
- the temperature programmed data obtained with gasoline indicate that retained sulphur species on the
- the inventors believe that the good catalytic properties of these materials are due to their high oxygen ion mobility at temperatures for use in such fuel processors, typically less than 800 °C. Firstly the presence of the oxygen ions at the catalyst surface promotes the fuel breakdown process. Secondly the oxygen ions oxidise any carbon or contaminants which may be deposited on the catalyst surface during the fuel breakdown reactions thereby reducing the likelihood of catalyst clogging, especially when using a fuel having high carbon to hydrogen ratio such as diesel. Thirdly the oxygen ions prevent contaminants, such as sulphur, becoming bonded to the surface which might otherwise de-activate the catalyst.
- the present invention is not limited to the specific compositions described and that further compositions are envisaged which are within the scope of the invention.
- the basic catalyst has been described in relation to LaCoO 3 though other rare earth metal (M) cobalt oxides (MCoO 3 ) having the perovskite crystal structure could be used.
- M rare earth metal
- MoO 3 cobalt oxides
- solid solutions with alkaline earth metals other than strontium such as calcium or barium can be used to increase the oxygen ion mobility.
- a catalyst in accordance with the invention can be used for other types of hydrocarbon fuels other than diesel and is especially suited to use with heavier hydrocarbon fuels.
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)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
L'invention concerne un catalyseur à utiliser dans un dispositif de traitement de carburant hydrocarboné, pour la conversion ou le reformage d'un carburant hydrocarboné, tel que le Diesel, en carburant simple, particulièrement en hydrogène. Ledit catalyseur comprend un oxyde de cobalt (McoO3) de métal rare, présentant une structure pérovskite. Dans une composition, le catalyseur comprend une solution solide présentant la structure pérovskite de l'oxyde de cobalt de métal rare, de préférence de l'oxyde de cobalt de lanthane LaCoCO3, de préférence de l'oxyde de cobalt de strontium SrCoO3. De manière que son activité catalytique soit encore augmentée, le catalyseur peut également comprendre un métal noble ou un oxyde de métal noble, tel que le platine ou le ruthénium.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9917583 | 1999-07-28 | ||
GBGB9917583.8A GB9917583D0 (en) | 1999-07-28 | 1999-07-28 | Hydrocarbon fuel processor catalyst |
PCT/GB2000/002893 WO2001007359A1 (fr) | 1999-07-28 | 2000-07-27 | Catalyseur pour dispositif de traitement de carburant hydrocarbone |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1208062A1 true EP1208062A1 (fr) | 2002-05-29 |
Family
ID=10857997
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00948168A Withdrawn EP1208062A1 (fr) | 1999-07-28 | 2000-07-27 | Catalyseur pour dispositif de traitement de carburant hydrocarbone |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1208062A1 (fr) |
JP (1) | JP2003505238A (fr) |
KR (1) | KR20020048378A (fr) |
CN (1) | CN1382104A (fr) |
AU (1) | AU6173200A (fr) |
CA (1) | CA2380503A1 (fr) |
GB (2) | GB9917583D0 (fr) |
IS (1) | IS6253A (fr) |
WO (1) | WO2001007359A1 (fr) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2002239297A1 (en) | 2000-11-16 | 2002-06-03 | Mydtv, Inc. | System and methods for determining the desirability of video programming events |
KR20030033203A (ko) * | 2001-10-19 | 2003-05-01 | 니로 스끼따 | 화석연료를 개질하는 촉매 |
US7507690B2 (en) | 2002-04-30 | 2009-03-24 | Uchicago Argonne, Llc. | Autothermal reforming catalyst having perovskite structure |
ES2304889B1 (es) | 2007-04-13 | 2009-10-30 | INSTITUTO NACIONAL DE TECNICA AEROESPACIAL "ESTEBAN TERRADAS" | Procedimiento para la obtencion de hidrogeno. |
CN101468295B (zh) * | 2007-12-28 | 2011-08-10 | 中国石油大学(北京) | 同时消除柴油机尾气四种污染物的组合催化剂和净化方法 |
EP2301889B1 (fr) * | 2008-07-04 | 2014-04-09 | Murata Manufacturing Co. Ltd. | Procédé de reformage au dioxyde de carbone |
TWI399241B (zh) * | 2009-10-30 | 2013-06-21 | Univ Nat Defense | 一種用於乙醇重組製氫的改質觸媒及其製造方法 |
FR2968016B1 (fr) * | 2010-11-29 | 2013-05-03 | Seb Sa | Appareil chauffant recouvert d'un revetement autonettoyant |
CN103785392B (zh) * | 2012-11-01 | 2016-04-27 | 中国石油化工股份有限公司 | 一种费托合成催化剂及其制备方法和应用 |
AU2015365613B2 (en) * | 2014-12-19 | 2020-03-05 | Johnson Matthey Public Limited Company | Catalyst manufacturing method |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3993459A (en) * | 1974-04-30 | 1976-11-23 | Siemens Aktiengesellschaft | Catalyst for the conversion of higher hydrocarbons and method of generating a fuel |
CA1062690A (fr) * | 1975-04-08 | 1979-09-18 | Alan Lauder | Catalyseurs stables a la perovskite |
CA1077011A (fr) * | 1975-04-08 | 1980-05-06 | Elrey L. Mccann (Iii) | Oxydes de metal catalytiques sur supports de perovskite |
GB1579733A (en) * | 1976-03-12 | 1980-11-26 | Johnson Matthey Co Ltd | Catalysts particularly for purification of exhaust gases |
US4321250A (en) * | 1979-11-21 | 1982-03-23 | Phillips Petroleum Company | Rhodium-containing perovskite-type catalysts |
JPS58119345A (ja) * | 1982-01-06 | 1983-07-15 | Hitachi Ltd | 水素富化ガス製造用触媒組成物及びその使用方法 |
US4812300A (en) * | 1987-07-13 | 1989-03-14 | Sri-International | Selective perovskite catalysts to oxidize ammonia to nitric oxide |
US5149516A (en) * | 1990-10-15 | 1992-09-22 | Mobil Oil Corp. | Partial oxidation of methane over perovskite catalyst |
JPH05200292A (ja) * | 1992-01-28 | 1993-08-10 | Mitsui Eng & Shipbuild Co Ltd | 燃料改質用触媒 |
FR2696109B1 (fr) * | 1992-09-28 | 1994-11-04 | Inst Francais Du Petrole | Catalyseur d'oxydation et procédé d'oxydation partielle du méthane. |
US5752995A (en) * | 1994-06-30 | 1998-05-19 | Kang; Chia-Chen Chu | Catalyst and process for the production of hydrogen and/or methane |
JP3667801B2 (ja) * | 1995-01-27 | 2005-07-06 | 出光興産株式会社 | ルテニウム触媒の製造方法及び該触媒を用いた炭化水素の水蒸気改質方法 |
-
1999
- 1999-07-28 GB GBGB9917583.8A patent/GB9917583D0/en not_active Ceased
-
2000
- 2000-07-27 AU AU61732/00A patent/AU6173200A/en not_active Abandoned
- 2000-07-27 KR KR1020027001194A patent/KR20020048378A/ko not_active Application Discontinuation
- 2000-07-27 WO PCT/GB2000/002893 patent/WO2001007359A1/fr not_active Application Discontinuation
- 2000-07-27 EP EP00948168A patent/EP1208062A1/fr not_active Withdrawn
- 2000-07-27 CA CA002380503A patent/CA2380503A1/fr not_active Abandoned
- 2000-07-27 JP JP2001512453A patent/JP2003505238A/ja active Pending
- 2000-07-27 GB GB0018506A patent/GB2352649B/en not_active Expired - Fee Related
- 2000-07-27 CN CN00813468A patent/CN1382104A/zh active Pending
-
2002
- 2002-01-28 IS IS6253A patent/IS6253A/is unknown
Non-Patent Citations (1)
Title |
---|
See references of WO0107359A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2380503A1 (fr) | 2001-02-01 |
CN1382104A (zh) | 2002-11-27 |
KR20020048378A (ko) | 2002-06-22 |
IS6253A (is) | 2002-01-28 |
AU6173200A (en) | 2001-02-13 |
GB9917583D0 (en) | 1999-09-29 |
GB2352649A (en) | 2001-02-07 |
JP2003505238A (ja) | 2003-02-12 |
GB2352649B (en) | 2001-11-07 |
GB0018506D0 (en) | 2000-09-13 |
WO2001007359A1 (fr) | 2001-02-01 |
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Legal Events
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
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