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WO2005035695A2 - Procede de production de sources d'energie multifonctionnelles et sources d'energie multifonctionnelles produites a l'aide de ce procede - Google Patents

Procede de production de sources d'energie multifonctionnelles et sources d'energie multifonctionnelles produites a l'aide de ce procede Download PDF

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Publication number
WO2005035695A2
WO2005035695A2 PCT/ZA2004/000125 ZA2004000125W WO2005035695A2 WO 2005035695 A2 WO2005035695 A2 WO 2005035695A2 ZA 2004000125 W ZA2004000125 W ZA 2004000125W WO 2005035695 A2 WO2005035695 A2 WO 2005035695A2
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WO
WIPO (PCT)
Prior art keywords
mes
fuel
cut
stream
blending components
Prior art date
Application number
PCT/ZA2004/000125
Other languages
English (en)
Other versions
WO2005035695A3 (fr
Inventor
Luis Pablo Fidel Dancuart Kohler
Delanie Lamprecht
Ian Stradling Myburgh
Original Assignee
Sasol Technology (Pty) Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sasol Technology (Pty) Ltd filed Critical Sasol Technology (Pty) Ltd
Priority to CA002542818A priority Critical patent/CA2542818A1/fr
Priority to CN2004800338949A priority patent/CN1882675B/zh
Priority to GB0607249A priority patent/GB2422842B/en
Priority to AU2004280647A priority patent/AU2004280647B2/en
Publication of WO2005035695A2 publication Critical patent/WO2005035695A2/fr
Publication of WO2005035695A3 publication Critical patent/WO2005035695A3/fr
Priority to US11/406,016 priority patent/US20060243640A1/en
Priority to US11/945,161 priority patent/US20080076949A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00—Engines characterised by fuel-air mixture compression
    • F02B1/12—Engines characterised by fuel-air mixture compression with compression ignition

Definitions

  • the invention relates to the production of multipurpose hydrocarbonaceous energy sources and to multipurpose hydrocarbonaceous fuels.
  • multipurpose hydrocarbonaceous energy sources is abbreviated to MES and is used in both the singular and the plural.
  • MES used in gas turbines, compression ignition (CI) engines, including Homogeneous Charge Compression Ignition (HCCI) systems or fuel cells is an attractive option for many energy users, especially for those operating in remote stranded locations where a single form of supply of energy is required and simplified logistics are necessary. These entities include users in many classes of human activity.
  • a synthetic multi-purpose fuel useful as a fuel cell fuel, diesel engine fuel, gas turbine engine fuel and furnace or boiler fuel are disclosed in PCT WO 01/59034.
  • the multipurpose fuel produced ranged from C9 to C22.
  • the inventor has now identified a need and a process for at least partially satisfying such an MES need.
  • the Fischer-Tropsch (FT) process is a well known process in which carbon monoxide and hydrogen are reacted over an iron, cobalt, nickel or ruthenium containing catalyst to produce a mixture of straight and branched chain hydrocarbons ranging from methane to waxes with molecular masses above 1400 and smaller amounts of oxygenates.
  • the feed for the FT process may be derived from coal, natural gas, biomass or heavy oil streams.
  • the term Gas-to-Liquid (GTL) process refers to schemes based on natural gas, which is mainly methane, to obtain the synthesis gas, and its subsequent conversion using in most instances an FT process.
  • the quality of the GTL FT synthetic products is essentially the same obtainable from the FT process here defined once the synthesis conditions and the product work-up are defined.
  • the complete process can include gas reforming which converts natural gas to synthesis gas (H 2 and CO) using well-established reforming technology.
  • synthesis gas can also be produced by gasification of coal or suitable hydrocarbonaceous feedstocks like petroleum based heavy fuel oils.
  • the synthesis gas is then converted into synthetic hydrocarbons.
  • the process can be effected using, among others, a fixed-bed tubular reactor or a three-phase slurry reactor.
  • FT products include waxy hydrocarbons, light liquid hydrocarbons, a small amount of unconverted synthesis gas and a water-rich stream.
  • the waxy hydrocarbon stream and, almost always, the light liquid hydrocarbons are then upgraded in the third step to synthetic fuels such as diesel, kerosene and naphtha.
  • Heavy species are hydrocracked and olefins and oxygenates are hydrogenated to form a final product that is highly paraffinic. Hydrocracking and hydrogenation processes belong to the group sometimes generally named hydroconversion processes.
  • a multipurpose carbonaceous energy source selected from: - a substantially C5 to C9 cut having an H:C molar ratio from 2.26 to 2.32; - a substantially C5 to C9 cut blended with a substantially C9 to C14 cut, said blend having an H:C molar ratio from 2.18 to 2.24; - a substantially C5 to C9 cut blended with a substantially C9 to C14 cut and a substantially C14 to C22 cut, said blend having an H:C ratio from 2.12 to 2.18; and - a substantially C5 to C9 cut blended with a substantially C14 to C22 cut, said blend having an H:C molar ratio from 2.13 to 2.19.
  • MES fuel multipurpose carbonaceous energy source
  • the MES fuel may, when combusted, have a CO 2 emission below 3.115 g CO 2 /g fuel combusted.
  • One or more of the C5 to C9, C9 to C14, and C14 to C22 cuts may be synthetic in origin.
  • One or more of the C5 to C9, C9 to C14, and C14 to C22 cuts may be Fischer-Tropsch process in origin.
  • the MES Fuel may be a partially or totally synthetic fuel.
  • the MES Fuel may be a Fischer-Tropsch process derived fuel.
  • a process for the production of synthetic multipurpose carbonaceous energy source including the steps of: a) oxidising a carbonaceous material to form a synthesis gas; b) reacting said synthesis gas under Fischer-Tropsch reaction conditions to form Fischer-Tropsch reaction products; c) fractionating the Fischer-Tropsch reaction products to form one or more MES blending components selected from the group including: A. a C5 to C9 cut; B. a C9 to C14 cut; and C.
  • a C14 to C22 cut ; and d) using said blending components in the production of the MES, provided that where at least one of the blending components is a blending component in the C9 to C14 or in the C14 to C22 boiling range then at least two blending components are used in the production of the MES, one of which is the C5 to C9 cut.
  • the C5 to C9 cut may be a light hydrocarbon blend, typically in the 35-160°C distillation range.
  • the C9 to C14 cut may be a medium hydrocarbon blend, typically in the 155-250°C distillation range.
  • the C14 to C22 cut may be a heavy hydrocarbon blend, typically in the 245-360°C distillation range.
  • the blending components A, B and C may be blended in a volumetric ratio of A:B:C of:
  • the blending components A, B and C may be blended in a volumetric ratio of A:B:C, wherein: A may be from 1 to 2; B may be from 0 to 1.5; and C may be from 0 to 2.5.
  • One or more of the blending components may be hydroconverted.
  • the MES may be a blend of both hydroconverted and unhydroconverted blending components.
  • the MES may be a product of one or more of only unhydroconverted blending components.
  • the MES may be a product of one or more only hydroconverted blending components.
  • the Fischer-Tropsch process of step b) may be the Sasol Slurry Phase DistillateTM process.
  • the carbonaceous material of step a) may be a natural gas stream, a natural gas derivatives stream, a petroleum gas stream, a petroleum gas derivatives stream, a coal stream, a waste hydrocarbons stream, a biomass stream, and in general any carbonaceous material stream.
  • hydrogen may be separated from the synthesis gas either during or after step a).
  • This hydrogen may be used in the hydroconversion of FT primary products, namely FT condensate and FT wax.
  • Table 2 gives a typical composition of the FT condensate and FT wax fractions.
  • Table 2 Typical Fischer-Tropsch product after separation into two fractions (vol% distilled)
  • the hydroconverted products are fractionated in a common distillation unit where at least three blending components are recovered:
  • a heavy hydrocarbon blend typically in the 245-360°C ASTM D86 distillation range, i.e. C14 to C22.
  • the FT condensate and FT wax are blended together before being fractionated into the blending components.
  • the FT condensate is transferred directly to the products fractionator without any hydroconversion stage.
  • the MES products benefit from the synergy of the composition and quality of the wax and condensate fractions.
  • MES fuels meet the fuel requirements of many classes of energy conversion systems including gas turbines, CI engines, including HCCI systems and fuel cells.
  • the MES compositions may have the following properties which make it suitable for fuel cells, gas turbine engine and CI engines (as shown in Table 3):
  • High Cetane Number Fuels with a high cetane number ignite quicker and hence exhibit a milder uncontrolled combustion because the quantity of fuel involved is less. A reduction of the uncontrolled combustion implies an extension of the controlled combustion, which results in better air/fuel mixing and more complete combustion with lower NOx emissions and better cold start ability. The shorter ignition delay implies lower rates of pressure rise and lower peak temperatures and less mechanical stress.
  • the cetane number of the MES compositions was determined according to ASTM D613 test method and an Ignition Quality Tester (IQT - ASTM D6890).
  • the sulphur content was determined according to the ASTM D5453 test method.
  • the less than 1 ppm sulphur present in the MES compositions not only make the components suitable for a fuel cell reformer catalyst, but also contribute to the lower exhaust emission in engines, such as CI engines.
  • the less than 1 ppm sulphur present in the MES composition either ensure compatible with certain exhaust catalyst devises or give improved compatibility with other.
  • Cold Filter Plugging Point is the lowest temperature at which the fuel can pass through a standard test filter under standard conditions (requires more than 1 minute for 20 ml to pass through a 45- /m filter). This test is done accordingly to the Institute of Petroleum IP 309 method or equivalent. Inadequate cold flow performance will lead to difficulties with starting and blockage of CI engine fuel filters under cold weather conditions.
  • Freezing point is one of the physical properties used to quantitatively characterise gas turbine engine fuel fluidity.
  • the low freezing point determined in accordance with the automated ASTM 5901 test method, or equivalent, can be attributed to the more than 60 mass% iso-paraffins present in MES compositions.
  • the thermal stability of the MES compositions was determined according to the Octel F21-61 test method where a visual rating was used to describe the relative stability.
  • the FT products lead to significantly less carbon deposition on the fuel cell reformer catalyst than would be expected from a conventional diesel type feedstock under comparative reaction conditions.
  • Oxygen stability is tested through the calculation of the amount of insolubles formed in the presence of oxygen. It measures the fuel's resistance to degradation by oxygen by the ASTM D2274 test method or equivalent.
  • the MES compositions are stable in the presence of oxygen with the formation of insolubles of less than 0.2 mg/100ml.
  • High Hydrogen To Carbon Content The highly paraffinic nature of the FT products and very low aromatic concentration contribute to the high H:C ratios of the MES compositions.
  • Table 1 four illustrative MES formulations are shown which have been found compatible with their proposed use in gas turbines, CI engines, including HCCI systems and fuel cells.
  • the expected quality and estimated yields of the MES formulations of Table 1 are presented in Table 3.
  • the MES compositions may be suitable for use in fuel cells, gas turbine engine and CI engines, including HCCI systems as they contain FT reaction derived products which are highly saturated with less than 2 volume% olefins, have ultra-low levels of sulphur with an almost zero aromatic hydrocarbon content, high linearity, high hydrogen to carbon ratio, very good cold flow properties, and high cetane number.
  • FT naphtha, kerosene or diesel Lower reformer temperatures in fuel cells are required with the use of FT naphtha, kerosene or diesel.
  • the FT products lead to significantly less carbon deposition on the catalyst than would be expected from a conventional diesel type feedstock under comparative reaction conditions and produce more steam.
  • the MES components have good cold flow properties as well as a high cetane number because of the predominantly mono-, and to a lesser extent other, branched forms of the paraffins which make these components suitable for application in gas turbine engines, CI engines, including HCCI systems and fuel cells.
  • This invention includes four possible processes for the production of MES components. Two of them are based in the use of natural gas as feed and, the other two make use of any hydrocarbonaceous feedstock possible of been gasified. Therefore, feeds for the latter include coal, waste, biomass and heavy oil streams.
  • the first process matter of this invention makes use of natural gas 11 which is converted to synthesis gas at suitable process conditions in reformer 1.
  • the reforming reaction makes use of oxygen 13 obtained from an air separation step 2 from atmospheric air 12. Water in the form of steam can also be used in the reforming process.
  • Syngas 14 from the reformer stage is converted in FT unit 3 to synthetic hydrocarbons including at least two liquid streams, as well as a gas stream and reaction water not shown.
  • a portion of the syngas might be derived from the hydrogen separation plant 4 where a hydrogen rich stream 17 is produced for use in hydroconversion.
  • hydrogen can be produced in an independent facility and transferred as stream 17.
  • the light synthetic hydrocarbons stream 15 sometimes named FT Condensate, includes paraffins, olefins and some oxygenates, mostly alcohols. This stream is transferred to hydrotreating unit 6 where olefins and oxygenates are hydrogenated into, mostly, the corresponding paraffin hydrocarbons. The process is completed at conditions such that the average carbon number of the feed remains essentially unchanged in hydrotreated product 18.
  • the heavy synthetic hydrocarbons 16, sometimes named FT Wax has a similar chemical composition as that of the lighter stream 15; however, under normal processing these species are solid at room temperature.
  • This stream is transferred to the hydroconversion unit 5, preferably a hydrocracker system, where (1 ) olefins and oxygenates are hydrogenated to the corresponding paraffins which in turn and together with the original long chain paraffins (2) undergo cracking reactions resulting in a significant reduction of its average carbon number compared with that of the feed.
  • the resulting hydrocracked product 19 is a mixture of normal and iso-paraffins.
  • the combined hydroconverted products 18 and 19 are fractionated in distillation unit 7 resulting in at least four process streams.
  • Stream 20 is a light hydrocarbon blend, typically in the 35-160°C ASTM D86 distillation range.
  • Stream 21 is a medium hydrocarbon blend, typically in the 155-250°C ASTM D86 distillation range.
  • Stream 22 is a heavy hydrocarbon blend, typically in the 245-360°C ASTM D86 distillation range.
  • Stream 23 includes unconverted species whose boiling points are above 360°C and is recycled to the hydrocracker to increase the production of the valuable species. The separation process also results in collecting a gas stream - not shown.
  • the MES products are produced using these streams on their own or in blends as shown in Table 1 above.
  • this invention provides the process scheme shown in Figure 3.
  • This concept makes use of coal, biomass or heavy oil which in the form of stream 11 is converted to synthesis gas at suitable process conditions in gasifier 1.
  • the gasification process makes use of oxygen 13 obtained from an air separation step 2 from atmospheric air 12.
  • Water in the form of steam can also be used in the process.
  • This process is then substantially similar to the one discussed before with reference to Figure 1. However, and as an additional stream, some liquids are produced during the gasification process and separated as stream 24. These might be recovered as a product or recycled to the gasifier to enhance production of the valuable streams.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Fuel Cell (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne une source d'énergie carbonée multifonctionnelle (combustible MES) sélectionnée à partir d'une fraction C5-C9, d'une fraction C5-C9 mélangée à une fraction C9-C14, d'une fraction C5-C9 mélangée à une fraction C9-C14 et à une fraction C14-C22, et d'une fraction C5-C9 mélangée à une fraction C14-C22. L'invention concerne également un procédé de préparation de ce combustible et d'utilisation de ce combustible dans un moteur à combustion par compression, un moteur à allumage par compression à charge homogène (ACCH), une turbine et/ou une pile à combustible.
PCT/ZA2004/000125 2003-10-17 2004-10-14 Procede de production de sources d'energie multifonctionnelles et sources d'energie multifonctionnelles produites a l'aide de ce procede WO2005035695A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002542818A CA2542818A1 (fr) 2003-10-17 2004-10-14 Procede de production de sources d'energie multifonctionnelles et sources d'energie multifonctionnelles produites a l'aide de ce procede
CN2004800338949A CN1882675B (zh) 2003-10-17 2004-10-14 生产压燃式发动机、燃气涡轮和燃料电池燃料的方法以及由所述方法生产的压燃式发动机、燃气涡轮和燃料电池燃料
GB0607249A GB2422842B (en) 2003-10-17 2004-10-14 Process for the production of multipurpose energy sources and multipurpose energy sources produced by said process
AU2004280647A AU2004280647B2 (en) 2003-10-17 2004-10-14 Process for the production of multipurpose energy sources and multipurpose energy sources produced by said process
US11/406,016 US20060243640A1 (en) 2003-10-17 2006-04-18 Process for the production of compression ignition engine, gas turbine, and fuel cell fuel and compression ignition engine, gas turbine, and fuel cell fuel by said process
US11/945,161 US20080076949A1 (en) 2003-10-17 2007-11-26 Process for the production of compression ignition engine, gas turbine, and fuel cell fuel and compression ignition engine, gas turbine, and fuel cell fuel by said process

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US51233003P 2003-10-17 2003-10-17
US60/512,330 2003-10-17
ZA2003/8080 2003-10-17
ZA200308080 2003-10-17

Related Child Applications (1)

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US11/406,016 Continuation US20060243640A1 (en) 2003-10-17 2006-04-18 Process for the production of compression ignition engine, gas turbine, and fuel cell fuel and compression ignition engine, gas turbine, and fuel cell fuel by said process

Publications (2)

Publication Number Publication Date
WO2005035695A2 true WO2005035695A2 (fr) 2005-04-21
WO2005035695A3 WO2005035695A3 (fr) 2005-08-11

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US (1) US20080076949A1 (fr)
AU (1) AU2004280647B2 (fr)
CA (1) CA2542818A1 (fr)
GB (1) GB2422842B (fr)
WO (1) WO2005035695A2 (fr)

Cited By (7)

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WO2008104556A1 (fr) * 2007-02-28 2008-09-04 Shell Internationale Research Maatschappij B.V. Composition de carburant pour moteurs diesels
EP2006361A1 (fr) * 2006-03-31 2008-12-24 Nippon Oil Corporation Composition de gazole
EP2006359A1 (fr) * 2006-03-31 2008-12-24 Nippon Oil Corporation Composition de gazole
EP2011851A1 (fr) * 2006-03-31 2009-01-07 Nippon Oil Corporation Compositions d'huile légère
EP2017326A1 (fr) * 2006-03-30 2009-01-21 Nippon Oil Corporation Composition d'huile légère
US8623103B2 (en) 2006-03-31 2014-01-07 Jx Nippon Oil & Energy Corporation Method for producing gas oil composition
US8795394B2 (en) 2006-05-31 2014-08-05 Nippon Oil Corporation Gas oil composition

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EP2077312A1 (fr) * 2007-12-17 2009-07-08 Nippon Oil Corporation Carburants pour moteurs à allumage par compression de mélange homogène
JP5393372B2 (ja) * 2008-09-25 2014-01-22 昭和シェル石油株式会社 パラフィン主体の燃料電池システム用炭化水素燃料油

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Publication number Priority date Publication date Assignee Title
EP2017326A1 (fr) * 2006-03-30 2009-01-21 Nippon Oil Corporation Composition d'huile légère
EP2420550A3 (fr) * 2006-03-30 2012-04-11 Nippon Oil Corporation Composition d'huile légère
EP2017326A4 (fr) * 2006-03-30 2011-05-25 Nippon Oil Corp Composition d'huile légère
EP2006361A4 (fr) * 2006-03-31 2011-07-20 Nippon Oil Corp Composition de gazole
EP2006361A1 (fr) * 2006-03-31 2008-12-24 Nippon Oil Corporation Composition de gazole
EP2006359A1 (fr) * 2006-03-31 2008-12-24 Nippon Oil Corporation Composition de gazole
EP2011851A4 (fr) * 2006-03-31 2011-05-25 Nippon Oil Corp Compositions d'huile légère
EP2006359A4 (fr) * 2006-03-31 2011-07-20 Nippon Oil Corp Composition de gazole
US8722947B2 (en) * 2006-03-31 2014-05-13 Nippon Oil Corporation Gas oil composition
US8080068B2 (en) 2006-03-31 2011-12-20 Jx Nippon Oil & Energy Corporation Light oil compositions
EP2011851A1 (fr) * 2006-03-31 2009-01-07 Nippon Oil Corporation Compositions d'huile légère
EP2423295A3 (fr) * 2006-03-31 2012-08-01 Nippon Oil Corporation Compositions d'huile légère
US8623103B2 (en) 2006-03-31 2014-01-07 Jx Nippon Oil & Energy Corporation Method for producing gas oil composition
US8623104B2 (en) 2006-03-31 2014-01-07 Jx Nippon Oil & Energy Corporation Gas oil composition production method
US8624068B2 (en) * 2006-03-31 2014-01-07 Nippon Oil Corporation Gas oil composition
US8628592B2 (en) 2006-03-31 2014-01-14 Jx Nippon Oil & Energy Corporation Method for producing gas oil composition
US8795394B2 (en) 2006-05-31 2014-08-05 Nippon Oil Corporation Gas oil composition
WO2008104556A1 (fr) * 2007-02-28 2008-09-04 Shell Internationale Research Maatschappij B.V. Composition de carburant pour moteurs diesels

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Publication number Publication date
WO2005035695A3 (fr) 2005-08-11
GB0607249D0 (en) 2006-05-17
US20080076949A1 (en) 2008-03-27
CA2542818A1 (fr) 2005-04-21
GB2422842A (en) 2006-08-09
GB2422842B (en) 2008-08-13
AU2004280647A1 (en) 2005-04-21
AU2004280647B2 (en) 2010-03-18

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