CA2591802A1 - Fuel compositions - Google Patents
Fuel compositions Download PDFInfo
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- CA2591802A1 CA2591802A1 CA002591802A CA2591802A CA2591802A1 CA 2591802 A1 CA2591802 A1 CA 2591802A1 CA 002591802 A CA002591802 A CA 002591802A CA 2591802 A CA2591802 A CA 2591802A CA 2591802 A1 CA2591802 A1 CA 2591802A1
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- Prior art keywords
- fuel
- fuel composition
- metal
- compression
- ignition engine
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Classifications
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- 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
Abstract
A fuel composition comprising a major amount of a fuel suitable for use in a compression-ignition engine, which fuel comprises one or more hydrocarbon components boiling within the diesel boiling range, at least one of which hydrocarbon components has been treated with a metal adsorbing or absorbing material in a different physical phase from the hydrocarbon component (s) , preferably to reduce the level of at least one metal, more preferably the level of at least one heavier metal, most preferably the level of zinc, in said at least one hydrocarbon component, for the purpose of reducing the emission of NOx, and optionally particulates, from a compression-ignition engine into the combustion chambers of which said fuel composition is introduced, said treatment including physical separation of the hydrocarbon component from the metal adsorbing or absorbing phase; a process for the preparation of such a composition; and the reduction of the emission of NOx, and optionally particulates, from such an engine.
Description
FUEL COMPOSITIONS
The present invention relates to fuel compositions, to processes for their preparation and to their use in the operation of compression-ignition engines.
It is known to treat hydrocarbons by passing them through filtering or adsorbing material such as Fuller's Earth or charcoal, e.g. as disclosed in US-A-2090007, US-A-2338142 or GB-A-614636.
GB-A-437023 discloses a process for refining cracked hydrocarbons of substantially gasoline boiling range by the treatment with a solid active adsorbent such as Fuller's Earth, clay or other suitable adsorptive catalysts, under conditions of elevated temperature and superatmospheric pressure adequate to maintain said hydrocarbons in substantially liquid phase, which comprises first removing from said hydrocarbons relatively unstable low boiling constituents, namely dissolved gases, propane, part or all of the butanes and their corresponding unsaturates, and reducing the vapour pressure of said hydrocarbons by submitting them to a stabilising fractionation and thereupon subjecting the stabilised hydrocarbons, whilst still hot, to said refining treatment.
US-A-3529944 discloses a method for clarifying and stabilising hydrocarbon liquids which are subject to oxidative deterioration, particularly jet fuels, which includes adding to the fuel a material which accelerates the oxidative deterioration of the fuel, such as a polyphenyl substituted lower alkane or lower alkylene, an alkanol ester of citric acid or acetoxy ethyl monobutylether; passing the hydrocarbon liquid through a solid, particulate, adsorbent media to remove microimpurities and the products of oxidative deterioration; and thereafter adding additional amounts of a stabilising material to stabilise the hydrocarbon liquid against further oxidative deterioration. Suitable adsorbent materials (column 5, lines 22 to 25) include various types of natural or synthetic clays, either treated or untreated, Fuller's Earth, attapulgite, silica gel and adsorbent catalysts. In the examples, jet fuels are treated by filtration through attapulgite clay.
In US-A-4225319, in order to suppress carburettor deposit formation, adsorbent-treated cat cracked gasoline is blended into a fuel composition for use in an internal combustion engine. In column 2, lines 57 to 62, it is stated that adsorbents which are useful "for treating the cat cracked gasoline include many of the well known adsorbents such as silica, alumina, silica-alumina, charcoal, carbon black, magnesium silicate, aluminium silicate, zeolites, clay, fuller's earth, magnesia, and the like". In the examples, the adsorbent used is silica-gel.
US-A-5951851 relates to a process for removing elemental sulphur from fluids, particularly fuels such as gasoline, jet fuel, diesel, kerosene and fuel additives such as ethers. The process involves contacting the sulphur contaminated fluid with layered double hydroxide (or hydrotalcite) Mg2AlNO3;mH2O or Mg3AlNO3;mH2O, where m is the number of waters of hydration. In Example 1, it is shown that Attapulgus clay, molecular sieve 5 A, silica gel, alumina, bayerite, tetraphenylphosphonium-montmorillonite, Kao-EG.9.4 A, Kao-tetraethylene glycol, A113 pillared montmorillonite, tetramethylammonium-montmorillonite, palygorskite-PF1-s, Kaolinite KGa-l, Kao-cellosolve and Iron (III) montmorillonite are ineffective in removing elemental sulphur, whilst the hydrotalcites A12LiCl, Mg2AlNO3, Mg2FeNO3, Mg3FeNO3 and Mg3AlNO3 are particularly effective in removing elemental sulphur.
The New Encylopaedia Britannica, Macropaedia, Volume 4, 15th Edition, 1984, ISBN 0-85229-413-1, pages 700 to 706 classifies clay minerals on the basis of variations of atomic structure and chemical composition into 9 groups, viz (1) allophane, (2) kaolinite, (3) halloysite, (4) smectite, (5) illite, (6) chlorite, (7) vermiculite, (8) sepiolite, attapulgite and palygorskite and (9) mixed layer clay minerals.
Group (8), sepiolite, attapulgite and palygorskite, are described as fibrous clay minerals, and these have, as an important structural element, the amphibole double silica chain which is orientated parallel to the c axis.
It is known that diesel fuels can contain a number of trace metals. The content of such metals depends on a number of factors, including the source(s) of crude oil from which the fuel is derived, the types of refinery processes employed, and the handling, storage and distribution history of the fuel.
It has now surprisingly been found that when at least one hydrocarbon component of a diesel fuel composition has been treated with a metal adsorbing or absorbing material in a different physical phase from the hydrocarbon component(s), which material may for example be in liquid form which is immiscible (including having minimal or low solubility) with the hydrocarbon component, or a solid, preferably a solid, to reduce the levels of trace metal contaminants, more preferably the levels of heavier metals, most preferably the level of zinc, in said component(s), the fuel composition exhibits reduced levels of emissions, particularly of NOx, and optionally particulates, when used in a compression-ignition engine to power such an engine.
Said treatment includes physical separation of the hydrocarbon component from the metal adsorbing or absorbing phase, for example by one or more of decanting of immiscible liquid, filtration, vortexing, centrifuging and gravity separation.
For the purpose of this disclosure, "heavier metals"
are defined as metals with atomic numbers of 20 or greater.
In accordance with the present invention there is provided a fuel composition comprising a major amount of a fuel suitable for use in a compression-ignition engine, which fuel comprises one or more hydrocarbon components boiling within the diesel boiling range, at least one of which hydrocarbon components has been treated with a metal adsorbing or absorbing material in a different physical phase from the hydrocarbon component(s), preferably to reduce the level of at least one metal, more preferably the level of at least one heavier metal, most preferably the level of zinc, in said at least one hydrocarbon component, for the purpose of reducing the emission of NOx, and optionally particulates, from a compression-ignition engine into the combustion chambers of which said fuel composition is introduced, said treatment including physical separation of the hydrocarbon component from the metal adsorbing or absorbing phase.
Preferably, the metal adsorbing or absorbing material is selected from fibrous clay minerals, diatomaceous earths, graphite, charcoal, polymeric adsorbents or absorbents, ion-exchange resins, and complexing or chelating agents, which materials may be in liquid form which is immiscible (including having minimal or low solubility) with the hydrocarbon component, or solids, more preferably solids. Said complexing or chelating agents preferably comprise molecules having one or more functional groups acting as a ligand or forming a complex or being otherwise metal-attracting.
The fibrous clay mineral of the sepiolite, attapulgite and palygorskite group must at least contain at least one mineral of the sepiolite, attapulgite and palygorskite groups. The term "Fuller's Earth" is used in published literature on clays in a number of different ways, but in the context of the present invention "Fuller's Earth" comprises at least one fibrous clay mineral of the sepiolite, attapulgite and palygorskite groups. One type of Fuller's Earth may comprise a mixture of montmorillonite and palygorskite.
Preferably the fibrous clay mineral is sepiolite, attapulgite, or Fuller's Earth.
Preferably, said polymeric material is selected from polyolefins such as polyacrylate or polystyrene, polyester, polyether, polyamide, polyamine and polysulphone materials, for example AMBERLITE XAD-4, AMBERLITE XAD-7 and AMBERLITE XAD-16 non-ionic polymeric adsorbents and polyethylene imine on silica gel (available ex. Aldrich), said polymeric materials being in solid form, or bound to a solid, or in liquid or suspension or dissolved form which is immiscible (including having minimal or low miscibility) with the hydrocarbon component.
Preferably, examples of said diatomaceous earths are DAMOLIN MOLER (available ex. Damolin) and HYFLO SUPER CEL
(available ex. Aldrich).
Preferably, said complexing or chelating agents are selected from nitrogen materials such as amines, amides, polyamines, cyclic polyamines including but not limited to porphyrins, derivatives of N,N'-disalicylidene-propanediamine, sulphur materials such as sulphides, sulphones, sulphoxides, sulphonates, thiols, anionic materials such as carboxylates, oxygen species such as alcohols, ketones, phenols and ethers, including polyethers and cyclic polyethers (crown ethers), and species containing both nitrogen and oxygen such as cryptands and oxazoles and derivatives thereof, said complexing or chelating agents being in solid form, or bound to a solid, or in liquid or suspension or dissolved form which is immiscible (including having minimal or low miscibility) with the hydrocarbon component.
Preferably, said ion-exchange resins are selected from mineral species, such as silica gels, and polymers with functional groups such as sulphonate and carboxylate such as some of the products available from Aldrich under the trade names AMBERLITE, AMBERLYST, DOWEX and SEPHADEX.
Preferably, a blend of at least two of said hydrocarbon components has been treated with the metal adsorbing or absorbing material.
In accordance with the present invention there is also provided a process for the preparation of a fuel composition according to the present invention which comprises treating with a metal adsorbing or absorbing material at least one hydrocarbon component boiling within the diesel boiling range, preferably to reduce the level of at least one metal, more preferably the level of at least one heavier metal, most preferably the level of zinc, in said at least one hydrocarbon component, and optionally blending said at least one hydrocarbon component, before or after said treatment, with at least one other hydrocarbon component boiling within the diesel boiling range, to form a fuel suitable for use in a compression-ignition engine.
The present invention relates to fuel compositions, to processes for their preparation and to their use in the operation of compression-ignition engines.
It is known to treat hydrocarbons by passing them through filtering or adsorbing material such as Fuller's Earth or charcoal, e.g. as disclosed in US-A-2090007, US-A-2338142 or GB-A-614636.
GB-A-437023 discloses a process for refining cracked hydrocarbons of substantially gasoline boiling range by the treatment with a solid active adsorbent such as Fuller's Earth, clay or other suitable adsorptive catalysts, under conditions of elevated temperature and superatmospheric pressure adequate to maintain said hydrocarbons in substantially liquid phase, which comprises first removing from said hydrocarbons relatively unstable low boiling constituents, namely dissolved gases, propane, part or all of the butanes and their corresponding unsaturates, and reducing the vapour pressure of said hydrocarbons by submitting them to a stabilising fractionation and thereupon subjecting the stabilised hydrocarbons, whilst still hot, to said refining treatment.
US-A-3529944 discloses a method for clarifying and stabilising hydrocarbon liquids which are subject to oxidative deterioration, particularly jet fuels, which includes adding to the fuel a material which accelerates the oxidative deterioration of the fuel, such as a polyphenyl substituted lower alkane or lower alkylene, an alkanol ester of citric acid or acetoxy ethyl monobutylether; passing the hydrocarbon liquid through a solid, particulate, adsorbent media to remove microimpurities and the products of oxidative deterioration; and thereafter adding additional amounts of a stabilising material to stabilise the hydrocarbon liquid against further oxidative deterioration. Suitable adsorbent materials (column 5, lines 22 to 25) include various types of natural or synthetic clays, either treated or untreated, Fuller's Earth, attapulgite, silica gel and adsorbent catalysts. In the examples, jet fuels are treated by filtration through attapulgite clay.
In US-A-4225319, in order to suppress carburettor deposit formation, adsorbent-treated cat cracked gasoline is blended into a fuel composition for use in an internal combustion engine. In column 2, lines 57 to 62, it is stated that adsorbents which are useful "for treating the cat cracked gasoline include many of the well known adsorbents such as silica, alumina, silica-alumina, charcoal, carbon black, magnesium silicate, aluminium silicate, zeolites, clay, fuller's earth, magnesia, and the like". In the examples, the adsorbent used is silica-gel.
US-A-5951851 relates to a process for removing elemental sulphur from fluids, particularly fuels such as gasoline, jet fuel, diesel, kerosene and fuel additives such as ethers. The process involves contacting the sulphur contaminated fluid with layered double hydroxide (or hydrotalcite) Mg2AlNO3;mH2O or Mg3AlNO3;mH2O, where m is the number of waters of hydration. In Example 1, it is shown that Attapulgus clay, molecular sieve 5 A, silica gel, alumina, bayerite, tetraphenylphosphonium-montmorillonite, Kao-EG.9.4 A, Kao-tetraethylene glycol, A113 pillared montmorillonite, tetramethylammonium-montmorillonite, palygorskite-PF1-s, Kaolinite KGa-l, Kao-cellosolve and Iron (III) montmorillonite are ineffective in removing elemental sulphur, whilst the hydrotalcites A12LiCl, Mg2AlNO3, Mg2FeNO3, Mg3FeNO3 and Mg3AlNO3 are particularly effective in removing elemental sulphur.
The New Encylopaedia Britannica, Macropaedia, Volume 4, 15th Edition, 1984, ISBN 0-85229-413-1, pages 700 to 706 classifies clay minerals on the basis of variations of atomic structure and chemical composition into 9 groups, viz (1) allophane, (2) kaolinite, (3) halloysite, (4) smectite, (5) illite, (6) chlorite, (7) vermiculite, (8) sepiolite, attapulgite and palygorskite and (9) mixed layer clay minerals.
Group (8), sepiolite, attapulgite and palygorskite, are described as fibrous clay minerals, and these have, as an important structural element, the amphibole double silica chain which is orientated parallel to the c axis.
It is known that diesel fuels can contain a number of trace metals. The content of such metals depends on a number of factors, including the source(s) of crude oil from which the fuel is derived, the types of refinery processes employed, and the handling, storage and distribution history of the fuel.
It has now surprisingly been found that when at least one hydrocarbon component of a diesel fuel composition has been treated with a metal adsorbing or absorbing material in a different physical phase from the hydrocarbon component(s), which material may for example be in liquid form which is immiscible (including having minimal or low solubility) with the hydrocarbon component, or a solid, preferably a solid, to reduce the levels of trace metal contaminants, more preferably the levels of heavier metals, most preferably the level of zinc, in said component(s), the fuel composition exhibits reduced levels of emissions, particularly of NOx, and optionally particulates, when used in a compression-ignition engine to power such an engine.
Said treatment includes physical separation of the hydrocarbon component from the metal adsorbing or absorbing phase, for example by one or more of decanting of immiscible liquid, filtration, vortexing, centrifuging and gravity separation.
For the purpose of this disclosure, "heavier metals"
are defined as metals with atomic numbers of 20 or greater.
In accordance with the present invention there is provided a fuel composition comprising a major amount of a fuel suitable for use in a compression-ignition engine, which fuel comprises one or more hydrocarbon components boiling within the diesel boiling range, at least one of which hydrocarbon components has been treated with a metal adsorbing or absorbing material in a different physical phase from the hydrocarbon component(s), preferably to reduce the level of at least one metal, more preferably the level of at least one heavier metal, most preferably the level of zinc, in said at least one hydrocarbon component, for the purpose of reducing the emission of NOx, and optionally particulates, from a compression-ignition engine into the combustion chambers of which said fuel composition is introduced, said treatment including physical separation of the hydrocarbon component from the metal adsorbing or absorbing phase.
Preferably, the metal adsorbing or absorbing material is selected from fibrous clay minerals, diatomaceous earths, graphite, charcoal, polymeric adsorbents or absorbents, ion-exchange resins, and complexing or chelating agents, which materials may be in liquid form which is immiscible (including having minimal or low solubility) with the hydrocarbon component, or solids, more preferably solids. Said complexing or chelating agents preferably comprise molecules having one or more functional groups acting as a ligand or forming a complex or being otherwise metal-attracting.
The fibrous clay mineral of the sepiolite, attapulgite and palygorskite group must at least contain at least one mineral of the sepiolite, attapulgite and palygorskite groups. The term "Fuller's Earth" is used in published literature on clays in a number of different ways, but in the context of the present invention "Fuller's Earth" comprises at least one fibrous clay mineral of the sepiolite, attapulgite and palygorskite groups. One type of Fuller's Earth may comprise a mixture of montmorillonite and palygorskite.
Preferably the fibrous clay mineral is sepiolite, attapulgite, or Fuller's Earth.
Preferably, said polymeric material is selected from polyolefins such as polyacrylate or polystyrene, polyester, polyether, polyamide, polyamine and polysulphone materials, for example AMBERLITE XAD-4, AMBERLITE XAD-7 and AMBERLITE XAD-16 non-ionic polymeric adsorbents and polyethylene imine on silica gel (available ex. Aldrich), said polymeric materials being in solid form, or bound to a solid, or in liquid or suspension or dissolved form which is immiscible (including having minimal or low miscibility) with the hydrocarbon component.
Preferably, examples of said diatomaceous earths are DAMOLIN MOLER (available ex. Damolin) and HYFLO SUPER CEL
(available ex. Aldrich).
Preferably, said complexing or chelating agents are selected from nitrogen materials such as amines, amides, polyamines, cyclic polyamines including but not limited to porphyrins, derivatives of N,N'-disalicylidene-propanediamine, sulphur materials such as sulphides, sulphones, sulphoxides, sulphonates, thiols, anionic materials such as carboxylates, oxygen species such as alcohols, ketones, phenols and ethers, including polyethers and cyclic polyethers (crown ethers), and species containing both nitrogen and oxygen such as cryptands and oxazoles and derivatives thereof, said complexing or chelating agents being in solid form, or bound to a solid, or in liquid or suspension or dissolved form which is immiscible (including having minimal or low miscibility) with the hydrocarbon component.
Preferably, said ion-exchange resins are selected from mineral species, such as silica gels, and polymers with functional groups such as sulphonate and carboxylate such as some of the products available from Aldrich under the trade names AMBERLITE, AMBERLYST, DOWEX and SEPHADEX.
Preferably, a blend of at least two of said hydrocarbon components has been treated with the metal adsorbing or absorbing material.
In accordance with the present invention there is also provided a process for the preparation of a fuel composition according to the present invention which comprises treating with a metal adsorbing or absorbing material at least one hydrocarbon component boiling within the diesel boiling range, preferably to reduce the level of at least one metal, more preferably the level of at least one heavier metal, most preferably the level of zinc, in said at least one hydrocarbon component, and optionally blending said at least one hydrocarbon component, before or after said treatment, with at least one other hydrocarbon component boiling within the diesel boiling range, to form a fuel suitable for use in a compression-ignition engine.
Preferably, said process comprises blending at least two hydrocarbon components boiling within the diesel boiling range and treating the resulting mixture with said metal adsorbing or absorbing material, to form a fuel suitable for use in a compression-ignition engine.
In accordance with the present invention there is further provided a method of operating a compression-ignition engine, which comprises bringing into the combustion chambers of such engine a fuel composition according to the present invention.
In accordance with the present invention there is still further provided a method of reducing the emission of NOx, and optionally particulates, from a compression-ignition engine which comprises bringing into the combustion chambers of such engine a fuel composition according to the present invention.
In accordance with the present invention there is still further provided the use in a compression-ignition engine of a fuel composition according to the present invention for the purpose of reducing the emission of NOx, and optionally particulates, from said engine.
In accordance with the present invention there is still further provided a method of reducing the emission of NOx, and optionally particulates, from a compression-ignition engine which comprises replacing a fuel composition therein by a fuel composition according to the present invention.
In this specification, the terms "reduce", "reducing" and "reduction" mean as compared to prior to the treatment with the metal adsorbing or absorbing material or as compared to when using a diesel fuel composition components of which have not been subjected to said treatment, as appropriate.
In accordance with the present invention there is further provided a method of operating a compression-ignition engine, which comprises bringing into the combustion chambers of such engine a fuel composition according to the present invention.
In accordance with the present invention there is still further provided a method of reducing the emission of NOx, and optionally particulates, from a compression-ignition engine which comprises bringing into the combustion chambers of such engine a fuel composition according to the present invention.
In accordance with the present invention there is still further provided the use in a compression-ignition engine of a fuel composition according to the present invention for the purpose of reducing the emission of NOx, and optionally particulates, from said engine.
In accordance with the present invention there is still further provided a method of reducing the emission of NOx, and optionally particulates, from a compression-ignition engine which comprises replacing a fuel composition therein by a fuel composition according to the present invention.
In this specification, the terms "reduce", "reducing" and "reduction" mean as compared to prior to the treatment with the metal adsorbing or absorbing material or as compared to when using a diesel fuel composition components of which have not been subjected to said treatment, as appropriate.
The processes of adsorption or absorption of trace elements on to clay are not completely understood. One possibility is that the metals bond to the surface in the same way that they bond to ligands. Ligands are molecules or ions that function as electron donors and attract metal atoms or ions.
The fuel compositions to which the present invention relates include diesel fuel compositions for use in automotive compression ignition engines, as well as in other types of engine such as for example marine, railroad and stationary engines, and industrial gas oils for use in heating applications (e.g. boilers), provided that these non-automotive fuels do not contain residual (non-distilled) components.
The base fuel may itself comprise a mixture of two or more different diesel fuel components, and/or be additivated as described below.
Such diesel fuel compositions will contain one or more base fuels which may typically comprise liquid hydrocarbon middle distillate gas oil(s), for instance petroleum derived gas oils. Such fuel compositions will typically have boiling points within the usual diesel range of 150 to 400 C, depending on grade and use. They will typically have a density from 750 to 1000 kg/m3, preferably for automotive uses from 780 to 860 kg/m3, at 15 C (e.g. ASTM D4502 or IP 365) and a cetane number (ASTM D613) of from 35 to 120, more preferably from 40 to 85. They will typically have an initial boiling point in the range 150 to 230 C and a final boiling point in the range 290 to 400 C. Their kinematic viscosity at 40 C
(ASTM D445) might suitably be from 1.5 to 6 mm2/s.
Such industrial gas oils will contain a base fuel which may comprise fuel fractions such as the kerosene or gas oil fractions obtained in traditional refinery processes, which upgrade crude petroleum feedstock to useful products. Preferably such fractions contain components having carbon numbers in the range 5 to 40, more preferably 5 to 31, yet more preferably 6 to 25, most preferably 9 to 25, and such fractions have a density at 15 C of 650 to 1000 kg/m3, a kinematic viscosity at 20 C of 1 to 80 mm2/s, and a boiling range of 150 to 400 C.
Optionally, non-mineral oil based fuels, such as Fischer-Tropsch derived fuels, biomass-derived materials, biofuel components such as fatty acid methyl esters, or shale oils, may also form or be present in the fuel composition. Such Fischer-Tropsch fuels may for example be derived from natural gas, natural gas liquids, petroleum or shale oil, petroleum or shale oil processing residues, coal or biomass.
The amount of Fischer-Tropsch derived fuel used in a diesel fuel composition may be from 0.5 to 100%v of the overall diesel fuel composition, preferably from 5 to 75%v. It may be desirable for the composition to contain 10%v or greater, more preferably 20%v or greater, still more preferably 30%v or greater, of the Fischer-Tropsch derived fuel. It is particularly preferred for the composition to contain 30 to 75%v, and particularly 30 or 70%v, of the Fischer-Tropsch derived fuel. The balance of the fuel composition is made up of one or more other fuels.
An industrial gas oil composition will preferably comprise more than 50 wt%, more preferably more than 70 wt%, of a Fischer-Tropsch derived fuel component.
Such a Fischer-Tropsch derived fuel component is any fraction of the middle distillate fuel range, which can be isolated from the (hydrocracked) Fischer-Tropsch synthesis product. Typical fractions will boil in the naphtha, kerosene or gas oil range. Preferably, a Fischer-Tropsch product boiling in the kerosene or gas oil range is used because these products are easier to handle in for example domestic environments. Such products will suitably comprise a fraction larger than 90 wt% which boils between 160 and 400 C, preferably to about 370 C. Examples of Fischer-Tropsch derived kerosene and gas oils are described in EP-A-0583836, WO-A-97/14768, WO-A-97/14769, WO-A-00/11116, WO-A-00/11117, WO-A-01/83406, WO-A-01/83648, WO-A-01/83647, WO-A-01/83641, WO-A-00/20535, WO-A-00/20534, EP-A-1101813, US-A-5766274, US-A-5378348, US-A-5888376 and US-A-6204426.
The Fischer-Tropsch product will suitably contain more than 80 wt% and more suitably more than 95 wt% iso and normal paraffins and less than 1 wt% aromatics, the balance being naphthenics compounds. The content of sulphur and nitrogen will be very low and normally below the detection limits for such compounds. For this reason the sulphur content of a fuel composition containing a Fischer-Tropsch product may be very low.
The fuel composition preferably contains no more than 5000 ppmw sulphur, more preferably no more than 500 ppmw, or no more than 350 ppmw, or no more than 150 ppmw, or no more than 100 ppmw, or no more than 50 ppmw, or most preferably no more than 10 ppmw sulphur.
The base fuel may itself be additivated (additive-containing) or unadditivated (additive-free). If additivated, e.g. at the refinery, it will contain minor amounts of one or more additives selected for example from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers), lubricity additives, antioxidants and wax anti-settling agents.
The fuel compositions to which the present invention relates include diesel fuel compositions for use in automotive compression ignition engines, as well as in other types of engine such as for example marine, railroad and stationary engines, and industrial gas oils for use in heating applications (e.g. boilers), provided that these non-automotive fuels do not contain residual (non-distilled) components.
The base fuel may itself comprise a mixture of two or more different diesel fuel components, and/or be additivated as described below.
Such diesel fuel compositions will contain one or more base fuels which may typically comprise liquid hydrocarbon middle distillate gas oil(s), for instance petroleum derived gas oils. Such fuel compositions will typically have boiling points within the usual diesel range of 150 to 400 C, depending on grade and use. They will typically have a density from 750 to 1000 kg/m3, preferably for automotive uses from 780 to 860 kg/m3, at 15 C (e.g. ASTM D4502 or IP 365) and a cetane number (ASTM D613) of from 35 to 120, more preferably from 40 to 85. They will typically have an initial boiling point in the range 150 to 230 C and a final boiling point in the range 290 to 400 C. Their kinematic viscosity at 40 C
(ASTM D445) might suitably be from 1.5 to 6 mm2/s.
Such industrial gas oils will contain a base fuel which may comprise fuel fractions such as the kerosene or gas oil fractions obtained in traditional refinery processes, which upgrade crude petroleum feedstock to useful products. Preferably such fractions contain components having carbon numbers in the range 5 to 40, more preferably 5 to 31, yet more preferably 6 to 25, most preferably 9 to 25, and such fractions have a density at 15 C of 650 to 1000 kg/m3, a kinematic viscosity at 20 C of 1 to 80 mm2/s, and a boiling range of 150 to 400 C.
Optionally, non-mineral oil based fuels, such as Fischer-Tropsch derived fuels, biomass-derived materials, biofuel components such as fatty acid methyl esters, or shale oils, may also form or be present in the fuel composition. Such Fischer-Tropsch fuels may for example be derived from natural gas, natural gas liquids, petroleum or shale oil, petroleum or shale oil processing residues, coal or biomass.
The amount of Fischer-Tropsch derived fuel used in a diesel fuel composition may be from 0.5 to 100%v of the overall diesel fuel composition, preferably from 5 to 75%v. It may be desirable for the composition to contain 10%v or greater, more preferably 20%v or greater, still more preferably 30%v or greater, of the Fischer-Tropsch derived fuel. It is particularly preferred for the composition to contain 30 to 75%v, and particularly 30 or 70%v, of the Fischer-Tropsch derived fuel. The balance of the fuel composition is made up of one or more other fuels.
An industrial gas oil composition will preferably comprise more than 50 wt%, more preferably more than 70 wt%, of a Fischer-Tropsch derived fuel component.
Such a Fischer-Tropsch derived fuel component is any fraction of the middle distillate fuel range, which can be isolated from the (hydrocracked) Fischer-Tropsch synthesis product. Typical fractions will boil in the naphtha, kerosene or gas oil range. Preferably, a Fischer-Tropsch product boiling in the kerosene or gas oil range is used because these products are easier to handle in for example domestic environments. Such products will suitably comprise a fraction larger than 90 wt% which boils between 160 and 400 C, preferably to about 370 C. Examples of Fischer-Tropsch derived kerosene and gas oils are described in EP-A-0583836, WO-A-97/14768, WO-A-97/14769, WO-A-00/11116, WO-A-00/11117, WO-A-01/83406, WO-A-01/83648, WO-A-01/83647, WO-A-01/83641, WO-A-00/20535, WO-A-00/20534, EP-A-1101813, US-A-5766274, US-A-5378348, US-A-5888376 and US-A-6204426.
The Fischer-Tropsch product will suitably contain more than 80 wt% and more suitably more than 95 wt% iso and normal paraffins and less than 1 wt% aromatics, the balance being naphthenics compounds. The content of sulphur and nitrogen will be very low and normally below the detection limits for such compounds. For this reason the sulphur content of a fuel composition containing a Fischer-Tropsch product may be very low.
The fuel composition preferably contains no more than 5000 ppmw sulphur, more preferably no more than 500 ppmw, or no more than 350 ppmw, or no more than 150 ppmw, or no more than 100 ppmw, or no more than 50 ppmw, or most preferably no more than 10 ppmw sulphur.
The base fuel may itself be additivated (additive-containing) or unadditivated (additive-free). If additivated, e.g. at the refinery, it will contain minor amounts of one or more additives selected for example from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers), lubricity additives, antioxidants and wax anti-settling agents.
Detergent-containing diesel fuel additives are known and commercially available. Such additives may be added to diesel fuels at levels intended to reduce, remove, or slow the build up of engine deposits.
Examples of detergents suitable for use in fuel additives for the present purpose include polyolefin substituted succinimides or succinamides of polyamines, for instance polyisobutylene succinimides or polyisobutylene amine succinamides, aliphatic amines, Mannich bases or amines and polyolefin (e.g.
polyisobutylene) maleic anhydrides. Succinimide dispersant additives are described for example in GB-A-960493, EP-A-0147240, EP-A-0482253, EP-A-0613938, EP-A-0557516 and WO-A-98/42808. Particularly preferred are polyolefin substituted succinimides such as polyisobutylene succinimides.
The additive may contain other components in addition to the detergent. Examples are lubricity enhancers; dehazer compositions, e.g. those containing alkoxylated phenol formaldehyde polymers; anti-foaming agents (e.g. polyether-modified polysiloxanes); ignition improvers (cetane improvers) (e.g. 2-ethylhexyl nitrate (EHN), cyclohexyl nitrate, di-tert-butyl peroxide and those disclosed in US-A-4208190 at column 2, line 27 to column 3, line 21); anti-rust agents (e.g. a propane-1,2-diol semi-ester of tetrapropenyl succinic acid, or polyhydric alcohol esters of a succinic acid derivative, the succinic acid derivative having on at least one of its alpha-carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group containing from 20 to 500 carbon atoms, e.g. the pentaerythritol diester of polyisobutylene-substituted succinic acid); corrosion inhibitors; reodorants; anti-wear additives; anti-oxidants (e.g. phenolics such as 2,6-di-tert-butylphenol, or phenylenediamines such as N,N'-di-sec-butyl-p-phenylenediamine); metal deactivators; and combustion improvers.
It is particularly preferred that the additive include a lubricity enhancer, especially when the fuel composition has a low (e.g. 500 ppmw or less) sulphur content. In the additivated fuel composition, the lubricity enhancer is conveniently present at a concentration of less than 1000 ppmw, preferably between 5 and 1000 ppmw. Suitable commercially available lubricity enhancers include ester- and acid-based additives. Other lubricity enhancers are described in the patent literature, in particular in connection with their use in low sulphur content diesel fuels, for example in:
- the paper by Danping Wei and H.A. Spikes, "The Lubricity of Diesel Fue1s", Wear, III (1986) 217-235;
- WO-A-95/33805 - cold flow improvers to enhance lubricity of low sulphur fuels;
- WO-A-94/17160 - certain esters of a carboxylic acid and an alcohol wherein the acid has from 2 to 50 carbon atoms and the alcohol has 1 or more carbon atoms, particularly glycerol monooleate and di-isodecyl adipate, as fuel additives for wear reduction in a diesel engine injection system;
- US-A-5490864 - certain dithiophosphoric diester-dialcohols as anti-wear lubricity additives for low sulphur diesel fuels; and - WO-A-98/01516 - certain alkyl aromatic compounds having at least one carboxyl group attached to their aromatic nuclei, to confer anti-wear lubricity effects particularly in low sulphur diesel fuels.
It is also preferred that the additive contain an anti-foaming agent, more preferably in combination with an anti-rust agent and/or a corrosion inhibitor and/or a lubricity additive.
Unless otherwise stated, the (active matter) concentration of each such additional component in the additivated fuel composition is preferably up to 10000 ppmw, more preferably in the range from 0.1 to 1000 ppmw, advantageously from 0.1 to 300 ppmw, such as from 0.1 to 150 ppmw. The (active matter) concentration of any dehazer in the fuel composition will preferably be in the range from 0.1 to 20 ppmw, more preferably from 1 to ppmw, still more preferably from 1 to 10 ppmw, advantageously from 1 to 5 ppmw. The (active matter) concentration of any ignition improver present will preferably be 2600 ppmw or less, more preferably 2000 15 ppmw or less, conveniently from 300 to 1500 ppmw.
If desired, the additive components, as listed above, may be co-mixed, preferably together with suitable diluent(s), in an additive concentrate, and the additive concentrate may be dispersed into the fuel, in suitable quantity to result in a composition of the present invention.
In the case of a diesel fuel composition, for example, the additive will typically contain a detergent, optionally together with other components as described above, and a diesel fuel-compatible diluent, which may be a carrier oil (e.g. a mineral oil), a polyether, which may be capped or uncapped, a non-polar solvent such as toluene, xylene, white spirits and those sold by Shell companies under the trade mark "SHELLSOL".
The total content of the additives may be suitably between 0 and 10000 ppmw and preferably below 5000 ppmw.
In this specification, amounts (concentrations, %v, ppmw, wt%) of components are of active matter, i.e.
exclusive of volatile solvents/diluent materials.
Examples of detergents suitable for use in fuel additives for the present purpose include polyolefin substituted succinimides or succinamides of polyamines, for instance polyisobutylene succinimides or polyisobutylene amine succinamides, aliphatic amines, Mannich bases or amines and polyolefin (e.g.
polyisobutylene) maleic anhydrides. Succinimide dispersant additives are described for example in GB-A-960493, EP-A-0147240, EP-A-0482253, EP-A-0613938, EP-A-0557516 and WO-A-98/42808. Particularly preferred are polyolefin substituted succinimides such as polyisobutylene succinimides.
The additive may contain other components in addition to the detergent. Examples are lubricity enhancers; dehazer compositions, e.g. those containing alkoxylated phenol formaldehyde polymers; anti-foaming agents (e.g. polyether-modified polysiloxanes); ignition improvers (cetane improvers) (e.g. 2-ethylhexyl nitrate (EHN), cyclohexyl nitrate, di-tert-butyl peroxide and those disclosed in US-A-4208190 at column 2, line 27 to column 3, line 21); anti-rust agents (e.g. a propane-1,2-diol semi-ester of tetrapropenyl succinic acid, or polyhydric alcohol esters of a succinic acid derivative, the succinic acid derivative having on at least one of its alpha-carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group containing from 20 to 500 carbon atoms, e.g. the pentaerythritol diester of polyisobutylene-substituted succinic acid); corrosion inhibitors; reodorants; anti-wear additives; anti-oxidants (e.g. phenolics such as 2,6-di-tert-butylphenol, or phenylenediamines such as N,N'-di-sec-butyl-p-phenylenediamine); metal deactivators; and combustion improvers.
It is particularly preferred that the additive include a lubricity enhancer, especially when the fuel composition has a low (e.g. 500 ppmw or less) sulphur content. In the additivated fuel composition, the lubricity enhancer is conveniently present at a concentration of less than 1000 ppmw, preferably between 5 and 1000 ppmw. Suitable commercially available lubricity enhancers include ester- and acid-based additives. Other lubricity enhancers are described in the patent literature, in particular in connection with their use in low sulphur content diesel fuels, for example in:
- the paper by Danping Wei and H.A. Spikes, "The Lubricity of Diesel Fue1s", Wear, III (1986) 217-235;
- WO-A-95/33805 - cold flow improvers to enhance lubricity of low sulphur fuels;
- WO-A-94/17160 - certain esters of a carboxylic acid and an alcohol wherein the acid has from 2 to 50 carbon atoms and the alcohol has 1 or more carbon atoms, particularly glycerol monooleate and di-isodecyl adipate, as fuel additives for wear reduction in a diesel engine injection system;
- US-A-5490864 - certain dithiophosphoric diester-dialcohols as anti-wear lubricity additives for low sulphur diesel fuels; and - WO-A-98/01516 - certain alkyl aromatic compounds having at least one carboxyl group attached to their aromatic nuclei, to confer anti-wear lubricity effects particularly in low sulphur diesel fuels.
It is also preferred that the additive contain an anti-foaming agent, more preferably in combination with an anti-rust agent and/or a corrosion inhibitor and/or a lubricity additive.
Unless otherwise stated, the (active matter) concentration of each such additional component in the additivated fuel composition is preferably up to 10000 ppmw, more preferably in the range from 0.1 to 1000 ppmw, advantageously from 0.1 to 300 ppmw, such as from 0.1 to 150 ppmw. The (active matter) concentration of any dehazer in the fuel composition will preferably be in the range from 0.1 to 20 ppmw, more preferably from 1 to ppmw, still more preferably from 1 to 10 ppmw, advantageously from 1 to 5 ppmw. The (active matter) concentration of any ignition improver present will preferably be 2600 ppmw or less, more preferably 2000 15 ppmw or less, conveniently from 300 to 1500 ppmw.
If desired, the additive components, as listed above, may be co-mixed, preferably together with suitable diluent(s), in an additive concentrate, and the additive concentrate may be dispersed into the fuel, in suitable quantity to result in a composition of the present invention.
In the case of a diesel fuel composition, for example, the additive will typically contain a detergent, optionally together with other components as described above, and a diesel fuel-compatible diluent, which may be a carrier oil (e.g. a mineral oil), a polyether, which may be capped or uncapped, a non-polar solvent such as toluene, xylene, white spirits and those sold by Shell companies under the trade mark "SHELLSOL".
The total content of the additives may be suitably between 0 and 10000 ppmw and preferably below 5000 ppmw.
In this specification, amounts (concentrations, %v, ppmw, wt%) of components are of active matter, i.e.
exclusive of volatile solvents/diluent materials.
The treatment according to the present invention may be applied before or after any additives are blended into the fuel composition, as appropriate.
The present invention is particularly applicable where the fuel composition is used or intended to be used in a direct injection diesel engine, for example of the rotary pump, in-line pump, unit pump, electronic unit injector or common rail type, in an indirect injection diesel engine or in a homogeneous charge compression ignition engine. The fuel composition may be suitable for use in heavy and/or light duty diesel engines.
As mentioned above, it is also applicable where the fuel composition is used in heating applications, for example boilers. Such boilers include standard boilers, low temperature boilers and condensing boilers, and are typically used for heating water for commercial or domestic applications such as space heating and water heating.
In the diesel fuel composition, hydrocarbons can be supplemented by oxygenates such as esters known for use in diesel fuel.
In the process of the present invention the treatment with the metal adsorbing or absorbing material is effected with the hydrocarbons in the liquid phase, very conveniently at ambient temperature. At ambient temperature, the treatment may very conveniently be effected at atmospheric pressure.
Whilst when it is known that a particular hydrocarbon refinery component or combination/components of a fuel composition is at least predominantly responsible for the presence of metals to be removed, that component or combination of components may be treated with the metal adsorbing or absorbing material before blending with at least the other hydrocarbon refinery component to form the fuel composition, the fully pre-blended fuel composition may also be treated.
The present invention will now be further described by reference to the following Examples, in which, unless otherwise indicated, parts and percentages are by weight, and temperatures are in degrees Celsius:
EXAMPLES
Example 1 The fuels referred to in Example 1 were as set out in Table 1:
Table 1 Property Fuel A Fuel B
Density @ 15 C 835.7 835.5 (kg/m3) Cetane 52.7 53.3 Sulphur mg/kg 212 210 Distillation ( C) IBP 183.0 185.3 10% rec 208.5 210.5 20% rec 221.5 222.8 30% rec 235.0 235.5 40% rec 248.5 249.1 50% rec 263.0 263.6 60% rec 277.5 278.2 70% rec 293.5 293.9 80% rec 311.5 310.6 90% rec 333.0 331.9 95% rec 350.0 348.3 FBP 361.0 361.1 HPLC aromatics (%m/m) Mono 26.8 26.7 Di 4.5 4.2 Tri 0.7 0.5 Total 32 31.4 Fuel A was a market fuel from Hungary that is compliant with EN590 and which was used without any further treatment. Fuel B was Fuel A which had been treated by being passed through a clay column as described below.
By comparing the characteristics of Fuels A and B
set out in Table 1 it can be seen that the physical properties (density and cetane number) were essentially unchanged by the clay treatment. It can also be seen that the aromatic (mono-, di- and tri-) content and sulphur content were also essentially unchanged by said treatment, as were the distillation characteristics.
Metals content and filtration The metal content of Fuel A was determined using the following technique, ICP-MS (Inductively Coupled Plasma-Mass Spectrometry). Said technique involves spraying the fuel containing the metals into a spray chamber to form a fine spray. Here the larger droplets are removed and 1 to 2% of the sample solution enters into the inductively coupled plasma. The plasma is produced in a quartz torch, via the interaction of an intense magnetic field and flowing argon. The plasma discharge has a high temperature, approximately 10000 C.
In ICP-MS the plasma is used to generate positively charged ions. Once the ions are produced in the plasma, they are directed into the mass spectrometer via the interface region from where the positive ions are focused down a quadruple mass spectrometer. The results (in ppbw) are set out in Table 2 below.
A glass column of about 1 metre in height and diameter of 7.5 cm, having a tap at the bottom and a loose glass cap on top, was fitted with a glass wool layer immediately above the tap and was then loaded with 0.5 kg of dry clay, in powder form. The clay filled the column to about 40 cm above the tap, and the glass wool layer prevented clay from falling into the tap.
Fuel A at ambient temperature (20 C) was then poured into the column, to a depth of 25 to 30 cm above the clay. Flow rate was adjusted to 1 litre/hour, and the column was regularly topped up with fuel. A total volume of 50 litres was passed through the column. The first litre of permeate was discarded, and subsequently 5 litre samples (Fuel B) were collected. The 2nd, 4th, 6th, 8th and final samples (Fuel B) were tested for metal content.
The average values (in ppbw) were as set out in Table 2 below:
Table 2 Metal Fuel A Fuel B
Ag <50 <50 B <50 <50 Cr 14 <5 Cu <50 <50 Fe 84 <5 Mg 76 <5 Mn 8 <5 Mo <50 <50 Ni <50 <50 Pb 50 <40 Sn <50 <50 Ti <50 <50 Zn 1500 26 V <50 <50 It is to be noted that the levels of chromium (Cr), iron (Fe), lead (Pb), magnesium (Mg), manganese (Mn) and zinc (Zn) were all reduced after the clay treatment. The reduction in the level of zinc was particularly marked.
The levels of metals could be further reduced by the optimisation of the operating conditions of the process, passing the fuel through a second bed of solid, or by other means.
The clay which was employed was Attapulgite, mesh size 30-60 (0.500 to 0.250 mm), ex. Wilfrid Smith Limited (manufactured by Millwhite). Other suitable clays include Fuller's Earth, e.g. mesh size 30-60, ex.
Aldrich, and Sepiolite, e.g. grade 30-60, ex. Steetly Bentonite & Absorbents Ltd.
Emissions behaviour The emissions behaviour of Fuels A and B was then measured using the vehicles listed in Table 3, which represent two major light duty fuel injection systems (direct injection (DI) and indirect injection (IDI)):
Table 3 Vehicle Engine No. of No. of Injection size (L) cylinders valves system VW Golf 1.9 4 8 DI
VW Passat 1.9 4 8 IDI
Fuels A and B were tested in the above vehicles in the sequence set out in Table 4:
Table 4 Vehicle Test fuel VW Golf A A B B A A B B
VW Passat A A B B A A B B
Each test comprised a standard ECE + EUDC cycle (ECE
1505M lls 221) in which total hydrocarbons, NOx, C0, CO2 and particulates were measured using a 2 + 2 + 1 bagging strategy.
Two vehicles were tested on one fuel during each days testing:
Day 1: pre-condition both vehicles on Fuel A;
Day 2: emission test VW Golf and VW Passat on Fuel A;
The present invention is particularly applicable where the fuel composition is used or intended to be used in a direct injection diesel engine, for example of the rotary pump, in-line pump, unit pump, electronic unit injector or common rail type, in an indirect injection diesel engine or in a homogeneous charge compression ignition engine. The fuel composition may be suitable for use in heavy and/or light duty diesel engines.
As mentioned above, it is also applicable where the fuel composition is used in heating applications, for example boilers. Such boilers include standard boilers, low temperature boilers and condensing boilers, and are typically used for heating water for commercial or domestic applications such as space heating and water heating.
In the diesel fuel composition, hydrocarbons can be supplemented by oxygenates such as esters known for use in diesel fuel.
In the process of the present invention the treatment with the metal adsorbing or absorbing material is effected with the hydrocarbons in the liquid phase, very conveniently at ambient temperature. At ambient temperature, the treatment may very conveniently be effected at atmospheric pressure.
Whilst when it is known that a particular hydrocarbon refinery component or combination/components of a fuel composition is at least predominantly responsible for the presence of metals to be removed, that component or combination of components may be treated with the metal adsorbing or absorbing material before blending with at least the other hydrocarbon refinery component to form the fuel composition, the fully pre-blended fuel composition may also be treated.
The present invention will now be further described by reference to the following Examples, in which, unless otherwise indicated, parts and percentages are by weight, and temperatures are in degrees Celsius:
EXAMPLES
Example 1 The fuels referred to in Example 1 were as set out in Table 1:
Table 1 Property Fuel A Fuel B
Density @ 15 C 835.7 835.5 (kg/m3) Cetane 52.7 53.3 Sulphur mg/kg 212 210 Distillation ( C) IBP 183.0 185.3 10% rec 208.5 210.5 20% rec 221.5 222.8 30% rec 235.0 235.5 40% rec 248.5 249.1 50% rec 263.0 263.6 60% rec 277.5 278.2 70% rec 293.5 293.9 80% rec 311.5 310.6 90% rec 333.0 331.9 95% rec 350.0 348.3 FBP 361.0 361.1 HPLC aromatics (%m/m) Mono 26.8 26.7 Di 4.5 4.2 Tri 0.7 0.5 Total 32 31.4 Fuel A was a market fuel from Hungary that is compliant with EN590 and which was used without any further treatment. Fuel B was Fuel A which had been treated by being passed through a clay column as described below.
By comparing the characteristics of Fuels A and B
set out in Table 1 it can be seen that the physical properties (density and cetane number) were essentially unchanged by the clay treatment. It can also be seen that the aromatic (mono-, di- and tri-) content and sulphur content were also essentially unchanged by said treatment, as were the distillation characteristics.
Metals content and filtration The metal content of Fuel A was determined using the following technique, ICP-MS (Inductively Coupled Plasma-Mass Spectrometry). Said technique involves spraying the fuel containing the metals into a spray chamber to form a fine spray. Here the larger droplets are removed and 1 to 2% of the sample solution enters into the inductively coupled plasma. The plasma is produced in a quartz torch, via the interaction of an intense magnetic field and flowing argon. The plasma discharge has a high temperature, approximately 10000 C.
In ICP-MS the plasma is used to generate positively charged ions. Once the ions are produced in the plasma, they are directed into the mass spectrometer via the interface region from where the positive ions are focused down a quadruple mass spectrometer. The results (in ppbw) are set out in Table 2 below.
A glass column of about 1 metre in height and diameter of 7.5 cm, having a tap at the bottom and a loose glass cap on top, was fitted with a glass wool layer immediately above the tap and was then loaded with 0.5 kg of dry clay, in powder form. The clay filled the column to about 40 cm above the tap, and the glass wool layer prevented clay from falling into the tap.
Fuel A at ambient temperature (20 C) was then poured into the column, to a depth of 25 to 30 cm above the clay. Flow rate was adjusted to 1 litre/hour, and the column was regularly topped up with fuel. A total volume of 50 litres was passed through the column. The first litre of permeate was discarded, and subsequently 5 litre samples (Fuel B) were collected. The 2nd, 4th, 6th, 8th and final samples (Fuel B) were tested for metal content.
The average values (in ppbw) were as set out in Table 2 below:
Table 2 Metal Fuel A Fuel B
Ag <50 <50 B <50 <50 Cr 14 <5 Cu <50 <50 Fe 84 <5 Mg 76 <5 Mn 8 <5 Mo <50 <50 Ni <50 <50 Pb 50 <40 Sn <50 <50 Ti <50 <50 Zn 1500 26 V <50 <50 It is to be noted that the levels of chromium (Cr), iron (Fe), lead (Pb), magnesium (Mg), manganese (Mn) and zinc (Zn) were all reduced after the clay treatment. The reduction in the level of zinc was particularly marked.
The levels of metals could be further reduced by the optimisation of the operating conditions of the process, passing the fuel through a second bed of solid, or by other means.
The clay which was employed was Attapulgite, mesh size 30-60 (0.500 to 0.250 mm), ex. Wilfrid Smith Limited (manufactured by Millwhite). Other suitable clays include Fuller's Earth, e.g. mesh size 30-60, ex.
Aldrich, and Sepiolite, e.g. grade 30-60, ex. Steetly Bentonite & Absorbents Ltd.
Emissions behaviour The emissions behaviour of Fuels A and B was then measured using the vehicles listed in Table 3, which represent two major light duty fuel injection systems (direct injection (DI) and indirect injection (IDI)):
Table 3 Vehicle Engine No. of No. of Injection size (L) cylinders valves system VW Golf 1.9 4 8 DI
VW Passat 1.9 4 8 IDI
Fuels A and B were tested in the above vehicles in the sequence set out in Table 4:
Table 4 Vehicle Test fuel VW Golf A A B B A A B B
VW Passat A A B B A A B B
Each test comprised a standard ECE + EUDC cycle (ECE
1505M lls 221) in which total hydrocarbons, NOx, C0, CO2 and particulates were measured using a 2 + 2 + 1 bagging strategy.
Two vehicles were tested on one fuel during each days testing:
Day 1: pre-condition both vehicles on Fuel A;
Day 2: emission test VW Golf and VW Passat on Fuel A;
Day 3: emission test VW Golf and VW Passat on Fuel A, change fuel and pre-condition both vehicles with Fuel B;
Day 4: emission test VW Golf and VW Passat on Fuel B;
etc.
In order to avoid trace metal contamination of the clay treated fuel, testing was conducted from lacquer-lined fuel cans and non-metallic fuel lines to each vehicle's fuel pump. Samples of fuels were retained at the end of each emissions test and submitted for elemental analysis. This confirmed that trace metal contamination had not occurred during the course of testing.
The results of the emissions testing are set out below, namely in Table 5 (NOx), Table 6 (particulates), Table 7 (CO), Table 8 (total hydrocarbons) and Table 9 (C02), the units in all said Tables being g/km:
Table 5 Fuel A Fuel B
W Golf 0.4236 0.3848 1W Passat 1.1849 1.1306 Fleet average 0.8043 0.7577 Table 6 Fuel A Fuel B
VW Golf 0.05665 0.05102 1W Passat 0.03843 0.03246 Fleet average 0.04754 0.04174 Table 7 Fuel A Fuel B
7W Golf 0.577 0.572 VW Passat 0.245 0.249 Fleet average 0.411 0.411 Table 8 Fuel A Fuel B
7W Golf 0.137 0.138 1W Passat 0.019 0.018 Fleet average 0.078 0.078 Table 9 Fuel A Fuel B
IVW Golf 133.75 127.65 IVW Passat 176.20 174.51 Fleet average 154.98 151.08 It can be seen from Tables 7, 8 and 9 that the levels of C0, total hydrocarbons and C02 were unchanged or essentially unchanged as between Fuels A and B. The benefits, i.e. percentage improvement, in levels of NOx and particulates using Fuel B as compared to using Fuel A
are set out below, namely in Table 10 (NOx) and Table 11 (particulates):
Table 10 NOx benefit [ o ]
IVW Golf 9.2 VW Passat 4.6 Fleet average 6.9 Table 11 Particulate benefit [%]
W Golf 9.9 W Passat 15.5 Fleet average 12.7 Example 2 The fuels referred to in Example 2 were as set out in Table 12:
Table 12 Property Fuel C Fuel D Fuel E Fuel F Fuel G
Density @ 15 C 0.8394 0.8391 0.8391 0.8394 0.8395 (g/cm3) Fuel C was a 275ppmw sulphur diesel fuel. Fuels D, E, F, and G were Fuel C which had been treated by being passed through DAMOLIN MOLER (diatomaceous earth ex.
Damolin), AMBERLITE XAD-7 (polymeric adsorbent ex.
Aldrich), polyethylene imine on silica gel (ex. Aldrich), and AMBERLYST 15 (ion-exchange resin, ex. Aldrich), respectively, as described below.
It can be seen that the density of Fuels C to G was essentially unchanged by the treatment.
Metals content and filtration The metals content of Fuel C was determined using the technique described in Example 1 with respect to Fuel A. The results (in ppbw) are set out in Table 13 below.
Fuel C was then treated at ambient temperature (20 C) with the metal adsorbing or absorbing materials DAMOLIN MOLER, AMBERLITE XAD-7, polyethylene imine on silica gel, and AMBERLYST 15, to produce Fuels D to G
respectively, as described below.
Fuel D was obtained when Fuel C was treated in a column approximately lm high with a diameter of about 7.5cm and a tap at the bottom. Approximately 250g of dry solid was loaded into the column, on top of a layer of glass wool. The solid filled the column to approximately 20cm above the tap. The fuel was passed once through the column with the first -100ml being discarded.
Fuels E, F, and G were obtained when Fuel C was treated in columns about 50cm high with a diameter of 2cm and a tap at the bottom. In each case, approximately 40g of solid was loaded into the column, on top of a layer of glass wool. The solid filled the column to approximately 30cm above the tap. The fuels were passed once through the columns, with the first -100ml being discarded.
Fuels D to G were then tested for metals content.
The average values (in ppbw) were as set out in Table 13 below:
Table 13 Metal Fuel C Fuel D Fuel E Fuel F Fuel G
Ag <20 <20 <20 <20 <20 Al <100 <100 <100 <100 Nd B <500 <500 <500 <500 Nd Cr <20 <20 <20 <20 <5 Cu 275 <10 30 145 130 Fe 10 <5 <5 <5 <5 Mg <100 <100 <100 <100 <5 Mn <5 <5 <5 <5 <5 Mo <20 <20 <20 <20 <20 Ni <20 <20 <20 <20 Nd Pb <100 <100 <100 <100 <50 Sn <50 <50 <50 <50 <50 Ti <20 <20 <20 <20 <20 V <50 <50 <50 <50 Nd Zn 1740 <5 5 160 590 nd = not determined It is to be noted that the levels of copper (Cu), iron (Fe) and zinc (Zn) were reduced after the treatment with each of the metal adsorbing or absorbing materials.
Day 4: emission test VW Golf and VW Passat on Fuel B;
etc.
In order to avoid trace metal contamination of the clay treated fuel, testing was conducted from lacquer-lined fuel cans and non-metallic fuel lines to each vehicle's fuel pump. Samples of fuels were retained at the end of each emissions test and submitted for elemental analysis. This confirmed that trace metal contamination had not occurred during the course of testing.
The results of the emissions testing are set out below, namely in Table 5 (NOx), Table 6 (particulates), Table 7 (CO), Table 8 (total hydrocarbons) and Table 9 (C02), the units in all said Tables being g/km:
Table 5 Fuel A Fuel B
W Golf 0.4236 0.3848 1W Passat 1.1849 1.1306 Fleet average 0.8043 0.7577 Table 6 Fuel A Fuel B
VW Golf 0.05665 0.05102 1W Passat 0.03843 0.03246 Fleet average 0.04754 0.04174 Table 7 Fuel A Fuel B
7W Golf 0.577 0.572 VW Passat 0.245 0.249 Fleet average 0.411 0.411 Table 8 Fuel A Fuel B
7W Golf 0.137 0.138 1W Passat 0.019 0.018 Fleet average 0.078 0.078 Table 9 Fuel A Fuel B
IVW Golf 133.75 127.65 IVW Passat 176.20 174.51 Fleet average 154.98 151.08 It can be seen from Tables 7, 8 and 9 that the levels of C0, total hydrocarbons and C02 were unchanged or essentially unchanged as between Fuels A and B. The benefits, i.e. percentage improvement, in levels of NOx and particulates using Fuel B as compared to using Fuel A
are set out below, namely in Table 10 (NOx) and Table 11 (particulates):
Table 10 NOx benefit [ o ]
IVW Golf 9.2 VW Passat 4.6 Fleet average 6.9 Table 11 Particulate benefit [%]
W Golf 9.9 W Passat 15.5 Fleet average 12.7 Example 2 The fuels referred to in Example 2 were as set out in Table 12:
Table 12 Property Fuel C Fuel D Fuel E Fuel F Fuel G
Density @ 15 C 0.8394 0.8391 0.8391 0.8394 0.8395 (g/cm3) Fuel C was a 275ppmw sulphur diesel fuel. Fuels D, E, F, and G were Fuel C which had been treated by being passed through DAMOLIN MOLER (diatomaceous earth ex.
Damolin), AMBERLITE XAD-7 (polymeric adsorbent ex.
Aldrich), polyethylene imine on silica gel (ex. Aldrich), and AMBERLYST 15 (ion-exchange resin, ex. Aldrich), respectively, as described below.
It can be seen that the density of Fuels C to G was essentially unchanged by the treatment.
Metals content and filtration The metals content of Fuel C was determined using the technique described in Example 1 with respect to Fuel A. The results (in ppbw) are set out in Table 13 below.
Fuel C was then treated at ambient temperature (20 C) with the metal adsorbing or absorbing materials DAMOLIN MOLER, AMBERLITE XAD-7, polyethylene imine on silica gel, and AMBERLYST 15, to produce Fuels D to G
respectively, as described below.
Fuel D was obtained when Fuel C was treated in a column approximately lm high with a diameter of about 7.5cm and a tap at the bottom. Approximately 250g of dry solid was loaded into the column, on top of a layer of glass wool. The solid filled the column to approximately 20cm above the tap. The fuel was passed once through the column with the first -100ml being discarded.
Fuels E, F, and G were obtained when Fuel C was treated in columns about 50cm high with a diameter of 2cm and a tap at the bottom. In each case, approximately 40g of solid was loaded into the column, on top of a layer of glass wool. The solid filled the column to approximately 30cm above the tap. The fuels were passed once through the columns, with the first -100ml being discarded.
Fuels D to G were then tested for metals content.
The average values (in ppbw) were as set out in Table 13 below:
Table 13 Metal Fuel C Fuel D Fuel E Fuel F Fuel G
Ag <20 <20 <20 <20 <20 Al <100 <100 <100 <100 Nd B <500 <500 <500 <500 Nd Cr <20 <20 <20 <20 <5 Cu 275 <10 30 145 130 Fe 10 <5 <5 <5 <5 Mg <100 <100 <100 <100 <5 Mn <5 <5 <5 <5 <5 Mo <20 <20 <20 <20 <20 Ni <20 <20 <20 <20 Nd Pb <100 <100 <100 <100 <50 Sn <50 <50 <50 <50 <50 Ti <20 <20 <20 <20 <20 V <50 <50 <50 <50 Nd Zn 1740 <5 5 160 590 nd = not determined It is to be noted that the levels of copper (Cu), iron (Fe) and zinc (Zn) were reduced after the treatment with each of the metal adsorbing or absorbing materials.
The reduction in the level of zinc was particularly marked.
The levels of metals in the fuel may be reduced further by optimisation of the conditions of the process, or by passing the fuel through a second process of contact with metal adsorbing or absorbing material, or by alternative means. Further reductions in metal level may be desirable to achieve the optimum reduction in the formation of NOx and particulates during engine operation.
The above data shows quite clearly that emissions of NOx and particulates were reduced by clay treating Fuel A. This was achieved without any essential effect on a number of fuel properties (Table 1) or on emissions of CO, total hydrocarbons and CO2 (Tables 7, 8 and 9).
Similar reductions in emissions of NOx and particulates are to be expected when pre-treating the hydrocarbon component(s) of the fuel with any metal adsorbing or absorbing material, such as those described above, particularly those which are effective in greatly reducing the levels of zinc in the fuel.
Therefore, the present invention provides a means for improving, i.e. reducing, emissions from a compression-ignition engine which comprises pre-treating with a metal adsorbing or absorbing material at least one hydrocarbon component of a fuel to be used in such an engine.
The levels of metals in the fuel may be reduced further by optimisation of the conditions of the process, or by passing the fuel through a second process of contact with metal adsorbing or absorbing material, or by alternative means. Further reductions in metal level may be desirable to achieve the optimum reduction in the formation of NOx and particulates during engine operation.
The above data shows quite clearly that emissions of NOx and particulates were reduced by clay treating Fuel A. This was achieved without any essential effect on a number of fuel properties (Table 1) or on emissions of CO, total hydrocarbons and CO2 (Tables 7, 8 and 9).
Similar reductions in emissions of NOx and particulates are to be expected when pre-treating the hydrocarbon component(s) of the fuel with any metal adsorbing or absorbing material, such as those described above, particularly those which are effective in greatly reducing the levels of zinc in the fuel.
Therefore, the present invention provides a means for improving, i.e. reducing, emissions from a compression-ignition engine which comprises pre-treating with a metal adsorbing or absorbing material at least one hydrocarbon component of a fuel to be used in such an engine.
Claims (10)
1. A fuel composition comprising a major amount of a fuel suitable for use in a compression-ignition engine, which fuel comprises one or more hydrocarbon components boiling within the diesel boiling range, at least one of which hydrocarbon components has been treated with a metal adsorbing or absorbing material in a different physical phase from the hydrocarbon component(s), preferably to reduce the level of at least one metal, more preferably the level of at least one heavier metal, most preferably the level of zinc, in said at least one hydrocarbon component, for the purpose of reducing the emission of NOx, and optionally particulates, from a compression-ignition engine into the combustion chambers of which said fuel composition is introduced, said treatment including physical separation of the hydrocarbon component from the metal adsorbing or absorbing phase.
2. A fuel composition according to claim 1 wherein the metal adsorbing or absorbing material is selected from fibrous clay minerals, diatomaceous earths, graphite and charcoal.
3. A fuel composition according to claim 1 wherein the metal adsorbing or absorbing material is selected from polymeric adsorbents or absorbents and ion-exchange resins.
4. A fuel composition according to claim 1 wherein the metal adsorbing or absorbing material is selected from complexing or chelating agents.
5. A process for the preparation of a fuel composition according to any one of claims 1 to 4 which comprises treating with a metal adsorbing or absorbing material at least one hydrocarbon component boiling within the diesel boiling range, preferably to reduce the level of at least one metal, more preferably the level of at least one heavier metal, most preferably the level of zinc, in said at least one hydrocarbon component, and optionally blending said at least one hydrocarbon component, before or after said treatment, with at least one other hydrocarbon component boiling within the diesel boiling range, to form a fuel suitable for use in a compression-ignition engine.
6. A process according to claim 5 which comprises blending at least two hydrocarbon components boiling within the diesel boiling range and treating the resulting mixture with said metal adsorbing or absorbing material, to form a fuel suitable for use in a compression-ignition engine.
7. A method of operating a compression-ignition engine, which comprises bringing into the combustion chambers of such engine a fuel composition according to any one of claims 1 to 4.
8. A method of reducing the emission of NOx, and optionally particulates, from a compression-ignition engine which comprises bringing into the combustion chambers of such engine a fuel composition according to any one of claims 1 to 4.
9. The use in a compression-ignition engine of a fuel composition according to any one of claims 1 to 4 for the purpose of reducing the emission of NOx, and optionally particulates, from said engine.
10. A method of reducing the emission of NOx, and optionally particulates, from a compression-ignition engine which comprises replacing a fuel composition therein by a fuel composition according to any one of claims 1 to 4.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04258093 | 2004-12-23 | ||
| EP04258093.6 | 2004-12-23 | ||
| EP05252267 | 2005-04-12 | ||
| EP05252267.9 | 2005-04-12 | ||
| PCT/EP2005/057156 WO2006067233A1 (en) | 2004-12-23 | 2005-12-23 | Fuel compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2591802A1 true CA2591802A1 (en) | 2006-06-29 |
Family
ID=36201233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002591802A Abandoned CA2591802A1 (en) | 2004-12-23 | 2005-12-23 | Fuel compositions |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20060163113A1 (en) |
| EP (1) | EP1833948A1 (en) |
| JP (1) | JP2008525555A (en) |
| AR (1) | AR053425A1 (en) |
| AU (1) | AU2005318109A1 (en) |
| BR (1) | BRPI0519222A2 (en) |
| CA (1) | CA2591802A1 (en) |
| NO (1) | NO20073822L (en) |
| WO (1) | WO2006067233A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG182698A1 (en) * | 2010-01-29 | 2012-08-30 | Evoenergy Llc | Plasma reactor for gas to liquid fuel conversion |
| RU2014140241A (en) | 2012-03-09 | 2016-04-27 | ЭВОЭНЕРДЖИ, Эл-Эл-Си | PLASMA-CHEMICAL DEVICE FOR TRANSFORMING GAS-HYDROCARBON HYDROCARBONS TO LIQUID FUEL |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2090007A (en) * | 1928-09-26 | 1937-08-17 | Texas Co | Manufacture of motor fuel |
| US2263102A (en) * | 1939-12-15 | 1941-11-18 | Standard Oil Co | Decolorizing oil |
| US2338142A (en) * | 1941-11-17 | 1944-01-04 | Berry V Stoll | Gasoline filtering process |
| US2593464A (en) * | 1950-12-27 | 1952-04-22 | Standard Oil Co | Process for sweetening hydrocarbon oils |
| US3529944A (en) * | 1967-01-23 | 1970-09-22 | Ashland Oil Inc | Process for clarifying and stabilizing hydrocarbon liquids |
| US4225319A (en) * | 1978-07-05 | 1980-09-30 | Phillips Petroleum Company | Adsorbent-treated cat cracked gasoline in motor fuels |
| US4383915A (en) * | 1980-05-06 | 1983-05-17 | Turbo Resources Ltd. | Clay contacting process for removing contaminants from waste lubricating oil |
| WO1982003226A1 (en) * | 1981-03-19 | 1982-09-30 | Beck Wayne H | Immobilization of vanadia deposited on sorbent materials during treatment of carbo-metallic oils |
| US4419273A (en) * | 1981-11-04 | 1983-12-06 | Chevron Research Company | Clay-based sulfur sorbent |
| US4912873A (en) * | 1989-02-17 | 1990-04-03 | Shell Oil Company | Removal of polar impurities from diesel and jet fuel |
| GB2246308A (en) * | 1990-07-25 | 1992-01-29 | Shell Int Research | Process for reducing the metal content of a hydrocarbon mixture |
| US5490864A (en) * | 1991-08-02 | 1996-02-13 | Texaco Inc. | Anti-wear lubricity additive for low-sulfur content diesel fuels |
| US5300218A (en) * | 1992-06-23 | 1994-04-05 | Shell Oil Company | Reduction of diesel engine particulate emissions by contacting diesel fuel with a carbon molecular sieve adsorbent |
| US5378348A (en) * | 1993-07-22 | 1995-01-03 | Exxon Research And Engineering Company | Distillate fuel production from Fischer-Tropsch wax |
| US6077421A (en) * | 1996-07-18 | 2000-06-20 | The United States Of America As Represented By The Secretary Of The Navy | Metal complexing |
| US5888376A (en) * | 1996-08-23 | 1999-03-30 | Exxon Research And Engineering Co. | Conversion of fischer-tropsch light oil to jet fuel by countercurrent processing |
| JPH10128003A (en) * | 1996-10-29 | 1998-05-19 | Taiyo Eng Kk | Removing method of arsenic and lead in liquid hydrocarbon |
| US5766274A (en) * | 1997-02-07 | 1998-06-16 | Exxon Research And Engineering Company | Synthetic jet fuel and process for its production |
| US5951851A (en) * | 1997-10-31 | 1999-09-14 | Poirier; Marc-Andre | Sulfur removal from hydrocarbon fluids by contacting said fluids with hydrololcite-like adsorbent material |
| US6204429B1 (en) * | 1998-04-03 | 2001-03-20 | Washington State University Research Foundation | Methods of remediation of chemical contaminants dispersed in geologic media |
| DE19845397C2 (en) * | 1998-10-02 | 2000-09-14 | Daimler Chrysler Ag | Method for desulfurizing a motor fuel on board a motor vehicle |
| US6893475B1 (en) * | 1998-12-08 | 2005-05-17 | Exxonmobil Research And Engineering Company | Low sulfur distillate fuels |
| JP2002241766A (en) * | 2001-02-20 | 2002-08-28 | Kobe Steel Ltd | Method for purifying waste oil |
| US6752919B2 (en) * | 2002-07-31 | 2004-06-22 | Chemical Products Industries, Inc. | Promoted absorbents for the removal of contaminants |
| US7160438B2 (en) * | 2002-12-19 | 2007-01-09 | W.R. Grace & Co. - Conn. | Process for removal of nitrogen containing contaminants from gas oil feedstreams |
| EA004234B1 (en) * | 2003-03-28 | 2004-02-26 | Ай Ку Эдванс Текнолоджи Лимитед | A method for treatment of liquid media |
-
2005
- 2005-12-21 US US11/314,543 patent/US20060163113A1/en not_active Abandoned
- 2005-12-22 AR ARP050105477A patent/AR053425A1/en unknown
- 2005-12-23 AU AU2005318109A patent/AU2005318109A1/en not_active Abandoned
- 2005-12-23 BR BRPI0519222-6A patent/BRPI0519222A2/en not_active IP Right Cessation
- 2005-12-23 JP JP2007547546A patent/JP2008525555A/en active Pending
- 2005-12-23 CA CA002591802A patent/CA2591802A1/en not_active Abandoned
- 2005-12-23 WO PCT/EP2005/057156 patent/WO2006067233A1/en active Application Filing
- 2005-12-23 EP EP05850497A patent/EP1833948A1/en not_active Withdrawn
-
2007
- 2007-07-20 NO NO20073822A patent/NO20073822L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AR053425A1 (en) | 2007-05-09 |
| WO2006067233A1 (en) | 2006-06-29 |
| JP2008525555A (en) | 2008-07-17 |
| BRPI0519222A2 (en) | 2009-01-06 |
| EP1833948A1 (en) | 2007-09-19 |
| US20060163113A1 (en) | 2006-07-27 |
| NO20073822L (en) | 2007-07-20 |
| AU2005318109A1 (en) | 2006-06-29 |
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