WO2005021688A1 - Compositions de combustible comprenant un combustible derive de fischer-tropsch - Google Patents

Compositions de combustible comprenant un combustible derive de fischer-tropsch Download PDF

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Publication number
WO2005021688A1
WO2005021688A1 PCT/EP2004/052014 EP2004052014W WO2005021688A1 WO 2005021688 A1 WO2005021688 A1 WO 2005021688A1 EP 2004052014 W EP2004052014 W EP 2004052014W WO 2005021688 A1 WO2005021688 A1 WO 2005021688A1
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Prior art keywords
fuel
fischer
composition
additives
tropsch derived
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PCT/EP2004/052014
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English (en)
Inventor
Christopher Russell Millington
Trevor Stephenson
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Shell Internationale Research Maatschappij B.V.
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Priority to JP2006525147A priority Critical patent/JP5390747B2/ja
Priority to BRPI0414040-0A priority patent/BRPI0414040A/pt
Priority to AU2004269169A priority patent/AU2004269169B2/en
Priority to EP04766686A priority patent/EP1664247A1/fr
Publication of WO2005021688A1 publication Critical patent/WO2005021688A1/fr

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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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene

Definitions

  • the present invention relates to fuel compositions, in particular automotive fuel compositions such as diesel fuel compositions, and to their preparation and their uses, as well as to the use of certain types of fuel in fuel compositions for new purposes.
  • Typical diesel fuels comprise liquid hydrocarbon middle distillate fuel oils having boiling points from about 150 to 400 °C.
  • Examples of such fuels include the reaction products of Fischer-Tropsch methane condensation processes, for example the process known as Shell Middle Distillate Synthesis (van der Burgt et al, "The Shell Middle Distillate Synthesis Process", paper delivered at the 5 th Synfuels Worldwide Symposium, Washington DC, November 1985; see also the November 1989 publication of the same title from Shell International Petroleum Company Ltd, London, UK) .
  • Diesel fuel compositions for use in typical current diesel (compression ignition) engines tend to include one or more additives to enhance their performance and properties.
  • additives include detergents, which can help to reduce and/or remove combustion related engine deposits; antifoaming agents to reduce foaming during engine refuelling; and dehazers, which help remove suspended water from the fuel.
  • detergents which can help to reduce and/or remove combustion related engine deposits
  • antifoaming agents to reduce foaming during engine refuelling
  • dehazers which help remove suspended water from the fuel.
  • the antifoaming agents typically preferred for use in automotive fuels are silicone based. Silicon has now been found in the deposits which accumulate in the fuel injectors of diesel engines. Since excessive deposits in these injectors can impair fuel atomisation and combustion and hence overall engine efficiency, it is desirable to reduce the use of any material which might contribute to deposit formation. Thus, although there is no definite link between the use of antifoaming additives and nozzle fouling, the risk of potential problems might be reduced if antifoaming performance could be improved in alternative ways. Moreover, although silicon free antifoaming agents are known, they tend to perform poorly when used in fuel compositions containing detergent additives, and can therefore be unsuitable for use in typical commercial diesel fuel compositions.
  • fuel compositions in particular diesel fuel compositions, having lower levels of or preferably no silicon containing additives, without undue loss of antifoaming performance and without undue effect on other fuel properties such as for example dehazing and detergency performance. It may also be desirable to provide fuel compositions containing lower levels of additives generally, in particular antifoaming, dehazing and/or detergent agents.
  • the present inventors have now found that certain fuel components can be used to replace, entirely or at least partially, such additives in fuel compositions, the components themselves having antifoaming, dehazing and/or detergency properties both alone and when blended with other fuel components.
  • the present invention provides the use of a Fischer-Tropsch derived fuel in a fuel composition, for the purpose of reducing the amount of additives (or additives other than detergent additives) in the composition.
  • the Fischer-Tropsch derived fuel may be used at least partly in place of additives which would otherwise have been present in the composition, suitably by performing at least part of the usual and/or intended function of those additives .
  • the Fischer-Tropsch derived fuel may be used for the purpose of reducing the amount of antifoaming and/or dehazing additives in the composition. It may be used so as to reduce the amount of silicon containing additives (especially silicon containing antifoaming additives) .
  • the ability to minimise additive levels, using the present invention, can have a number of advantages. Clearly it can reduce the cost of formulating the fuel composition. It may also appeal to consumers. In addition, it can reduce the potential for (possibly detrimental) interactions between the various additives which might otherwise be incorporated together in the composition; this in turn may make it easier to formulate effective fuel-additive combinations and lend more flexibility to the additive combinations that are possible. It might even allow the inclusion of additives that would otherwise have been excluded due to their interactions with other components of the composition.
  • Additives which the fuel composition might contain less of, or even none of, as a result of using the Fischer-Tropsch derived fuel in it include for example lubricity enhancers, ignition improvers, anti-rust agents, corrosion inhibitors, reodorants, anti-wear additives, anti-oxidants, metal deactivators, anti-static agents, pipeline drag reducers, flow improvers, wax anti- settling agents and mixtures thereof.
  • the Fischer-Tropsch derived fuel is preferably a gas oil, although in some contexts it may be a Fischer- Tropsch derived naphtha or kerosene fuel.
  • the fuel composition is preferably an automotive fuel composition, more preferably for use in an internal combustion engine, and most preferably it is a diesel fuel composition.
  • a Fischer-Tropsch derived fuel in a fuel composition means incorporating the Fischer-Tropsch fuel into the composition, typically as a blend (ie, a physical mixture) with one or more other fuel components and/or fuel additives, conveniently before the composition is introduced into an internal combustion engine or other system which is to be run on the fuel composition.
  • "Use” also embraces using the Fischer-Tropsch derived fuel on its own as a fuel composition.
  • the term "reducing” embraces reduction to zero; in other words, the Fischer-Tropsch derived fuel may be used to replace the relevant material (s) either partially or completely.
  • the reduction may be as compared to the level of the relevant additive (s) which would otherwise have been incorporated into the fuel composition in order to achieve the properties and performance required and/or desired of it in the context of its intended use.
  • This may for instance be the level of the additive (s) which were present in the fuel composition prior to the realisation that a Fischer-Tropsch derived fuel could be used in the way provided by the present invention, and/or which were present in an otherwise analogous fuel composition intended (eg, marketed) for use in an analogous context, prior to increasing the amount of the Fischer-Tropsch derived fuel that it contained.
  • certain minimum antifoaming, dehazing and/or detergency properties may be desirable in order for the composition to meet current fuel specifications, and/or to safeguard engine performance, and/or to satisfy consumer demand.
  • the present invention makes it possible to use a Fischer- Tropsch derived fuel at least partly in place of the additive (s) that would otherwise be needed to achieve such properties.
  • the Fischer-Tropsch derived fuel may be used to itself achieve at least part of that effect instead of the additive.
  • the resultant composition can contain a lower level of the additive but without loss of, or without undue loss of, preferably even with an improvement in, the relevant desired properties or performance.
  • the Fischer-Tropsch derived fuel is used to reduce the w/w concentration of the relevant additive (s) in the fuel composition by at least 10 %, more preferably by at least 20 or 30 %, yet more preferably by at least 50 or 70 or 80 or even 90 %. It may, as described above, be used to replace the relevant additive (s) entirely, leaving a concentration of such additive (s) in the composition of 0 % w/w, ie, the fuel composition is free of the relevant additive (s).
  • antifoaming additive s
  • concentration of antifoaming additives remaining in the fuel composition is 10 ppmw (parts per million by weight) or less, preferably less than 10 ppmw, more preferably 5 ppmw or less, yet more preferably less than 5 ppmw, still more preferably 4 or even 3 ppmw or less.
  • antifoaming additive substantially entirely, the fuel composition being nearly or essentially free of such additives and containing for example 2 ppmw or less, preferably 1 ppmw or less, more preferably 0.5 ppmw or less of antifoaming additives.
  • antifoaming additive a reagent, or a formulation containing such a reagent, which is suitable for inclusion in a fuel composition (in particular a diesel fuel composition) and which has the effect of improving the antifoaming properties of that composition for instance in the manner described below.
  • a fuel composition in particular a diesel fuel composition
  • Known silicone based antifoaming fuel additives include the polyether-modified polysiloxanes commercially available as TEGOPRENTM 5851 (ex Goldschmidt) , Q 25907 (ex Dow Corning), SAGTM TP-325 (ex OSi) and RHODORSILTM (ex Rhone Poulenc) .
  • Known silicon free antifoaming additives include various alcohols, (poly) ethers and (poly) acrylates, such as LaurexTM DF (ex A & ) , HD-OcenolTM 70/75 (ex Henkel) , X702 (ex Mobil), NalflocTM 71-D5 (ex Nalfloc) and UnemTM 4420 (ex Unichema) .
  • the Fischer-Tropsch derived fuel may be used to reduce the concentration of silicon containing additives, in particular silicon containing antifoaming additives, in the composition to 10 ppmw or less, preferably 5 ppmw or less, more preferably 4 ppmw or less, yet more preferably 3 or 2 ppmw or less.
  • silicon containing additives in particular silicon containing antifoaming additives
  • it is suitably used to replace such silicon containing additives substantially entirely, the fuel composition being nearly or essentially free of .
  • the fuel composition will contain no (ie, 0 % w/w) silicon containing additives, in particular silicon containing antifoaming additives.
  • the fuel composition ideally contains 1000 ppbw (parts per billion by weight) or less of silicon, preferably 500 ppbw or less (ideally less) , more preferably 400 or 300 or 200 ppbw or less, yet more preferably 100 or 50 or even 20 or 10 ppbw or less, most preferably no silicon or at least only trace amounts attributable to environmental contamination (dust) .
  • the Fischer-Tropsch derived fuel may be used to replace dehazing additive (s) to an extent that the concentration of dehazing additives remaining in the fuel composition is 15 ppmw or less, preferably 10 ppmw or less, more preferably 5 ppmw or less. Most preferably it may be used to replace dehazing additive (s) substantially entirely, the fuel composition being nearly or essentially free of such additives and containing for example 3 ppmw or less, preferably 2 ppmw or less, more preferably 1 or even 0.5 ppmw or less of dehazing additives .
  • dehazing additive is meant a reagent, or a formulation containing such a reagent, which is suitable for inclusion in a fuel composition (in particular' a diesel fuel composition) and which has the effect of improving the dehazing performance of that composition for instance in the manner described below.
  • Known dehazing fuel additives include alkoxylated phenol formaldehyde polymers such as those commercially available as NALCOTM EC5462A (formerly 7D07) (ex Nalco) and TOLADTM 2683 (ex Petrolite) .
  • detergent additive is meant a detergent, or a formulation containing a detergent, suitable for inclusion in a fuel composition, in particular a diesel fuel composition.
  • a detergent is an agent (suitably a surfactant) which can act to remove, and/or to prevent the build up of, combustion related deposits within a fuel combustion system, in particular in the fuel injection system of an engine such as in the injector nozzles.
  • Such materials are sometimes referred to as dispersant additives.
  • known detergents include polyolefin substituted succinimides or succinamides of polyamines, for instance polyisobutylene succinimides or polyisobutylene amine succinamides, aliphatic amines, Mannich bases or reaction products of amines and polyolefin (eg, 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.
  • Detergent- containing diesel fuel additives are known and commercially available for instance from Infineu (eg, F7661 and F7685) , Octel (eg, OMA 4130D) and Lubrizol (eg, the Lz8043 series) .
  • a diesel fuel composition includes a detergent
  • typical concentrations lie in the range 20 to 500 ppmw active matter detergent based on the overall fuel composition, more preferably 40 to 500 ppmw, most preferably 40 to 300 ppmw or 100 to 300 ppmw or 150 to 300 ppmw.
  • preferred concentrations may be 400 ppmw or less, more preferably 300 ppmw or less, yet more preferably 200 or 100 ppmw or less, most preferably 50 ppmw or 20 ppmw or less, such as from 10 to 100 ppmw or from 10 to 50 ppmw, active matter detergent based on the overall fuel composition.
  • any detergent additives present are preferably incorporated at levels no higher than, preferably lower than, more preferably 0.8 times or less, yet more preferably 0.5 times or less, their standard recommended single treat rate(s). Still more preferably, as described above, the fuel composition contains no detergents.
  • a Fischer-Tropsch derived fuel in a fuel composition for the purpose of improving the antifoaming and/or dehazing properties of the composition, and preferably also for the purpose of improving the detergency properties of the composition.
  • the improvement may be as compared to the relevant property (ies) of the fuel composition prior to the realisation that a Fischer-Tropsch derived fuel could be used in the way provided by the present invention, and/or of an otherwise analogous fuel composition intended (eg, marketed) for use in an analogous context, prior to increasing the amount of the Fischer-Tropsch derived fuel that it contained.
  • the fuel composition is preferably an automotive fuel composition, typically for use in an internal combustion engine, and is more preferably a diesel fuel composition.
  • the Fischer-Tropsch derived fuel is preferably a gas oil.
  • the antifoaming properties of a fuel composition may be assessed with reference to the volume of foam generated when a sample of the composition is filled into an appropriate vessel, and/or to the rate at which the thus generated foam dissipates.
  • Standard test procedures may be used to assess such parameters, such as the Association Francais de Normalisation (AFNOR) procedure NF M 07-075 and/or tests based on such procedures, for example the method used in Examples 1 and 2 below.
  • AFNOR Association Francais de Normalisation
  • NF M 07-075 the Association Francais de Normalisation
  • an improvement in antifoaming properties may be manifested by a reduction in foam volume, and/or a reduction in foam dissipation time or foam collapse time (which equates to an increase in foam dissipation rate) , when the fuel composition is tested in this way.
  • the Fischer-Tropsch derived fuel is used in an amount sufficient to achieve a reduction in foam volume of at least 2 %, more preferably at least 4 %, yet more preferably at least 6 or 10 %, most preferably at least 12 or 15 or 20 %, even up to 22 or 25 % or more, of that generated under the same test conditions by the same fuel composition but without, or with less of (suitably with 5 % v/v or less of, more suitably with 1 % v/v or less of) , the Fischer-Tropsch derived fuel present, and/or of that generated by the same fuel composition under the same test conditions prior to replacement, in accordance with the present invention, of some or all of its antifoaming or other additive (s) by the Fischer-Tropsch derived fuel.
  • the Fischer-Tropsch derived fuel is used in an amount sufficient to achieve a reduction in foam dissipation time of at least 15 %, more preferably at least 18 %, most preferably at least 20 or 30 or 40 %, even up to 50 or 60 or 70 or 75 % or more, of that exhibited under the same test conditions by the same fuel composition but without, or with less of (suitably with 5 % v/v or less of, more suitably with 1 % v/v or less of) , the Fischer-Tropsch derived fuel present, and/or of that exhibited by the same fuel composition under the same test conditions prior to replacement, in accordance with the invention, of some or all of its antifoaming or other additive (s) by the Fischer-Tropsch derived fuel.
  • a foam volume of 105 ml or less is used in an amount sufficient to achieve a foam volume of 105 ml or less, more preferably 100 ml or 90 ml or less, when a 100 ml sample of the resultant fuel composition is tested according to the Association Francais de Normalisation (AFNOR) procedure NF M 07-075 or a test based on that procedures, for instance as in Examples 1 and 2 below.
  • AFNOR Association Francais de Normalisation
  • NF M 07-075 a test based on that procedures
  • the dehazing, or water shedding, properties of a fuel composition may be assessed by mixing a sample of the composition with an aqueous phase and observing the appearance of the resultant fuel and/or aqueous layers, and/or of their interface, after an appropriate settling period (for example 2 hours or more, preferably 3 or 4 or 5 hours or more) . Poorer dehazing properties will be indicated in particular by a more "cloudy" fuel layer containing suspended moisture droplets and/or by a less distinct boundary between the two layers.
  • dehazing properties may be assessed with reference to the water content of the resulting fuel layer for instance using a Karl Fischer or similar meter, again after an appropriate period of settling (for example 12 hours or more, preferably 24 hours or more) .
  • Standard test procedures may be used to assess such parameters, such as the ASTM procedure D1094 ("Water reaction of aviation fuels") or a version thereof modified for use with the particular fuel composition under test, such as for example the method used in Examples 4 to 6 below.
  • ASTM procedure D1094 Water reaction of aviation fuels
  • a version thereof modified for use with the particular fuel composition under test such as for example the method used in Examples 4 to 6 below.
  • an improvement in dehazing properties may be manifested by an improvement (ie, less cloudiness) in the visual appearance of the settled fuel and/or aqueous layers and/or of their interface in a test of the type described above. It may instead or in addition be manifested by a reduction in the amount of water lost to the fuel layer, and/or by a reduction in the water content of the settled fuel layer.
  • the Fischer-Tropsch derived fuel is used in an amount sufficient to achieve at least a noticeable improvement, more preferably at least a 30 % improvement, yet more preferably at least a 50 % or 75 % or 100 % improvement, in the visual appearance of the settled fuel and/or aqueous layers and/or of their interface, compared to that observed under the same test conditions for the same fuel composition but without, or with less of
  • the Fischer-Tropsch derived fuel present, and/or to that observed for the same fuel composition under the same test conditions prior to replacement, in accordance with the present invention, of some or all of its dehazing or other additive (s) by the Fischer-Tropsch derived fuel.
  • the Fischer-Tropsch derived fuel is used in an amount sufficient to achieve a reduction in fuel layer water content of at least 5 %, more preferably at least 9 or 10 %, most preferably at least 15 or 20 or 30 or 40 or 50 %, even up to 60 or 70 or 75 % or more, of that exhibited under the same test conditions by the same fuel composition but without, or with less of (suitably with 5 % v/v or less of, more suitably with 1 % v/v or less of) , the Fischer-Tropsch derived fuel present, and/or of that exhibited by the same fuel composition under the same test conditions prior to replacement, in accordance with the present invention, of some or all of its dehazing or other additive (s) by the Fischer-Tropsch derived fuel.
  • an appropriate test of dehazing performance may be the Institute of Petroleum test method IP 452 ("Determination of water shedding properties (WASP) of aviation kerosene”) .
  • the borderline for pass/fail is a residual water content of ⁇ 500-600 mg/1, a lower value therefore indicating better peformance.
  • the Fischer-Tropsch derived fuel is used in an amount sufficient to achieve a residual water content when tested in this way which is at least 20 % lower, more preferably at least 30 % lower, yet more preferably at least 40 or 50 or 60 % lower, than that achieved under the same test conditions by the same fuel composition but without, or with less of (suitably with 5 % v/v or less of, more suitably with 1 % v/v or less of) , the Fischer-Tropsch derived fuel present, and/or of that exhibited by the same fuel composition under the same test conditions prior to replacement, in accordance with the present invention, of some or all of its dehazing or other additive (s) by the Fischer-Tropsch derived fuel.
  • a fuel composition or of a fuel additive in a fuel composition, may be assessed with reference to the effect of running a fuel combustion system (for example a diesel engine) using the composition, on the level of combustion related deposits in the system. Such deposits may accumulate for instance in the fuel injection system of an engine, causing fouling of the injector nozzles.
  • a fuel combustion system for example a diesel engine
  • Detergent effects may be manifested by a reduction in previously incurred nozzle fouling, when an engine is subsequently run on the relevant fuel composition; an improved detergency performance may therefore be manifested by a higher such reduction, when the engine is run for a given period of time on a fuel composition prepared according to the present invention, than when the same engine is run, for the same period of time and under the same conditions, on the same fuel composition but without, or with less of (suitably with 5 % v/v or less of, more suitably with 1 % v/v or less of) , the Fischer-Tropsch derived fuel present, and/or on the same fuel composition prior to replacement, in accordance with the present invention, of some or all of its detergent or other additive (s) by the Fischer-Tropsch derived fuel.
  • An improvement in detergency performance may instead or in addition be manifested by a reduction in the rate of build up of subsequent fouling compared to that which would be incurred by running the engine, for the same period of time and under the same conditions, on the same fuel composition but without, or with less of (suitably with 5 % v/v or less of, more suitably with 1 % v/v or less of) , the Fischer-Tropsch derived fuel present, and/or on the same fuel composition under the same test conditions prior to replacement, in accordance with the present invention, of some or all of its detergent or other additive (s) by the Fischer-Tropsch derived fuel.
  • Degree of nozzle fouling may be assessed in a number of ways, for instance visually, by measuring the mass of deposits in a fouled nozzle or by measuring the fluid flow (for instance, fuel flow or more preferably air flow) properties of the fouled nozzle relative to those of the clean nozzle.
  • An appropriate test might for example determine the degree of nozzle fouling (conveniently in the form of a percentage injector fouling index) under steady state conditions in a suitable engine such as a diesel engine, for instance based on the change in air flow rate through one or more of the fuel injector nozzles as a result of using the fuel composition under test. Conveniently the results are averaged over all of the injector nozzles of the engine.
  • the CEC standard test method F-23-T-00 which involves injector nozzle air flow measurements, may for instance be used to assess engine fouling.
  • the Fischer-Tropsch derived fuel is preferably included in the fuel composition at a concentration sufficient to achieve a reduction in engine fouling (measured for instance as outlined above) of at least 5 %, preferably at least 8 %, more preferably at least 10 %, most preferably at least 20 %, as compared to that which results from using (under the same or comparable conditions) the same fuel composition but without, or with less of (suitably with 5 % v/v or less of, more suitably 1 % v/v or less of) , the Fischer-Tropsch derived fuel present, and/or from using the same fuel composition prior to replacement, in accordance with the present invention, of some or all of its detergent or other additive (s) by the Fischer-Tropsch derived fuel.
  • the Fischer-Tropsch derived fuel is included at a concentration sufficient to remove, at least partially, combustion related deposits which have built up in an engine's fuel injection system, in particular in the injector nozzles, during a previous period of running using another automotive fuel (typically a fuel containing no, or less than 5 % v/v, or less than 1 % v/v, Fischer-Tropsch derived fuels) , when the engine is subsequently run on the Fischer-Tropsch fuel containing composition.
  • This concentration is preferably sufficient to remove at least 5 % of the previously incurred injector deposits (measured for instance as described above) , more preferably at least 10 %, most preferably at least 15 or 20 or 25 %.
  • the removal of combustion related deposits may be achieved by running the engine on the Fischer-Tropsch fuel containing composition for instance for the same period of time as that during which the deposits accumulated, or more preferably for 75 %, yet more preferably 50 % or even 40 % or 30 %, of the period of deposit accumulation, conveniently under comparable conditions.
  • at least partial removal of combustion related deposits is achieved by running the engine on the Fischer-Tropsch fuel containing composition for five hours or less, preferably for three hours or less, more preferably for two hours or less.
  • the fuel composition may, in order to achieve the desired purpose (s), consist essentially of the Fischer-Tropsch derived fuel - in other words it may contain a major proportion (by which is meant preferably 99 % v/v or more of the fuel composition, more preferably 99.5 % v/v or more, most preferably 99.8 % v/v or more, even up to 100 %), of the Fischer-Tropsch derived fuel, optionally with a minor proportion of one or more suitable fuel additives such as are known in the art (though ideally without antifoaming, dehazing and/or detergent additives), but with no other fuel components present.
  • suitable fuel additives such as are known in the art (though ideally without antifoaming, dehazing and/or detergent additives), but with no other fuel components present.
  • the fuel composition may contain, in addition to the Fischer-Tropsch derived fuel, one or more other fuel components of conventional type, in particular diesel fuel components such as a diesel base fuel (which may itself comprise a blend of two or more diesel fuel components) .
  • diesel fuel components such as a diesel base fuel (which may itself comprise a blend of two or more diesel fuel components) .
  • concentration of the Fischer-Tropsch derived fuel in the composition will be chosen to achieve the desired antifoaming and/or dehazing and/or detergency properties, and may also be influenced by other properties (for example, density, cetane number and/or emissions performance) required of the overall composition.
  • the concentration of the Fischer-Tropsch derived fuel in the composition is preferably 15 % v/v or greater, more preferably 20 % or 25 % v/v or greater, still more preferably 30 % or 40 % or 50 % v/v or greater. It may be up to 40 % or 50 % or 60 % or 70 % or 80 % or 90 % or 95 % or 98 % v/v of the overall composition. Suitable concentrations might lie, for instance, from 20 to 90 % v/v or from 25 to 80 % v/v or from 25 to 50 % v/v or from 30 to either 70 or 60 or 50 % v/v. Any additional fuel component (s) in the composition may be fuels of conventional type.
  • diesel fuels are preferably low or ultra low sulphur fuels, or sulphur free fuels, for instance containing at most 500 ppmw, preferably no more than 350 ppmw, most preferably no more than 100 or 50 ppmw, or even 10 ppmw or less, of sulphur.
  • typical diesel fuel components may comprise liquid hydrocarbon middle distillate fuel oils, for instance petroleum derived gas oils. They may be organically or synthetically derived, although not Fischer-Tropsch derived. Such fuels will typically have boiling points within the usual diesel range of 150 to 400 'C, depending on grade and use.
  • Fischer-Tropsch derived fuel and any other fuel component (s) present in the composition, will suitably all be in liquid form under ambient conditions.
  • the Fischer-Tropsch derived fuel is a gas oil
  • it is preferably suitable for use as a diesel fuel. Its components (or the majority, for instance 95 % w/w or greater, thereof) should therefore have boiling points within the typical diesel fuel (“gas oil”) range, ie, from about 150 to 400 ° C or from 170 to 370 °C. It will suitably have a 90 % w/w distillation temperature of from 300 to 370 °C.
  • Fischer-Tropsch derived is meant that the fuel is, or derives from, a synthesis product of a Fischer- Tropsch condensation process.
  • Hydrogen: carbon monoxide ratios other than 2:1 may be employed if desired.
  • the carbon monoxide and hydrogen may themselves be derived from organic or inorganic, natural or synthetic sources, typically either from natural gas or from organically derived methane.
  • Gas oil, naphtha and kerosene products may be obtained directly from the Fischer-Tropsch reaction, or indirectly for instance by fractionation of Fischer- Tropsch synthesis products or from hydrotreated Fischer- Tropsch synthesis products.
  • Hydrotreat ent can involve hydrocracking to adjust the boiling range (see, eg, GB-B-2077289 and EP-A-0147873) and/or hydroisomerisation which can improve cold flow properties by increasing the proportion of branched paraffins.
  • EP-A-0583836 describes a two step hydrotreatment process in which a Fischer- Tropsch synthesis product is firstly subjected to hydroconversion under conditions such that it undergoes substantially no isomerisation or hydrocracking (this hydrogenates the olefinic and oxygen-containing components) , and then at least part of the resultant product is hydroconverted under conditions such that hydrocracking and isomerisation occur to yield a substantially paraffinic hydrocarbon fuel.
  • the desired gas oil fraction (s) may subsequently be isolated for instance by distillation.
  • Typical catalysts for the Fischer-Tropsch synthesis of paraffinic hydrocarbons comprise, as the catalytically active component, a metal from Group VIII of the periodic table, in particular ruthenium, iron, cobalt or nickel. Suitable such catalysts are described for instance in EP-A-0583836 (pages 3 and 4).
  • Fischer-Tropsch based process is the SMDS (Shell Middle Distillate Synthesis) described in "The Shell Middle Distillate Synthesis Process", van der Burgt et al [ supra) .
  • This process also sometimes referred to as the ShellTM “Gas-to-Liquids” or “GtL” technology
  • produces middle distillate range products by conversion of a natural gas (primarily methane) derived synthesis gas into a heavy long chain hydrocarbon (paraffin) wax which can then be hydroconverted and fractionated to produce liquid transport fuels such as the gas oils useable in diesel fuel compositions.
  • a version of the SMDS process utilising a fixed bed reactor for the catalytic conversion step, is currently in use in Bintulu, Malaysia and its products have been blended with petroleum derived gas oils in commercially available automotive fuels.
  • Gas oils, naphtha fuels and kerosenes prepared by the SMDS process are commercially available for instance from the Royal Dutch/Shell Group of Companies.
  • Fischer-Tropsch derived gas oils are described in EP-A-0583836, EP-A-1101813, WO-A-97/14768, WO-A-97/14769, WO-A-00/20534, WO-A-00/20535, WO-A-00/11116, WO-A-00/11117, WO-A-01/83406, WO-A-01/83641, WO-A-01/83647 , WO-A-01/83648 and US-A-6204426.
  • a Fischer-Tropsch derived gas oil will consist of at least 70 % w/w, preferably at least 80 % w/w, more preferably at least 90 % w/w, most preferably at least 95 % w/w, of paraffinic components, preferably iso- and linear paraffins.
  • the weight ratio of iso-paraffins to normal paraffins will suitably be greater than 0.3 and may be up to 12; suitably it is from 2 to 6. The actual value for this ratio will be determined, in part, by the hydroconversion process used to prepare the gas oil from the Fischer-Tropsch synthesis product. Some cyclic paraffins may also be present.
  • a Fischer- Tropsch derived fuel has essentially no, or undetectable levels of, sulphur and nitrogen. Compounds containing these heteroatoms tend to act as poisons for Fischer- Tropsch catalysts and are therefore removed from the synthesis gas feed. This can yield additional benefits, in terms of effect on catalyst performance, in fuel compositions prepared in accordance with the present invention.
  • the Fischer-Tropsch process as usually operated produces no or virtually no aromatic components,
  • the aromatics content of a Fischer-Tropsch derived fuel suitably determined by ASTM D4629, will typically be below 1 % w/w, preferably below 0.5 % w/w and more preferably below 0.1 % w/w.
  • Fischer-Tropsch derived fuels have relatively low levels of polar components, in particular polar surfactants, for instance compared to petroleum derived fuels. It is believed that this contributes to their improved antifoaming and dehazing performance.
  • polar components may include for example oxygenates, and sulphur and nitrogen containing compounds.
  • a low level of sulphur in a Fischer-Tropsch derived fuel is generally indicative of low levels of both oxygenates and nitrogen containing compounds, since all are removed by the same treatment processes.
  • a Fischer-Tropsch derived gas oil useable in the present invention will typically have a density from 0.76 to 0.79 g/cm 3 at 15 °C; a cetane number (ASTM D613) greater than 70, suitably from 74 to 85; a kinematic viscosity (ASTM D445) from 2 to 4.5, preferably 2.5 to 4.0, more preferably from 2.9 to 3.7, centistokes (mm ⁇ /s) at 40 °C; and a sulphur content (ASTM D2622) of 5 ppmw or less, preferably of 2 ppmw or less.
  • it is a product prepared by a Fischer- Tropsch methane condensation reaction using a hydrogen/carbon monoxide ratio of less than 2.5, preferably less than 1.75, more preferably from 0.4 to 1.5, and ideally using a cobalt containing catalyst.
  • it will have been obtained from a hydrocracked Fischer-Tropsch synthesis product (for instance as described in GB-B-2077289 and/or EP-A-0147873), or more preferably a product from a two-stage hydroconversion process such as that described in EP-A-0583836 (see above) .
  • preferred features of the hydroconversion process may be as disclosed at pages 4 to 6, and in the examples, of EP-A-0583836.
  • the Fischer-Tropsch derived fuel is a naphtha fuel
  • it will be a liquid hydrocarbon middle distillate fuel with a final boiling point of typically up to 220 °C or preferably of 180 °C or less. Its initial boiling point is preferably higher than 25 °C, more preferably higher than 35 °C. Its components (or the majority, for instance 95 % w/w or greater, thereof) are typically hydrocarbons having 5 or more carbon atoms; they are usually paraffinic. The distillation properties of such a naphtha fuel tend to be comparable to those of gasoline. As with the corresponding gas oils, Fischer-Tropsch derived naphtha fuels tend to be low in undesirable fuel components such as sulphur, nitrogen and aromatics.
  • a Fischer- Tropsch derived naphtha fuel preferably has a density of from 0.67 to 0.73 g/cm 3 at 15 °C and/or a sulphur content of 5 ppmw or less, preferably 2 ppmw or less. It preferably contains 95 % w/w or greater of iso- and normal paraffins, preferably from 20 to 98 % w/w or greater of normal paraffins. It is preferably the product of a SMDS process, preferred features of which may be as described above in connection with Fischer- Tropsch gas oils.
  • the Fischer-Tropsch derived fuel is a kerosene fuel
  • it will be a liquid hydrocarbon middle distillate fuel with a distillation range suitably from about 150 to 250 °C or from about 150 to 200 °C. It will have a final boiling point of typically from 190 to 260 °C, for instance from 190 to 210 °C for a typical "narrow-cut" kerosene fraction or from 240 to 260 °C for a typical "full-cut” fraction. Its initial boiling point is preferably from 140 to 160 °C.
  • Fischer-Tropsch derived kerosenes tend to be low in undesirable fuel components such as sulphur, nitrogen and aromatics.
  • a Fischer-Tropsch derived kerosene fuel preferably has a density of from 0.730 to 0.760 g/cm 3 at 15 °C - for instance from 0.730 to 0.745 g/cm 3 for a narrow-cut fraction and from 0.735 to 0.760 g/cm 3 for a full-cut fraction -, and/or a sulphur content of 5 ppmw or less.
  • the Fischer- Tropsch derived fuel is conveniently a gas oil as used in
  • more than one Fischer-Tropsch derived fuel of the types described above may be used in a fuel composition.
  • the present invention may be applicable where the fuel composition is suitable for, and/or intended for, use in any system which can be powered by or otherwise consume a fuel, in particular a diesel fuel, composition.
  • an internal or external (preferably internal) combustion engine more particularly for use as an automotive fuel and most particularly for use in an internal combustion engine of the compression ignition (diesel) type.
  • a diesel engine may be of the direct injection type, for example of the rotary pump, in-line pump, unit pump, electronic unit injector or common rail type, or of the indirect injection type. It may be a heavy or a light duty diesel engine.
  • the fuel composition is such an automotive diesel fuel composition, it preferably falls within applicable current standard specification (s) such as for example EN 590:99.
  • the fuel composition may be suitable for, and/or intended for, use as an industrial gas oil, for instance for use in a heating or other fuel combustion system.
  • any fuel component or fuel composition may be additivated (additive containing) or unadditivated (additive free) .
  • Such additives may be added at various stages during the production of a fuel composition; in the case of automotive fuels those added to a base fuel at the refinery for example might be selected from anti-static agents, pipeline drag reducers, flow improvers (eg, ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers) and wax anti-settling agents (eg, those commercially available under the Trade Marks "PARAFLOW” (eg, PARAFLOWTM 450, ex Infineum) , "OCTEL” (eg, OCTELTM W 5000, ex Octel) and "DODIFLOW” (eg, DODIFLOWTM v 3958, ex Hoechst) .
  • PARAFLOW eg, PARAFLOWTM 450, ex Infineum
  • OCTEL OCTELTM W 5000, ex Octel
  • DODIFLOW DODIFLOWTM v 3958, ex Hoechst
  • the fuel composition contains additives, they will typically although not necessarily be incorporated together with one or more of the constituent fuel components (including the Fischer-Tropsch derived component) , whether at or downstream of the refinery.
  • the composition will contain only a minor proportion (preferably less than 1 % w/w, more preferably less than 0.5 % w/w (5000 ppmw) and most preferably less than 0.2 % w/w (2000 ppmw)) of any such fuel additives.
  • Components which may be incorporated in fuel additives, in particular for use in diesel fuels include lubricity enhancers such as EC 832 and PARADYNETM 655 (ex Infineum) , HITECTM E580 (ex Ethyl Corporation) and VEKTRONTM 6010 (ex Infineum) and amide based additives such as those available from the Lubrizol Chemical Company, for instance LZ 539 C; ignition improvers (cetane improvers) (eg, 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 (eg, that sold commercially by Rhein Chemie, Mannheim, Germany as "RC 4801", a propane-1, 2-diol semi-ester of tetrapropenyl succinic acid, or polyhydric alcohol esters of a
  • the fuel composition contains any additives at all, and in particular when it is a diesel fuel composition, it may be particularly preferred for it to include at least a lubricity enhancer, especially when the composition has a low (eg, 500 ppmw or less) sulphur content.
  • a lubricity enhancer is conveniently present at a concentration from 50 to 1000 ppmw, preferably from 100 to 1000 ppmw, based on the overall fuel composition.
  • the (active matter) concentration of any ignition improver present will preferably be 600 ppmw or less, more preferably 500 ppmw or less, conveniently from 300 to 500 ppmw.
  • the (active matter) concentration of any other type of additive in the overall fuel composition is preferably up to 1 % w/w, more preferably in the range from 5 to 1000 ppmw, advantageously from 75 to 300 ppmw, such as from 95 to 150 ppmw.
  • a Fischer-Tropsch derived fuel, and/or of a fuel composition containing it to reduce loss of efficiency of fuel atomisation and/or combustion in a fuel consuming system which is running on, or is to be run on, the fuel or composition.
  • “Fuel consuming” includes fuel powered.
  • a fourth aspect provides the use of a Fischer- Tropsch derived fuel, and/or of a fuel composition containing it, to reduce build up of deposits, in particular silicon deposits, in a fuel consuming system which is running on, or is to be run on, the fuel or composition.
  • "use" of the fuel or fuel composition includes introducing it into the system and suitably also operating the system using the fuel or composition.
  • "Use" of a Fischer-Tropsch derived fuel in this context may involve incorporating it into a fuel composition, typically as a blend (ie, a physical mixture) with one or more other fuel components and/or fuel additives, introducing the composition into the fuel consuming system and suitably also operating the system using the fuel composition.
  • the use may involve introducing the Fischer-Tropsch derived fuel alone into the system, and suitably also operating the system using it.
  • the fuel consuming system is preferably, or is part of, a combustion system, in particular comprising an internal combustion engine for an automotive vehicle, such as a diesel engine; it may in particular be a fuel injection system within such a combustion system.
  • the deposits in question are likely to build up in its fuel injection system such as in and around the injector nozzles.
  • Efficiency of fuel atomisation and/or combustion in a fuel powered (typically fuel combustion) system may be assessed with reference to the efficiency of fluid flow through the atomisation nozzle (s), for instance as described above in connection with injector fouling.
  • Any deposits accumulated in the nozzle (s) will reduce the area through which fluid can flow and hence the atomisation and combustion efficiency.
  • a suitable method for measuring air flow through fuel injector nozzles is ISO 4010-1977.
  • a reduction in fuel atomisation and/or combustion efficiency may also be manifested by a loss of power output, and/or by an increase in undesirable emissions, from the system, for instance in a vehicle driven by a combustion engine .
  • Preferred degrees of reduction in atomisation and combustion efficiency may be as described in connection with nozzle fouling in the context of the first and second aspects of the present invention.
  • the Fischer-Tropsch derived fuel is used in an amount sufficient to achieve, and/or in a context suitable for achieving, a reduction in fuel atomisation and/or combustion efficiency which is at least 2 % lower than, more preferably at least 5 % or 8 % or 10 % lower than, that caused over the same time period and under the same test conditions by running the system on a non- Fischer-Tropsch derived fuel, and/or by running the system on the same fuel composition but without, or with less of (suitably 5 % v/v or less of, more suitably 1 % v/v or less of) , the Fischer-Tropsch derived fuel present, and/or by running the system on the same fuel composition prior to replacement, in accordance with the present invention, of some or all of its antifoaming, dehazing, detergent and/or other additive (s) by the Fischer-Tropsch derived fuel.
  • Levels of deposits in a fuel consuming system may be assessed for instance using a scanning electron microscope, and/or by X-ray or other spectroscopic analysis of components of the system (in particular fuel injector nozzles), over a period of running the system on the fuel or fuel composition in question.
  • the Fischer-Tropsch derived fuel is used in an amount sufficient to achieve, and/or in a context suitable for achieving, a reduction in the level of silicon deposits caused over the same time period and under the same test conditions by running the system on a non-Fischer-Tropsch derived fuel, and/or by running the system on the same fuel composition but without, or with less of (suitably 5 % v/v or less of, more suitably 1 % v/v or less of) , the Fischer-Tropsch derived fuel present, and/or by running the system on the same fuel composition prior to replacement, in accordance with the present invention, of some or all of its antifoaming, dehazing, detergent and/or other additive (s) by the Fischer-Tropsch derived fuel.
  • the reduction may be assessed over any appropriate test period, for instance 10 operating hours or more, suitably 100 or 200 or 500 operating hours or more. It may be assessed over the lifetime or expected lifetime of the system, for instance up to 5,000 operating hours for a typical passenger vehicle or up to 50,000 operating hours for a commercial vehicle or a stationary generator.
  • a method of operating a fuel consuming system involves introducing into the system, preferably into a combustion chamber of the system, a fuel composition containing a Fischer-Tropsch derived fuel, for one or more of the purposes described above in connection with the first to the fourth aspects of the present invention.
  • the system again suitably comprises an internal or external combustion engine, more preferably the former, most preferably a diesel engine.
  • the fifth aspect of the present invention encompasses a method of operating a machine which is powered by a fuel combustion system, especially a vehicle which is driven by a combustion engine, in particular a diesel powered vehicle.
  • a sixth aspect of the present invention provides a process for the preparation of a fuel composition, which process involves blending a Fischer-Tropsch derived fuel with one or more other fuel components and/or with one or more fuel additives.
  • the blending is ideally carried out for one or more of the purposes described in connection with the first to the fifth aspects of the present invention, either in relation to the properties of the fuel composition and/or to its effect on a fuel consuming system into which it is or is intended to be introduced.
  • preferred features of this sixth aspect of the present invention in particular regarding the natures and relative proportions of components of the blend (including fuel additives where present) may be as described above in connection with the first to the fifth aspects .
  • the present invention provides a fuel composition, in particular an automotive fuel composition such as a diesel fuel composition, comprising either : i) a Fischer-Tropsch derived fuel and a silicon free or substantially silicon free antifoaming additive, optionally together with one or more other fuel components, the composition preferably being free of detergent additives; ii) a Fischer-Tropsch derived fuel and one or more (suitably non-detergent) fuel additives, optionally together with one or more other fuel components, wherein the composition is free of antifoaming additives and/or of silicon containing (in particular silicone based) antifoaming additives and/or of dehazing additives, and is preferably also free of detergent additives; or iii) a Fischer-Tropsch derived fuel and one or more (suitably non-detergent) fuel additives, optionally together with one or more other fuel components, wherein the composition is free of dehazing additives; or iv) a Fischer-Tropsch derived
  • the one or more non- detergent fuel additives may be selected from the group consisting of antifoaming additives, dehazing additives, lubricity enhancers, ignition improvers, anti-rust agents, corrosion inhibitors, reodorants, anti-wear additives, anti-oxidants, metal deactivators, anti-static agents, pipeline drag reducers, flow improvers, wax anti- settling agents and mixtures thereof. They might typically be diesel fuel additives.
  • diesel fuel ignition improvers such as organic nitrates and/or nitrites.
  • substantially free is intended to encompass 50 ppbw or less silicon, preferably 20 or 10 ppbw or less.
  • a low level may be for example 300 ppmw or less, preferably 200 or 100 ppmw or less.
  • a low level may be for example 10 ppmw or less, preferably 5 ppmw or less.
  • a low level may be for example 100 ppmw or less, preferably 50 or 20 ppmw or less .
  • a composition according to the seventh aspect of the present invention may be prepared using a process according to the sixth, and/or used in the ways described in connection with the first to the fifth aspects.
  • An eighth aspect of the present invention provides a method of operating a fuel consuming system, the method involving introducing into the system, and preferably running the system on, a fuel composition according to the seventh aspect.
  • a ninth aspect provides a method of operating a fuel consuming system, in particular an internal combustion engine such as a diesel engine, the method involving introducing into the system, and preferably running the system on, a fuel composition prepared by putting any of the first to the sixth aspects of the present invention into effect.
  • a fuel composition is preferably free of antifoaming and/or silicon containing and/or dehazing additives, more preferably is also free of detergent additives, and yet more preferably is completely free of additives.
  • the composition may instead of being free of the relevant additive contain only low levels of it, as described in connection with the seventh aspect of the present invention.
  • the composition is preferably free or substantially free of silicon.
  • Other preferred features of the seventh, eighth and ninth aspects of the present invention may be as described in connection with the first to the sixth aspects .
  • a reduced level of silicon for the purpose of : (a) reducing loss of efficiency of fuel atomisation and/or combustion in a fuel consuming system which is running on, or is to be run on, the fuel or composition; and/or (b) reducing build up of deposits, in particular silicon deposits, in a fuel consuming system which is running on, or is to be run on, the fuel or composition.
  • "use" of a particular level of silicon includes preparing a fuel composition with that level of silicon in it (which may include removing silicon or silicon containing components from the composition) , and/or running a fuel consuming system using such a fuel composition.
  • a reduced level of silicon may be as compared to the level of silicon which would otherwise have been incorporated into the fuel composition in order to achieve the properties and performance required and/or desired of it in the context of its intended use. This may for instance be the level of silicon which was present in the fuel composition prior to the realisation that silicon levels could be reduced in order to achieve the effects (a) and/or (b) provided by the present invention, and/or which was present in an otherwise analogous fuel composition intended (eg, marketed) for use in an analogous context.
  • the reduced level is preferably achieved by reducing the concentration of additive (s), in particular antifoaming additive (s), in the fuel composition.
  • a "reduced level" encompasses no or substantially no silicon at all.
  • Example 1 A Fischer-Tropsch (SMDS) derived gas oil fuel FI was blended in various proportions with a conventional petroleum derived ultra low sulphur diesel fuel F2, and the antifoaming properties assessed for the blends as well as for the neat fuels FI and F2. Both fuels were commercially available and were sourced from the Royal Dutch/Shell Group of Companies Their properties are shown in Table A. Table A
  • the gas oil FI had been obtained from a Fischer- Tropsch (SMDS) synthesis product via a two-stage hydroconversion process analogous to that described in EP-A-0583836.
  • Antifoaming performance for each fuel or blend was assessed using a test procedure based on the Association Frangais de Normalisation (AFNOR) procedure NF M 07-075.
  • AFNOR Association Frangais de Normalisation
  • NF M 07-075 A 100 ml sample of the fuel or blend was pumped under controlled conditions into a measuring cylinder, as laid down in NF M 07-075, and the volume of foam produced was measured. The foam was then allowed to collapse and its dissipation time recorded. The results are shown in Table 1.
  • Table 1 Table 1
  • the Fischer-Tropsch derived fuel Fl clearly outperforms all the other commercially available petroleum derived diesel fuels in the context of antifoaming properties, both in terms of initial foam volumes and more particularly foam dissipation rates. Moreover Example 1 showed that the incorporation of as little as 30 % v/v of Fl into a petroleum derived diesel base fuel can lead to a significant improvement in the antifoaming performance of the blend compared to that of the base fuel alone.
  • a Fischer-Tropsch derived fuel component may be used at least partly to replace a conventional antifoaming additive in a diesel fuel composition, potentially making possible compositions which are completely free of antifoaming agents and yet still have acceptable overall antifoaming performance.
  • Example 3 The potential effect of silicone based antifoaming agents in diesel fuel compositions was observed on a diesel engine.
  • the fuel injectors of a VolvoTM D16A diesel engine were examined under a scanning electron microscope (SEM) following a period of normal use running on standard commercially available (UK) diesel fuels. Such fuels are highly likely to contain silicone based antifoaming additives .
  • Silicon deposits were detected in the small holes of the fuel injectors, as confirmed both by SEM photographs and also by X-ray analysis of the injector surfaces performed at the same time.
  • the basic constitution of the injector metal in regions unaffected by fuel contact, showed a silicon content of 0.34 % w/w.
  • the silicon content was 8.16 % w/w, indicating significant deposits of the element which at these levels are postulated to derive from fuel additives passing through the injectors as well as simple environmental pollution (dust, sand and the like) . It is possible that such deposits could contribute, certainly over an extended period of use, to a reduction in fuel atomisation and/or combustion efficiency.
  • Examples 1 and 2 demonstrate that the present invention may be used to provide such fuels, by using a Fischer- Tropsch derived fuel at least partially to replace conventional silicon containing additives.
  • Example 4 The Fischer-Tropsch derived gas oil Fl was blended in various proportions with the petroleum derived diesel base fuel F2, and the dehazing performance assessed for the blends as well as for the neat fuels Fl and F2.
  • the dehazing test procedure used was based on the ASTM procedure D1094 ("Water reaction of aviation fuels") , but with certain modifications for use with diesel engine fuels.
  • An 80 ml sample of fuel was mixed with 20 ml of an aqueous buffer solution in a measuring cylinder, shaken vigorously and allowed to stand under controlled conditions. The water separated out at the bottom of the sample and the diesel, interface and aqueous layers were then visually rated by their appearance. Volume of loss from the aqueous layer was also visually assessed.
  • sample preparation was identical to that in the ASTM method, the settling time was increased to 4 hours and the rating procedure was modified to recognise six rather than four degrees of hazing (clouding) .
  • Example 6 The dehazing performance of Fl was compared, using the method of Examples 4 and 5, with those of the diesel base fuels F3 to F7 tested in Example 2. The results are shown in Table 5. Table 5
  • Fischer-Tropsch derived fuel Fl outperforms the other diesel fuels, in particular with respect to their 24 hour residual water contents.
  • the Fischer-Tropsch fuel Fl alone has excellent dehazing (water shedding) properties, even in the absence of dehazing additives, and is thus potentially useable as an additive free, or at least a dehazer free fuel, or as a low additive fuel.
  • Fischer-Tropsch derived fuels in particular gas oils, have also been found to have detergency properties, and to be of use in diesel fuel compositions for reducing combustion related deposits in engines into which the compositions are introduced and/or for removing previously incurred engine deposits. In other words, they have been shown to be of use in maintaining and even in improving engine cleanliness, by contributing to a reduction in, and/or a reversal of, fuel injector fouling.
  • a Fischer-Tropsch derived fuel, or a fuel composition containing it can additionally contain reduced if any levels of detergent additives, again raising the possibility of completely or substantially additive free fuel compositions based on the present invention.
  • compositions containing Fischer-Tropsch fuel components may also give the opportunity for the use of silicon free antifoaming additives, with the associated benefits of lower overall silicon levels and hence reduced engine fouling. Again there is potential for completely silicon free fuel compositions.

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Abstract

L'invention concerne l'utilisation d'un combustible dérivé de Fischer-Tropsch dans une composition de combustible, aux fins de réduction de la quantité d'additifs, notamment des additifs anti-mousse et/ou de débrumage, dans la composition. Le combustible de Fischer-Tropsch peut être utilisé pour réduire la quantité d'additifs renfermant du silicium dans la composition ou, d'une manière générale, pour réduire les taux de silicium et pour réduire ainsi les pertes de rendement de l'atomisation et/ou combustion du combustible dans un système consommant du combustible mis en oeuvre au moyen de la composition de combustible et/ou pour réduire l'accumulation de dépôts, notamment des dépôts de silicium, dans un tel système. Le combustible dérivé de Fischer-Tropsch est, de préférence, un gasoil et la composition de combustible est conçue, de manière appropriée, comme une composition de carburant diesel.
PCT/EP2004/052014 2003-09-03 2004-09-02 Compositions de combustible comprenant un combustible derive de fischer-tropsch WO2005021688A1 (fr)

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BRPI0414040-0A BRPI0414040A (pt) 2003-09-03 2004-09-02 uso de um combustìvel derivado de fischer-tropsch, e, composição de combustìvel
AU2004269169A AU2004269169B2 (en) 2003-09-03 2004-09-02 Fuel compositions comprising Fischer-Tropsch derived fuel
EP04766686A EP1664247A1 (fr) 2003-09-03 2004-09-02 Compositions de combustible comprenant un combustible derive de fischer-tropsch

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AU2004269169B2 (en) 2008-11-13
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JP5390747B2 (ja) 2014-01-15

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