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WO2003091364A2 - Compositions de carburant diesel - Google Patents

Compositions de carburant diesel Download PDF

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Publication number
WO2003091364A2
WO2003091364A2 PCT/EP2003/004359 EP0304359W WO03091364A2 WO 2003091364 A2 WO2003091364 A2 WO 2003091364A2 EP 0304359 W EP0304359 W EP 0304359W WO 03091364 A2 WO03091364 A2 WO 03091364A2
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WO
WIPO (PCT)
Prior art keywords
engine
fuel composition
fischer
fuel
diesel
Prior art date
Application number
PCT/EP2003/004359
Other languages
English (en)
Other versions
WO2003091364A3 (fr
Inventor
Richard Hugh Clark
Christopher Russell Millington
Rodney Glyn Williams
Steven Douthwaite Matchett
Original Assignee
Shell Internationale Research Maatschappij B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to AU2003229732A priority Critical patent/AU2003229732B2/en
Priority to DK03722551.3T priority patent/DK1497398T3/en
Priority to JP2003587903A priority patent/JP5179700B2/ja
Priority to EP03722551.3A priority patent/EP1497398B1/fr
Priority to US10/512,140 priority patent/US20050241216A1/en
Priority to BR0309479-0A priority patent/BR0309479A/pt
Priority to CN038115034A priority patent/CN1656199B/zh
Priority to CA2483200A priority patent/CA2483200C/fr
Publication of WO2003091364A2 publication Critical patent/WO2003091364A2/fr
Publication of WO2003091364A3 publication Critical patent/WO2003091364A3/fr
Priority to NO20045114A priority patent/NO20045114L/no

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal

Definitions

  • This invention relates to diesel fuel compositions, their preparation and their use in diesel engines, and to the use of certain types of fuel in diesel fuel compositions.
  • 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
  • Fischer-Tropsch derived gas oils are low in undesirable fuel components such as sulphur, nitrogen and aromatics and tend to lead to lower vehicle emissions. They are typically blended with other diesel base fuels, for instance petroleum derived gas oils, at concentrations of for instance from 10 to 30% w/w, to modify the base fuel properties.
  • Diesel engines running on conventional diesel fuels can suffer from the build up of combustion related deposits in their fuel injection systems, in particular in the injector nozzles. This injector fouling can impair engine performance.
  • a detergent-containing additive may be included in the fuel, or the proportion of heavier components in the fuel may be adjusted so as to lower its endpoint .
  • Fischer-Tropsch derived fuels can themselves contribute to a reduction in, and/or reversal of, injector fouling.
  • a fuel composition containing such components can therefore be used to help maintain and/or improve engine cleanliness.
  • a Fischer-Tropsch derived gas oil in a diesel fuel composition, for the purpose of reducing subsequent combustion related deposits in a diesel- engine into which the fuel composition is introduced.
  • the Fischer-Tropsch derived gas oil may instead or in addition be used for the purpose of removing previously incurred combustion related deposits (ie, to "clean up” the engine) .
  • “reducing” includes complete prevention and “removing” embraces both complete and partial removal.
  • "Use” of the Fischer-Tropsch derived gas oil in a fuel composition means incorporating the fuel into the composition, typically as a blend (ie, a physical mixture) with one or more other fuels, conveniently before the composition is introduced into the engine .
  • the Fischer-Tropsch derived gas oil should be 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.
  • a gas oil product may be obtained directly from this reaction, or indirectly for instance by fractionation of a Fischer-Tropsch synthesis product or from a hydrotreated Fischer-Tropsch synthesis product.
  • Hydrotreatment 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).
  • An example of a Fischer-Tropsch based process is the
  • SMDS Shell Middle Distillate Synthesis
  • This process 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 used in petroleum derived gas oil blends in commercially available automotive fuels.
  • Gas oils prepared by the SMDS process are commercially available for instance from the Royal Dutch/Shell Group of Companies. Further examples of 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.
  • the 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 gas oil 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. Further, the process as usually operated produces no or virtually no aromatic components..
  • the aromatics content of a Fischer-Tropsch gas oil as determined by ASTM D 4629, will typically be below 1% w/w, preferably below 0.5% w/w and more preferably below 0.1% w/w.
  • the Fischer-Tropsch derived gas oil used 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 from 2.0 to 4.5, preferably from 2.5 to 4.0, more preferably from 2.9 to 3.7, centistokes at 40 °C; and a sulphur content of 5 pp w (parts per million by weight) 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 level of combustion related deposits in a diesel engine may be measured in its fuel injection system, with reference to the degree of fouling of the injector nozzles.
  • 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 diesel engine, for instance based on the change in air flow rate through one or more of the nozzles as a result of using the fuel composition. Conveniently the results are averaged over all of the injector nozzles of the engine.
  • a suitable test protocol using an indirect injection diesel engine, is described below in connection with the experimental examples.
  • the CEC standard test method F-23-T-00 which again involves injector nozzle air flow measurements, may also be used to assess engine fouling.
  • the invention may be 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, or in an indirect injection diesel engine.
  • the fuel composition may be suitable for use in heavy and/or light duty diesel engines.
  • the amount of the Fischer-Tropsch derived gas oil used may be from 0.5 to 100% w/w of the overall diesel fuel composition, suitably from 1 to 60% w/w, preferably from 5 to 50% w/w,- more preferably from 10 to 30% w/w. It may be desirable for the composition to contain 8% w/w or greater, more preferably 10% w/w or greater, most preferably 20% w/w or greater, of the Fischer-Tropsch gas oil.
  • Other fuel components of the composition may be diesel fuels of conventional type, typically comprising liquid hydrocarbon middle distillate fuel oils, for instance petroleum derived gas oils. Such fuel components will typically have boiling points within the usual diesel range of 150 to 400 °C, depending on grade and use.
  • the diesel fuel composition may, in order to achieve a reduction and/or removal of engine deposits, consist essentially of the Fischer-Tropsch derived gas oil - in other words it may contain a major proportion (by which is meant preferably 99% w/w or more of the fuel composition, more preferably 99.5% w/w or more, most preferably 99.8% w/w or more, even up to 100% w/w) of the Fischer- Tropsch derived gas oil, optionally with a minor proportion of one or more diesel fuel additives such as are known in the art but with no other diesel fuels.
  • a major proportion by which is meant preferably 99% w/w or more of the fuel composition, more preferably 99.5% w/w or more, most preferably 99.8% w/w or more, even up to 100% w/w
  • one or more diesel fuel additives such as are known in the art but with no other diesel fuels.
  • the overall fuel composition preferably has a low or ultra low sulphur content, for instance at most 1000 ppmw (parts per million by weight) , preferably no more than 500 ppmw, most preferably no more than 100 or 50 or even 10 ppmw. It preferably has a cetane number (ASTM D613) from 40 to 85, more preferably from 45 to 75. Its " density will typically be from 0.75 to 0.9 g/cm 3 , preferably from 0.8 to
  • the Fischer-Tropsch derived gas oil may in particular be used to enhance the performance of a fuel or fuel blend which would otherwise cause relatively high levels of combustion related deposits, for instance a fuel having a relatively high endpoint and/or containing relatively high levels of aromatic components, and/or of a fuel or blend which causes, after three hours' engine running, a reduction in the achievable air flow rate through one or more of the engine nozzles of greater than 35 or 40 or 45% for instance measured using the test protocol described below.
  • the diesel fuel composition may or may not contain additives, it is preferred that it includes a detergent, since this may enhance the cleaning effect of the Fischer-Tropsch derived gas oil.
  • the first aspect of the present invention may therefore involve the use of both a Fischer-Tropsch derived gas oil and a detergent, in a diesel fuel composition, for the purpose of reducing subsequent combustion related deposits in a diesel engine into which the fuel composition is introduced and/or for the purpose of removing previously incurred combustion related deposits.
  • agent an agent (suitably a surfactant) which can act to remove, and/or to prevent the build up of, combustion related deposits within the engine, in particular in the fuel injection system such as in the injector nozzles.
  • agent suitably a surfactant
  • Such materials are sometimes referred to as dispersant additives.
  • the Fischer-Tropsch derived gas oil 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 the Fischer-Tropsch gas oil.
  • the reduction may be relative to the degree of engine fouling which results from the use (under the same or comparable conditions) of a fuel composition containing no, or less than 1% w/w, Fischer-Tropsch derived fuels and no, or less than 50 or even 20 ppmw of, detergent.
  • the Fischer-Tropsch derived gas oil is included at a concentration sufficient to remove, at least partially, combustion related deposits which have built up in the engine's fuel injection system, in particular in the injector nozzles, during a previous period of running using another diesel fuel (typically a fuel containing no, or less than 1% w/w, Fischer-Tropsch derived fuels and no, or less than 50 or even 20 ppmw of, detergent) , 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 or 30%.
  • 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 tha.t 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.
  • preferred 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.
  • this may mean that the additive is incorporated at levels higher than the standard recommended single treat rate, for example between 1.2 and 3 times, preferably between 1.'5 and 2.5 times, such as about twice the standard single treat rate.
  • Lower detergent levels for example, corresponding to between 0.5 and 1.2 times, preferably the same as, the standard single treat rate) may however be used to help reduce or prevent further engine fouling and/or power loss.
  • detergents suitable for use in accordance with the present invention include polyolefin substituted succinimides or succinamides of polyamines, for instance polyisobutylene succinimides or polyisobutylene amine succinamides, aliphatic amines, Mannich bases or 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-0557561 and WO-A-98/42808.
  • Particularly preferred are polyolefin substituted succinimides such as polyisobutylene succinimides .
  • Detergent-containing diesel fuel additives are known and commercially available, for instance from Infineum (eg, F7661 and F7685) and Octel (eg, OMA 4130D) .
  • the fuel composition may contain other components in addition to the Fischer-Tropsch derived fuel and if applicable the detergent. Typically such components will be incorporated in fuel additives, for instance in combination with a detergent.
  • lubricity enhancers such as EC 832 and PARADYNETM (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; dehazers, eg, alkoxylated phenol formaldehyde polymers such as those commercially available as NALCOTM EC5462A (formerly 7D07) (ex Nalco) , and TOLADTM 2683 (ex Petrolite) ; anti- foaming agents (eg, the polyether-modified polysiloxanes commercially available as TEGOPRENTM 5851 and Q 25907 (ex Dow Corning), SAGTM TP-325 (ex OSi) and RHODORSILTM (ex Rhone Poulenc) ) ; ignition improvers (cetane improvers) (eg, 2- ethylhexyl nitrate
  • RC 4801 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, eg, the pentaerythritol diester of polyisobutylene-substituted succinic acid) ; corrosion inhibitors; reodorants; anti-wear additives; anti-oxidants (eg, phenolics such as 2, 6-di-tert-butylphenol, or phenylenediamines such as N, '-di-sec-butyl-p- phenylenediamine) ; and metal deactivators .
  • phenolics such as 2, 6-di-tert-butylphenol, or phenylenediamines such as N, '
  • the (active matter) concentration of each such additional component 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 lubricity enhancer be included in the fuel composition, especially when it has a low (eg, 500 ppmw or less) sulphur content.
  • the 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 dehazer in the fuel composition will preferably be in the- range from 1 to 20 ppmw, more preferably from 1 to 15 ppmw, still more preferably from 1 to 10 ppmw and advantageously from 1 to 5 ppmw.
  • 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.
  • a second aspect of the present invention provides a method of operating a diesel engine, and/or a vehicle which is driven by a diesel engine, which method involves introducing into a combustion chamber of the engine a diesel fuel composition incorporating a Fischer-Tropsch derived gas oil, and optionally also a detergent, for the purpose of reducing subsequent combustion related deposits in the engine and/or removing previously incurred combustion related deposits in the engine.
  • Preferred features of the second aspect of the invention for instance regarding the engine type, the nature of the diesel fuel composition, the nature and concentration of the Fischer-Tropsch derived gas oil and if present the detergent, as well as of other components of the fuel composition, and the ways in which engine fouling may be assessed, may all be as described above in connection with the first aspect.
  • a diesel fuel composition which includes a major proportion of a fuel or fuel blend for an internal combustion engine of the compression ignition type, wherein the fuel or fuel blend comprises at least 30% w/w of a Fischer-Tropsch derived gas oil, preferably at least 40% w/w, more preferably at least 50% w/w, most preferably at least 60% w/w.
  • the fuel or. fuel blend may comprise up to 100% w/w of the Fischer-Tropsch derived gas oil, preferably up to 95% w/w, more preferably up to 90% w/w, most preferably up to 80% w/w or 70% w/w.
  • This fuel composition preferably also contains a minor proportion of a detergent-containing additive.
  • minor proportion is meant preferably less than 1% w/w of the fuel composition, more preferably less than 0.5% w/w (5000 ppmw) and most preferably less than 0.2% w/w (2000 ppmw); references to “major proportion” may be construed accordingly.
  • a fuel or fuel blend may be additivated (additive-containing) or unadditivated (additive-free) . If additivated, it will contain a minor proportion of one or more additives, in particular a detergent containing additive.
  • Such additives may be added at various stages during the production of the fuel composition; those added at the refinery for example might be selected from anti- static agents, pipeline drag reducers, flow improvers (eg, ethylene/vinyl acetate copoly ers 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 eg, OCTELTM W 5000,- ex Octel
  • DODIFLOW eg, DODIFLOWTM v 3958, ex Hoechst
  • a method of operating a diesel engine, and/or a vehicle which is driven by a diesel engine which method involves introducing into a combustion chamber of the engine a diesel fuel composition according to the third aspect .
  • a fifth aspect of the invention provides a process for the preparation of a diesel fuel composition, such as a composition according to the third aspect, which process involves blending a Fischer-Tropsch derived gas oil with a non Fischer-Tropsch derived diesel fuel, optionally together with a detergent. Again the blending is ideally carried out with the aim of reducing subsequent combustion related deposits in a diesel engine into which the fuel composition is introduced and/or for the purpose of removing previously incurred combustion related deposits in the engine.
  • Fischer-Tropsch gas oils can at least partly remove existing engine deposits may be put to use in the "clean-up" of a fouled engine.
  • a Fischer-Tropsch derived gas oil and/or of a fuel composition containing a Fischer-Tropsch , derived gas oil, to clean (ie, to remove combustion related deposits from)- the fuel injection system of a diesel engine.
  • "Use” in this way means running the engine, or a part thereof such as its fuel injection system, on the gas oil or fuel composition for a period of time sufficient to effect at least partial removal of the combustion related deposits. It need not necessarily involve driving the vehicle.
  • a Fischer-Tropsch derived gas oil, or a fuel composition containing such a gas oil may therefore in accordance with the invention be packaged together with instructions for its use to clean a diesel engine in the manner described above.
  • the sixth aspect of the invention also encompasses a method of cleaning the fuel injection system of a diesel engine, by introducing into a combustion chamber of the engine a Fischer-Tropsch derived gas oil and/or a fuel composition containing a Fischer-Tropsch derived gas oil.
  • Preferred features of the third to the sixth aspects of the invention for instance regarding the nature and concentrations of the Fischer-Tropsch derived gas oil, any detergent present and any other fuel components and additives present, may be as described above in connection with the first and second aspects of the invention.
  • the present invention provides a method for assessing the performance of a candidate diesel fuel composition, comprising the steps of:
  • the "standard" fuel composition suitably contains no, or less than 50 or even 20 ppmw, active matter detergent.
  • It is suitably a low or ultra low sulphur diesel fuel, as described above, and is preferably unadditivated.
  • the level of combustion related deposits may be measured by assessing the degree of fouling of the injector nozzles in the fuel injection system of the engine, as described above.
  • the test cycles involve running- the engine on the relevant fuel composition for a given period of time and/or for a given number of miles.
  • the tests may be conducted on the engine alone or driving a vehicle - in the latter case they may be conducted under simulated driving conditions (such as using a chassis dynamometer) or involve regular road driving (preferably under urban as opposed to motorway conditions) .
  • the engine running and/or driving conditions should be the same or comparable for both the first and the second test cycles.
  • the duration of the first test cycle should be sufficient to cause a significant, and at least detectable, build up of combustion related deposits ⁇ compared to that measured in step 1 of the test.
  • a typical first test cycle might last from 1 to 5 hours, preferably 2 hours or more, more preferably 3 hours or more.
  • An appropriate duration for the second test cycle is typically from 10 to 100%, preferably from 50 to 100%, most suitably 100%, of that of the first test cycle. It may in cases be 80% or -75% or even 50% or less of the duration of the first test cycle. For assessing reductions in (as opposed to removal of) combustion related deposits, it may be up to 120% or 150% or even 200% of the duration of the first test cycle.
  • the engine used for the test may for instance be an indirect injection diesel engine, such as a VolkswagenTM PassatTM engine, for instance the PassatTM AAZ 1.9 TD engine.
  • the . test may be conducted on only a part of the engine (eg, the fuel injection system) or on a simulated engine or engine part .
  • the assessment method of the invention is particularly applicable to a candidate diesel fuel composition which incorporates a Fischer-Tropsch derived gas oil, more particularly to one which also incorporates a detergent.
  • the method may therefore be used to identify and/or evaluate fuel compositions according to the third aspect of the invention.
  • the method may also be used to assess the performance of a diesel engine, and/or to assess the performance of a fuel injection system for use in a diesel engine, and/or to assess the performance of a vehicle ' driven by a diesel engine.
  • An eighth aspect of the present invention provides a diesel fuel composition which, when used as the candidate fuel composition in the assessment method of the seventh aspect, leads to removal of at least 5%, preferably at least 10% or 15% or 20% or 25% or 30%, of the combustion related deposits accumulated in the engine prior to step 5 of the test, when the duration of the second test cycle is the same as or less than, more preferably 80% or 75% or even 50% or less of, the duration of the first test cycle, and the duration of the first test cycle is preferably at least 2 hours, more preferably 3 hours or more.
  • Such a fuel composition ideally contains, in accordance with the present invention, a Fischer-Tropsch derived gas oil, preferably together with a detergent.
  • the two fuels used in the tests were a petroleum derived low sulphur diesel fuel FI and a Fischer-Tropsch (SMDS) derived gas oil F2, both alone and in blends containing varying proportions of the two. Their properties are shown in Table A.
  • the gas oil F2 had been obtained from a Fischer- Tropsch (SMDS) synthesis product via a two-stage hydroconversion process analogous to that described in EP-A-0583836.
  • SMDS Fischer- Tropsch
  • Additive A is a detergency additive available from Infineum which passes the Cummins L10 heavy duty detergency test and contains inter alia a detergent, a lubricity additive, an anti-foam agent and a corrosion inhibitor. It was added at a concentration of 842 ppmw (double its standard treat rate) ; this resulted in an active matter detergent concentration of greater than 100 ppmw in the additivated fuel/blend.
  • the engine used was a VolkswagenTM PassatTM AAZ 1.9 TD indirect injection diesel engine having the following specification:
  • Injector body 2FH KCA 275 77
  • Nozzle type DNO SD 308
  • Nozzle needle lift 0.81 mm (+/- 0.02)
  • Nozzle pre lift 0.010 mm (+/- 0.001)
  • Nozzle opening pressure (1) 150 bar (+8/-0)
  • Nozzle opening pressure (2) 235 bar (+/10/-0)
  • Nozzle nut torque 70 Nm
  • Injection pump . VE No. 0 460 494 314.
  • the injector blanking plugs used were also BoschTM, 133-9802. High pressure injection pipes were used between the injection pump and the injectors. Prior to the start of . each test, the four clean nozzles were air flowed at a needle lift of 0.05 mm, and at 0.1 to 0.8 mm in steps of 0.1 mm, and the results recorded. The fuel filter was also changed prior to each test, and the fuel supply bled and the systems returned with 9 litres of the test fuel or blend.
  • each test began with a 20 minute engine warm up cycle, using the same injectors as for the subsequent deposit accumulation stage. During the warm up the engine speed was 1500 r/min (+/- 25 r/min) and the applied torque 25 Nm (+/- 2.5 Nm) .
  • Oil temp (into cooler): 90°C (+/- 4°C)
  • Coolant temp (out of engine): 90°C (+/- 4°C)
  • Fuel pressure to injection pump 0.35 bar (gauge) (+/- 0.05 bar)
  • Nominal fuel flow 5.1 kg/h (85 g/min)
  • Nominal fuel supplied 35 litres.
  • the engine was allowed to stabilise for 5-7 minutes at these test conditions. A series of manual readings was taken, including a Bosch smoke measurement. After reaching test conditions but before starting the test, the engine was returned to idle and the blow by measured. Test conditions were then re-established.
  • the injectors were removed taking care not to disturb or contaminate the deposits on the nozzle faces. They were dismantled and the nozzles removed. The nozzle body and needle were dipped separately in clean n-heptane or another suitable solvent to remove ' excess fuel, taking care not to disturb the deposits, and then allowed to drain prior to drying in an oven at 50 °C- . for a minimum of 1 hour. The dried nozzles were allowed to cool to ambient temperature for a minimum of 1 hour. Their air flow was then measured at needle lifts of 0.05 mm, and at 0.1 to 0.8 mm in steps of 0.1 mm, and the results recorded.
  • fouling index For each nozzle, fouling numbers F n were calculated using the flow rates measured at needle lifts of 0.1, 0.2 and 0.3 mm, with the nozzles clean and fouled:
  • This example demonstrates a reduction in engine fouling due to the use of a Fischer-Tropsch gas oil in a petroleum derived diesel fuel composition.
  • Example 2 This example demonstrates that a Fischer-Tropsch derived fuel may be used to "clean up" fouled injectors, ie, to remove deposits which have built up through use of another fuel.
  • Example 2 This demonstrates the cumulative benefits of using a Fischer-Tropsch derived diesel fuel and a detergent containing additive.
  • Example 1 was repeated but with additive A (at twice its standard treat rate) added to each fuel or blend. The results are shown in Table 2.
  • a Fischer- Tropsch derived fuel may be combined with a detergent to provide yet further improvements in fouling performance in a diesel engine, either as or as part of a diesel fuel composition.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Testing Of Engines (AREA)
  • Combined Controls Of Internal Combustion Engines (AREA)

Abstract

L'invention concerne un gazole dérivé Fischer-Tropsch dans une composition de carburant diesel, éventuellement, avec un détergent, pour réduire et/ou nettoyer l'encrassement d'un moteur. L'invention concerne également l'utilisation d'un gazole dérivé Fischer-Tropsch, et/ou une composition de carburant le contenant, pour nettoyer un moteur diesel. L'invention traite aussi d'un procédé pour évaluer une composition de carburant diesel, y compris des niveaux d'encrassement du moteur. L'invention a aussi pour objet une composition de carburant diesel fondée sur un mélange de carburant ou sur un carburant qui comprend au moins 30% en poids d'un gazole dérivé Fischer-Tropsch.
PCT/EP2003/004359 2002-04-25 2003-04-24 Compositions de carburant diesel WO2003091364A2 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
AU2003229732A AU2003229732B2 (en) 2002-04-25 2003-04-24 Diesel fuel compositions
DK03722551.3T DK1497398T3 (en) 2002-04-25 2003-04-24 USING A FISCHER-TROPSCH GAS OIL FOR REDUCING OR REMOVING DEPOSITS IN A DIESEL ENGINE
JP2003587903A JP5179700B2 (ja) 2002-04-25 2003-04-24 ディーゼル燃料組成物
EP03722551.3A EP1497398B1 (fr) 2002-04-25 2003-04-24 Utilisation d'un gasoil de fischer-tropsch pour réduire ou enlever des dépots dans un moteur diesel
US10/512,140 US20050241216A1 (en) 2002-04-25 2003-04-24 Diesel fuel compositions
BR0309479-0A BR0309479A (pt) 2002-04-25 2003-04-24 Uso de gasóleo derivado de fischer-tropsch, método para operar um motor a diesel, e/ou um veìculo que é acionado por um motor a diesel, uso de uma composição contendo um gasóleo derivado de fischer-tropsch, método para avaliar o desempenho de composição de combustìvel diesel candidata, e, composição de combustìvel diesel
CN038115034A CN1656199B (zh) 2002-04-25 2003-04-24 柴油燃料组合物
CA2483200A CA2483200C (fr) 2002-04-25 2003-04-24 Compositions de carburant diesel
NO20045114A NO20045114L (no) 2002-04-25 2004-11-24 Dieseldrivstoffsammensetninger

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EP02252946 2002-04-25
EP02252946.5 2002-04-25

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WO2003091364A3 WO2003091364A3 (fr) 2004-04-01

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WO2012034140A1 (fr) * 2010-09-07 2012-03-15 Sasol Technology (Pty) Ltd Amélioration du rendement d'un moteur diesel
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EP1705234A1 (fr) * 2005-03-24 2006-09-27 Basf Aktiengesellschaft Utilisation d'additifs détergents afin d'empêcher ou de réduire la formation des dépôts dans les systèmes d'injection pour moteurs diesel à injection directe
WO2006100083A1 (fr) * 2005-03-24 2006-09-28 Basf Aktiengesellschaft Utilisation d'additifs detergents pour reduire la quantite de particules dans des emissions de gaz d'echappement de moteurs diesels a injection directe
US8623104B2 (en) 2006-03-31 2014-01-07 Jx Nippon Oil & Energy Corporation Gas oil composition production method
US8628592B2 (en) 2006-03-31 2014-01-14 Jx Nippon Oil & Energy Corporation Method for producing gas oil composition
US7914593B2 (en) 2006-03-31 2011-03-29 Nippon Oil Corporation Fuel composition
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US8231695B2 (en) 2006-08-09 2012-07-31 Afton Chemical Corporation Fuel compositions comprising hydrocarbon oil carriers and methods for using the same
US8778034B2 (en) 2006-09-14 2014-07-15 Afton Chemical Corporation Biodegradable fuel performance additives
US9562498B2 (en) 2006-09-14 2017-02-07 Afton Chemical Corporation Biodegradable fuel performance additives
WO2011140572A1 (fr) 2010-05-06 2011-11-10 Sasol Technology (Pty) Ltd Améliorations apportées aux injecteurs de moteur diesel vis-à-vis de l'encrassement, avec un mazout léger hautement paraffinique
US9080118B2 (en) 2010-05-06 2015-07-14 Sasol Technology (Pty) Ltd Diesel engine injector fouling improvements with a highly paraffinic distillate fuel
AU2011249852B2 (en) * 2010-05-06 2016-11-24 Sasol Technology (Pty) Ltd Diesel engine injector fouling improvements with a highly paraffinic distillate fuel
WO2012034140A1 (fr) * 2010-09-07 2012-03-15 Sasol Technology (Pty) Ltd Amélioration du rendement d'un moteur diesel
WO2020156941A1 (fr) * 2019-01-31 2020-08-06 Total Marketing Services Utilisation d'une composition de carburant à base d'hydrocarbures paraffiniques pour nettoyer les parties internes des moteurs diesels
FR3092334A1 (fr) * 2019-01-31 2020-08-07 Total Marketing Services Utilisation d’une composition de carburant à base d’hydrocarbures paraffiniques pour nettoyer les parties internes des moteurs diesels

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BR0309479A (pt) 2005-02-01
PL371868A1 (en) 2005-07-11
NO20045114L (no) 2004-11-24
ZA200408311B (en) 2006-07-26
CA2483200A1 (fr) 2003-11-06
CA2483200C (fr) 2011-07-26
EP1497398A2 (fr) 2005-01-19
JP5179700B2 (ja) 2013-04-10
US20050241216A1 (en) 2005-11-03
AR043292A1 (es) 2005-07-27
MY140444A (en) 2009-12-31
WO2003091364A3 (fr) 2004-04-01
JP2005523973A (ja) 2005-08-11
AU2003229732B2 (en) 2009-06-25
AU2003229732A1 (en) 2003-11-10
CN1656199A (zh) 2005-08-17
DK1497398T3 (en) 2018-08-27
EP1497398B1 (fr) 2018-05-23
CN1656199B (zh) 2010-11-03

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