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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine

Definitions

• the present invention relates to diesel fuel compositions, their preparation and their use in diesel engines, and to the use of additives in diesel fuel compositions.
• the problem may also be more marked when using fuels with a low volumetric energy content, for example low or ultra low sulphur fuels or fuels with a relatively low density (such as those containing Fischer-Tropsch methane condensation products).
• fuels with a low volumetric energy content for example low or ultra low sulphur fuels or fuels with a relatively low density (such as those containing Fischer-Tropsch methane condensation products).
• Such fuels are often used where lower vehicle emissions are a priority, or where there are constraints on the nature or level of undesirable fuel components.
• a detergent-containing fuel additive in a diesel fuel composition, for the purpose of reducing subsequent power loss in a diesel engine into which the fuel composition is introduced.
• a detergent-containing fuel additive in a diesel fuel composition, for the purpose of reversing a previously incurred power loss in a diesel engine into which the fuel composition is introduced.
• reducing includes complete prevention, and “reversing” embraces both complete and partial reversal.
• “Use” of the additive in a fuel composition means incorporating the additive into the fuel composition, conveniently before the composition is introduced into the engine.
• Power loss in the engine may be manifested by, for example, a reduction in tractive effort and/or acceleration rate in a vehicle being driven by the engine.
• reversal of a previously incurred power loss will mean an increase in engine power output, which may be manifested by an increase in vehicle tractive effort and/or a reduction in acceleration times.
• a reduction in subsequent power loss will inhibit the reduction in tractive effort and/or acceleration rate which would otherwise have been expected, for instance extrapolating from previous performance, in particular compared to that which would have occurred had the engine been run on an unadditivated fuel or a fuel containing less, or no, detergent.
• a detergent-containing additive may be incorporated into a fuel composition with the aim of achieving these indirect effects.
• the present invention is particularly applicable where the fuel composition is used or intended to be used in a direct injection diesel engine, for example of the rotary pump, electronic unit injector or common rail type. It may be of particular value for rotary pump engines, in which power loss can be especially marked, and in other diesel engines which rely on mechanical actuation of the fuel injectors and/or a low pressure pilot injection system.
• the diesel fuel composition may be of an otherwise conventional type, typically comprising liquid hydrocarbon middle distillate fuel oils. However it may in particular comprise a low or ultra low sulphur content fuel, for instance containing at most 500 ppmw (parts per million by weight) sulphur, preferably less than 300 ppmw, more preferably less than 250 ppmw, still more preferably no more than 100 ppmw, most preferably no more than 60 or 50 or even 10 ppmw.
• ppmw parts per million by weight
• reaction products of a Fischer-Tropsch methane condensation process such as the process known as Shell Middle Distillate Synthesis (SMDS)—such reaction products suitably have boiling points within the typical diesel fuel range (between about 150 and 370° C.), a density of between about 0.76 and 0.79 g/cm 3 at 15° C., a cetane number greater than 72.7 (typically between about 75 and 82), a sulphur content of less than 5 ppmw, a viscosity between about 2.9 and 3.7 centistokes (mm 2 /s) at 40° C. and an aromatics content of no greater than 1% w/w.
• SMDS Shell Middle Distillate Synthesis
• the diesel fuel composition may comprise a relatively low density fuel, such as a fuel having a density of less than 0.840 g/cm 3 , preferably less than 0.835 g/cm 3 , at 15° C.
• a relatively low density fuel such as a fuel having a density of less than 0.840 g/cm 3 , preferably less than 0.835 g/cm 3 , at 15° C.
• the detergent-containing additive may be used for the purpose of compensating for the fuel's inherently lower energy content.
• the additive may be used generally to increase the power provided by a fuel composition during subsequent use.
• the additive must contain a detergent, by which is meant 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.
• a detergent by which is meant 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.
• agents suitably a surfactant
• dispersant additives Such materials are sometimes referred to as dispersant additives.
• the detergent is preferably included in the fuel composition at a concentration sufficient to recover, at least partially, power lost in the engine during a period of running using another fuel (typically unadditivated, or containing only low levels of, if any, detergent).
• This is generally 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. It will depend on the nature of the detergent, but preferred values lie in the range 100 to 500 ppmw active matter detergent based on the overall additivated fuel composition, more preferably 150 to 300 ppmw. In the case of most commercially available detergent-containing diesel fuel additives, this will mean incorporating the additive 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 may be used to reduce, ideally to prevent, further power losses as opposed to reversing previously incurred losses.
• the quantity of detergent-containing additive used is sufficient to recover at least 25%, more preferably at least 50% or 75% or 90% or 95%, most preferably 100%, of power lost in the engine during a previous period of use with a different fuel composition, when the engine is subsequently run on the detergent-containing fuel composition for a comparable number of miles and under comparable driving conditions.
• the amount of detergent present is sufficient to provide the stated recovery of power (which may equate to a corresponding reduction in combustion related deposits) when the engine is subsequently run on the detergent-containing fuel composition for 75%, yet more preferably 50% or even 40% or 30%, of the number of miles covered on the previous fuel, again under comparable driving conditions.
• the previous fuel may for instance be an unadditivated diesel fuel composition, or one containing no, or no more than 50 or even 20 ppmw, active matter detergent.
• the detergent-containing additive may be used in a quantity sufficient to reduce by at least 25%, preferably at least 50%, more preferably at least 75%, most preferably at least 90%, such as by 100%, the amount of power loss incurred (which may equate to a corresponding increase in combustion related deposits) when running the engine on the fuel composition, as compared to that incurred when running the engine, under comparable driving conditions, on an unadditivated fuel composition or one containing no, or no more than 50 or 20 ppmw, active matter detergent.
• engine power may be assessed with reference to, for example, vehicle tractive effort and/or acceleration times.
• the degree of power recovery achievable by using, in accordance with the invention, a detergent-containing additive may conveniently be assessed using a method according to the seventh aspect of the invention, described below.
• Detergent-containing diesel fuel additives are known and commercially available, for instance from Infineum (eg, F7661 and F7685) and Octel (eg, OMA 4130D).
• Infineum eg, F7661 and F7685
• Octel eg, OMA 4130D
• Infineum eg, F7661 and F7685
• Octel eg, OMA 4130D
• additives have been added to diesel fuels at relatively low levels (their “standard” treat rates providing typically less than 100 ppmw active matter detergent in the overall additivated fuel composition) intended merely to reduce or slow the build up of engine deposits.
• the additives have not to our knowledge been used for the purpose of increasing engine power, and in particular not at levels high enough to reverse previously incurred power loss. That they are capable of achieving this is especially surprising.
• detergents suitable for use in fuel additives for the present purpose include polyolefin substituted succinimides or succinamides of polyamines, for instance polyisobutylene succinimides or polyisobutylene amine succinamides, aliphatic amines, Mannich bases or amines and polyolefin (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.
• the additive may contain other components in addition to the detergent.
• lubricity enhancers 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), or RHODORSILTM (ex Rhone Poulenc)); ignition improvers (cetane improvers) (eg, 2-ethylhexyl nitrate (EHN), cyclohexyl nitrate, di-tert-butyl peroxide and those disclosed in U.S.
• dehazers eg, alkoxylated phenol formaldehyde polymers such as those commercially available as NALCOTM
• 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 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,N′-di-sec-butyl-p-phenylenediamine); and metal deactivators.
• RC 4801 propane-1, 2-diol semi-ester
• the additive include a lubricity enhancer, especially when the fuel composition has a low (eg, 500 ppmw or less) sulphur content.
• the lubricity enhancer is conveniently present at a concentration between 50 and 1000 ppmw, preferably between 100 and 1000 ppmw.
• Suitable commercially available lubricity enhancers include EC 832 and PARADYNETM 655 (ex Infineum), HITECTM E580 (ex Ethyl Corporation), VEKTRONTM 6010 (ex Infineum) and amide-based additives such as those available from the Lubrizol Chemical Company, for instance LZ 539 C.
• Other lubricity enhancers are described in-the patent literature, in particular in connection with their use in low sulphur content diesel fuels, for example in:
• WO-A-94/17160 (Exxon)—certain esters of a carboxylic acid and an alcohol wherein the acid has from 2 to 50 carbon atoms and the alcohol has 1 or more carbon atoms, particularly glycerol monooleate and di-isodecyl adipate, as fuel additives for wear reduction in a diesel engine injection system;
• WO-A-98/01516 certain alkyl aromatic compounds having at least one carboxyl group attached to their aromatic nuclei, to confer anti-wear lubricity effects particularly in low sulphur diesel fuels.
• the additive contain an anti-foaming agent, more preferably in combination with an anti-rust agent and/or a corrosion inhibitor and/or a lubricity additive.
• the (active matter) concentration of each such additional component in the additivated 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.
• 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) concentrations of other components will each preferably be in the range from 0 to 20 ppmw, more preferably from 0 to 10 ppmw.
• the (active matter) concentration of any ignition improver present will preferably be between 0 and 600 ppmw and more preferably between 0 and 500 ppmw, conveniently between 300 and 500 ppmw.
• the additive will typically contain the detergent, optionally together with other components as described above, and a diesel fuel-compatible diluent, which may be a carrier oil (eg, a mineral oil), a polyether, which may be capped or uncapped, a non-polar solvent such as toluene, xylene, white spirits and those sold by member companies of the Royal Dutch/Shell Group under the trade mark “SHELLSOL”, and/or a polar solvent such as an ester and, in particular, an alcohol, eg, hexanol, 2-ethylhexanol, decanol, isotridecanol and alcohol mixtures such as those sold by member companies of the Royal Dutch/Shell Group under the trade mark “LINEVOL”, especially LINEVOLTM 79 alcohol which is a mixture of C 7-9 primary alcohols, or the C 12-14 alcohol mixture commercially available from Sidobre Sinnova, France under the trade mark “SIPOL”.
• a diesel fuel-compatible diluent which may
• the additive may be suitable for use in heavy and/or light duty diesel engines.
• a detergent-containing additive in accordance with the present invention, may give rise to additional benefits associated with engine emissions, in particular lower smoke levels and lower particulate mass.
• a detergent-containing additive may be used both to reduce smoke and/or particulate emissions, whilst at the same time (despite the fact that the additive will generally lower the density of the fuel composition) increasing or at least maintaining power levels.
• This dual action is a further feature of the present invention. It may be put to particular use in higher density fuel compositions (which have previously been associated with higher smoke and particulate emissions), to improve their environmental performance but without a compromise in power output.
• the present invention thus also provides, according to a third aspect, the use of a detergent-containing fuel additive in a diesel fuel composition, for the purpose of reducing smoke and/or particulate emissions in a diesel engine into which the fuel composition is introduced. More preferably, the use has the purpose of achieving the concurrent effects of (a) a reduction and/or reversal of power loss (as defined above), and/or an increase in power output, and (b) reduced smoke and/or particulate emissions. Reduced emissions may conveniently be identified with reference to the unadditivated diesel fuel composition.
• the unadditivated fuel composition may be of a relatively high density, for example greater than 0.845 g/cm 3 at 15° C.
• a fourth 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 the combustion chambers of the engine a diesel fuel composition incorporating a detergent-containing fuel additive, for one or more of the following purposes:
• the engine type, the nature of the diesel fuel composition, the nature and concentration of the detergent in the fuel composition as well as of other components in the additive, and the ways in which power and emission levels may be assessed, may all be as described above in connection with the first aspect of the present invention.
• a diesel fuel composition which includes a major proportion of a fuel for an internal combustion engine of the compression ignition type, and a minor proportion of a detergent-containing additive, wherein the active matter detergent concentration in the composition is between 100 and 500 ppmw.
• 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.
• Preferred detergent concentrations and types are as described in connection with the first aspect of the present invention, as are other features of the fuel and the detergent-containing additive.
• the diesel fuel composition preferably contains between 150 and 300 ppmw active matter detergent.
• the fuel may be any fuel suitable for use in a diesel engine. It will typically have an initial distillation temperature of about 160° C. and a final distillation temperature of between 290 and 360° C., depending on its grade and use. Vegetable oils may also be used as diesel fuels per se or in blends with hydrocarbon fuels.
• the fuel may in particular be a low or ultra low sulphur content fuel, or contain a proportion (for instance, 10% v/v or more) of, reaction products of a Fischer-Tropsch methane condensation process such as the process known as Shell Middle Distillate Synthesis (SMDS), as described in connection with the first aspect of the present invention.
• SMDS Shell Middle Distillate Synthesis
• the fuel may itself be additivated (additive-containing) or unadditivated (additive-free). If additivated, it will contain minor amounts of one or more additives selected for example 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).
• additives selected for example 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
• a method of operating a diesel engine, and/or a vehicle which is driven by a diesel engine which method involves introducing into the combustion chambers of the engine a diesel fuel composition according to the fifth aspect.
• a seventh aspect of the present invention provides a process for the preparation of a diesel fuel composition according to the fifth aspect, which process involves admixing a major proportion of a diesel engine fuel, as described above, with a minor proportion of a detergent-containing additive, also as described above. Said minor proportion is sufficient to give an active matter detergent concentration in the fuel composition of between 100 and 500 ppmw.
• the present invention provides a method for assessing the performance of a candidate diesel fuel composition, comprising the steps of:
• the test should proceed only if significant power loss is observed during the first driving cycle.
• significant power loss is meant at least a 2% reduction in power, preferably at least 4%, more preferably at least 5% or 7%.
• power losses may be appropriate to repeat the test using a different fuel injector system in the engine, and/or a different vehicle, since power losses have in cases been found to be sensitive to such variables. Higher power losses, for instance 10% or more, may be observed when testing indirect injection diesel engines.
• the “standard” fuel composition is suitably a low or ultra low sulphur diesel fuel, as described above, and is preferably unadditivated.
• the driving cycles involve accumulation of engine miles, which may be under simulated conditions (such as using a chassis dynamometer) but preferably involve regular road driving, more preferably a mixture of driving conditions including both urban and motorway mileage.
• the first number of miles should be sufficient to cause a significant loss in power compared to that measured in step 1 of the test.
• a typical first driving cycle might involve between 1000 and 4000 miles (1600 and 6400 km), preferably 1500 miles (2400 km) or more, more preferably 2000 (3200 km) or 3000 miles (4800 km) or more.
• An appropriate number of miles for the second driving cycle is typically between 10 and 100%, preferably between 10 and 80%, more preferably between 10 and 60%, such as around 50%, of the first number of miles.
• the engine used for the test is preferably of the rotary pump or common rail type, more preferably rotary pump. It is suitably a light duty diesel engine.
• a Ford EnduraTM engine as used in the Ford FocusTM vehicle, such as the 1753 cc Ford EnduraTM Di C9DC engine which has a BoschTM VP-30 rotary distributor type fuel pump. Engines having mechanically actuated injectors are preferred.
• Engine power may suitably be measured in the ways mentioned above in connection with the first aspect of the present invention. In particular, it may be assessed by measuring vehicle tractive effort (VTE) and/or acceleration times for the engine.
• VTE vehicle tractive effort
• a reduction in power corresponds to a reduction in VTE and/or an increase in acceleration times
• power recovery corresponds to a recovery of (ie, increase in) VTE and acceleration rate, and therefore a reduction in acceleration times.
• Such power measurements may be conducted using the standard fuel composition; conventional measurement procedures may be used.
• acceleration times are measured under two or more, preferably three, different driving conditions (for instance, in 3rd, 4th and 5th gears) and the results averaged.
• VTE measurements are preferably averaged over two or more, preferably three, different driving speeds, for instance at 50, 85 and 100 kilometres per hour (kph) in 4th gear. Acceleration time and VTE results may be combined and averaged to give an overall power rating.
• Engine emissions may also be measured and compared before and after the first and second driving cycles. Again, conventional measurement procedures may be used, and run on the standard fuel composition. Smoke measurements are preferably averaged over two or more, preferably three, engine speeds, for example 70, 85 and 100 kph in 4th gear.
• the assessment method of the present invention is particularly applicable to a candidate fuel composition which incorporates a detergent-containing additive, more particularly to an additivated low or ultra low sulphur fuel and/or to an additivated fuel containing a proportion (for instance, 10% v/v or more) of, reaction products of a Fischer-Tropsch methane condensation process such as the process known as Shell Middle Distillate Synthesis (SMDS).
• SMDS Shell Middle Distillate Synthesis
• the method may also be used to assess the performance of a diesel engine, in particular a direct injection diesel engine, more particularly of the rotary pump type, 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.
• a diesel engine in particular a direct injection diesel engine, more particularly of the rotary pump type, 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 ninth 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 of the present invention, causes at least a 25% recovery of the power lost during the first driving cycle, preferably a 50%, a 75%, a 90% or a 100% recovery, when the second number of miles is the same as or more preferably 75% or even 50% of the first number of miles, and the first number of miles is preferably at least 1500 (2400 km), more preferably 3000 (4800 km) or more.
• Such a fuel composition ideally contains, in accordance with the present invention, a detergent-containing additive.
• references to “dirty-up” vehicle tests are generally to the running of a vehicle using a typical unadditivated diesel fuel, expected to result in power loss. Such tests, unless otherwise stated, used mixed driving cycles, ie, road driving including both urban and motorway mileage, typically for 3000 miles (4800 km). References to “clean-up” vehicle tests are to the running of a vehicle, again typically using a mixed driving cycle, on a fuel in accordance with the present invention, expected to reduce and/or reverse power loss.
• VTE vehicle tractive effort
• gated acceleration times were assessed on the basis of (i) vehicle tractive effort (VTE), measured in 4th gear at 50, 85 and 100 kph and (ii) gated acceleration times in 3rd (30-80 kph), 4th (40-100 kph) and 5th (60-120 kph) gears. Where indicated, results were averaged over the three driving speeds.
• the type of engine used in all of the tests was a 1753 cc Ford EnduraTM Di C9DC engine, which is a direct injection engine having a BoschTM VP-30 rotary distributor type fuel pump chain driven from the crankshaft. It is a four cylinder (in-line configuration) engine which features turbo-charging and after-cooling.
• the fuel injectors are of the slim five-hole type (pencil fuel injectors) located centrally over the piston recess. The injectors are mechanically actuated and operate at a fuel injection pressure of approximately 1100 bar (110 MPa). Fuel injection is electronically controlled.
• the exhaust gas recirculation (EGR) system of the EnduraTM engine recycles measured quantities of exhaust gas back through the engine where they mix with the incoming air charge, and incorporates an EGR cooler to cool the recirculated exhaust gas therefore lowering the combustion temperature and reducing the formation of nitrogen oxides.
• EGR exhaust gas recirculation
• the vehicle is either mounted on a chassis dynamometer or driven under test track conditions.
• the vehicle and/or chassis dynamometer are initially warmed up over a suitable period of time in order to stabilise oil and coolant temperatures.
• the engine is flushed with an ULSD base fuel to ensure there is no cross-contamination between fuels. Also at each change, the vehicle is pre-conditioned with five consecutive accelerations (4th gear full throttle from 30 mph (48 kph) to 60 mph (96 kph)). Eight further consecutive accelerations are then carried out to allow the engine management system to adapt to the fuel and test conditions.
• Vehicle acceleration times are measured between two chosen speeds. Data logging commences 2 kph below the chosen start point and finishes 2 kph above the end point. The engine is driven with a clean and progressive full throttle movement, keeping below 4500 rpm at all times, and full throttle is held until the end point has been exceeded. The vehicle is allowed to decelerate at the same rate that it accelerated, which is achieved using the foot brake, although normal unaided deceleration is allowed for the final 200 rpm. Three acceleration measurements are carried out for each test condition, and the results averaged.
• VTE Vehicle tractive effort
• the vehicle used was a Ford FocusTM equipped with an EnduraTM engine, as described above. Its fuel injectors were new at the start of the experiment and were subjected to 3000 miles of “dirty-up” on an ULSD base fuel during step 1.
• the base fuel which contained no additives, had the following specification (Table A): TABLE A Property Test method Density @ 15° C. (g/cm 3 ) IP 365/ASTM D4052 0.8301 Distillation: IP 123/ASTM D86 IBP (° C.) 169.5 10% 204.0 20% 225.0 30% 244.0 40% 260.0 50% 273.5 60% 285.0 70% 297.0 80% 310.0 90% 328.0 95% 345.0 FBP 356.0 Cetane number ASTM D613 54.5 Sulphur (ppmw) ASTM D2622 54.5
• Step 2 of the experiment involved a 1500 mile “clean-up”, for which a detergent-containing additive A was added to the base fuel in accordance with the present invention.
• Additive A is a top-tier detergency additive available from Infineum (F7661) containing a polyisobutylene substituted succinimide detergent, an anti-foam agent, an anti-rust agent, a dehazer, EHN as an ignition improver, and a lubricity enhancer. It was added at a concentration of 1870 ppmw (double its standard treat rate); this results in an active matter detergent concentration of 162 ppmw in the additivated fuel.
• Step 3 3000 mile (4800 km) dirty-up on the base fuel.
• Step 4 1500 mile (2400 km) clean-up (base fuel+additive A (935 ppmw)).
• Step 5 Further 1500 mile (2400 km) dirty-up (base fuel).
• step 5 verifies that this effect is due to the presence of the additive rather than a peak in power loss having been attained—it can be seen that the further dirty-up results in yet further power losses.
• additive A in the fuel can be seen to be of use in both maintaining engine power and, at higher concentrations, reversing previously incurred power losses.
• a second hand EnduraTM engined Ford FocusTM (different to that used in Example 1), which had run around 11,000 miles (17600 km), was fuelled with an unadditivated ULSD base fuel having the following properties (Table B): TABLE B Property Test method Density @ 15° C. (g/cm 3 ) IP 365/ASTM D4052 0.834 Distillation: IP 123/ASTM D86 IBP (° C.) 166.0 10% 209.5 20% 231.5 30% 253.5 40% 269.5 50% 281.5 60% 292.0 70% 302.0 80% 314.5 90% 331.5 95% 347.0 FBP 355.5 Cetane number ASTM D613 54.6 Sulphur (ppmw) ASTM D2622 45
• Step 1 Further 1500 mile (2400 km) dirty-up (base fuel).
• Step 2 Fit and condition a new injector set.
• Step 3 Replace old injector set; 1500 mile (2400 km) clean-up on (base fuel+1870 ppmw of additive A).
• Step 4 1500 mile (2400 km) dirty-up (base fuel).
• Step 5 Further 1500 mile (2400 km) dirty-up (base fuel).
• Step 6 1500 (2400 km) mile clean-up (base fuel+1920 ppmw of additive A).
• Steps 4 to 6 were included to demonstrate the repeatability of steps 1 to 3.
• Additive B is an additive available from Infineum (F7685) which passes the Cummins L10 heavy duty detergency test and contains inter alia a detergent, an anti-foam agent and a corrosion inhibitor.
• Additive C is an additive available from Octel (OMA 4130D) of use for low sulphur fuels and contains a detergent, an anti-foam agent, an anti-rust agent and a dehazer.
• additive B gave approximately 80% power recovery
• additive C approximately 50%.
• VTE results are shown in Table 7.
• NTP corrected VTE (kW) at - Test point 50 kph 85 kph 100 kph Start of test 15.19 42.10 45.85 Middle of test 15.66 43.69 48.12 (750 miles (1200 km)) End of test 16.33 44.62 48.33 (1500 miles (2400 km))
• the “base” fuel composition for these experiments had the following properties (Table C): TABLE C Property Test method Density @ 15° C. (g/cm 3 ) IP 365/ 0.8377 ASTM D4052 C (% m/m) 86.3 H (% m/m) 13.7 N (% m/m) ⁇ 0.1 Calorific value (gross heat 10945 of combustion) (cal (IT)/g) Calorific value (net heat of 10251 combustion) (cal (IT)/g)
• a blend of this base fuel was also prepared with 15% v/v of a mixture of Shell Middle Distillate Synthesis (Fischer-Tropsch) reaction products having the following properties (Table D): TABLE D Property Test method Density @ 15° C. (g/cm 3 ) IP 365/ 0.776 ASTM D4052 Distillation: IP 123/ASTM D86 IBP (° C.) 183.5 10% 214.1 20% 228.4 30% 243.6 40% 259.5 50% 275.4 60% 291.2 70% 306.9 80% 322.9 90% 340 95% 351.3 FBP 359 Cetane number ASTM D613 81 Sulphur (ppmw) IP 373 0
• Step 1 Using the base fuel alone, record start-of-test (SOT) acceleration, VTE and smoke measurements, followed by particulate emission levels.
• SOT start-of-test
• Step 2 Using the blended fuel, together with 1042 ppmw of additive B, record start-of-test acceleration, VTE and smoke measurements, followed by particulate emission levels.
• Step 3 Using the blended fuel together with 1870 ppmw of additive A, record start-of-test acceleration, VTE and smoke measurements, followed by particulate emission levels.
• Step 4 Remove the fuel lines and change to the ULSD base fuel of Example 1, but containing 1042 ppmw of additive B.
• Step 5 “Clean-up” cycle—1500 miles (2400 km) of mixed driving using the fuel referred to in step 4.
• Step 6 Refit auxiliary fuel lines and record acceleration and VTE measurements using the ULSD base fuel alone.
• Step 7 Using the blended fuel together with 1042 ppmw of additive B, record end-of-test (ie, post clean-up, EOT) acceleration, VTE and smoke measurements, followed by particulate emission levels.
• EOT post clean-up
• Step 8 Using the blended fuel together with 1870 ppmw of additive A, record end-of-test acceleration, VTE and smoke measurements, followed by particulate emission levels.
• Particulate emissions were tested using a chassis dynamometer. Testing used the standard ECE 1505(m) 11s 221 cycle, with sampling including cranking and start up emissions. A 40 second idle (Euro 2) was run prior to sampling. The cycle comprises four ECE cycles and one EUDC cycle with the results presented in a three phase format which includes the combined the first and second ECE cycles (cold engine), the combined third and fourth ECE cycles (hot engine) and the EUDC cycle. Particulate measurements were made for each phase. Results quoted below are for the full cycle.
• VTE results are shown in Table 10.
• Table 10 Average NTP corrected VTE (kW) - Fuel composition Start of test End of test ULSD base fuel 33.49 36.99
• the lower density blended fuel generally gave significantly lower (on average 20% across the three test phases) smoke levels, compared to the Example 6 base fuel.

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