EP3519538A1 - Method of improving the oxidative stability of a lubricating composition - Google Patents

Method of improving the oxidative stability of a lubricating composition

Info

Publication number
EP3519538A1
EP3519538A1 EP17777580.6A EP17777580A EP3519538A1 EP 3519538 A1 EP3519538 A1 EP 3519538A1 EP 17777580 A EP17777580 A EP 17777580A EP 3519538 A1 EP3519538 A1 EP 3519538A1
Authority
EP
European Patent Office
Prior art keywords
range
base fuel
engine
olefins
boiling point
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP17777580.6A
Other languages
German (de)
French (fr)
Inventor
Roger Francis Cracknell
Allen Ambwere ARADI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP3519538A1 publication Critical patent/EP3519538A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • 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
    • 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
    • C10L10/08—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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/08—Inhibitors
    • C10L2230/081—Anti-oxidants
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/78—Fuel contamination
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

Definitions

  • This invention relates to a method of improving the oxidative stability of a lubricating composition which is used for lubricating a spark ignition combustion engine, the spark ignition combustion engine being housed in the powertrain of a hybrid electric vehicle.
  • Hybrid Electric Vehicles make use of both electrical energy stored in re-chargeable batteries and the mechanical energy converted from fuel, usually hydrocarbon based, by a conventional internal combustion engine (ICE) .
  • the batteries are charged during driving operation by the ICE and also by recovering kinetic energy during deceleration and braking. This process is offered by a number of vehicle original equipment
  • HEVs typically provide a normal driving experience, with the principle advantage of improved fuel consumption in comparison to conventional ICE only vehicles.
  • Plug-in Hybrid Electric Vehicles (PHEVs) have similar
  • HEVs HEVs
  • the battery can also be connected to the mains electrical system for recharging when the vehicle is parked.
  • PHEVs typically have larger battery packs than HEVs which affords some all-electric range capability.
  • Dynamic driving will use electric power and ICE, though the area of operation using an internal combustion engine (ICE) for propulsion may be restricted to cruising and
  • thermodynamic efficiency of an internal combustion engine cannot be fully optimised across a wide range of
  • the ICE has a relatively narrow dynamic range.
  • OEMs vehicle manufacturers
  • Electrical machines can be designed to have a very wide dynamic range, e.g., are able to deliver maximum torgue at zero speed. This control flexibility is well
  • electrical machines can be controlled using sophisticated electronics to give very smooth torque delivery, tailored to the demand requirements. However it may be possible to provide different torque delivery profiles that are more appealing to drivers. Hence this is likely to be an area of interest going forward for automotive designers.
  • electrical drive systems tend to be limited by the heat rejection capacity of the power electronics and the cooling system for the electric motor itself. Additional considerations for high torque motors at high speeds are associated with the mass of the rotating components, where very high centrifugal forces can be produced at high speeds.
  • the lubricating composition tends to be exposed to more extreme conditions and greater oxidative stresses in an HEV/PHEV environment.
  • crank-case lubricant does not fully warm up in an HEV or PHEV which therefore presents severe conditions for oxidation of the lubricant.
  • a decrease in oxidative stability of the lubricant can lead to increased engine deposits which in turn can lead to undesirable effects such as reduced fuel economy, and the like.
  • the oxidative stability of the fuel composition also needs to be considered in the case of a HEV/PHEV.
  • WO2004/113476 discloses gasoline compositions meeting certain parameters whose use as a fuel in a spark ignition engine results in improved stability of engine crank case lubricant. However, there is no mention in this document of the use of such a fuel in an HEV or PHEV vehicle, or of the specific benefits of using such a fuel for hybrid vehicles.
  • a method of improving the oxidative stability of a lubricating composition which is used to lubricate a spark ignition internal combustion engine, the spark- ignition engine being comprised within the powertrain of a hybrid electric vehicle comprising the step of introducing into the combustion chamber of the spark-ignition engine a gasoline composition wherein the gasoline composition comprises a hydrocarbon base fuel containing 10 to 20% v olefins, not greater than 5% v olefins of at least 10 carbon atoms, and not greater than 5% v aromatics of at least 10 carbon atoms, based on the base fuel, initial boiling point in the range 30 to 40°C, T10 in the range 45 to 57°C, T50 in the range 82 to 104°C, T90 in the range 140 to 150°C and final boiling point not greater than 220°C.
  • HEV or a PHEV is improved.
  • crank-case lubricant in spark ignition internal combustion engines fuelled by gasoline compositions of the present invention which are comprised in the powertrain of a hybrid electric vehicle.
  • Frequent engine stops and starts in a HEV and a PHEV where the ICE is only in use for some of the time and for short periods . means that the crank-case lubricant does not fully warm up and presents severe conditions for oxidation of the lubricant.
  • the effects of these start/stop driving cycles are more severe in HEV/PHEV vehicles than they are in conventional ICE vehicles.
  • High front-end volatility (low T ⁇ o, ) and specified olefin content are believed to result in reduction in blowby of harmful combustion gases into the engine crank-case.
  • not greater than 5% v olefins of at least 10 carbon atoms and “not greater than 5% v aromatics of at least 10 carbon atoms” is meant that the hydrocarbon base fuel contains amounts of olefins having 10 carbon atoms or more and amounts of aromatics having 10 carbon atoms or more, respectively in the range 0 to 5% v, based on the base fuel.
  • Gasolines contain mixtures of hydrocarbons, the optimal boiling ranges and distillation curves thereof varying according to climate and season of the year.
  • the hydrocarbons in a gasoline as defined above may
  • Oxygenates may be incorporated in gasolines, and these include alcohols (such as methanol, ethanol, isopropanol, tert.butanol and isobutanol) and ethers, preferably ethers containing 5 or more carbon atoms per molecule, e.g. methyl tert. butyl ether (MTBE) or ethyl tert. butyl ether (ETBE) .
  • alcohols such as methanol, ethanol, isopropanol, tert.butanol and isobutanol
  • ethers preferably ethers containing 5 or more carbon atoms per molecule, e.g. methyl tert. butyl ether (MTBE) or ethyl tert. butyl ether (ETBE) .
  • MTBE methyl tert. butyl ether
  • ETBE ethyl tert. butyl ether
  • the ethers containing 5 or more carbon atoms per molecule may be used in amounts up to 15% v/v, but if methanol is used, it can only be in an amount up to 3% v/v, and stabilisers will be reguired. Stabilisers may also be needed for ethanol, which may be used up to 5% to 10% v/v. Isopropanol may be used up to 10% v/v, tert-butanol up to 7% v/v and isobutanol up to 10% v/v.
  • preferred gasoline compositions of the present invention contain 0 to 10% by volume of at least one oxygenate selected from methanol, ethanol, isopropanol and isobutanol.
  • gasoline compositions of the present invention will further enhance stability of engine lubricant, particularly under cooler engine operating conditions. Accordingly, it is preferred that gasoline compositions of the present invention contain up to 10% by volume of ethanol, preferably 2 to 10% v, more
  • Gasoline compositions according to the present invention are advantageously lead-free (unleaded) , and this may be reguired by law. Where permitted, lead-free anti-knock compounds and/or valve-seat recession protectant compounds (e.g. known potassium salts, sodium salts or phosphorus compounds) may be present.
  • lead-free anti-knock compounds and/or valve-seat recession protectant compounds e.g. known potassium salts, sodium salts or phosphorus compounds
  • Modern gasolines are inherently low-sulphur fuels, e.g. containing less than 200 ppmw sulphur, preferably not greater than 50 ppmw sulphur.
  • Hydrocarbon base fuels as define above may be any suitable Hydrocarbon base fuels as define above.
  • hydrocarbon e.g. refinery
  • Olefin content may be boosted by inclusion of olefin-rich refinery streams and/or by addition of synthetic components such as diisobutylene, in any relative proportions.
  • Diisobutylene also known as 2 , 4 , 4-trimethyl-l- pentene ( Sigma-Aldrich Fine Chemicals)
  • 2 , 4 4-trimethyl-l- pentene
  • yield is typically 90%, of a mixture of 80% dimers and 20% trimers.
  • Gasoline compositions as defined above may variously include one or more additives such as anti-oxidants , corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers and synthetic or mineral oil carrier fluids.
  • additives such as anti-oxidants , corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers and synthetic or mineral oil carrier fluids.
  • Additive components can be added separately to the gasoline or can be blended with one or more diluents, forming an additive concentrate, and together added to base fuel.
  • a preferred gasoline composition for use in the method of the present invention comprises one or more antioxidants in order to improve the oxidative stability of the gasoline composition.
  • Any antioxidant additive which is suitable for use in a gasoline composition can be used herein.
  • a preferred anti-oxidant for use herein is a hindered phenol, for example BHT (butylated hydroxy toluene) . It is preferred that the gasoline composition comprises from 10 ppmw to 100 ppmw of antioxidant.
  • Preferred gasoline compositions used in the method of the present invention have one or more of the following features :-
  • the hydrocarbon base fuel contains at least 10% v olefins ,
  • the hydrocarbon base fuel contains at least 12% v olefins
  • the hydrocarbon base fuel contains at least 13% v olefins
  • the hydrocarbon base fuel contains up to 20% v olefins
  • the hydrocarbon base fuel contains up to 18% v olefins
  • the base fuel has initial boiling point (IBP) of at least 28°C
  • the base fuel has IBP of at least 30°C
  • the base fuel has IBP up to 42°C
  • the base fuel has T ]_ Q of at least 80°C,
  • the base fuel has Tgg at least 135°C
  • the base fuel has Tgg of at least 140°C
  • the base fuel has Tgg of at least 142°C
  • the base fuel has Tgg up to 150°C
  • the base fuel has final boiling point (FBP) not greater than 200°C
  • the base fuel has FBP of at least 165°C
  • the base fuel has FBP of at least 168°C.
  • Examples of preferred combinations of the above features include (i) and (iv) ; (ii) and (v) ; (iii) and (v) ; (vi), (viii), (x) , (xii) , (xvi) , (xix) , (xxii) , (xxv) and (xxix) ; (vii) , (ix) , (xi) , (xiv) , (xvii) , (xx) , (xxiii) , (xxvi) and (xxxiii) ; and (vii), (ix), (xii), (xv) , (xviii) , (xxi) , (xxiv) , (xxviii) , (xxxvi) and
  • Use of the gasoline composition described herein as fuel for a spark-ignition engine in a PHEV or HEV can give one of a number of benefits in addition to providing improved stability of engine lubricant (crank-case lubricant) .
  • These benefits include reduced frequency of oil changes, reduced engine wear, e.g. engine bearing wear, engine component wear (e.g. camshaft and piston crank wear) , improved acceleration performance, higher maximum power output, and/or improved fuel economy.
  • the invention additionally provides the use of a gasoline composition as defined above as a fuel for a spark-ignition engine for improving oxidative stability of engine crank case lubricant and/or for reducing frequency of engine lubricant changes, wherein the spark-ignition engine is comprised in the powertrain of a hybrid electric vehicle.
  • a bench engine, Renault Megane (K7M702) 1.6 1, 4- cylinder spark-ignition (gasoline) engine was modified by honing to increase cylinder bore diameter and grinding ends of piston rings to increase butt gaps, in order to increase rate of blow-by of combustion gases.
  • a by-pass pipe was fitted between cylinder head wall, above the engine valve deck, and the crankcase to provide an additional route for blow-by of combustion gases to the crank case.
  • a jacketed rocker arm cover (RAC) was fitted to facilitate control of the environment surrounding the engine valve train.
  • Table 1 was replaced by a modified stage in which during a 10 min idle period (850 ⁇ 100 rpm) a 25 g oil sample was removed. (Every second day and on the seventh day (only) was sample removed) . The engine was then stopped and allowed to stand for 20 minutes. During the next 12 minutes the oil dipstick reading was checked and engine oil was topped up (only during test, not at end of test) . During the final 3 minutes of this 45-minute stage the engine was restarted.
  • TBN wear metals
  • Comparative Example A was a base fuel as widely employed in fuels sold in The Netherlands in 2002. Comparative Example B corresponded to Comparative Example A with addition of heavy platformate (the higher boiling
  • Example 1 corresponded to Comparative Example A, with addition of light cat-cracked gasoline (the lower boiling fraction of a refinery stream produced by catalytic cracking of heavier hydrocarbons), to increase olefins. Sulphur contents of the fuels were adjusted to 50 ppmw S by addition, where necessary, of dimethylsulphide, in order to eliminate possible effects arising from
  • Example A Density at 15°C 0.7216 0.7316 0.754
  • RVP (rabar) 561 512 672
  • the point at which TAN/TBN crossover occurs is considered to be an indicator of the point at which significant oxidative change is occurring in the oil.
  • Example 1 The above results give a good indication that use of the fuel of Example 1 had a highly beneficial effect on oxidative stability of the crank case lubricant, leading to extended lubricant life, lower frequency of engine lubricant changes (extended service intervals) , and reduced engine wear.
  • Tin levels are most likely to be associated with wear in engine bearings. Iron levels are associated with engine component wear (camshaft and piston cranks).
  • Comparative Example C was a base fuel as widely employed in fuels sold in The Netherlands in 2002.
  • Comparative Example D corresponded to Comparative Example C with addition of heavy platformate, to increase aromatics.
  • Example 1 corresponded to Comparative Example C, with addition of 15 parts by volume diisobutylene per 85 parts by volume base fuel of Comparative Example C.
  • the diisobutylene was a mixture of 2 , , 4-trimethyl-l-pentene and 2, , 4-trimethyl-2-pentene, in proportions resulting from commercial manufacture.
  • Example 3 corresponded to Comparative Example C, with addition of an ex-refinery stream of C5 and Cg-olefins, in proportion of 15 parts by volume olefins per 85 parts by volume base fuel of
  • Example 4 diisobutylene and 5% v/v ethanol.
  • the resulting gasoline contained 13.02%v olefins, had initial boiling point 40°C, final boiling point 168.5°C, and met the other parameters of the present invention. This fuel was tested in a Toyota Avensis 2.0 1 VVT-i direct
  • Comparative Example F injection spark-ignition engine relative to Comparative Example E and relative to the same base fuel containing 5% v/v ethanol. Both Comparative Example E and Comparative Example F are outside the parameters of the present invention by virtue of their olefin contents (total olefins of 3.51% v/v and 3.33% v/v, respectively) . Details of the fuels are given in Table 6:-
  • Example 4 Under acceleration testing (1200-3500 rpm, 5th gear, wide open throttle (WOT) , 1200-3500 rpm, 4th gear, WOT, and 1200-3500 rpm, 4th gear 75% throttle), Example 4 gave consistently superior performance (acceleration time) relative to either of Comparative Examples E and F.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Lubricants (AREA)

Abstract

Method of improving the oxidative stability of a lubricating composition which is used to lubricate a spark ignition internal combustion engine, the spark- ignition engine being comprised within the powertrain of a hybrid electric vehicle, wherein the method comprises the step of introducing into the combustion chamber of the spark-ignition engine a gasoline composition wherein the gasoline composition comprises a hydrocarbon base fuel containing 10 to 20% v olefins, not greater than 5% v olefins of at least 10 carbon atoms, and not greater than 5% v aromatics of at least 10 carbon atoms, based on the base fuel, initial boiling point in the range 30 to 40°C, T10 in the range 45 to 57°C, T50 in the range 82 to 104°C, T90 in the range 140 to 150°C and final boiling point not greater than 220 °C.

Description

METHOD OF IMPROVING THE OXIDATIVE STABILITY OF A
LUBRICATING COMPOSITION
Field of the Invention
This invention relates to a method of improving the oxidative stability of a lubricating composition which is used for lubricating a spark ignition combustion engine, the spark ignition combustion engine being housed in the powertrain of a hybrid electric vehicle.
Background of the Invention
The rising costs of hydrocarbon-based fuels and increasing concern about the environmental effects of carbon dioxide emissions have resulted in a growing demand for motor vehicles that operate either partly or entirely on electrical energy.
Hybrid Electric Vehicles (HEV) make use of both electrical energy stored in re-chargeable batteries and the mechanical energy converted from fuel, usually hydrocarbon based, by a conventional internal combustion engine (ICE) . The batteries are charged during driving operation by the ICE and also by recovering kinetic energy during deceleration and braking. This process is offered by a number of vehicle original equipment
manufacturers (OEMs) for some of their vehicle models. HEVs typically provide a normal driving experience, with the principle advantage of improved fuel consumption in comparison to conventional ICE only vehicles. Plug-in Hybrid Electric Vehicles (PHEVs) have similar
functionality to HEVs, but in this application the battery can also be connected to the mains electrical system for recharging when the vehicle is parked. PHEVs typically have larger battery packs than HEVs which affords some all-electric range capability. Dynamic driving will use electric power and ICE, though the area of operation using an internal combustion engine (ICE) for propulsion may be restricted to cruising and
intercity driving. Consequently the fuel appetite of vehicles may well be different from that required currently for conventional ICE or HEV equipped vehicles. For vehicles based exclusively in an urban environment, the increased EV mode capacity and plug-in charging function further reduce the level of ICE activity. This can lead to significantly extended residence time for the fuel tank contents compared to HEV and conventional ICE vehicles .
Conventional ICE vehicles typically deliver about 600 km (400 miles) range for a propulsion system weight of about 200 kg and require a re-fill time of around 2 minutes. In comparison, it is considered that a battery pack based on current Li-ion technology that could offer comparable range and useful battery life would weigh about 1700 kg. The additional weight of the motor, power electronics and vehicle chassis would result in a much heavier vehicle than the conventional ICE equivalent.
In a conventional ICE vehicle, the engine torque and power delivery from the engine must cover the full range of vehicle operating dynamics. However, the
thermodynamic efficiency of an internal combustion engine cannot be fully optimised across a wide range of
operating conditions. The ICE has a relatively narrow dynamic range. Hence a major challenge for the vehicle manufacturers (OEMs) is to develop engine technologies and transmission systems that allow the engine torque and power delivery from the engine to operate over the full range of vehicle operating dynamics. Electrical machines on the other hand can be designed to have a very wide dynamic range, e.g., are able to deliver maximum torgue at zero speed. This control flexibility is well
recognised as a useful feature in industrial drive applications and offers potential in automotive
applications. Within their operating envelope,
electrical machines can be controlled using sophisticated electronics to give very smooth torque delivery, tailored to the demand requirements. However it may be possible to provide different torque delivery profiles that are more appealing to drivers. Hence this is likely to be an area of interest going forward for automotive designers. At higher speeds, electrical drive systems tend to be limited by the heat rejection capacity of the power electronics and the cooling system for the electric motor itself. Additional considerations for high torque motors at high speeds are associated with the mass of the rotating components, where very high centrifugal forces can be produced at high speeds. These can be
destructive. In HEVs and PHEVs, the electric motor is therefore able to provide only some of the dynamic range. However, this can allow the efficiency of the ICE to be optimised over a narrower range of operation. This offers some advantages in terms of engine design.
Hence, current hydrocarbon fuels developed for a full range ICE may not be optimised or indeed beneficial for HEV or PHEV ICE units. Fuels have been formulated and regulated for conventional ICE vehicles for many years and may therefore be considered to have stabilised, with degrees of freedom in the formulation space well understood. The relatively recent introduction of hybrid technology presents an opportunity to consider the fuel formulation space from an entirely new perspective. Further, in order to maximise efficient operation of a HEV or a PHEV ICE unit, consideration must also be given to the lubricating composition which is used to lubricate the ICE within the powertrain of a HEV or PHEV. Due to the different operating cycles in an HEV or PHEV
ICE unit compared with a conventional ICE unit, the lubricating composition tends to be exposed to more extreme conditions and greater oxidative stresses in an HEV/PHEV environment.
It is already known that the automotive industry has designed specific requirements for lubricant compositions operating under certain driving conditions, such as the "Aunt Minnie" driving cycle (a driving cycle that
simulates a vehicle being used infrequently for short- distance trips, without the engine fully warming up to optimal operating temperatures before shutoff in cold climates) . In an HEV or PHEV ICE unit, there are
frequent engine stops and starts such that the ICE is only used for short periods of time and doesn't fully warm up before shutting off. In general, the ICE in a hybrid vehicle will be more prone to the dangers of "Aunt Minnie" type drive cycles because the ICE will be used less for the same drive pattern. This means that the crank-case lubricant does not fully warm up in an HEV or PHEV which therefore presents severe conditions for oxidation of the lubricant. A decrease in oxidative stability of the lubricant can lead to increased engine deposits which in turn can lead to undesirable effects such as reduced fuel economy, and the like. As mentioned above, this problem of stop/start is more severe in HEVs and PHEVs than in conventional ICE units, and therefore careful consideration has to be given to improving the oxidative stability of the lubricant in a HEV/PHEV. It would therefore be desirable to find ways of improving the oxidative stability of a lubricating composition in a PHEV/HEV vehicle in order to maximise the efficient operation of the PHEV/HEV vehicle.
At the same, the oxidative stability of the fuel composition also needs to be considered in the case of a HEV/PHEV.
WO2004/113476 discloses gasoline compositions meeting certain parameters whose use as a fuel in a spark ignition engine results in improved stability of engine crank case lubricant. However, there is no mention in this document of the use of such a fuel in an HEV or PHEV vehicle, or of the specific benefits of using such a fuel for hybrid vehicles.
Summary of the Invention
According to the present invention there is provided a method of improving the oxidative stability of a lubricating composition which is used to lubricate a spark ignition internal combustion engine, the spark- ignition engine being comprised within the powertrain of a hybrid electric vehicle, wherein the method comprises the step of introducing into the combustion chamber of the spark-ignition engine a gasoline composition wherein the gasoline composition comprises a hydrocarbon base fuel containing 10 to 20% v olefins, not greater than 5% v olefins of at least 10 carbon atoms, and not greater than 5% v aromatics of at least 10 carbon atoms, based on the base fuel, initial boiling point in the range 30 to 40°C, T10 in the range 45 to 57°C, T50 in the range 82 to 104°C, T90 in the range 140 to 150°C and final boiling point not greater than 220°C.
It has surprisingly been found that by selecting a gasoline composition meeting certain parameters the oxidative stability of the lubricating composition in a
HEV or a PHEV is improved.
Detailed Description of the Invention
Light olefin content together with the T ^ Q range of
38 to 60°C are believed to be key parameters in achieving enhanced stability of engine lubricant (crank-case lubricant) , in spark ignition internal combustion engines fuelled by gasoline compositions of the present invention which are comprised in the powertrain of a hybrid electric vehicle. Frequent engine stops and starts in a HEV and a PHEV where the ICE is only in use for some of the time and for short periods . means that the crank-case lubricant does not fully warm up and presents severe conditions for oxidation of the lubricant. The effects of these start/stop driving cycles are more severe in HEV/PHEV vehicles than they are in conventional ICE vehicles. High front-end volatility (low T^o, ) and specified olefin content are believed to result in reduction in blowby of harmful combustion gases into the engine crank-case.
By "not greater than 5% v olefins of at least 10 carbon atoms" and "not greater than 5% v aromatics of at least 10 carbon atoms" is meant that the hydrocarbon base fuel contains amounts of olefins having 10 carbon atoms or more and amounts of aromatics having 10 carbon atoms or more, respectively in the range 0 to 5% v, based on the base fuel.
Gasolines contain mixtures of hydrocarbons, the optimal boiling ranges and distillation curves thereof varying according to climate and season of the year. The hydrocarbons in a gasoline as defined above may
conveniently be derived in known manner from straight-run gasoline, synthetically-produced aromatic hydrocarbon mixtures, thermally or catalytically cracked
hydrocarbons, hydrocracked petroleum fractions or catalytically reformed hydrocarbons and mixtures of these. Oxygenates may be incorporated in gasolines, and these include alcohols (such as methanol, ethanol, isopropanol, tert.butanol and isobutanol) and ethers, preferably ethers containing 5 or more carbon atoms per molecule, e.g. methyl tert. butyl ether (MTBE) or ethyl tert. butyl ether (ETBE) . The ethers containing 5 or more carbon atoms per molecule may be used in amounts up to 15% v/v, but if methanol is used, it can only be in an amount up to 3% v/v, and stabilisers will be reguired. Stabilisers may also be needed for ethanol, which may be used up to 5% to 10% v/v. Isopropanol may be used up to 10% v/v, tert-butanol up to 7% v/v and isobutanol up to 10% v/v.
It is preferred to avoid inclusion of tert.butanol or MTBE. Accordingly, preferred gasoline compositions of the present invention contain 0 to 10% by volume of at least one oxygenate selected from methanol, ethanol, isopropanol and isobutanol.
Theoretical modelling has suggested that inclusion of ethanol in gasoline compositions of the present invention will further enhance stability of engine lubricant, particularly under cooler engine operating conditions. Accordingly, it is preferred that gasoline compositions of the present invention contain up to 10% by volume of ethanol, preferably 2 to 10% v, more
preferably 4 to 10% v, e.g. 5 to 10% v ethanol.
Gasoline compositions according to the present invention are advantageously lead-free (unleaded) , and this may be reguired by law. Where permitted, lead-free anti-knock compounds and/or valve-seat recession protectant compounds (e.g. known potassium salts, sodium salts or phosphorus compounds) may be present.
The octane level, (R+M)/2, will generally be above
85.
Modern gasolines are inherently low-sulphur fuels, e.g. containing less than 200 ppmw sulphur, preferably not greater than 50 ppmw sulphur.
Hydrocarbon base fuels as define above may
conveniently be prepared in known manner by blending suitable hydrocarbon, e.g. refinery, streams in order to, meet the defined parameters, as will readily be
understood by those skilled in the art. Olefin content may be boosted by inclusion of olefin-rich refinery streams and/or by addition of synthetic components such as diisobutylene, in any relative proportions.
Diisobutylene, also known as 2 , 4 , 4-trimethyl-l- pentene ( Sigma-Aldrich Fine Chemicals) , is typically a mixture of isomers (2 , , 4-trimethyl-l-pentene and 2,4,4- trimethyl-2-pentene) prepared by heating the sulphuric acid extract of isobutylene from a butene isomer
separation process to about 90°C. As described in Kirk- Othmer, "Encyclopedia of Chemical Technology", 4th Ed. Vol. 4, Page 725, yield is typically 90%, of a mixture of 80% dimers and 20% trimers.
Gasoline compositions as defined above may variously include one or more additives such as anti-oxidants , corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers and synthetic or mineral oil carrier fluids.- Examples of suitable such additives are
described generally in US Patent No. 5,855,629 and DE-A- 19955651.
Additive components can be added separately to the gasoline or can be blended with one or more diluents, forming an additive concentrate, and together added to base fuel.
A preferred gasoline composition for use in the method of the present invention comprises one or more antioxidants in order to improve the oxidative stability of the gasoline composition. Any antioxidant additive which is suitable for use in a gasoline composition can be used herein. A preferred anti-oxidant for use herein is a hindered phenol, for example BHT (butylated hydroxy toluene) . It is preferred that the gasoline composition comprises from 10 ppmw to 100 ppmw of antioxidant.
Preferred gasoline compositions used in the method of the present invention have one or more of the following features :-
(i) the hydrocarbon base fuel contains at least 10% v olefins ,
(ii) the hydrocarbon base fuel contains at least 12% v olefins,
(iii) the hydrocarbon base fuel contains at least 13% v olefins,
(iv) the hydrocarbon base fuel contains up to 20% v olefins,
(v) the hydrocarbon base fuel contains up to 18% v olefins,
(vi) the base fuel has initial boiling point (IBP) of at least 28°C,
(vii) the base fuel has IBP of at least 30°C,
(viii) the base fuel has IBP up to 42°C,
(ix) the base fuel has IBP up to 40°C,
(x) the base fuel has Τ ο of at least 42°C,
(xi) the base fuel has T ^ Q of at least 45°C,
(xii) the base fuel has T^g °f at least 46°C, (xiii) the base fuel has T]_n up to 58°C,
(xiv) the base fuel has T ^ Q UP to 57°C,
(xv) the base fuel has ^ Q UP to 5 6°C ,
(xvi) the base fuel has T ]_ Q of at least 80°C,
(xvii) the base fuel has T]_n of at least 82°C,
(xviii) the base fuel has T ]_ Q of at least 83°C,
(xix) the base fuel has T ]_ Q up to 105°C,
(xx) the base fuel has ^ Q up to 104°C,
(xxi) the base fuel has Τχη UP to 103°C,
(xxii) the base fuel has Tgg at least 135°C,
(xxiii) the base fuel has Tgg of at least 140°C,
(xxiv) the base fuel has Tgg of at least 142°C,
(xxv) the base fuel has Tgg up to 170°C,
(xxvi) the base fuel has Tgg up to 150°C,
(xxvii) the base fuel has Tgg up to 145°C,
(xxviii) the base fuel has Tgg up to 143°C,
(xxix) the base fuel has final boiling point (FBP) not greater than 200°C,
(xxx) the base fuel has FBP not greater than 195°C,
(xxxi) the base fuel has FBP not greater than 190°C,
(xxxii) the base fuel has FBP not greater than 185°C
(xxxiii) the base fuel has FBP not greater than 180°C
(xxxiv) the base fuel has FBP not greater than 175°C
(xxxv) the base fuel has FBP not greater than 172°C,
(xxxvi) the base fuel has FBP of at least 165°C, and
(xxxvii) the base fuel has FBP of at least 168°C.
Examples of preferred combinations of the above features include (i) and (iv) ; (ii) and (v) ; (iii) and (v) ; (vi), (viii), (x) , (xii) , (xvi) , (xix) , (xxii) , (xxv) and (xxix) ; (vii) , (ix) , (xi) , (xiv) , (xvii) , (xx) , (xxiii) , (xxvi) and (xxxiii) ; and (vii), (ix), (xii), (xv) , (xviii) , (xxi) , (xxiv) , (xxviii) , (xxxvi) and
(xxxvii) .
Use of the gasoline composition described herein as fuel for a spark-ignition engine in a PHEV or HEV can give one of a number of benefits in addition to providing improved stability of engine lubricant (crank-case lubricant) . These benefits include reduced frequency of oil changes, reduced engine wear, e.g. engine bearing wear, engine component wear (e.g. camshaft and piston crank wear) , improved acceleration performance, higher maximum power output, and/or improved fuel economy.
Accordingly, the invention additionally provides the use of a gasoline composition as defined above as a fuel for a spark-ignition engine for improving oxidative stability of engine crank case lubricant and/or for reducing frequency of engine lubricant changes, wherein the spark-ignition engine is comprised in the powertrain of a hybrid electric vehicle.
The invention will be understood from the following illustrative examples, in which, unless indicated
otherwise, temperatures are in degrees Celsius and parts, percentages and ratios are by volume. Those skilled in the art will readily appreciate that the various fuels were prepared in known manner from known refinery streams and are thus readily reproducible from a knowledge of the composition parameters given.
In the examples, oxidative stability tests on lubricant in engines fuelled by test fuels were effected using the following procedure.
A bench engine, Renault Megane (K7M702) 1.6 1, 4- cylinder spark-ignition (gasoline) engine was modified by honing to increase cylinder bore diameter and grinding ends of piston rings to increase butt gaps, in order to increase rate of blow-by of combustion gases. In addition, a by-pass pipe was fitted between cylinder head wall, above the engine valve deck, and the crankcase to provide an additional route for blow-by of combustion gases to the crank case. A jacketed rocker arm cover (RAC) was fitted to facilitate control of the environment surrounding the engine valve train.
Before test and between each test, the engine was cleaned thoroughly, to remove all trace of possible contamination. The engine was then filled with 15W/40 engine oil meeting API SG specification, and the cooling systems, both for engine coolant and RAC coolant, were filled with 50:50 water : antifreeze mixture.
Engine tests were run for 7 days according to a test cycle wherein each 24 hour period involved five 4-hour cycles according to Table 1 : - Table 1
followed by an oil sampling cycle wherein Stage 3 of
Table 1 was replaced by a modified stage in which during a 10 min idle period (850 ± 100 rpm) a 25 g oil sample was removed. (Every second day and on the seventh day (only) was sample removed) . The engine was then stopped and allowed to stand for 20 minutes. During the next 12 minutes the oil dipstick reading was checked and engine oil was topped up (only during test, not at end of test) . During the final 3 minutes of this 45-minute stage the engine was restarted.
Test measurements on oil samples were made to assess heptane insolubles (according to DIN 51365 except that oleic acid was not used as coagulant) , total acid number (TAN) (according to IP177), total base number
(TBN) (according to ASTM D4739) , and amounts of wear metals (Sn, Fe and Cr) (according to ASTM 5185 except that sample was diluted by a factor of 20 in white spirit, instead of a factor of 10) . From the TAN and TBN values (units are mg KOH/g lubricant) , TAN/TBN crossover points were calculated (test hours) .
Example 1
Three hydrocarbon base fuel gasolines were tested. Comparative Example A was a base fuel as widely employed in fuels sold in The Netherlands in 2002. Comparative Example B corresponded to Comparative Example A with addition of heavy platformate (the higher boiling
fraction of a refinery steam manufactured by reforming naphtha over a platinum catalyst), to increase aromatics . Example 1 corresponded to Comparative Example A, with addition of light cat-cracked gasoline (the lower boiling fraction of a refinery stream produced by catalytic cracking of heavier hydrocarbons), to increase olefins. Sulphur contents of the fuels were adjusted to 50 ppmw S by addition, where necessary, of dimethylsulphide, in order to eliminate possible effects arising from
differences in sulphur levels.
The resulting fuels had properties as given in Table
2:-
Table 2
Base Fuel Example 1 Comparative Comparative
Example A Example B Density at 15°C 0.7216 0.7316 0.754
DIN 51757/V4
RVP (rabar) 561 512 672
Distillation
(ISO 3405/88)
IBP (°C) 30 32.5 35
10% 46 49.5 54
50% 83.5 107.5 109.5
90% 143 147.5 168.5
FBP 168.5 173 205.5
S(ASTM D 2622-94) 50 50 50
(ppmw)
Paraffins (%v) 52.86 64.19 53.79
Olefins (%v) 16.4 0.61 0.43
Olefins of CIO or 0.00 0.00 0.00 greater %v)
Naphthenes (%v) 2.87 2.88 4.1
(saturated)
Aromatics (%v) 27.01 31.41 40.74
Aromatics of CIO 0.46 0.57 7.10 or greater (%v)
Oxygenates 0 0 0
RON 95.3 96.1 95.8
MON 85.3 87.7 86.6
Results of tests on these fuels are given in Table
3 : -
Table 3
Base Fuel Example 1 Comparative Comparative
Example A Example B
TAN/TBN crossover 101 47 50 (hours)
Wear Metals
(mg metal/g
lubricant )
Cr (after 96 hours) less than 1 less than 1 less than 1 Cr (after 7 days) less than 1 less than 1 less than 1
Fe (after 96 hours) 14 15 17 Fe (after 7 days) 18 23 22
Sn (after 96 hours) 4 8 14
The point at which TAN/TBN crossover occurs is considered to be an indicator of the point at which significant oxidative change is occurring in the oil.
The above results give a good indication that use of the fuel of Example 1 had a highly beneficial effect on oxidative stability of the crank case lubricant, leading to extended lubricant life, lower frequency of engine lubricant changes (extended service intervals) , and reduced engine wear.
Tin levels are most likely to be associated with wear in engine bearings. Iron levels are associated with engine component wear (camshaft and piston cranks).
Examples 2 and 3
Four hydrocarbon base fuel gasolines were tested. Comparative Example C was a base fuel as widely employed in fuels sold in The Netherlands in 2002. Comparative Example D corresponded to Comparative Example C with addition of heavy platformate, to increase aromatics. Example 1 corresponded to Comparative Example C, with addition of 15 parts by volume diisobutylene per 85 parts by volume base fuel of Comparative Example C. The diisobutylene was a mixture of 2 , , 4-trimethyl-l-pentene and 2, , 4-trimethyl-2-pentene, in proportions resulting from commercial manufacture. Example 3 corresponded to Comparative Example C, with addition of an ex-refinery stream of C5 and Cg-olefins, in proportion of 15 parts by volume olefins per 85 parts by volume base fuel of
Comparative Example C.
The resulting fuels had properties as given in Table 4:- Table 4
Results of tests on these fuels are given in Table 5:-
Table 5
The above results overall give a good indication that use of the fuels of Examples 2 and 3 give overall unexpected benefits on oxidative stability of the crank case lubricant, with similar consequences as described above in Example 1.
Example 4
A fuel similar to Comparative Example C (Comparative Example E) was blended with diisobutylene and ethanol to give a gasoline composition containing 10% v/v
diisobutylene and 5% v/v ethanol (Example 4) . The resulting gasoline contained 13.02%v olefins, had initial boiling point 40°C, final boiling point 168.5°C, and met the other parameters of the present invention. This fuel was tested in a Toyota Avensis 2.0 1 VVT-i direct
injection spark-ignition engine relative to Comparative Example E and relative to the same base fuel containing 5% v/v ethanol (Comparative Example F) . Both Comparative Example E and Comparative Example F are outside the parameters of the present invention by virtue of their olefin contents (total olefins of 3.51% v/v and 3.33% v/v, respectively) . Details of the fuels are given in Table 6:-
Table 6
(saturated) aromatics (%v) 26.62 31.93 30.15 aromatxcs of CIO or greater 0.49 0.59 0.55
(%v)
oxygenates 5.54 0 5.47
RON 99.7 95.2 97.5
MON 87.8 87.1 87.6
Under acceleration testing (1200-3500 rpm, 5th gear, wide open throttle (WOT) , 1200-3500 rpm, 4th gear, WOT, and 1200-3500 rpm, 4th gear 75% throttle), Example 4 gave consistently superior performance (acceleration time) relative to either of Comparative Examples E and F.
Significantly higher power was developed both at 1500 rpm and at 2500 rpm when the engine was fuelled with Example 4, relative to Comparative Example E or Comparative
Example F.

Claims

C L A I M S
1. Method of improving the oxidative stability of a lubricating composition which is used to lubricate a spark ignition internal combustion engine, the spark- ignition engine being comprised within the powertrain of a hybrid electric vehicle, wherein the method comprises the step of introducing into the combustion chamber of the spark-ignition engine a gasoline composition wherein the gasoline composition comprises a hydrocarbon base fuel containing 10 to 20% v olefins, not greater than 5% v olefins of at least 10 carbon atoms, and not greater than 5% v aromatics of at least 10 carbon atoms, based on the base fuel, initial boiling point in the range 30 to 40°C, T10 in the range 45 to 57°C, T50 in the range 82 to 104°C, T90 in the range 140 to 150°C and final boiling point not greater than 220°C.
2. Method according to Claim 1 wherein the gasoline composition contains 0 to 10%v of at least one oxygenate selected from methanol, ethanol, isopropanol and
isobutanol .
3. Method according to Claim 1 or 2 wherein the
hydrocarbon base fuel contains 10 to 20% v olefins.
4. Method according to any of Claims 1 to 3 wherein the hydrocarbon base fuel contains 12 to 18% v olefins.
5. Method according to any one of Claims 1 to 4 wherein the base fuel has initial boiling point in the range 28 to 42°C, Τ ο in the range 42 to 58°C, T50 in the range 80 to 105°C, T90 in the range 135 to 170°C and final boiling point not greater than 200°C.
6. Method according to any one of Claims 1 to 5 wherein the base fuel has initial boiling point in the range 30 to 40°C, T]_o in the range 45 to 57°C, 50 in the range 82 to 104°C, T90 in the range 140 to 150°C, and final boiling point not greater than 180°C.
7. Method according to any of Claims 1 to 6 wherein the gasoline composition.
8. Method according to any of Claims 1 to 7 wherein the fuel composition comprises one or more antioxidants.
9. Method according to any of Claims 1 to 8 wherein the gasoline composition comprises an antioxidant of the hindered phenol type.
10. Method according to any of Claims 1 to 9 wherein the hybrid electric vehicle is a plug-in hybrid electric vehicle .
11. Use of a gasoline composition as a fuel for a spark- ignition engine for improving oxidative stability of engine crank case lubricant and/or for reducing frequency of engine lubricant changes, wherein the spark-ignition engine is comprised in the powertrain of a hybrid electric vehicle, wherein the gasoline composition comprises a hydrocarbon base fuel containing 10 to 20% v olefins, not greater than 5% v olefins of at least 10 carbon atoms, and not greater than 5% v aromatics of at least 10 carbon atoms, based on the base fuel, initial boiling point in the range 30 to 40°C, T10 in the range 45 to 57°C, T50 in the range 82 to 104°C, T90 in the range 140 to 150°C and final boiling point not greater than 220°C.
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