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)

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• 2017
  • 2017-09-29 US US16/338,538 patent/US20190249097A1/en not_active Abandoned
  • 2017-09-29 EP EP17777580.6A patent/EP3519538A1/de not_active Withdrawn
  • 2017-09-29 BR BR112019006319-6A patent/BR112019006319B1/pt active IP Right Grant
  • 2017-09-29 WO PCT/EP2017/074884 patent/WO2018065331A1/en active Application Filing
  • 2017-09-29 JP JP2019517884A patent/JP2019533045A/ja active Pending
  • 2017-09-29 CN CN201780060514.8A patent/CN109790479A/zh active Pending
• 2019
  • 2019-03-01 ZA ZA2019/01304A patent/ZA201901304B/en unknown
  • 2019-04-02 PH PH12019500716A patent/PH12019500716A1/en unknown
• 2022
  • 2022-01-04 JP JP2022000118A patent/JP2022058477A/ja active Pending

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