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
  • C10L1/143—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
  • C10L1/16—Hydrocarbons
  • C10L1/1608—Well defined compounds, e.g. hexane, benzene
• • 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
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
• • 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
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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

Definitions

• the present invention relates to a liquid fuel composition, in particular to a liquid fuel composition which provides improved engine power and which has a reduced burn duration in an internal combustion engine.
• the present invention also relates to methods of improving the power output of an internal combustion engine as well as increasing efficiency and reducing emissions, by fueling the internal combustion engine with the liquid fuel composition described herein below.
• the present invention also relates to methods of reducing the burn duration of a liquid fuel composition.
• gasoline fuel compositions containing specially formulated refinery components with high octane and flame speed/burn duration properties can deliver increases in power and/or acceleration as well as fuel economy.
• it would be desirable to be able to use market available, standard exchange gasoline fuel for upgrading power, acceleration and fuel efficiency performance So-called high reactivity polybutene polymers have relatively high proportions (i.e. >30%) of polymer molecules having a terminal vinylidene group.
• US 6,048,373 discloses a fuel composition comprising a spark ignition fuel, a Mannich detergent and a polybutene having a molecular weight distribution of less than 1.4 for controlling intake valve deposits and minimizing valve sticking in spark ignition internal combustion engines.
• Preferred polybutenes disclosed therein have a number average molecular weight (Mn) of from about 500 to about 2000, and high reactivity polyisobutylenes (PIBs) are disclosed.
• Preferred treat rates for the polybutene(s) having a molecular weight distribution of 1.4 or less are stated to fall within the range of about 0.5 to about 50 ptb, preferably in the range of about 1.5 to about 40 ptb.
• the treat rate of the high reactivity PIB used in Example 2 is 53.2 ptb which is equivalent to about 151 ppm.
• a low molecular weight polybutene polymer at selected treat rates for providing increased engine power and reduced burn duration.
• Co-pending US patent application 63/390715 discloses a fuel composition comprising a gasoline base fuel and a high-reactivity polybutene polymer for providing improved engine power.
• Co-pending US patent application 63/179767 discloses a fuel composition comprising a base fuel and a tetraalkylethane compound such as dicumene for providing improved engine power.
• a low molecular weight polybutene such as a low molecular weight polyisobutylene (PIB), especially a low molecular weight, high reactivity, polyisobutylene (PIB) in combination with a selected tetraalkylethane compound in a gasoline fuel composition, preferably at selected additive treat rates, can provide synergistic benefits in terms of improved power output (increased P max ) and reduced burn duration, even when a standard exchange gasoline fuel is used.
• a reduction in burn duration leads to a more complete burn per cycle, which improves engine efficiency as well as lowers harmful emissions including particulate matter (PM/PN).
• a fuel composition comprising:
• polybutene polymer (b) a polybutene polymer; wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol, wherein greater than 30% of the polymer molecules in the polybutene polymer have a terminal vinylidene group;
• the fuel compositions of the present invention provide improved power output as reflected in increased P max , as well as reduced burn duration of the fuel. Further the fuel compositions of the present invention exhibit excellent acceleration, energy efficiency and fuel economy.
• liquid fuel composition for improving power output of an internal combustion engine, wherein the liquid fuel composition comprises:
• polybutene polymer (b) a polybutene polymer; wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol, preferably wherein the polybutene is a high reactivity polybutene wherein greater than 30% of the polymer molecules in the polyisobutylene polymer have a terminal vinylidene group; and
• each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH 2 )nOH or (CH 2 ) n NH 2 , wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX 2 group is a hydrogen atom.
• a method of reducing the burn duration of a liquid fuel composition in an internal combustion engine comprising adding a polybutene and a tetraalkylethane compound to a gasoline base fuel to produce a gasoline fuel composition, wherein the polybutene has a number average molecular weight in the range from 200 to 10,000 g/mol, preferably wherein greater than 30% of the polymer molecules in the polybutene polymer have a terminal vinylidene group; and wherein the tetraalkylethane compound has the formula (I): wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH 2 ) n OH or (CH 2 ) n NH 2 , wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX3 group is a hydrogen
• Figure 5 is a graphical representation of the Pmax measurements for Examples 14-27 and their reference base fuel.
• power output refers to the amount of resistance power required to maintain a fixed speed at wide open throttle conditions in Chassis Dynamometer testing.
• 'P max ' refers to the direct measurement of the force generated by decomposition of the fuel.
• the term "improving" embraces any degree of improvement.
• the improvement may for instance be 0.05% or more, preferably 0.1% or more, more preferably 0.2% or more, even more preferably 0.5% or more, especially 1% or more, more especially 2% or more, even more especially 5% or more, of the power output or Pmax provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention.
• the improvement in power output or Pmax may even be as high as 10% of the power output or P ma x provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention.
• a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound may also be used to improve the acceleration of an internal combustion engine.
• acceleration refers to the amount of time required for the engine to increase in speed between two fixed speed conditions in a given gear.
• the term “improving” embraces any degree of improvement, and may be improved by the same percentages as the power and or Pmax is increased above.
• the power output and acceleration provided by a fuel composition may be determined in any known manner for instance using the standard test methods as set out in SAE Paper 2005- 01-0239 and SAE Paper 2005-01-0244.
• 'burn duration' as used herein means the time required (in engine crank angle degrees) for combustion to progress from 10% to 90% (referred to as Al 10-90 in the Examples below).
• Al 50-90 is also used in relation to burn duration and means the time required (in engine crank angle degrees) for combustion to progress from 50% to 90%.
• a method of reducing the burn duration of a gasoline fuel composition comprising adding a polybutene polymer and a tetraalkylethane compound to the gasoline fuel composition, wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol and wherein the tetraalkylethane compound has the formula (I):
• the burn duration of a fuel composition may be determined in any known manner, for instance using the test method disclosed in the Examples section hereinbelow.
• the term "reducing the burn duration" embraces any degree of reduction.
• the reduction may for instance be 0.05% or more, preferably 0.1% or more, more preferably 0.2% or more, even more preferably 0.5% or more, especially 1% or more, more especially 2% or more and even more especially 4% or more, or 5% or more reduction of the burn duration provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention.
• the reduction in burn duration may even be as high as a 10% reduction of the burn duration provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention.
• LES laminar flame speed'
• LFS Laminar Burning Velocity
• the following method for measuring flame speed uses a net pressure method: Mittal, M., Zhu, G. and Schock H., 'Fast mass-fraction-burned calculation using the net pressure method for real-time applications', Proc. Instn Meeh Engrs, Part D: J. Automobile Engineering 223 (3) (2009): 389-394.
• the liquid fuel composition of the present invention comprises a base fuel suitable for use in an internal combustion engine, a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound.
• the base fuel suitable for use in an internal combustion engine is a gasoline or a diesel fuel, and therefore the liquid fuel composition of the present invention is typically a gasoline composition or a diesel fuel composition.
• the base fuel is a gasoline base fuel.
• the polybutene for use herein is preferably a high reactivity polybutene.
• a high reactivity polybutene is a polybutene having a relatively high proportion, i.e. greater than 30%, of polymer molecules having a terminal vinylidene group.
• the term 'polybutene' as used herein includes polymers made from pure or substantially pure 1- butene or isobutene, and polymers made from mixtures of two or all three of 1-butene, 2-butene and isobutene, as well as including polymers containing minor amounts, preferably less than 10% by weight, more preferably less than 5% by weight, of C2, C3, and C5 and higher olefins as well as diolefins.
• the polybutene is a polyisobutene (also referred to as 'polyisobutylene') preferably wherein at least 90% by weight, more preferably at least 95% by weight, of the polymer is derived from isobutene.
• the polybutene is a high reactivity polyisobutylene.
• the high reactivity polybutene has greater than 40% of polymer molecules having a terminal vinylidene group.
• the high reactivity polybutene polymer has greater than 50% of polymer molecules having a terminal vinylidene group.
• the high reactivity polybutene has more than 85% of its double bonds located in the terminal position of the molecule.
• the high reactivity polybutene polymer for use herein preferably has a molecular mass distribution of 1.5 or greater, preferably 1.6 or greater, more preferably 1.7 or greater, even more preferably 1.8 or greater.
• the polybutene polymer is present at a level of from 500ppm to 5000ppm. In one embodiment, the polybutene polymer is present at a level of from 1000 ppm to 5000 ppm. In another embodiment the polybutene polymer is present at a level of from 2500 to 5000 ppm, by weight of the fuel composition. Examples of preferred levels of polybutene include lOOOppm, 2500ppm and 5000ppm, by weight of the fuel composition.
• One or more polybutene polymer can be used in the fuel compositions herein. When more than one polybutene polymer is used herein, the total level of polybutene polymer is the same as the ranges given in the previous paragraph.
• the polybutene polymer for use herein is a low molecular weight polybutene polymer.
• the term 'low molecular weight polybutene' means a polybutene polymer having a number average molecular weight (M n ) in the range from 200 to 10,000 g/mol, preferably from 500 to 5000 g/mol, more preferably from 1000 to 5000 g/mol.
• the polybutenes, preferably high reactivity polybutenes, for use herein have a number average molecular weight (M n ) from 1000 to 2300 g.mol.
• the polybutenes for use herein have a number average molecular weight (M n ) from 2300 to 5000 g/mol.
• M n number average molecular weight
• the number average molecular weight of the polybutene polymer can be determined using Gel Permeation Chromatography.
• the high reactivity polybutenes for use herein may be bioderived or non-bioderived.
• the polybutene is a low molecular weight, high reactivity polyisobutylene which is derived from
• the high reactivity polybutenes for use herein preferably contain less than 1 mg/kg of chlorine.
• the high reactivity polybutene polymer for use herein has a kinematic viscosity at 100°C of 190 mm 2 /s or greater, preferably in the range of 190 mm 2 /s to 1500 mm 2 /s, more preferably in the range from 430 to 1500 mm 2 /s.
• a preferred high reactivity polybutene for use herein has an alpha olefin content of greater than 85%.
• Suitable high reactivity polybutenes for use herein include those commercially available from BASF under the tradename Glissopal (RTM) such as Glissopal (RTM) 1000, Glissopal (RTM) 1300 and Glissopal (RTM) 2300.
• Glissopal RTM
• RTM Glissopal
• Glissopal (RTM) 1000 has a number average molecular weight (M n ) of 1000 g/mol, a molecular mass distribution (M w /M n ) of 1.6, an alpha olefin content of greater than 85%, a kinematic viscosity at 100°C of 190 mm 2 /s and a chlorine content of less than 1 mg/kg.
• Glissopal (RTM) 1300 has a number average molecular weight (M n ) of 1300 g/mol, a molecular mass distribution (M w /M n ) of 1.7, an alpha olefin content of greater than 85%, a kinematic viscosity at 100°C of 190 mm 2 /s and a chlorine content of less than 1 mg/kg.
• Glissopal 1000, 1300 and 2300 BMBcert (TM) which are low molecular weight, highly reactive polyisobutenes derived from 100% renewable feedstock, commercially available from BASF.
• the polybutene polymer may be blended together with any other additives in addition to the tetraalkylethane compound e.g. additive performance package(s) to produce an additive blend.
• the additive blend is then added to a base fuel to produce a liquid fuel composition.
• the tetraalkylethane compound used herein is a compound having the formula (I): wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 saturated or unsaturated alkyl group, (CH2)nOH, (CH2)nNH2, wherein n is in the range from 1 to 9, preferably in the range from 1 to 6, more preferably in the range from 1 to 4, even more preferably in the range from 1 to 3, provided that at least one of the X groups in each CX3 group is a hydrogen atom.
• Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 saturated or unsaturated alkyl group, (CH2)nOH, (CH2)nNH2, wherein n is in the range from 1 to 9, preferably in the range from 1 to 6, more preferably in the range from 1 to 4, even
• each CX3 group is a hydrogen atom.
• three of the X groups in each CX3 group is a hydrogen atom.
• the Ar of the tetraalkylethane compound is a substituted or unsubstituted aromatic group, such as a phenyl, biphenyl, naphthyl, thienyl or anthracyl. More preferably, Ar is an unsubstituted phenyl group.
• cumene which is commercially available.
• dicumene can be prepared by several known methods, as described in US4,072,811.
• each X group is independently selected from a hydrogen atom and an unsubstituted, straight chain or branched, saturated or unsaturated C1-C6, more preferably C 1 -C 3 , alkyl group, provided that at least one of the X groups in each CX3 group is a hydrogen atom. More preferably, each X group is independently selected from a hydrogen atom and an unsubstituted, straight chain or branched, saturated C1-C6, preferably C1-C3, alkyl group, provided that at least one of the X groups in each CX 3 group is a hydrogen atom.
• the tetralkylethane compound is 1,1'(1,1,2,2-tetramethyl-l,1-ethanediyl)bis- benzene Dicumene is commercially available from Aldrich and various other chemical suppliers.
• the tetraalkylethane compound is preferably present in the fuel composition at a level from 30ppm to 10 wt%, preferably from 100ppm to 5 wt%, more preferably from 100ppm to 1 wt%, even more preferably from 100ppm to 5000ppm. In one embodiment, the tetraalkylethane is present at a level from 313ppm to 5000ppm, by weight of the fuel composition.
• a further preferred additive for use in the fuel compositions herein, in combination with the tetralkylethane compound and the polybutene polymer is an alkylbenzene compound having the f n each R1-R6 gr R1 R2ormula (II) wherei R R65 R4 R3ently selected from hydrogen and a C 1 -C 6 alkyl group, wherein at least one of the R1-R6 groups is a C1-C6 alkyl group.
• three R1-R6 groups in the alkylbenzene compound are independently selected from a C1-C6 alkyl group.
• the alkylbenzene compound is a trimethylbenzene compound.
• the alkykbenzene compound is 1,3,5-trimethylbenzene. 1,3,5-trimethylbenzene is commercially available from Aldrich and other chemical suppliers.
• the alkylbenzene compound is a mixture of trimethylbenzene isomers (known as mesitylene).
• the alkylbenzene compound is preferably present in the fuel composition at a level from 30ppm to 2 wt%, preferably from lOOppm to 1 wt%, more preferably from lOOppm to 5000ppm, even more preferably from 500ppm to 2000ppm, by weight of the fuel composition.
• the alkylbenzene compound, the tetraalkylethane compound and the polybutene polymer may be blended together with any other additives e.g. additive performance package(s) to produce an additive blend.
• the additive blend is then added to a base fuel to produce a liquid fuel composition.
• the gasoline may be any gasoline suitable for use in an internal combustion engine of the spark-ignition (petrol) type known in the art, including automotive engines as well as in other types of engine such as, for example, off road and aviation engines.
• the gasoline used as the base fuel in the liquid fuel composition of the present invention may conveniently also be referred to as 'base gasoline'.
• the gasoline may also comprise various levels of bio-components and bio-streams at any level while maintaining appropriate analytical specifications.
• the bio-components may come from any biomass conversion processes including variations of uncatalyzed and catalyzed biomass pyrolyses, hydro-thermal liquefaction, non-thermal biomass conventions such as microbe catalyzed biochemical processes, etc. Any biomass suitable as feedstock to these processes is ideal.
• Gasolines typically comprise mixtures of hydrocarbons boiling in the range from 25 to 230°C (EN- ISO 3405), the optimal ranges and distillation curves typically varying according to climate and season of the year.
• the hydrocarbons in a gasoline may be derived by any means known in the art, conveniently the hydrocarbons may be derived in any known manner from straight-run gasoline, synthetically-produced aromatic hydrocarbon mixtures, thermally or catalytically cracked hydrocarbons, hydro-cracked petroleum fractions, catalytically reformed hydrocarbons or mixtures of these.
• the specific distillation curve, hydrocarbon composition, research octane number (RON) and motor octane number (MON) of the gasoline are not critical.
• the olefinic hydrocarbon content of the gasoline is in the range of from 0 to 40 percent by volume based on the gasoline (ASTM D1319); preferably, the olefinic hydrocarbon content of the gasoline is in the range of from 0 to 30 percent by volume based on the gasoline, more preferably, the olefinic hydrocarbon content of the gasoline is in the range of from 0 to 20 percent by volume based on the gasoline.
• the gasoline preferably has a low or ultra low sulphur content, for instance at most 1000 ppmw (parts per million by weight), preferably no more than 500 ppmw, more preferably no more than 100, even more preferably no more than 50 and most preferably no more than even 10 ppmw.
• the oxygenate concentration will have a minimum concentration selected from any one of 0, 0.2, 0.4, 0.6, 0.8, 1.0, and 1.2 percent by weight, and a maximum concentration selected from any one of 12, 8, 7.2, 5, 4.5, 4.0, 3.5, 3.0, and 2.7 percent by weight.
• the amount of oxygenated hydrocarbons present in the gasoline is selected from one of the following amounts: up to 85 percent by volume; up to 70 percent by volume; up to 65 percent by volume; up to 30 percent by volume; up to 20 percent by volume; up to 15 percent by volume; and, up to
• the gasoline may contain at least 0.5, 1.0 or 2.0 percent by volume oxygenated hydrocarbons.
• gasoline blending components which can be derived from sources other than crude oil, such as low carbon gasoline fuels from either biomass or CO2, and blends thereof which each other or with fossil-derived gasoline streams and components.
• sources other than crude oil such as low carbon gasoline fuels from either biomass or CO2
• blends thereof which each other or with fossil-derived gasoline streams and components.
• suitable examples of such fuels include:
• Biomass derived a. Straight run bio-naphthas from hydrodeoxygenation of biomass, and b. cracked and/or isomerized products of syn-wax (biomass gasification to syngas (CO/H2) then to syn-wax by the Fischer-Tropsch (FT) process, which is then hydrocracked/hydroisomerized to yield a slate of products including cuts in the gasoline distillation range.
• FT Fischer-Tropsch
• Methanol derived a. Biomass gasification to syngas (CO/H2), then to Methanol and then gasoline by the MTG process (MTG is 'methanol-to-gasoline' process).
• MTG is 'methanol-to-gasoline' process.
• H2 used in all processes would be renewable (green) H2 from electrolysis of water using renewable electricity such as from wind and solar.
• gasoline blending components which can be derived from a biological source. Examples of such gasoline blending components can be found in W02009/077606, W02010/028206, WO2010/000761, European patent application nos. 09160983.4, 09176879.6, 09180904.6, and US patent application serial no. 61/312307.
• the base gasoline or the gasoline composition of the present invention may conveniently include one or more optional fuel additives, in addition to the low molecular weight, preferably high reactivity, polybutene and the tetraalkylethane compound.
• concentration and nature of the optional fuel additive(s) that may be included in the base gasoline or the gasoline composition of the present invention is not critical.
• Non-limiting examples of suitable types of fuel additives that can be included in the base gasoline or the gasoline composition of the present invention include anti-oxidants, corrosion inhibitors, detergents, dehazers, antiknock additives, metal deactivators, valve-seat recession protectant compounds, dyes, solvents, carrier fluids, diluents and markers. Examples of suitable such additives are described generally in US Patent No. 5,855,629.
• the fuel additives can be blended with one or more solvents to form an additive concentrate, the additive concentrate can then be admixed with the base gasoline or the gasoline composition of the present invention.
• the (active matter) concentration of any optional additives present in the base gasoline or the gasoline composition of the present invention is preferably up to 1 percent by weight, more preferably in the range from 5 to 2000 ppmw, advantageously in the range of from 300 to 1500 ppmw, such as from 300 to 1000 ppmw.
• corrosion inhibitors for example based on ammonium salts of organic carboxylic acids, said salts tending to form films, or of heterocyclic aromatics for nonferrous metal corrosion protection; dehazers; anti-knock additives; metal deactivators; solvents; carrier fluids; diluents; antioxidants or stabilizers, for example based on amines such as phenyldiamines, e.g.
• p-phenylenediamine N,N'-di- sec-butyl-p-phenyldiamine, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert- butylphenol or 3,5-di-tert-butyl-4-hydroxy- phenylpropionic acid; anti-static agents; metallocenes such as ferrocene; methylcyclopentadienylmanganese tricarbonyl; lubricity additives, such as certain fatty acids, alkenylsuccinic esters, bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; and also dyes (markers).
• phenols such as 2,4-di-tert- butylphenol or 3,5-di-tert-butyl-4-hydroxy- phenylpropionic acid
• anti-static agents metallocenes such as ferrocene
• anti valve seat recession additives such as sodium or potassium salts of polymeric organic acids.
• the gasoline compositions herein can also comprise a detergent additive.
• Suitable detergent additives include those disclosed in W02009/50287, incorporated herein by reference.
• Preferred detergent additives for use in the gasoline composition herein typically have at least one hydrophobic hydrocarbon radical having a number-average molecular weight (Mn) of from 85 to 20000 and at least one polar moiety selected from:
• the hydrophobic hydrocarbon radical in the above detergent additives which ensures the adequate solubility in the base fluid, has a number-average molecular weight (Mn) of from 85 to 20000, especially from 113 to 10000, in particular from 300 to 5000.
• Typical hydrophobic hydrocarbon radicals especially in conjunction with the polar moieties (Al), (A8) and (A9), include polyalkenes (polyolefins), such as the polypropenyl, polybutenyl and polyisobutenyl radicals each having Mn of from 300 to 5000, preferably from 500 to 2500, more preferably from 700 to 2300, and especially from 700 to 1000.
• Non-limiting examples of the above groups of detergent additives include the following:
• Additives comprising mono- or polyamino groups are preferably polyalkenemono- or polyalkenepolyamines based on polypropene or conventional (i.e. having predominantly internal double bonds) polybutene or polyisobutene having Mn of from 300 to 5000.
• polybutene or polyisobutene having predominantly internal double bonds are used as starting materials in the preparation of the additives, a possible preparative route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions.
• the amines used here for the amination may be, for example, ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylene- triamine, triethylenetetramine or tetraethylenepentamine.
• Corresponding additives based on polypropene are described in particular in WO-A-94/24231.
• Further preferred additives comprising monoamino groups (A1) are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization of from 5 to 100, with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-97/03946.
• additives comprising monoamino groups (A1) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A-196 20 262.
• Additives comprising polyoxy-C 2 -C 4 -alkylene moieties are preferably polyethers or polyetheramines which are obtainable by reaction of C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 -C 30 -alkylamines, C 1 -C 30 - alkylcyclohexanols or C 1 -C 30 -alkylphenols with from 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyether-amines, by subsequent reductive amination with ammonia, monoamines or polyamines.
• Additives comprising moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups are preferably corresponding derivatives of polyisobutenylsuccinic anhydride which are obtainable by reacting conventional or highly reactive polyisobutene having Mn of from 300 to 5000 with maleic anhydride by a thermal route or via the chlorinated polyisobutene.
• derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such additives are described in particular in US-A-4849572.
• Additives comprising moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
• the polyisobutenyl-substituted phenols may stem from conventional or highly reactive polyisobutene having Mn of from 300 to 5000. Such "polyisobutene-Mannich bases" are described in particular in EP-A-831141.
• amounts (concentrations, % vol, ppmw, % wt) of components are of active matter, i.e. exclusive of volatile solvents/diluent materials.
• the internal combustion engine herein is a spark ignition internal combustion engine operating in either PFI (Port fuel injection) or GDI (gasoline direct injection) mode.
• PFI Port fuel injection
• GDI gasoline direct injection
• Combustion enhancement could be shown in basically two modes: pre-ignition delay (octane boosting, important for reduced knock at high compression ratio) or flame speed improver (shortened burn duration leading to improved power).
• Example 1 used an E10 base fuel having a RON of 92.3
• Examples 2-4 used an E10 base fuel having a RON of 96.7
• Examples 5-13 used an E10 base fuel having a RON of 96.5.
• High reactivity polyisobutylene (HR-PIB) and/or dicumene were added into the base fuel at the treat rates indicated in Tables 1 and 2 below. Some of the Examples also included mesitylene, as indicated. Mesitylene is a mixture of trimethylbenzene isomers. Tables 1 and 2 also show the RON and MON values for each fuel formulation.
• the engine used for these experiments was the Gasoline single cylinder engine in PFI mode. This engine was manufactured by AVL and based on the EA8882.OL Audi TFSI/VW TSI (Euro 6). The single cylinder bench engine details are shown in Table 3 below.
• Figure 1 is a graphical representation of the Pmax measurements for Example 1 and its reference base fuel (the Example number being on the x axis and Pmax being on the y axis).
• Figure 2 is a graphical representation of the Pmax measurements for Examples 2-4 and their reference base fuel (the Example number being on the x axis and Pmax being on the y axis).
• Figure 3 is a graphical representation of the Pmax measurements for Examples 5-13 and their reference base fuel (the Example number being on the x axis and P max being on the y axis).
• the Example number is on the x axis and the average % difference in burn duration and average % difference in P max is on the y axis. Examples 14-27
• Combustion enhancement could be shown in basically two modes: pre-ignition delay (octane boosting, important for reduced knock at high compression ratio) or flame speed improver (shortened burn duration leading to improved power).
• the engine used for these experiments was the Gasoline single cylinder engine in GDI mode. This engine was manufactured by AVL and based on the EA8882.0L Audi
• Figure 5 is a graphical representation of the Pmax measurements for Examples 14-27 and their reference base fuel.
• the Example number is on the x axis and the Pmax is on the y axis).
• Figure 6 shows the average % difference in Pmax and average % difference in burn duration (Al 10-90) between the test blend (Examples 14-27) and the base fuel control at 1300 rpm, 15 IMEP, IGN at TDC.
• the Example number is on the x axis and the average % difference in burn duration and average % difference in Pmax is on the y axis.

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• 2023
  • 2023-10-17 EP EP23793704.0A patent/EP4605501A1/de active Pending
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