EP3191568B1 - Utilisations pour maîtriser les émissions de particules dans un moteur à combustion interne - Google Patents

Utilisations pour maîtriser les émissions de particules dans un moteur à combustion interne Download PDF

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EP3191568B1
EP3191568B1 EP15760464.6A EP15760464A EP3191568B1 EP 3191568 B1 EP3191568 B1 EP 3191568B1 EP 15760464 A EP15760464 A EP 15760464A EP 3191568 B1 EP3191568 B1 EP 3191568B1
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examples
hydrocarbyl
fuel composition
ppm
aromatic compound
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EP3191568A1 (fr
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Robert Edward Allan
Timothy Hugh Lake
Charmaine NATHANIEL
David Michael Williamson
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BP Oil International Ltd
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    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • 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
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    • C10L1/14—Organic compounds
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    • C—CHEMISTRY; METALLURGY
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
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    • 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
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
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    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
    • 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
    • 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
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

  • This invention relates to uses of controlling particulate emissions from a direct-injection spark-ignition internal combustion engine, and in other aspects to the use of a combination of additives as a particulate emissions controlling additive in a fuel composition for a direct-injection spark-ignition internal combustion engine.
  • the invention also relates to the use of a combination of additives as an additive for controlling the generation of complex poly-aromatic nuclei (CPAN) in a fuel composition for a direct-injection spark-ignition internal combustion engine.
  • CPAN complex poly-aromatic nuclei
  • spark-ignition internal combustion engines which are classified according to the type of system for delivering fuel to the engine combustion chambers:
  • Vehicle emissions include particulate pollutants (PM), as well as ozone precursors such as nitrogen oxides (NO x ) and hydrocarbons.
  • PM particulate pollutants
  • NO x nitrogen oxides
  • hydrocarbons hydrocarbons
  • CPAN are thought to be precursors in the generation of particulate emissions.
  • Particulate emissions from gasoline direct injection engines are now being mandated by legislation.
  • An example of this is EU Commission Regulation No 582/2011, known as 'The Euro VI' emissions regulation, which came into force on 31 December 2013.
  • Particulate emissions can impact the performance of an engine. For instance, within the gas flow of an engine, they can lead to clogging of the exhaust gas recirculation system, the exhaust gas after treatment system and the gasoline particulate filters. Particulate emissions can also lead to increases in turbo lag and response times in the engine.
  • CPAN can also impact the performance of an engine in other ways. For instance, it is known in the art that CPAN can form soot-like particles that interfere with the anti-wear additive function in the lubricant pathway. Accordingly, CPAN can lead to wear on components in the lubricant pathway, such as the turbo, the timing chain, the crank train, and the camshaft and valve train assembly, including associated bearings and sealing systems. Control of CPAN generation and subsequent ingress into the lubricant will also maintain the performance of the lubricant including the lubricant additive chemistries thereby extending the required lubricant drain interval, especially under severe engine operating conditions. Other CPAN derived materials are believed to congregate within the combustion chamber. This can lead to an increase in octane requirement, as well as greater propensity for pre-ignition in the engine.
  • US2004/118036 discloses that a fuel composition containing an alkylene oxide-adducted hydrocarbyl amide having from about 3 to 50 moles of alkylene oxide per mole of hydrocarbyl amide may reduce the particulate emissions in an internal combustion engine.
  • US2006/0277820 relates to a deposit control additive composition for a fuel comprising polyisobutylene amine (PIBA) having an average molecular weight of about 700 to about 1000 and a Mannich Base as synergistic components of the deposit control additive formulation.
  • PIBA polyisobutylene amine
  • GB-A-2 010 324 relates to a dispersant additive for use in a hydrocarbon fuel, especially a fuel for a compression ignition engine, comprising a mixture of a polyalkylene amine and a Mannich base reaction product of an alkylphenol, an aldehyde and an amine.
  • the additive provides unexpected stability in preventing thermal degradation of fuels, particularly diesel fuels.
  • US-A-2003/029077 discloses a fuel composition
  • a fuel composition comprising a hydrocarbon fuel, a combination of nitrogen-containing detergents that includes a hydrocarbyl-substituted polyamine and a Mannich reaction product, and optionally a fluidizer.
  • Methods of operating and of controlling deposits in an internal combustion engine involve fueling the engine with the fuel composition which results in unexpectedly effective and efficient control of deposits in the fuel induction system. Therefore, there remains a need for methods and uses aspects of which reduce or at least mitigate problems, for example as identified above.
  • a particulate emissions controlling additive in a fuel composition for a direct-injection spark-ignition internal combustion engine or a compression-ignition gasoline internal combustion engine of:
  • an additive composition comprising a combination of:
  • a CPAN generation controlling additive in a fuel composition for a direct-injection spark-ignition internal combustion engine or a compression-ignition gasoline internal combustion engine of:
  • the hydrocarbyl-substituted aromatic compound is a Mannich base additive.
  • the polyalkylene amine is a polyisobutylene amine.
  • aspects of the present invention address the technical problems identified and others, by the use in combination of the hydrocarbyl-substituted aromatic compound and a polyalkylene amine.
  • a fuel composition comprising a combination of a hydrocarbyl-substituted aromatic compound and a polyalkylene amine exhibits beneficial particulate emissions control, such as control of the number of particles emitted, when used in a direct-injection spark-ignition internal combustion engine or a compression-ignition gasoline internal combustion engine.
  • a fuel composition comprising a combination of a hydrocarbyl-substituted aromatic compound and a polyalkylene amine may also exhibit beneficial CPAN generation control when used in a direct-injection spark-ignition internal combustion engine or a compression-ignition gasoline internal combustion engine.
  • the polyalkylene amine may be a poly C 1-10 -alkylene amine.
  • the polyalkylene amine may be polyethylene amine, a polypropylene amine, a polybutylene amine, a polypentylene amine or a polyhexylene amine.
  • the polyalkylene amine is a polybutylene amine, in particular a polyisobutylene amine.
  • Polyisobutylene amines are also sometimes called polyisobutylamine or PIBA.
  • suitable polyisobutylene amines include mono-amines, di-amines and polyamines of polyisobutylene including for example, polyisobutylene that is a homopolymer of isobutylene and polyisobutylene that is a polymer of isobutylene with minor amounts (for example up to 20% by weight), of one or more other monomers including for example n-butene, propene and mixtures thereof.
  • suitable polyisobutylene amines include polyisobutylene amines disclosed in, and/or obtained or obtainable by methods described in, US4832702 , US6140541 , US6909018 and/or US7753970 .
  • suitable polyisobutylene amines include polyisobutylene amines disclosed in, and/or obtained or obtainable by methods described in, US4832702 .
  • suitable polyisobutylene amines include compounds represented by the structural formula I:
  • R 2 and R 3 are identical or different and are each independently:
  • R 2 and R 3 together with the nitrogen atom to which they are bonded form a morpholinyl, pyridyl, piperidyl, pyrrolyl, pyrimidinyl, pyrolinyl, pyrrolidinyl, pyrazinyl or pyridazinyl group.
  • R 1 is a polybutyl or polyisobutyl group containing 20 to 400 carbon atoms which is derived or derivable from isobutene and up to 20% by weight n-butene.
  • R 1 is a polybutyl or polyisobutyl group containing 32 to 200 carbon atoms which is derived or derivable from isobutene and up to 20% by weight n-butene and R 2 and R 3 identical or different and are each independently: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, phenyl, - CH 2 - CH 2 - NH 2 , - CH 2 - CH 2 - CH 2 -N(CH 3 ) 2 , or -[- CH 2 - CH 2 -NH] p - CH 2 - CH 2 -NH 2 where p is an integer from 1 to 7, for example 1 to 3, - CH 2 - CH 2 - OH, -[- CH 2 - CH 2 -O] q - CH 2 -
  • suitable polyisobutylene amines additives also include polyisobutylene amines disclosed in, and/or obtained or obtainable by methods described in, described in US6140541 and US6909018 .
  • suitable polyisobutylene amines include compounds represented by the formula (V): wherein R 7 , R 8 , R 9 and R 10 independently of one another, are each hydrogen or an unsubstituted or substituted, saturated or mono- or polyunsaturated aliphatic group exhibiting a number average molecular weight of up to 40000, at least one of the groups R 7 to R 10 exhibiting a number average molecular weight of from 150 to 40000, and R 11 and R 12 independently of each other are each H; an alkyl group, for example a C 1 to C 18 alkyl group; a cycloalkyl group; a hydroxyalkyl group; an aminoalkyl group; an alkenyl group; an alkynyl group, an aryl group; an
  • each of R 11 , R 12 , R 13 and R 14 are independently substituted by further alkyl groups carrying hydroxy or amino groups.
  • suitable polyisobutylene amines additives also include polyisobutylene amines disclosed in, and/or obtained or obtainable by methods described in, US7753970 .
  • suitable polyisobutylene amines include polyisobutylene amines that are derived or derivable from polyisobutenes derived or derivable from isobutene or an isobutenic monomer mixture, for example a mixture of isobutene and up to 20% by weight of n-butene.
  • Suitable polyisobutylene amines include polyisobutene amines derived or derivable from polyisobutylene that is derived or derivable by the polymerisation of identical or different straight-chain or branched C 4 olefin monomers, which in at least some examples, are suitably randomised in the polymerisation product.
  • Suitable polyisobutylene amines include polyisobutylene amines that are derived or derivable from highly reactive polyisobutenes.
  • Highly reactive polyisobutenes contain a high content of terminal double bonds (also sometimes referred to alpha-olefinic double bonds and/or vinylidene double bonds), for example at least 20 %, or at least 50%, or at least 70% of the total olefinic double bonds in the polyisobutene. These are sometimes represented by the general structure:
  • Highly reactive polyisobutenes may be made by methods described for example in US4152499 .
  • the polyisobutylene amine contains a polyisobutenic group that exhibits a number average molecular weight of from about 200 to about 10000, for example from about 500 to about 5000 or from about 700 to about 1500 or from about 800 to about 1200 or from about 850 to about 1100, for example about 1000.
  • the polyisobutylene amine is derived from or derivable from a polyisobutene that exhibits at least one of the following properties:
  • each polyalkylene amine may be a polyisobutylene amine.
  • the polyalkylene amine is present/used in the fuel composition at a concentration of actives of at least about 50 ppm, for example at a concentration of actives of at least about 70 ppm. In at least some examples the polyalkylene amine is present/used in the fuel composition at a concentration as actives of up to about 500 ppm, for example at a concentration of up to about 300 ppm. In at least some examples the polyalkylene amine is present/used in the fuel composition at a concentration of actives in the range of from about 50 ppm to about 500 ppm, such as from about 70 ppm to about 300 ppm. Concentration of actives means the concentration of the active polyalkylene amine disregarding for example, any solvent and the like. As will be clear to the skilled person, the concentration of actives expressed herein in terms of ppm is ppm by weight.
  • the polyalkylene amine will be present/used in the fuel composition at a concentration of actives of from about 50 ppm to about 160 ppm. In some examples, however, higher treat rates may be used. In such instances, the polyalkylene amine may be present/used in the fuel composition at a concentration of from about 160 ppm to about 500 ppm.
  • the total concentration of the polyalkylene amines is as described herein.
  • the hydrocarbyl-substituted aromatic compound used in the fuel composition which may be a hydrocarbyl-substituted hydroxyaromatic compound, such as a hydrocarbyl-substituted phenol compound, is a Mannich base additive.
  • the hydrocarbyl substituent may attach at the ortho-, meta- or para- position of the phenol ring.
  • the hydrocarbyl substituent of the hydrocarbyl-substituted aromatic compound may exhibit a number average molecular weight of from about 700 to about 1500, such as from about 900 to about 1300.
  • Mannich Base additives include those obtained or obtainable by the reaction of a hydrocarbyl-substituted hydroxyaromatic compound, an amine and an aldehyde under Mannich condensation reaction conditions.
  • Suitable reaction conditions include at least one (for example, all) of the following conditions:
  • aldehydes suitable for the preparation of Mannich Base additives include:
  • formaldehyde precursors including for example paraformaldehyde and aqueous formaldehyde solutions including for example formalin.
  • hydrocarbyl substituents of the hydrocarbyl-substituted hydroxyaromatic compound include for example, polyolefin polymers for example polypropylene, polybutenes, polyisobutylene, ethylene alpha-olefin copolymers and the like.
  • polyolefin polymers for example polypropylene, polybutenes, polyisobutylene, ethylene alpha-olefin copolymers and the like.
  • Other examples include copolymers of butylene and/or isobutylene and/or propylene and one or more mono-olefinic comonomers copolymerisable therewith (for example ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene and the like) where the comonomer molecule contains at least 50% by weight of butylene and/or isobutylene and/or propylene units.
  • the copolymers are aliphatic and in some examples contain non-aliphatic groups (for example styrene, o-methylstyrene, p-methylstyrene, divinyl benzene and the like), in any case the resulting polymers are substantially aliphatic hydrocarbon polymers.
  • non-aliphatic groups for example styrene, o-methylstyrene, p-methylstyrene, divinyl benzene and the like
  • Mannich Base additives examples include Mannich Base additives in which the hydrocarbyl substituent of the aromatic group is or comprises polyisobutylene. Such compounds are sometimes called PIB-Mannich Base additives.
  • hydrocarbyl substituents of the hydrocarbyl-substituted hydroxyaromatic compound include polymers obtained or obtainable from pure or substantially pure 1-butene; polymers obtained or obtainable from pure or substantially pure isobutene; and polymers obtained or obtainable from mixtures of 1-butene, 2-butene and isobutene.
  • the hydrocarbyl-substituted hydroxyaromatic reactant is obtained or obtainable from high reactive polyisobutene.
  • High reactive polyisobutenes contain a high content of terminal double bonds (also sometimes referred to alpha-olefinic double bonds and/or vinylidene double bonds), for example at least 20 %, or at least 50%, or at least 70% of the total olefinic double bonds in the polyisobutene.
  • terminal double bonds also sometimes referred to alpha-olefinic double bonds and/or vinylidene double bonds
  • Examples of high reactivity polybutylenes containing relatively high proportions of polymer molecules comprising a terminal vinylidene group include those that are obtained or obtainable by methods described in US4152499 and DE2904314 .
  • hydrocarbyl substituents contain some residual unsaturation but in general they are substantially saturated.
  • the hydrocarbyl substituent is a polymer exhibiting a polydispersity of from 1 to 4, for example from 1 to 2, for example as determined by gel permeation chromatography (sometimes also referred to as GPC).
  • the hydrocarbyl substituent of the hydroxyaromatic compound used to prepare the Mannich Base additive which in some instances is or comprises polyisobutylene, may exhibit a number average molecular weight of from about 700 to about 1500, such as from about 900 to about 1300.
  • Mannich Base additives include those disclosed in, and/or obtained or obtainable by methods described in, US5634951 , US5697988 , US6800103 , US7597726 and/or US20090071065 .
  • Mannich Base additives include those disclosed in, and/or obtained or obtainable by methods described in, US5634951 .
  • suitable Mannich Base additives include those obtainable or obtained by the reaction of (i) one mole part of at least one hydroxyaromatic compound comprising on the ring an aliphatic hydrocarbyl substituent derived from a polyolefin exhibiting a number average molecular weight in the range of 500 to 3000, (ii) from 0.8 to 1.3 mole part(s) of at least one aldehyde, and (iii) from 0.8 to 1.5 mole part(s) of at least one aliphatic polyamine comprising in the molecule one primary or secondary amino group capable of undergoing a Mannich condensation reaction with (i) and (ii), the other amino group or groups (if any) in the molecule being substantially inert towards participation in such Mannich condensation reaction, with the proviso that the mole ratio of aldehyde to amine is 1.2 or less.
  • Suitable hydroxyaromatic compounds (i) include high molecular weight alkyl-substituted hydroxyaromatic compounds including polypropylphenol (including those formed by alkylating phenol with polypropylene), polybutylphenols (including those formed by alkylating phenol with polybutenes and/or polyisobutylene), and polybutyl-co-polypropylphenols (including those formed by alkylating phenol with a copolymer of butylene and/or isobutylene and propylene).
  • polypropylphenol including those formed by alkylating phenol with polypropylene
  • polybutylphenols including those formed by alkylating phenol with polybutenes and/or polyisobutylene
  • polybutyl-co-polypropylphenols including those formed by alkylating phenol with a copolymer of butylene and/or isobutylene and propylene.
  • hydroxyaromatic compounds include for example, long chain alkylphenols for example those made by alkylating phenol with copolymers of butylene and/or isobutylene and/or propylene and one or more mono-olefinic comonomers copolymerisable therewith (including for example ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene and the like), for example those in which the copolymer contains at least 50% by weight of butylene and/or isobutylene and/or propylene units.
  • long chain alkylphenols for example those made by alkylating phenol with copolymers of butylene and/or isobutylene and/or propylene and one or more mono-olefinic comonomers copolymerisable therewith (including for example ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene and the like), for example those in which the copolymer contains at
  • the comonomers may be aliphatic and can also contain non-aliphatic groups (for example styrene, o-methylstyrene, p-methylstyrene, divinyl benzene and the like).
  • Suitable examples include polybutylphenols (for example, formed by alkylating phenol with polybutylene), which polybutylene includes for example, polymers made from pure or substantially pure 1-butene or isobutene and mixtures made from two, or all three of 1-butene, 2-butene and isobutene.
  • High reactivity polybutylenes are also suitable examples for making suitable hydrocarbyl-substituted hydroxyaromatic compounds.
  • hydrocarbyl-substituted hydroxyaromatic compounds include para-substituted hydroxyaromatic compounds.
  • hydrocarbyl-substituted hydroxyaromatic compounds include those with one, two or more than two hydrocarbyl substituents.
  • suitable polyamine reactants (iii) include alkylene polyamines for example containing a single reactive primary or secondary amino group. Examples include those comprising other groups including for example hydroxyl, cyano, amido and etc. Examples of suitable polyamines include aliphatic diamines, for example, those containing one primary or secondary amino group and one tertiary amino group.
  • Examples include N,N,N",N"-tetraalkyldialkylenetriamines; N,N,N',N"-tetraalkyltrialkylenetetramines; N,N,N',N",N"'-pentaalkyltrialkylenetetramines; N,N-dihydroxyalkyl- ⁇ , ⁇ -alkylenediamines; N,N,N'-trihydroxyalkyl- ⁇ , ⁇ -alkylenediamines; tris(dialkylaminoalkyl)aminoalkylmethanes etc.
  • alkyl groups are the same or different, including those that typically contain no more than 12 carbon atoms, for example 1 to 4 carbon atoms each e.g. methyl and/or ethyl.
  • polyamines containing one reactive primary or secondary amino group that can participate in the Mannich condensation reaction and at least one sterically hindered amino group that cannot participate directly in the Mannich reaction include for example, N - ( tert- butyl)-1,3-propanediamine; N-neopentyl-1,3-propranediamine; N-( tert -butyl)-1-methyl-1,2-ethanediamine; N-( tert -butyl)-1-methyl-1,3-propanediamine and 3,5-di(tert-butyl)aminoethylpiperazine.
  • Mannich Base additives also include those disclosed in, and/or obtained or obtainable by methods described in US5697988 .
  • suitable Mannich Base additives include Mannich reaction products of (i) a high molecular weight alkyl-substituted phenol, (ii) amine and (iii) aldehyde wherein (i), (ii) and (iii) are reacted in a ratio in the range of from 1.0:0.1-10.0:0.1-10.
  • the Mannich reaction products are obtained or obtainable by condensing an alkyl-substituted hydroxyaromatic compound whose alkyl-substituent has a number average molecular weight (Mn) in the range of from 600 to 14000 for example polyalkylphenol whose polyalkyl substituent is derived or derivable from 1-mono-olefin polymers exhibiting a number average molecular weight in the range of from 600 to 3000, for example in the range of from 750 to 1200; an amine containing at least one >NH group, for example an alkylene polyamine as represented by the formula: H 2 N-(A-NH-) x H in which A is a divalent alkylene group containing 1 to 10 carbon atoms and x is an integer in the range of from 1 to 10; and an aldehyde, for example formaldehyde in the presence of a solvent.
  • Suitable reaction conditions include one or more of the following:
  • Mannich reaction products include those derived or derivable by reacting an alkylphenol, an ethylene polyamine and a formaldehyde in respective molar ratio of 1.0:0.5-2.0:1.0-3.0 wherein the alky group of the alkyl phenol exhibits a number average molecular weight (Mn) in the range of from 600 to 3000, for example in the range of from 740 to 1200 or in the range of from 800 to 950 or for example 900.
  • alkyl-substituted hydroxyaromatic compounds include para-substituted mono-alkylphenols and ortho mono-alkylphenols and dialkyl phenols.
  • amine reactants include polyamines, for example polyethylene amines.
  • amine reactants also include mono and di-amino alkanes and their substituted analogs, for example ethylamine, dimethylamine, dimethylaminopropyl amine and diethanol amine; aromatic diamines, (e.g. phenylene diamine and diamine naphthalenes); heterocyclic amines (e.g. morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine and piperidine); melamine; and their substituted analogs.
  • aromatic diamines e.g. phenylene diamine and diamine naphthalenes
  • heterocyclic amines e.g. morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine and piperidine
  • melamine melamine
  • amine reactants include alkylene polyamines, for example polyamines that are linear, branched or cyclic; mixtures of linear and/or branched and/or cyclic polyamines wherein each alkylene group contains from 1 to 10 carbon atoms, for example from 2 to 20 carbon atoms.
  • alkylene polyamines for example polyamines that are linear, branched or cyclic; mixtures of linear and/or branched and/or cyclic polyamines wherein each alkylene group contains from 1 to 10 carbon atoms, for example from 2 to 20 carbon atoms.
  • polyamines include those containing from 3 to 7 nitrogen atoms.
  • Mannich Base additives also include those disclosed in, and/or obtained or obtainable by methods described in, US6800103 .
  • suitable Mannich Base additives include those obtained or obtainable by reacting a mixture of (i) at least one substituted hydroxyaromatic compound containing on the ring both (a) an aliphatic hydrocarbyl substituent derived from a polyolefin exhibiting a number average molecular weight in the range of 500 to 3000 and (b) a C 1-4 alkyl; (ii) at least one secondary amine; and (iii) at least one aldehyde.
  • components (ii) and (iii) are pre-reacted to from an intermediate prior to addition of component (i).
  • a mixture formed from components (i), (ii) and (iii) is heated at a temperature above 40°C at which Mannich condensation reaction takes place.
  • the Mannich reaction products is obtained or obtainable by reacting a di-substituted hydroxyaromatic compound in which the hydrocarbyl substituent (a) comprises polypropylene, polybutylene or an ethylene alpha-olefin copolymer exhibiting a number average molecular weight in the range of 500 to 3000 and a polydispersity in the range of 1 to 4, one or more secondary amines and at least one aldehyde.
  • the hydrocarbyl substituent (a) comprises polypropylene, polybutylene or an ethylene alpha-olefin copolymer exhibiting a number average molecular weight in the range of 500 to 3000 and a polydispersity in the range of 1 to 4, one or more secondary amines and at least one aldehyde.
  • dibutyl amine as the amine, formaldehyde or formalin as the aldehyde and a molar ratio of the substituted hydroxyaromatic compound to dibutyl amine to formaldehyde of 1 : 0.8-1.5 : 0.8-1.5 respectively, for example 1 : 0.9-1.2 : 0.9-1.2, respectively.
  • Examples of representative di-substituted hydroxyaromatic compounds include those represented by the general formula (VII): in which each R is H, C 1-4 alkyl or a hydrocarbyl substituent exhibiting a number average molecular weight in the range of 500 to 3000, with the proviso that one R is H, one R is a C 1-4 alkyl and one R is a hydrocarbyl substituent.
  • Examples of representative hydrocarbyl substituents of the hydrocarbyl-substituted hydroxyaromatic compound (ii) include polyolefin polymers for example polypropylene, polybutenes, polyisobutylene, ethylene alpha-olefin copolymers and the like.
  • Other examples include copolymers of butylene and/or isobutylene and/or propylene and one or more mono-olefinic comonomers copolymerisable therewith (for example ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene and the like) where the comonomer molecule contains at least 50% by weight of butylene and/or isobutylene and/or propylene units.
  • the copolymers are aliphatic and in some examples contain non-aliphatic groups (for example styrene, o-methylstyrene, p-methylstyrene, divinyl benzene and the like), in any case the resulting polymers are substantially aliphatic hydrocarbon polymers.
  • High reactivity polybutylenes are also suitable for making suitable hydrocarbyl-substituted hydroxyaromatic compounds.
  • Suitable di-substituted hydroxyaromatic compounds include those obtained or obtainable by alkylating o-cresol with the high molecular weight polymers described above.
  • the hydrocarbyl substituent is in the para-position of the disubstituted hydroxyaromatic compound and the C 1-4 alkyl substituent is in the ortho-position.
  • Examples of representative secondary amines (ii) include those represented by the general formula (VIII): in which R' and R" are each independently alkyl, cycloalkyl, aryl, alkaryl or aralkyl groups containing from 1 to 30 carbon atoms, for example 1 to 18 carbon atoms or 1 to 6 carbon atoms. Examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine and dicyclohexylamine.
  • Mannich Base additives also include those disclosed in, and/or obtained or obtainable by methods described in US7597726 .
  • suitable Mannich Base additives include Mannich condensation reaction products of (i) a polyamine containing a sterically-hindered primary amino group, (ii) a hydrocarbyl-substituted hydroxyaromatic compound and (iii) and aldehyde.
  • polyamines (i) containing a sterically-hindered primary amino group include (A) aliphatic cyclic polyamines containing a sterically-hindered primary amino group, (B) acyclic aliphatic polyamines containing a sterically-hindered primary amino group and combinations thereof.
  • the Mannich reaction product is obtained or obtainable by reacting (1) 1,2-diaminocyclohexane, (2) polyisobutylene-substituted cresol and/or phenol, and (3) formaldehyde, for example in which the reactants (1), (2) and (3) are reacted in equimolar proportions in a Mannich reaction.
  • the Mannich reaction product is dispersed in a liquid carrier fluid.
  • the polyamine reactant contains an amino group that does not participate in the Mannich condensation reaction with the hydrocarbyl-substituted hydroxyaromatic reactant in addition to at least one reactive amino group in the same polyamine molecule that takes part in the Mannich reaction.
  • Examples of reactive amino groups include primary and secondary amino groups, for example non-sterically hindered reactive primary amino groups.
  • polyamines containing a reactive amino group and a sterically-hindered amino group include those represented by the formula (IX): wherein X and Z each is methylene, Y is an alkylene or alkyleneamino group, n is 0 or 1, Q is an optional alkylene group suitable for forming a ring structure with X and Z, E is a hydrocarbyl group, t is 0 or 1, R 1 is a hydrocarbyl group or hydrogen provided that R 1 is hydrocarbyl if n is 1, R 2 is hydrogen or a hydrocarbyl group, m is 0 or 1 provided that m is 0 if Q is present.
  • R 1 and/or R 2 is hydrocarbyl
  • examples of such hydrocarbyl groups include C 1 to C 8 alkyl (for example methyl, ethyl, propyl, isopropyl, t-butyl and the like).
  • Y include C 1 to C 8 alkylene; alkyleneamino (for example methyleneamino, (-CH 2 N(H)-), dimethyleneamino (-CH 2 N(H)-CH 2 -), methyleneamino-ethylmethyleneamino (-CH 2 N(H)-C 2 H 4 N(H)-CH 2 -) and the like).
  • examples of E include methylene, ethylene, isopropylene and the like.
  • examples of Q include alkylene chains, for example C 2 -C 4 alkylene chains.
  • polyamines containing a sterically hindered primary amino group include aliphatic cyclic polyamines, including for example, polyaminocycloalkanes, for example polyaminocyclohexanes, including 1,2-diaminodicyclohexanes, 1,3-diaminodicyclohexanes and 1,4-diaminodicyclohexanes, for example as represented by the following formulae Xa, Xb and Xc:
  • a sterically hindering hydrocarbyl group generally is bonded to the same carbon atom from which the sterically-hindered primary amino group is bonded when the hindered/protected and reactive amino groups are present in an arrangement other than an ortho configuration relative to each other.
  • a reactive amino group is present as a moiety of an intervening substituent that is directly attached to the ring structure.
  • mixtures of isomers are used.
  • Suitable acyclic aliphatic polyamine reactants include alkylene polyamines containing a primary amino group that is physically sterically-protected to prevent or at least significantly hinder its ability to participate in the Mannich condensation reaction.
  • the sterically hindered primary amino group is generally attached to either a secondary or tertiary carbon atom in the polyamine compound.
  • the acyclic aliphatic polyamine has a suitably reactive amino group (for example primary or secondary) in the same molecule for participating in the Mannich condensation reaction.
  • substituents are present, for example hydroxyl, cyano, amido and the like.
  • Examples of acyclic aliphatic polyamines containing a sterically hindered primary amino group include those represented by formulae XIa, XIb, XIc and XId: wherein each R 1 and R 2 are a hydrocarbyl group or a hydrogen provided that at least one thereof is a hydrocarbyl group.
  • Examples of hydrocarbyl groups include C 1 to C 8 alkyl e.g. methyl, ethyl, propryl, isopropyl and the like;
  • hydrocarbyl-substituted hydroxyaromatic compounds (ii) include those represented by formula XII: in which each R is H, C 1-4 alkyl or a hydrocarbyl substituent exhibiting an average molecular weight (Mw) in the range of 300 to 2000, for example 500 to 1500, for example as measured by gel permeation chromatorgraphy, with the proviso that at least one R is H and one R is a hydrocarbyl substituent as hereinbefore defined.
  • Examples of representative hydrocarbyl substituents of the hydrocarbyl-substituted hydroxyaromatic compound (ii) include polyolefin polymers for example polypropylene, polybutenes, polyisobutylene, ethylene alpha-olefin copolymers and the like.
  • Other examples include copolymers of butylene and/or isobutylene and/or propylene and one or more mono-olefinic comonomers copolymerisable therewith (for example ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene and the like) where the comonomer molecule contains at least 50% by weight of butylene and/or isobutylene and/or propylene units.
  • the copolymers are aliphatic and in some examples contain non-aliphatic groups (for example styrene, o-methylstyrene, p-methylstyrene, divinyl benzene and the like), in any case the resulting polymers are substantially aliphatic hydrocarbon polymers.
  • non-aliphatic groups for example styrene, o-methylstyrene, p-methylstyrene, divinyl benzene and the like
  • hydrocarbyl substituents include polymers obtained or obtainable from pure or substantially pure 1-butene; polymers obtained or obtainable from pure or substantially pure isobutene; and polymer obtained or obtainable from mixtures of 1-butene, 2-butene and isobutene.
  • the hydrocarbyl-substituted hydroxyaromatic reactant is obtained or obtainable from highly reactive polyisobutene.
  • a suitable di-substituted hydroxyaromatic compound is obtained or obtainable by alkylating o-cresol with a high molecular weight hydrocarbyl polymer, for example a hydrocarbyl polymer exhibiting an average molecular weight in the range of from 300 to 2000, for example by alkylating o-cresol or o-phenol with polyisobutylene exhibiting an average molecular weight in the range of from 300 to 2000, for example in the range of from 500 to 1500.
  • a hydrocarbyl polymer for example a hydrocarbyl polymer exhibiting an average molecular weight in the range of from 300 to 2000
  • polyisobutylene exhibiting an average molecular weight in the range of from 300 to 2000, for example in the range of from 500 to 1500.
  • Mannich Base additives also include those disclosed in, and/or obtained or obtainable by methods described in US20090071065 .
  • suitable Mannich Base additives include Mannich condensation reaction products of: (i) a polyamine having primary amino groups, (ii) a hydrocarbyl-substituted hydroxyaromatic compound, and (iii) an aldehyde, where the Mannich reaction is conducted at an overall molar ratio of (i):(ii):(iii) such that, for example, the polyamine (i) is reactable with the hydrocarbyl-substituted hydroxyaromatic compound (ii) so as to obtain the substantially pure intermediate, which intermediate is reactable with the aldehyde (iii) to obtain the Mannich reaction product, for example in a one-pot reaction process.
  • polyamine (i) examples include 1,2-diaminocyclohexane, 1,3-diamino propane and 1,2-diamino ethane.
  • suitable molar ratios (i):(ii):(iii) examples include 1:2:3 and 1:1:2.
  • hydrocarbyl-substituted hydroxyaromatic compounds include those represented by formula (XIII): in which each R is H, C 1-4 alkyl, or a hydrocarbyl substituent exhibiting an average molecular weight (Mw) in the range of 300 to 2000, for example 500 to 1500, for example as determined by gel permeation chromatography, with the proviso that at least R is H and one R is a hydrocarbyl substituent as hereinbefore defined.
  • hydrocarbyl substituents include polyolefin polymers, for example polypropylene, polybutylene, polyisobutylene and ethylene alpha-olefin copolymers and also copolymers of butylene and/or isobutylene and/or propylene and one or more mono-olefinic comonomers copolymerisable therewith (for example ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene and the like) wherein the copolymer contains at least 50% by weight of butylene and/or isobutylene and/or propylene units.
  • polyolefin polymers for example polypropylene, polybutylene, polyisobutylene and ethylene alpha-olefin copolymers and also copolymers of butylene and/or isobutylene and/or propylene and one or more mono-olefinic comonomers copolymerisable therewith (for example ethylene,
  • polyolefin polymer hydrocarbyl substituents contain at least 20%, for example 50%, or 70% of their olefin double bonds at a terminal position on the carbon chain as the highly reactive vinylidene isomer.
  • hydrocarbyl substituents include those obtained or obtainable from polyisobutylene, for example polyisobutylene obtained or obtainable from pure or substantially pure 1-butene or isobutene and polymers obtained or obtainable from mixtures of two or three of 1-butene, 2-butene and isobutene.
  • hydrocarbyl substituents include those obtained or obtainable from high reactivity polyisobutylene which have a relatively high proportion of polymer having terminal vinylidene groups, for example at least 20%, 50% or 70% of the total terminal olefinic double bonds in the polyisobutylene comprise an alkyl vinylidene isomer.
  • each hydrocarbyl-substituted aromatic compound may be a Mannich base additive.
  • the hydrocarbyl-substituted aromatic compound is present/used in the fuel composition at a concentration of actives of at least about 20 ppm, for example at a concentration of actives of at least about 30 ppm. In at least some examples, the hydrocarbyl-substituted aromatic compound is present/used in the fuel composition at a concentration of actives of up to about 300 ppm, for example at a concentration of up to about 120 ppm. In at least some examples, the hydrocarbyl-substituted aromatic compound is present/used in the fuel composition at a concentration of actives in the range of from about 20 ppm to about 300 ppm, such as from about 30 ppm to about 120 ppm. Concentration of actives means the concentration of the active hydrocarbyl-substituted aromatic compound disregarding, for example, any solvent and the like.
  • the hydrocarbyl-substituted aromatic compound will be present/used in the fuel composition at a concentration of actives of from about 20 ppm to about 70 ppm. In some examples, however, higher treat rates may be used. In such instances, the hydrocarbyl-substituted aromatic compound may be present/used in the fuel composition at a concentration of from about 70 ppm to about 300 ppm.
  • the total concentration of the hydrocarbyl-substituted aromatic compounds is as described herein.
  • the polyalkylene amine is present/used in the fuel composition at a concentration of actives of from about 50 ppm to about 500 ppm and the hydrocarbyl-substituted aromatic compound is present/used in the fuel composition at a concentration of actives of from about 20 ppm to about 300 ppm.
  • the polyalkylene amine may be present/used in the fuel composition at a concentration of actives of from about 50 ppm to about 160 ppm and the hydrocarbyl-substituted aromatic compound may be present/used in the fuel composition at a concentration of actives of from about 20 ppm to about 70 ppm.
  • the polyalkylene amine may be present/used in the fuel composition at a concentration of actives of from about 160 ppm to about 500 ppm and the hydrocarbyl-substituted aromatic compound may be present/used in the fuel composition at a concentration of actives of from about 70 ppm to about 300 ppm.
  • the weight ratio of actives of the polyalkylene amine : the hydrocarbyl-substituted aromatic compound is in the range of about 10:1 to about 1:10 for example about 5:1 to about 1:5. Where more than one polyalkylene amine and/or more than one hydrocarbyl-substituted aromatic compound is present/used, the weight ratio of actives of all of the polyalkylene amines : all of the hydrocarbyl-substituted aromatic compound is as described herein.
  • the polyalkylene amine contains a polyalkylene group that exhibits a number average molecular weight of from about 700 to about 1500 ( e.g . from about 800 to about 1200) and the hydrocarbyl substituent of the hydrocarbyl-substituted aromatic compound, which in some instances is or comprises polyisobutylene, exhibits a number average molecular weight of from about 700 to about 1500 ( e.g . about 900 to about 1300).
  • a carrier fluid (sometimes also called induction aid or fluidiser) is present/used in the fuel composition, the uses and/or the methods. In at least some examples more than one carrier fluid is present/used.
  • the carrier fluid is provided with the polyalkylene amine. In at least some examples the carrier fluid is provided with the hydrocarbyl-substituted aromatic compound. In at least some examples a carrier fluid is provided with each of the polyalkylene amine and the hydrocarbyl-substituted aromatic compound, which carrier fluids may be the same or different. In at least some examples the carrier fluid is provided independently of the polyalkylene amine and the hydrocarbyl-substituted aromatic compound.
  • suitable carrier fluids are described for example in US2009/0071065 at paragraphs [0038] to [0053].
  • suitable carrier fluid include liquid poly-alpha olefin oligomers, liquid polyalkene hydrocarbons (for example polypropylene, polybutenes, polyisobutene and the like), liquid hydrotreated polyalkene hydrocarbons (for example hydrotreated polypropylene, hydrotreated polybutenes, hydrotreated polyisobutene and the like), mineral oils, liquid poly(oxyalkylene) compounds, liquid alcohols, liquid polyols, liquid esters and the like.
  • liquid poly-alpha olefin oligomers for example polypropylene, polybutenes, polyisobutene and the like
  • liquid hydrotreated polyalkene hydrocarbons for example hydrotreated polypropylene, hydrotreated polybutenes, hydrotreated polyisobutene and the like
  • mineral oils for example hydrotreated polypropylene, hydrotreated polybutenes, hydrotreated polyis
  • carrier fluids include (1) a mineral oil or blend of mineral oils, for example those exhibiting a viscosity index of less than 120; (2) one or a blend of poly alpha olefins, for example those exhibiting an average molecular weight in the range of from 500 to 1500; (3) polyethers including poly(oxyalkylene) compounds, for example those exhibiting an average molecular weight in the range of from 500 to 1500; (4) one or more liquid polyalkylenes; and (5) mixtures of two or more selected from the group consisting of (1), (2), (3) and (4).
  • suitable mineral oil carrier fluids include paraffinic, naphthenic and asphaltic oils, for example hydrotreated oils.
  • mineral oils exhibit a viscosity at 40 °C of less than 1600 SUS, for example 300 to 1500 SUS and/or exhibit a viscosity index of less than 100, for example in the range 30 to 60.
  • suitable poly alpha olefin carrier fluids include hydrotreated and unhydrotreated poly alpha olefins.
  • suitable poly alpha olefin carrier fluids include hydrotreated and unhydrotreated poly alpha olefins.
  • poly alpha olefins include trimmers, tetramers and pentamers of alpha olefin monomers containing 6 to 12 carbon atoms.
  • suitable polyether carrier fluids include poly(oxyalkylene) compounds exhibiting an average molecular weight in the range of from 500 to 1500, including for example hydrocarbyl-terminated poly(oxyalkylene) monols.
  • poly(oxyalkylene) compounds include one or a mixture of alkylpoly(oxyalkylene)monols which in its undiluted state is a gasoline-soluble liquid exhibiting a viscosity of at least 70 cSt at 40° C and at least 13 cSt at 100° C, including such monols formed by propoxylation of one or a mixture of alkanols containing at least 8 carbon atoms, for example 10 to 18 carbon atoms.
  • suitable poly(oxyalkylene) carrier fluids include those exhibiting a viscosity in the undiluted state of at least 60 cSt at 40° C (for example at least 70 cSt at 40° C) and at least 11 cSt at 100° C (for example at least at least 13 cSt at 100° C).
  • suitable poly(oxyalkylene) carrier fluids include those exhibiting viscosities in their undiluted state of no more than 400 cSt at 40° C (for example no more than 300 cSt at 40° C) and no more than 50 cSt at 100° C (for example no more than 40 cSt at 100° C).
  • poly(oxyalkylene) compounds include poly(oxyalkylene) glycol compounds and monoether derivatives thereof, for example those that satisfy the above viscosity requirements, including those that are obtained or obtainable by reacting an alcohol or polyalcohol with an alkylene oxide, for example propylene oxide and/or butylene oxide with or without the use of ethylene oxide, for example products in which at least 80 mol. % of the oxyalkylene groups in the molecule are derived or derivable from 1,2-propylene groups.
  • an alkylene oxide for example propylene oxide and/or butylene oxide with or without the use of ethylene oxide
  • poly(oxyalkylene) compounds examples include those disclosed in, and/or obtained or obtainable by methods described in, US248664 , US2425845 , US2425755 and US2457139 .
  • the poly(oxyalkylene) carrier compounds should contain sufficient branched oxyalkylene units (for example methyldimethyleneoxy units and/or ethyldimethyleneoxy units) to render the poly(oxyalkylene) compound gasoline soluble.
  • polyalkylene carrier fluids examples include polypropenes, polybutenes, polyisobutenes, polyamylenes, copolymers of propene and butene, copolymers of butene and isobutene, copolymers of propene and isobutene and copolymers of propene, butene and isobutene and mixtures thereof.
  • polyalkylene carrier fluids also include hydrotreated polypropylenes, hydrotreated polybutenes, hydrotreated polyisobutenes and the like.
  • polybutenes carrier fluids include those exhibiting a narrow molecular weight distribution, for example as expressed as the ratio M w / M n that is, (mass average molecular mass)/(the number average molecular mass), this ratio is sometimes called the polydispersity index.
  • polybutenes carrier fluids include those exhibiting a narrow molecular weight distribution, expressed as the ratio M w (mass average molecular mass) / M n the number average molecular mass of 1.4 or less, for example as described in US6048373 .
  • Methods of determining mass average molecular mass include static light scattering, small angle neutron scattering, X-ray scattering, and sedimentation velocity. Number average molecular mass or weight (M n ) can be determined by gel permeation chromatography.
  • the carrier fluid is present/used in the fuel composition at a concentration of at least about 10 ppm, for example at a concentration of at least about 35 ppm. In at least some examples, the carrier fluid is present/used in the fuel composition at a concentration of up to about 500 ppm, for example at a concentration of up to about 200 ppm. In at least some examples, the carrier fluid is present/used in the fuel composition at a concentration in the range of from about 10 ppm to about 500 ppm, such as from about 35 ppm to about 200 ppm.
  • the total concentration of the carrier fluid is as described herein.
  • the fuel composition is suitable for use for example, in a spark ignition internal combustion engine.
  • the fuel composition has a sulphur content of up to 50.0 ppm by weight, for example up to 10.0 ppm by weight.
  • suitable fuel compositions include leaded and unleaded fuel compositions.
  • the fuel composition meets the requirements of EN 228, for example as set out in BS EN 228:2012. In at least some examples the fuel composition meets the requirements of ASTM D 4814-14.
  • the fuel composition for spark-ignition internal combustion engines exhibits one or more (for example all) of the following, for example, as defined according to BS EN 228:2012 :- a minimum research octane number of 95.0, a minimum motor octane number of 85.0 a maximum lead content of 5.0 mg/l, a density of 720.0 to 775.0 kg/m 3 , an oxidation stability of at least 360 minutes, a maximum existent gum content (solvent washed) of 5 mg/100 ml, a class 1 copper strip corrosion (3 h at 50 °C), clear and bright appearance, a maximum olefin content of 18.0 % by weight, a maximum aromatics content of 35.0 % by weight, and a maximum benzene content of 1.00 % by volume.
  • suitable fuel compositions include for example hydrocarbon fuels, oxygenate fuels and combinations thereof.
  • Hydrocarbon fuels may be derived from mineral sources and/or from renewable sources such as biomass (e.g. biomass-to-liquid sources) and/or from gas-to-liquid sources and/or from coal-to-liquid sources.
  • biomass e.g. biomass-to-liquid sources
  • gas-to-liquid sources e.g. gas-to-liquid sources
  • coal-to-liquid sources e.g. coal-to-liquid sources
  • suitable oxygenate fuel components in the fuel composition include straight and/or branched chain alkyl alcohols having from 1 to 6 carbon atoms, for example methanol, ethanol, n-propanol, n-butanol, isobutanol, tert-butanol.
  • Suitable oxygenate components in the fuel composition for spark-ignition internal combustion engines or compression-ignition gasoline internal combustion engines include ethers, for example having 5 or more carbon atoms, for example methyl tert-butyl ether and ethyl tert-butyl ether.
  • the fuel composition has a maximum oxygen content of 2.7% by mass.
  • fuel composition has maximum amounts of oxygenates as specified in EN 228, for example methanol: 3.0% by volume, ethanol: 5.0% by volume, iso-propanol: 10.0 % by volume, iso-butyl alcohol: 10.0 % by volume, tert-butanol: 7.0% by volume, ethers (for example having 5 or more carbon atoms): 10% by volume and other oxygenates (subject to suitable final boiling point): 10.0% by volume.
  • fuel composition comprises ethanol complying with EN 15376 at a concentration of up to 15 % by volume, for example up to 10 % by volume or up to 5.0% by volume.
  • oxygenate-containing fuel compositions include E5, E10, E15 and fuel compositions containing ethanol at higher concentrations, for example up to E85.
  • the hydrocarbyl-substituted aromatic compound and the polyalkylene amine are incorporated into the fuel composition separately or together as components of one or more additive concentrates, one or more additive packages and/or one or more additive part packs.
  • the fuel composition and/or additive concentrates, and/or additive packages and/or additive part packs comprise at least one other fuel additive.
  • the method of reducing the particulate emitting tendency and/or CPAN generating tendency of a fuel composition comprises incorporating in one or more steps at least one other fuel additive.
  • the additives are admixed and/or incorporated as one or more additive concentrates and/or additive part packs, optionally comprising solvent or diluent.
  • the fuel composition is prepared by admixing in one or more steps, one or more base fuels (for example hydrocarbon fuels, oxygenate fuels and combinations thereof) and components therefor, optionally with one or more additives and/or part additive package concentrates.
  • one or more base fuels for example hydrocarbon fuels, oxygenate fuels and combinations thereof
  • additives and/or part additive package concentrates are admixed with the fuel or components therefor in one or more steps.
  • Examples of such other fuel additives include friction modifiers, anti-wear additives, corrosion inhibitors, dehazers/demulsifiers, dyes, markers, odorants, octane improvers, combustion modifiers, anti-oxidants, anti-microbial agents, lubricity improvers and valve seat recession additives.
  • each type of additive is present. In at least some examples, within each type of additive, more than one class of that type of additive is present. In at least some examples more than one additive of each class of additive is present. In at least some examples additives are suitably supplied by manufacturers and/or suppliers in solvent or diluents.
  • Table 1 Fuel Composition ADDITIVE TYPE Suitable amount (actives), (by weight) More suitable amount (actives), if present (by weight) Hydrocarbyl-substituted aromatic compounds 20 - 300 ppm 30 - 120 ppm Polyalkylene amines 50 - 500 ppm 70 - 300 ppm Carrier fluid 10 - 500 ppm 35 - 200 ppm Friction modifiers/anti-wear additives 10 - 200 ppm Corrosion inhibitors 1- 20 ppm Octane improvers and/or combustion improvers 5 - 30000 ppm Anti-oxidants 0.1 - 20 ppm Dehazers/demulsifiers 0.1 - 20 ppm Dyes and/or markers 0.1 - 20 ppm Odorants 1 - 20 ppm Anti-microbial agents 1 - 20 ppm Lubricity improvers 10 - 200 ppm Valve seat recession additives 1 - 15000 ppm
  • suitable friction modifiers and anti-wear additives include those that are ash-producing additives or ashless additives.
  • suitable friction modifiers and anti-wear additives include esters (for example glycerol mono-oleate) and fatty acids (for example oleic acid and stearic acid).
  • Suitable corrosion inhibitors include ammonium salts of organic carboxylic acids, amines and heterocyclic aromatics, for example alkylamines, imidazolines and tolyltriazoles.
  • non-metallic octane improvers examples include N-methyl aniline.
  • suitable metal-containing octane improvers include methylcyclopentadienyl manganese tricarbonyl, ferrocene and tetra-ethyl lead.
  • the fuel composition is free of all added metallic octane improvers including methyl cyclopentadienyl manganese tricarbonyl and other metallic octane improvers including for example, ferrocene and tetraethyl lead.
  • Suitable anti-oxidants include phenolic anti-oxidants (for example 2,4-di-tert-butylphenol and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid) and aminic anti-oxidants (for example para-phenylenediamine, dicyclohexylamine and derivatives thereof).
  • phenolic anti-oxidants for example 2,4-di-tert-butylphenol and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid
  • aminic anti-oxidants for example para-phenylenediamine, dicyclohexylamine and derivatives thereof.
  • valve seat recession additives examples include inorganic salts of potassium or phosphorus.
  • the additive composition comprises solvent.
  • suitable solvents include polyethers and aromatic and/or aliphatic hydrocarbons, for example heavy naphtha e.g. Solvesso (Trade mark), xylenes and kerosene.
  • the additives are present in the fuel composition at a total amount in the range of 20 to 25000 ppm by weight. Therefore, the concentrations of each additive in an additive concentrate will be correspondingly higher than in the fuel composition, for example by a ratio of 1: 0.00002 to 0.025.
  • the additives are used as part-packs, for example part of the additives (sometimes called refinery additives) being added at the refinery during manufacture of a fungible fuel and part of the additives (sometimes called terminal or marketing additives) being added at a terminal or distribution point.
  • hydrocarbyl-substituted aromatic compound and the polyalkylene amine are incorporated or admixed with other components of the fuel composition as a refinery additive or as a marketing additive.
  • hydrocarbyl-substituted aromatic compound and the polyalkylene amine are incorporated or admixed with other components of the fuel composition as a marketing additive, for example at a terminal or distribution point.
  • Suitable direct injection spark-ignition internal combustion engines include boosted direct injection spark-ignition internal combustion engines, for example turbocharged boosted direct injection engines and supercharged boosted direct injection engines.
  • Suitable engines include 2.0L boosted direct injection spark-ignition internal combustion engines.
  • Suitable direct injection engines include those that have side mounted direct injectors and/or centrally mounted direct injectors.
  • Particulate emissions may be measured by assessing the number of particles emitted from an engine.
  • the particles may have a size in the range of from 23 nm to 2.5 ⁇ m.
  • Methods for assessing the number of particles emitted from an engine include those in which a Condensation Particle Counter is fitted to an engine.
  • the Condensation Particle Counter preferably measures the concentration of particles with a size in the range of from 23 nm to 2.5 ⁇ m.
  • the Condensation Particle Counter preferably meets the legislative requirements of the European Commission's Particle Measurement Programme (PMP).
  • Particulate emissions may be measured from a turbocharged boosted direct injection spark-ignition internal combustion engine (2.0 litre or less).
  • the number of particles that are emitted from the engine may be assessed once the engine has run for more than 12 hours, such as for more than 15 hours.
  • the engine may be run at a single load point.
  • the load point may be representative of real-world engine operation, such as motorway driving operation (for example, at a speed of from about 80 km/h to 160 km/h).
  • the fuel compositions used in the present invention control particulate emissions, such as the number of particles emitted, but it is desirable that they also exhibit good detergency in the rest of the engine. This may be determined by measuring the intake valve deposit keep-clean performance of the fuel composition in a spark-ignition internal combustion engine. Methods of measuring the intake valve deposit keep-clean performance of a fuel composition for use in a spark-ignition internal combustion engine include those based upon the industry standard test method: CEC-F-20-A-98, also known as the M111 test.
  • Mannich Base additive may be, but does not have to be, a hydrocarbyl-substituted aromatic compound.
  • FIG. 1 represents, in graph form, the particulate emissions control performance for the fuel compositions tested.
  • Intake valve deposit keep-clean performance were assessed using the industry standard test method: CEC-F-20-A-98 (Issue 12). An E0 gasoline base fuel with a Research Octane Number of 95 was used. The fuel was EN 228 compliant.
  • Particulate emissions were measured by assessing the number of particles emitted using a Condensation Particle Counter fitted to a 1.6 litre turbocharged direct-injection spark ignition internal engine.
  • the Condensation Particle Counter used in the tests meets the legislative requirements of the European Commission's Particle Measurement Programme (PMP).
  • PMP European Commission's Particle Measurement Programme
  • the number of particles that were emitted from the engine was assessed after the engine had been running for 15 hours.
  • the fuel that was used to determine the intake valve deposit keep-clean performance was splash blended with ethanol to form an E10 gasoline base fuel for use in the engine tests.
  • the particulate emissions control performance of a fuel containing a combination of two Mannich Base additives was assessed.
  • the combined amount of Mannich Base additives used in the experiment was selected to give a typical port fuel injection valve keep-clean performance and which was comparable to that of the fuel composition used in Experiment A.
  • the particulate emissions control performance of a fuel containing PIBA additive was assessed.
  • the amount of PIBA additive used in the experiment was selected to give a typical port fuel injection valve keep-clean performance and which was comparable to that of the fuel composition used in Experiments A and B.
  • Example 1 combination of Mannich Base additive and polyisobutylene amine
  • the particulate emissions control performance of a fuel containing a combination of Mannich Base additive and PIBA additive was assessed.
  • the combined amount of Mannich Base and PIBA additives used in the experiment was selected to give a typical port fuel injection valve keep-clean performance and which was comparable to that of the fuel composition used in Experiments A, B and C.
  • the data shown in Figure 1 demonstrates that the fuel composition comprising a Mannich Base additive in combination with a polyisobutylene amine exhibits beneficial particulate emissions control in a direct-injection spark-ignition internal combustion engine.
  • the data show that the fuel composition comprising a Mannich Base additive in combination with a polyisobutylene amine exhibits greater particulate emissions control in a direct-injection spark-ignition internal combustion engine than an un-additised fuel, a fuel containing only polyisobutylene amine or only a Mannich Base additive, and a fuel containing a combination of Mannich Base additives.
  • the comparison of the fuels is made at concentrations of additives providing comparable keep-clean performance, when measured using the industry standard test method: CEC-F-20-A-98.
  • CPAN is controlled by a fuel composition
  • a fuel composition comprising a Mannich Base additive and a polyisobutylene amine.
  • the data also illustrate the use as a particulate emissions controlling additive in a fuel composition for a direct-injection spark-ignition internal combustion engine of:
  • the data also illustrate a method of reducing the particulate emitting tendency of a fuel composition for use in a direct-injection spark-ignition internal combustion engine which method comprises incorporating into the fuel composition in one or more steps:
  • the data also illustrate that the particulate emissions control performance of a fuel composition comprising a combination of a hydrocarbyl-substituted aromatic compound and a polyalkylene amine is improved relative to that of a fuel composition which comprises a polyalkylene amine but does not comprise a hydrocarbyl-substituted aromatic compound, and relative to that of a fuel composition which comprises a hydrocarbyl-substituted aromatic compound but does not comprise a polyalkylene amine.
  • an additive composition comprising a combination of:

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Claims (10)

  1. Utilisation en tant qu'additif pour maîtriser les émissions de particules dans une composition de carburant pour un moteur à combustion interne à allumage commandé à injection directe de :
    a. un composé aromatique substitué par un groupe hydrocarbyle ; et
    b. une polyalkylène-amine,
    dans laquelle le composé aromatique substitué par un groupe hydrocarbyle est un additif de type base de Mannich.
  2. Utilisation d'une composition d'additif comprenant une combinaison de :
    a. un composé aromatique substitué par un groupe hydrocarbyle ; et
    b. une polyalkylène-amine,
    dans laquelle le composé aromatique substitué par un groupe hydrocarbyle est un additif de type base de Mannich, pour améliorer la performance de maîtrise des émissions de particules d'une composition de carburant dans un moteur à combustion interne à allumage commandé à injection directe.
  3. Utilisation selon la revendication 1 ou 2, dans laquelle la polyalkylène-amine est une polyisobutylène-amine.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, dans laquelle le composé aromatique substitué par un groupe hydrocarbyle est présent dans la composition de carburant à une concentration d'ingrédients actifs de 20 ppm à 300 ppm.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, dans laquelle le substituant hydrocarbyle du composé aromatique présente un poids moléculaire moyen en nombre de 700 à 1 500.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, dans laquelle le substituant hydrocarbyle du composé aromatique est ou comprend du polyisobutylène.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, dans laquelle la polyalkylène-amine est présente dans la composition de carburant à une concentration d'ingrédients actifs de 50 ppm à 500 ppm.
  8. Utilisation selon l'une quelconque des revendications 1 à 7, dans laquelle la polyalkylène-amine contient un groupe polyalkylène qui présente un poids moléculaire moyen en nombre de 700 à 1 500.
  9. Utilisation selon l'une quelconque des revendications 1 à 8, dans laquelle le rapport pondéral des ingrédients actifs de la polyalkylène-amine/le composé aromatique substitué par un groupe hydrocarbyle dans la composition de carburant est dans la plage de 5/1 à 1/5.
  10. Utilisation en tant qu'additif pour maîtriser les noyaux poly-aromatiques complexes (CPAN) dans une composition de carburant pour un moteur à combustion interne à allumage commandé à injection directe de :
    a. un composé aromatique substitué par un groupe hydrocarbyle ; et
    b. une polyalkylène-amine,
    dans laquelle le composé aromatique substitué par un groupe hydrocarbyle est un additif de type base de Mannich.
EP15760464.6A 2014-09-11 2015-09-10 Utilisations pour maîtriser les émissions de particules dans un moteur à combustion interne Active EP3191568B1 (fr)

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GBGB1416082.4A GB201416082D0 (en) 2014-09-11 2014-09-11 Method and uses
PCT/EP2015/070691 WO2016038130A1 (fr) 2014-09-11 2015-09-10 Procédés et utilisations pour maîtriser les émissions de particules dans un moteur à combustion interne

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EP (1) EP3191568B1 (fr)
CN (1) CN107207979A (fr)
AU (1) AU2015314193A1 (fr)
GB (1) GB201416082D0 (fr)
WO (1) WO2016038130A1 (fr)

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GB201805238D0 (en) * 2018-03-29 2018-05-16 Innospec Ltd Composition, method and use

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Publication number Priority date Publication date Assignee Title
US4166726A (en) * 1977-12-16 1979-09-04 Chevron Research Company Diesel fuel containing polyalkylene amine and Mannich base
GB9817383D0 (en) * 1998-08-10 1998-10-07 Ass Octel Diesel fuel compositions
US20030029077A1 (en) * 2001-08-07 2003-02-13 The Lubrizol Corporation, A Corporation Of The State Of Ohio Fuel composition containing detergent combination and methods thereof
US20060277820A1 (en) * 2005-06-13 2006-12-14 Puri Suresh K Synergistic deposit control additive composition for gasoline fuel and process thereof
AU2014314325B2 (en) * 2013-08-27 2017-09-21 Bp Oil International Limited Methods and uses for intake-valve and direct-injector deposit clean-up.
RU2695347C2 (ru) * 2013-08-27 2019-07-23 Бп Ойл Интернешнл Лимитед Способы и применения для борьбы с отложениями на клапанах в двигателях с искровым зажиганием с прямым впрыскиванием топлива

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WO2016038130A1 (fr) 2016-03-17
US20170253820A1 (en) 2017-09-07
CN107207979A (zh) 2017-09-26
GB201416082D0 (en) 2014-10-29
AU2015314193A1 (en) 2017-03-23

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