EP3191567A1 - Procédés et utilisations pour maîtriser les boues dans des moteurs - Google Patents

Procédés et utilisations pour maîtriser les boues dans des moteurs

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Publication number
EP3191567A1
EP3191567A1 EP15763555.8A EP15763555A EP3191567A1 EP 3191567 A1 EP3191567 A1 EP 3191567A1 EP 15763555 A EP15763555 A EP 15763555A EP 3191567 A1 EP3191567 A1 EP 3191567A1
Authority
EP
European Patent Office
Prior art keywords
hydrocarbyl
examples
fuel composition
internal combustion
combustion engine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15763555.8A
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German (de)
English (en)
Inventor
Robert Edward Allan
Ross Alexander DEWHURST
Michael John Grundy
David Michael Williamson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP Oil International Ltd
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BP Oil International Ltd
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Filing date
Publication date
Application filed by BP Oil International Ltd filed Critical BP Oil International Ltd
Publication of EP3191567A1 publication Critical patent/EP3191567A1/fr
Withdrawn legal-status Critical Current

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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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • 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
    • 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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • 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 methods and uses and in particular aspects to a method of controlling sludge formation in a spark-ignition internal combustion engine or a compression-ignition gasoline internal combustion engine, and in other aspects to the use of a combination of additives as a sludge controlling additive in a fuel composition for a spark-ignition internal combustion engine.
  • the invention also relates to methods for maintaining oil pathways and lubrication in an engine.
  • the crankcase lubricant oil can become diluted with fuel, water and/or coolant.
  • the lubricant oil can also become contaminated with chemical species which can accelerate lubricant oil oxidation. Examples of these chemical species include wear metals and oxidative non-metallic substances which can enter the crankcase through blow-by.
  • the lubricant oil is also subject to high temperatures. As a result of these chemical and physical conditions, oxidation, polymerisation and agglomeration of the lubricant oil may occur, creating a highly viscous tar-like material known as sludge from the degraded oil.
  • the sludge may also incorporate species derived from fuel, water, coolant, soot and wear metals. Sludge can build up on many components of the engine, including the rocker cover(s), the camshaft baffle, the timing chain cover, the oil pan and its baffle, the oil screen and the valve deck area.
  • Sludge can reduce the performance of an engine. For instance, engine sludge can be a factor in compromised oil pathways and engine lubrication. This can lead to engine failure.
  • a lubricating oil containing a hydrocarbyl- substituted amine ashless detergent, a polyoxyalkylene derivative and an alkaline earth metal reduces or prevents the formation of varnish, sludge and deposits on the inner metallic surfaces of internal combustion engines.
  • US2013/000584 discloses a fuel composition comprising one or more poly(hydroxycarboxylic acid) derivatives having a terminal amine group for inhibiting the formation of sludge.
  • the detergency of the fuel composition is not disclosed in US2013/000584.
  • 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
  • Mannich bases have been used in isolation or in combination with diamine to reduce deposits on carburet [t] or surfaces. As disclosed in the present
  • a method of controlling sludge formation in a spark-ignition internal combustion engine or a compression-ignition gasoline internal combustion engine which method comprises supplying to the engine a fuel composition which comprises a combination of:
  • a sludge controlling additive in a fuel composition for a spark-ignition internal combustion engine or a compression-ignition gasoline internal combustion engine of:
  • a method of reducing the sludge forming tendency of a fuel composition for use in a spark-ignition internal combustion engine or a compression-ignition gasoline internal combustion engine which method comprises incorporating into the fuel composition in one or more steps: a. a hydrocarbyl-substituted aromatic compound; and
  • an additive composition comprising a combination of:
  • a method of maintaining oil pathways and/or lubrication in a spark-ignition internal combustion engine or a compression-ignition gasoline internal combustion engine comprises supplying to the engine a fuel composition which comprises a combination of:
  • an oil pathway and/or lubrication maintaining additive in a fuel composition for a 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.
  • combination of a hydrocarbyl-substituted aromatic compound and a polyalkylene amine exhibits beneficial sludge formation control when used in a spark-ignition 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.
  • polyisobutylene amines examples include polyisobutylene amines disclosed in, and/or obtained or obtainable by methods described in, US4832702,
  • 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:
  • Rj is a polybutyl- or polyisobutyl group derivable or derived from isobutene and up to 20% by weight of n-butene and
  • R 2 and R 3 are identical or different and are each independently:
  • an aliphatic or aromatic hydrocarbyl group a primary or secondary, aromatic or aliphatic aminoalkylene group or polyaminoalkylene group;
  • R 2 and R 3 are identical or different and are each independently:
  • R 4 is alkylene and R 5 and R6 are identical or different and are each independently: hydrogen; alkyl; aryl; hydroxyalkyl; polybutyl; or polyisobutyl; or
  • R4 groups are the same or different and the R 5 groups are the same or different and R 4 , R 5 and Re have the above meaning and m is an integer from 2 to 8; or
  • R 2 and R 3 together with the nitrogen atom to which they are bonded form a morpholinyl, pyridyl, piperidyl, pyrrolyl, pyrimidinyl, pyrolinyl, pyrrol- idinyl, pyrazinyl or pyridazinyl group.
  • Ri 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 ⁇ 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, - CH2 - CH2 - NH2,
  • p is an integer from 1 to 7, for example 1 to 3, - CH 2 - CH 2 - OH,
  • 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):
  • R 8 R 10 R 12 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
  • Rn and R 12 independently of each other are each H; an alkyl group, for example a Ci to C 18 alkyl group; a cycloalkyl group; a hydroxyalkyl group; an aminoalkyl group; an alkenyl group; an alkynyl group, an aryl group; an arylalkyl group; an alkylaryl group; a heteroaryl group; an alkylene-imine group represented by the formula (VI):
  • Alk is a straight-chain or branched alkylene
  • n is an integer from 0 to 10;
  • RB and R 14 are each H; an alkyl group, for example a Ci to C 18 alkyl group; a cycloalkyl group; a hydroxyalkyl group; an aminoalkyl group; an alkenyl group; an alkynyl group, an aryl group; an arylalkyl group; an alkylaryl group; a heteroaryl group or, together with the nitrogen atom to which they are bonded, form a heterocyclic structure, or
  • Rn and R 12 together with the nitrogen atom to which they are bonded, form a heterocyclic structure.
  • each of Rn, R 12 , R13 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
  • 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.
  • 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 may be a hydrocarbyl-substituted hydroxyaromatic compound, such as a hydrocarbyl-substituted phenol compound.
  • 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.
  • a Mannich Base additive may be used in the fuel composition.
  • 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:
  • reaction time in the range of from 2 to 4 hours
  • aldehydes suitable for the preparation of Mannich Base additives include:
  • aliphatic aldehydes including for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caprioaldehyde, heptaldehyde and stearaldehyde;
  • aromatic aldehydes including for example, benzaldehyde and salicylaldehyde; and heterocyclic aldehydes including for example, furfural aldehyde and thiophene aldehyde.
  • 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.
  • 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 poly amine 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
  • 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; ⁇ , ⁇ , ⁇ ', ⁇ "- tetraalkyltrialkylenetetramines; N,N,N',N",N"'-pentaalkyltrialkylenetetramines; N,N- dihydroxyalkyl-a,GD-alkylenediamines; N,N,N'-trihydroxyalkyl-a,Q-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)-l,3-propanediamine; N-neopentyl-l,3-propranediamine; N-(fert-butyl)-l-methyl- 1,2-ethanediamine; N-(tert-butyl)-l -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: H2N-(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:
  • formaldehyde e.g. formalin
  • reaction mixture o heating the reaction mixture at an elevated temperature (for example 120°C to
  • inert stripping gas e.g. nitrogen, carbon dioxide and the like
  • 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.
  • suitable 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.
  • dibutyl amine as the amine
  • 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): /
  • 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.
  • 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):
  • 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 ⁇ to C 8 alkyl (for example methyl, ethyl, propyl, isopropyl, t-butyl and the like).
  • Y include Ci 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, Xlb, XIc and Xld:
  • each 3 ⁇ 4 and R 2 are a hydrocarbyl group or a hydrogen provided that at least one thereof is a hydrocarbyl group.
  • hydrocarbyl groups include Q to C 8 alkyl e.g. methyl, ethyl, propryl, isopropyl and the like;
  • hydrocarbyl-substituted hydroxyaromatic compounds (ii) include those represented by formula XII:
  • 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.
  • Mw average molecular weight
  • Examples of representative hydrocarbyl substituents of the hydrocarbyl-substituted hydroxyaromatic compound (ii) include polyolefm 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.
  • 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):
  • 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.
  • Mw average molecular weight
  • 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).
  • Carrier fluid is 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.
  • 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 paraffmic, 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-propy lene groups .
  • poly(oxyalkylene) compounds 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 Mw / Mn 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 Mw (mass average molecular mass) / Mn 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 (Mn) 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 or a compression-ignition gasoline 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
  • 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/1, 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, El 5 and fuel compositions containing ethanol at higher concentrations, for example up to E85.
  • a method of reducing the sludge forming tendency of a fuel composition for use in a spark-ignition internal combustion engine or a compression-ignition gasoline internal combustion engine which method comprises incorporating into the fuel composition in one or more steps: a. a hydrocarbyl-substituted aromatic compound; and
  • 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 sludge forming 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
  • 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
  • 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 antioxidants (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 antioxidants 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.
  • spark-ignition internal combustion engines which are classified according to the type of system for delivering fuel to the engine combustion chambers.
  • Port Fuel Injection (PFI) engines are engines in which a mixture of fuel and air is injected into intake ports and then passes into combustion chambers of the engine through one or more intake valves (sometimes also called inlet valves or inlet port valves).
  • intake valves sometimes also called inlet valves or inlet port valves.
  • suitable port fuel injection, spark-ignition internal combustion engines include any suitable port fuel injection, spark-ignition internal combustion engine including for example BMW 318i engine, Ford 2.3L Ranger engine and MB Mi l l engine.
  • Direct Injection (DI) engines are engines in which fuel is injected directly into combustion chambers of the engine through injectors (sometimes also called direct injectors or direct injector nozzles) and air is introduced into the combustion chambers through one or more air intake valves (sometimes also called air inlet valves or air inlet port valves).
  • injectors sometimes also called direct injectors or direct injector nozzles
  • air intake valves sometimes also called air inlet valves or air inlet port valves.
  • 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.
  • the fuel compositions disclosed herein preferably control the overall formation of sludge in the engine, referred to herein as engine sludge.
  • the fuel compositions may also control the formation of sludge on particular components of the engine, including the rocker cover(s), the camshaft baffle, the timing chain cover, the oil pan and its baffle, the oil screen and the valve deck area.
  • the fuel compositions control the formation of rocker cover sludge.
  • Methods for assessing the sludge control performance of a fuel composition include those based upon the US industry standard test method: ASTM D-6593 (version 10), this is sometimes also called the Ford 4.6L "Sequence VG" engine test.
  • ASTM D-6593 version 10
  • Ford 4.6L Speed VG
  • This test is used for determining the performance of lubricants.
  • the performance of fuels may be tested by using the standard reference lubricant as the lubricant, and the standard reference base fuel with the additives of interest added thereto as the fuel.
  • This test may be used to measure engine sludge (referred to in the test as 'average engine sludge') and rocker cover sludge.
  • the fuel compositions used in the present invention control sludge formation, but it is desirable that they also exhibit good detergency in the rest of the engine, for instance on an intake valve. This may be determined by measuring intake valve keep-clean performance of the fuel composition. 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 US industry standard test method: ASTM D-6201 (version 04, 2009), this is sometimes also called the Ford 2.3L "Ranger” engine test after the engine that is used.
  • Mannich Base additive may be, but does not have to be, a Mannich Base additive
  • FIG. 1 represents, in graph form, the sludge control performance for the fuel compositions tested relative to a base fuel reference.
  • Intake valve deposit (IVD) keep-clean performance were assessed using the US industry standard test method: ASTM D-6201 (version 04, 2009) using a Ford 2.3 L port fuel injection spark-ignition internal combustion engine. Intake valve deposit (IVD) keep- clean performance was studied using an El 0 gasoline base fuel.
  • the engine sludge and rocker cover sludge control performance of a fuel containing PIBA additive was assessed.
  • the amount of PIBA used in the experiment was selected to give a typical port fuel injection valve keep-clean performance.
  • the engine sludge and rocker cover sludge control performance is shown in graph form in Figure 1 as relative % sludge control performance (relative to a base fuel reference).
  • Example 1 combination of Mannich Base additive and polyisobutylene amine
  • the engine sludge and rocker cover sludge control performance of a fuel containing a combination of Mannich Base additive and PIBA additive was assessed.
  • the amount of Mannich Base additive and PIBA used in the experiment was selected to give a typical port fuel injection valve keep-clean performance which was comparable to that of the fuel composition used for Experiment A.
  • the engine sludge and rocker cover sludge control performance is shown in form in Figure 1 as relative % sludge control performance (relative to a base fuel reference).
  • the data shown in Table 2 and in Figure 1 show that the fuel composition comprising Mannich Base additive in combination with a polyisobutylene amine exhibits beneficial sludge control in a 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 sludge control in a spark-ignition internal combustion engine than an un-additised fuel and a fuel containing only polyisobutylene amine.
  • the comparison with the fuel containing polyisobutylene amine is made for example at concentrations of additives providing comparable detergency performance, when measured using a Ford 2.3 L port fuel injection spark-ignition internal combustion engine according to the industry standard test method: ASTM D-6201.
  • the data also illustrate the use as a sludge controlling additive in a fuel composition for a spark-ignition internal combustion engine of:
  • a hydrocarbyl-substituted aromatic compound a hydrocarbyl-substituted aromatic compound
  • b a polyalkylene amine
  • the data also illustrate a method of reducing the sludge forming tendency of a fuel composition for use in a spark-ignition internal combustion engine which method comprises incorporating into the fuel composition in one or more steps:
  • the data also illustrate that the sludge 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.
  • the sludge control performance of a fuel composition comprising a combination of a hydrocarbyl-substituted aromatic compound and a polyalkylene amine may also be improved 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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Abstract

Cette invention concerne l'utilisation d'un additif pour maîtriser les boues dans une composition de carburant pour moteur à combustion interne à allumage commandé ou moteur à combustion interne à essence à allumage par compression, ledit additif étant constitué d'une combinaison de : a. un composé aromatique substitué par un hydrocarbyle; et b. une polyalkylène amine. La composition de carburant peut également être utilisée pour maintenir les voies de circulation d'huile et/ou la lubrification dans un moteur.
EP15763555.8A 2014-09-11 2015-09-10 Procédés et utilisations pour maîtriser les boues dans des moteurs Withdrawn EP3191567A1 (fr)

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GBGB1416073.3A GB201416073D0 (en) 2014-09-11 2014-09-11 Methods and uses
PCT/EP2015/070690 WO2016038129A1 (fr) 2014-09-11 2015-09-10 Procédés et utilisations pour maîtriser les boues dans des moteurs

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US4166726A (en) * 1977-12-16 1979-09-04 Chevron Research Company Diesel fuel containing polyalkylene amine and Mannich base
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
US20080202561A1 (en) * 2007-02-22 2008-08-28 Dumont Richard J Methods and Compositions for Reducing Deposits In Engines Combusting Alcohol-Containing Fuels

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CN107001960A (zh) 2017-08-01
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US20170260470A1 (en) 2017-09-14
AU2015314192A1 (en) 2017-03-23

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