EP2361295B1 - Stickstofffreie brennstoffadditive zur bekämpfung von ablagerungen - Google Patents

Stickstofffreie brennstoffadditive zur bekämpfung von ablagerungen Download PDF

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Publication number
EP2361295B1
EP2361295B1 EP09744556.3A EP09744556A EP2361295B1 EP 2361295 B1 EP2361295 B1 EP 2361295B1 EP 09744556 A EP09744556 A EP 09744556A EP 2361295 B1 EP2361295 B1 EP 2361295B1
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EP
European Patent Office
Prior art keywords
carbon atoms
hydrocarbyl group
additive
fuel
group containing
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Not-in-force
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EP09744556.3A
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English (en)
French (fr)
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EP2361295A1 (de
Inventor
Paul R. Stevenson
David J. Moreton
Jonathan S. Vilardo
Seth Crawley
James C. Ray
Kurt F. Wollenberg
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Lubrizol Corp
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Lubrizol Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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

Definitions

  • the present invention relates to fuel additives, fuel additive compositions and fuel compositions as well as a method for fueling an internal combustion engine, providing improved deposit control inside the engine, as well as other benefits, with additives that are free of nitrogen.
  • Hydrocarbon based fuels generally contain numerous deposit-forming substances. When used in internal combustion engines (ICE), deposits from these substances can form on and around constricted areas of the engine which come in contact with the fuel. In these ICE, such as automobile engines, deposits can build on engine intake valves leading to progressive restriction of the gaseous fuel mixture flow into the combustion chamber, in turn reducing the maximum power of the engine, decreasing fuel economy, increasing engine emissions, and hindering engine startability.
  • ICE internal combustion engines
  • fuel detergent additives include additives that can be described as ashless dispersants. These additives consist of hydrocarbyl backbones, including polyisobutylene (PIB) backbones, that have been combined with polar, nitrogen-containing head groups.
  • PIB polyisobutylene
  • the primary fuel detergent additives used today include PIB amines, PIB succinimides and PIB phenol Mannich amines.
  • One key aspect of these fuel detergent additives is the presence of an active nitrogen-containing group, which is believed to be required for good performance of the additives.
  • nitrogen-containing additives can lead to undesirable effects, such as seal degradation, particularly in the case of elastomer containing seals. Nitrogen-free additives would be free of these potential disadvantages.
  • a new class of fuel detergents have been discovered which offer improvements over traditional fuel detergents such as Polyisobutylene (PIB) phenol Mannich detergents.
  • This new class of detergents does not contain any nitrogen, traditionally believed to be essential to the good performance of fuel detergent additives while still delivering comparable and/or improved performance compared td the nitrogen-containing additives commonly used today.
  • the present invention provides a composition comprising a nitrogen-free detergent fuel additive represented by Formula I;
  • the additives of the present invention are represented by Formula II: wherein: R 1 is hydrogen or a hydrocarbyl group containing 1 to 6 carbon atoms; R 2 is a hydrocarbyl group containing 1 to 6 carbon atoms; wherein when n is 0 R 3 is hydrogen or a hydrocarbyl group containing 1 to 6 carbon atoms; and when n is 1, R 3 is a hydrocarbyl group containing 1 to 6 carbon atoms; R 4 is a hydrocarbyl group containing 1 to 150 carbon atoms and is derived from a polyisobutylene group having a number average molecular weight of 350 to 5000; and R 6 is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms or -(R 7 ) m -OR 8 wherein R 7 is a hydrocarbyl group containing 1 to 10 carbon atoms, R 8 is a hydrocarbyl group containing 1 to 50 carbon atoms and m is 0 or 1.
  • R 1 is hydrogen
  • the additive of the present invention comprises a mixture of one or more additives from the following list: a) the additive represented by Formula II wherein R 3 is hydrogen and R 6 is hydrogen; b) the additive represented by Formula II wherein R 3 is a hydrocarbyl group containing 1 to 6 carbon atoms and R 6 is hydrogen; c) the additive represented by Formula II wherein R 3 is hydrogen and R 6 is a hydrocarbyl group containing 1 to 6 carbon atoms; d) the additive represented by Formula II wherein R 3 is a hydrocarbyl group containing 1 to 6 carbon atoms and R 6 is a hydrocarbyl group containing 1 to 6 carbon atoms
  • the additive of the present invention comprises a mixture of one or more additives from the following list: a) the additive represented by Formula I wherein R 3 is hydrogen, each R 5 is hydrogen and R 6 is hydrogen; b) the additive represented by Formula I wherein R 3 is a hydrocarbyl group containing 1 to 6 carbon atoms, each R 5 is hydrogen and R 6 is hydrogen; c) the additive represented by Formula I wherein R 3 is hydrogen, each R 5 is hydrogen and R 6 is a hydrocarbyl group containing 1 to 6 carbon atoms; d) the additive represented by Formula I wherein R 3 is a hydrocarbyl group containing 1 to 6 carbon atoms, each R 5 is hydrogen and R 6 is a hydrocarbyl group containing 1 to 6 carbon atoms.
  • the additives of the present invention are represented by either Formula I and/or Formula II above wherein R 1 is hydrogen; R 2 is independently a methylene group, an ethylene group, a propylene group or a butylene group; R 3 is independently hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group; R 5 is hydrogen; R 6 is independently hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group; or combinations thereof.
  • R 2 is a methylene group
  • R 3 is a methyl group
  • R 6 is a hydrogen group, hydroxy group or a methyl group.
  • the present invention also provides for a fuel additive composition and/or concentrate comprising: one or more of the nitrogen-free detergent additives described herein; an optional solvent; and one or more optional additional performance additives.
  • the present invention also provides for a fuel composition
  • a fuel composition comprising: one or more of the nitrogen-free detergent additives described herein; a fuel; and one or more optional additional performance additives.
  • the present invention also provides for a method of operating an internal combustion engine, comprising supplying to said engine a fuel composition comprising one or more of the nitrogen-free detergent additives described herein; a fuel; and one or more optional additional performance additives.
  • the present invention also provides for a process for making the nitrogen-free detergent fuel additives of the present invention comprising reacting a hydrocarbyl-substituted hydroxy aromatic compound and an aldehyde wherein the reaction is optionally carried out in the presence of a catalyst.
  • the present invention involves a fuel additive, a fuel additive composition, a fuel composition and a method for fueling an internal combustion engine, where the fuel additive is free of nitrogen.
  • the fuel additive composition of the invention shows comparable and/or improved engine deposit control, allowing for improved engine performance, including but not limited to reductions in deposit-caused engine power losses, reduction in deposit-caused fuel economy losses and decreases in deposit-caused engine emissions.
  • the fuel detergent additive may also be used as a corrosion inhibitor or a lubricity aid.
  • the nitrogen-free fuel detergent additives of the present invention have been shown to effectively control the formation of engine deposits, including intake valve deposits. This result is unexpected as it is generally believed that a nitrogen-containing polar group is required for a fuel additive to provide effective deposit control in an engine. While not wishing to be bound by theory, the polar nitrogen-containing group is believed to be necessary for good performance as the polar head may effectively associate with dirt and/or deposit particles in an engine, allowing them to be dispersed by the fuel additive and facilitate for their removal from, and/or prevent their initial deposit on, engine surfaces. With no polar group present, it is believed the additive would be much less effective at associating with dirt and deposit particles in the engine, and so would be much less effective at controlling engine deposits.
  • the present invention provides nitrogen-free fuel detergent additives that are effective at controlling engine deposits, despite the fact that they are free of nitrogen, and so free of any polar nitrogen-containing groups.
  • the nitrogen-free fuel detergent additives provide effective deposit control due, at least in part, to the proximity of the ortho-polar group in the adjacent position to the phenolic (or cresol) hydroxyl group or ether, as illustrated in Formula I, and Formula II, shown above.
  • the fuel detergent additive of the present invention is represented by Formula I, shown above, wherein: R 1 is independently hydrogen or a hydrocarbyl group containing 1 to 50, 1 to 25, 1 to 10, or 1 to 6 carbon atoms; R 2 is independently a hydrocarbyl group containing 1 to 10, or 1 to 6 carbon atoms; n is 0 or 1; wherein when n is 0 R 3 is independently hydrogen or a hydrocarbyl group containing 1 to 50, 1 to 25, 1 to 10, or 1 to 6 carbon atoms; and when n is 1, R 3 is a hydrocarbyl group containing 1 to 50, 1 to 25, 1 to 10, or 1 to 6 carbon atoms R 4 is a hydrocarbyl group containing 1 to 150 carbon atoms and is derived from polyisobutylene having a number average molecular weight of 350 to 5000; each R 5 is independently hydrogen or a hydroxyl group; R 6 is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms or -(R 7 )
  • Suitable hydrocarbyl groups include polyolefins prepared by polymerizing olefin monomers by well known polymerization methods that are also commercially available.
  • Suitable olefin monomers include monoolefins, including monoolefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene, isobutylene, and 1-decene.
  • An especially useful monoolefin source is a C 4 refinery stream having a 35 to 75 weight percent butene content and a 30 to 60 weight percent isobutene content.
  • Useful olefin monomers also include diolefins such as isoprene and 1,3-butadiene.
  • Olefin monomers can also include mixtures of two or more monoolefins, of two or more diolefins, or of one or more monoolefins and one or more diolefins.
  • Useful polyolefins include polyisobutylenes having a number average molecular weight of 140 to 5000, in another instance of 400 to 2500, and in a further instance of 140 or 500 to 1500 or 1100.
  • the polyisobutylene can have a vinylidene double bond content of 5 to 69%, in a second instance of 50 to 69%, and in a third instance of 50 to 95%.
  • the polyolefin can be a homopolymer prepared from a single olefin monomer or a copolymer prepared from a mixture of two or more olefin monomers. Also possible as the hydrocarbyl substituent source are mixtures of two or more homopolymers, two or more copolymers, or one or more homopolymers and one or more copolymers.
  • the hydrocarbyl-substituted phenol can be prepared by alkylating phenol with an olefin or polyolefin described above, such as a polyisobutylene or polypropylene, using well-known alkylation methods.
  • the vinylidene content of the R 4 hydrocarbyl group in Formula I and/or Formula II can comprise at least about 30 mole % vinylidene groups, at least about 50 mole % vinylidene groups, or at least about 70 mole % vinylidene groups.
  • Such material and methods for preparing them are described in U.S. Pat. Nos. 5,071,919 ; 5,137,978 ; 5,137,980 ; 5,286,823 , 5,408,018 , 6,562,913 , 6,683,138 , 7,037,999 and U.S. Publication Nos. 20040176552A1 , 20050137363 and 20060079652A1 .
  • Such products are commercially available from BASF, under the tradename GLISSOPAL® and from Texas Petrochemicals LP, under the tradename TPC 1105TM and TPC 595TM.
  • R 4 hydrocarbyl group in Formula I and/or Formula II can comprise a polyisobutylene substituent derived from a conventional PIB and a high vinylidene PIB with a number average molecular weight as described above.
  • Conventional PIBs generally can contain a) 45 mole % or greater, 50 mole % or greater, 55 mole % or greater, 45 to 85 mole %, 50 to 75 mole %, or 55 to 70 mole % of trisubstituted double bond isomer, b) 5 to 45 mole %, 10 to 35 mole %, 15 to 30 mole %, or 20 to 25 mole % of tetrasubstituted double bond isomer, c) 30 mole % or less, 25 mole % or less, 1 to 30 mole %, 2 to 30 mole %, or 5 to 25 mole % of alpha- and/or beta-vinylidene double bond isomer, and can have d) a 1.1 to 4, 1.2 to 3.5, or 1.5 to 3 polydispersity defined as the ratio of weight average molecular weight to number average molecular weight.
  • the conventional PIB has a vinylidene double bond isomer content as described above that comprises the alpha-vinylidene double bond isomer.
  • Conventional PIBs are prepared by polymerizing isobutylene or an isobutylene containing composition, such as a C 4 hydrocarbon stream from a petroleum catalytic cracking unit, with an active acidic polymerization catalyst such as AlCl 3 .
  • Conventional PIBs are available commercially under numerous trade names including Parapol® from Exxon and Lubrizol® 3104 from Lubrizol.
  • High vinylidene PIBs generally can contain a) 70 mole % or greater, 80 mole % or greater, 90 mole % or greater, 70 to 99.9 mole %, 80 to 99.5 mole %, or 85 to 99 mole % of alpha- and/or beta-vinylidene double bond isomer, b) 0.1 to 15 mole %, 0.5 to 12 mole %, or 1 to 10 mole % of tetrasubstituted double bond isomer, and can have c) a 1.0 or 1.1 to 3.5, a 1.2 to 3, or a 1.3 to 2.5 polydispersity.
  • the high vinylidene PIB can have an alpha-vinylidene double bond isomer content of 75 to 95 mole % or 80 to 90 mole %, and in another embodiment the high vinylidene PIB can have an alpha-vinylidene double bond isomer content of 50 to 70 mole % or 55 to 65 mole %.
  • High vinylidene PIBs are prepared by polymerizing isobutylene or an isobutylene containing composition with a milder acidic polymerization catalyst such as BF 3 . High vinylidene PIBs are available commercially from several producers to include BASF and Texas Petroleum Chemicals.
  • the polyisobutylene substituent derived from a conventional PIB and a high vinylidene PIB can have a) an alpha- and/or beta-vinylidene double bond isomer content of 97 mole % or less, 85 mole % or less, 75 mole % or less, less than 70 mole %, 50 to 95 or 97 mole %, 55 to 80 mole %, 60 to 75 mole %, or 55 to 69 mole %, b) a trisubstituted double bond isomer content of 4 or 5 to 40 mole %, 10 to 30 mole %, or 15 to 25 mole %, c) a tetrasubstituted double bond isomer content of 5 to 20 mole %, 6 to 18 mole %, or 7 to 15 mole %, and can have d) a polydispersity of 1.1 to 3.8, 1.2 to 3.5, or 1.3 to 2.8.
  • the PIB can generally have 50 to 95 mole % of alpha- and/or beta-vinylidene double bond isomer and 4 to 40 mole % of trisubstituted double bond isomer, and in other embodiments can have 60 to 75 or 55 to 69 mole % of alpha- and/or beta-vinylidene double bond isomer and 15 to 25 mole % of trisubstituted double bond isomer.
  • the PIB of the PIB alkylated hydroxyaromatic compound is derived from a conventional PIB and high vinylidene PIB where the weight ratio of conventional PIB to high vinylidene PIB is respectively 0.1:99.9 to 99.9:0.1,15:85 to 60:40, or 25:75 to 40:60.
  • R 4 is derived from a polyisobutylene group with a molecular weight of 350 to 5000, 500 to 2500 or 750 to 1200.
  • the groups R 1 , R 2 , R 3 and R 6 are each independently either hydrogen or a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms.
  • the fuel detergent additive is represented by Formula II, shown above, wherein: R 1 is independently hydrogen or a hydrocarbyl group containing 1 to 50, 1 to 25, 1 to 10, or 1 to 6 carbon atoms; R 2 is independently a hydrocarbyl group containing 1 to 10, or 1 to 6 carbon atoms; n is 0 or 1; wherein when n is 0 R 3 is independently hydrogen or a hydrocarbyl group containing 1 to 50, 1 to 25, 1 to 10, or 1 to 6 carbon atoms and wherein n is 1, R 3 is a hydrocarbyl group containing 1 to 50, 1 to 25,1 to 10, or 1 to 6 carbon atoms; R 4 is a hydrocarbyl group containing 1 to 150, 10 to 150, or 50 to 150 carbo atoms and is derived from polyisobutylene having a number average molecular weight of 350 to 5000; R 6 is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms or -(R 7 ) m -
  • the present invention is represented by Formula II wherein: R 1 is hydrogen or a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms; R 2 is a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms; wherein when n is 0 R 3 is hydrogen or a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms and when n is 1, R 3 is a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms; R 4 is a polyisobutylene group having a number average molecular weight of 350 to 5000, or 500 to 2500, 550 to 2000, or 750 to 1100; and R 6 is hydrogen or a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms.
  • the R 2 group described above in Formula I and/or Formula II is a methylene group.
  • the R 3 group is a methyl group and the R 6 group is a hydrogen or a methyl group.
  • R 4 is a polyisobutylene group with a number average molecular weight of 500 to 2500.
  • the fuel detergent additive is prepared by reacting a hydrocarbyl-substituted hydroxy aromatic compound with an aldehyde, optionally in the presence of a base catalyst.
  • the hydrocarbyl-substituted hydroxy aromatic compound is a hydrocarbyl phenol, a hydrocarbyl cresol, or a mixture thereof.
  • the hydrocarbyl-substituted hydroxy aromatic compounds suitable for use in the present invention have at least one hydrocarbyl group attached to the ring structure.
  • the compound has only one hydrocarbyl group, however in other embodiments the compound may have 2, 3 4 or five hydrocarbyl groups in addition to the hydroxy group, all attached to the ring structure.
  • the hydrocarbyl group in the para position to the hydroxy group is typically the largest group while the other hydrocarbyl groups tend to be smaller, if they are present at all.
  • the hydrocarbyl groups that are not in the para position contain from 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • these hydrocarbyl groups are each independently hydrogen or methyl groups, such as the group present in cresol.
  • the hydrocarbyl group located in the para position (represented by R 4 in Formula I and Formula II shown above) generally contains an average of at least 8, or 30, or 35 up to 350, or to 200, or to 100 carbon atoms.
  • the hydrocarbyl group is derived from a polyalkene.
  • Suitable polyalkenes include homopolymers and interpolymers of polymerizable olefin monomers of 2 to 16 or to 6, or to 4 carbon atoms.
  • the olefins may be monoolefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; or a polyolefinic monomer, such as diolefinic monomer, such 1,3-butadiene and isoprene.
  • the interpolymer is a homopolymer.
  • An example of a polymer is a polybutene. In one instance 50% of the polybutene is derived from isobutylene.
  • the polyalkenes are prepared by conventional procedures.
  • the hydrocarbyl substituent of the hydrocarbyl-substituted hydroxy aromatic compound is derived from a polyisobutylene.
  • the hydrocarbyl groups are derived from polyalkenes having a number average molecular weight of least 250, 350, 500, or 750 up to 5000, or to 3000, or to 2000, or to 1500.
  • the polyalkene is polyisobutylene with a molecular weight of 800 to 1200.
  • the hydroxy aromatic compound from which the hydrocarbyl-substituted hydroxy aromatic compound is derived can comprise phenol, a polyhydroxy benzene such as catechol, an alkyl-substituted phenol such as ortho-cresol, an alkyl-substituted polyhydroxy benzene such as 3-methylcatechol, or mixtures thereof.
  • the hydrocarbyl-substituted hydroxy aromatic compound can be prepared by well known alkylation methods generally involving alkylation of the hydroxy aromatic compound with a polyolefin in the presence of acidic catalyst.
  • the acidic catalyst can include for example mineral acids such as a sulfuric acid acidified clay, Lewis acid catalysts such as a complex of boron trifluoride with diethyl ether or with phenol, and acidic ion exchange resins such as the Amberlyst® series of strongly acidic macroreticular resins available from Rohm and Haas.
  • phenol is alkylated with a conventional polyisobutylene, a highly reactive polyisobutylene or a mixture of conventional and highly reactive polyisobutylenes in the presence of a solvent or diluent and a BF 3 catalyst between 0 and 50°C as described in U. S. Patent No. 5,876,468 .
  • phenol is used herein, it is to be understood that this term is not intended to limit the aromatic group of the phenol to benzene. Accordingly, it is to be understood that the aromatic group represented in this specification may be mononuclear or polynuclear.
  • aldehydes suitable for use in the present invention are hydrocarbon-based aldehydes, preferably lower aliphatic aldehydes.
  • Suitable aldehydes include formaldehyde, benzaldehyde, acetaldehyde, the butyraldehydes, hydroxybutyraldehydes and heptanals, as well as aldehyde precursors which react as aldehydes under the conditions of the reaction such as paraformaldehyde, paraldehyde, and formalin.
  • the aldehyde is Formaldehyde and/or its precursors and reaction synthons (e.g., paraformaldehyde, trioxane). Mixtures of aldehydes may be used to prepare the additive of the present invention.
  • the catalyst is not overly limited and may include an esterification catalyst such as toluenesulfonic acid, sulfuric acid, aluminum chloride, boron trifluoride-triethylamine, methanesulfonic acid, hydrochloric acid, ammonium sulfate, phosphoric acid, sodium methoxide and the like. These conditions and variations thereof are well known in the art.
  • the additive of the present invention is prepared in the presence of sodium methoxide.
  • the fuel detergents of the present invention can be solids, semi-solids, or liquids (oils) depending on the particular alcohol(s) and/or amine(s) used in preparing them.
  • the fuel detergents are advantageously soluble and/or stably dispersible in such oleaginous compositions.
  • compositions intended for use in fuels are typically fuel-soluble and/or stably dispersible in a fuel in which they are to be used.
  • fuel-soluble as used in this specification and appended claims does not necessarily mean that all the compositions in question are miscible or soluble in all proportions in all fuels.
  • composition is soluble in a fuel (hydrocarbon, non-hydrocarbon, mixtures, etc) in which it is intended to function to an extent which permits the solution to exhibit one or more of the desired properties.
  • a fuel hydrocarbon, non-hydrocarbon, mixtures, etc
  • solutions it is not necessary that such "solutions" be true solutions in the strict physical or chemical sense. They may instead be micro-emulsions or colloidal dispersions which, for the purpose of this invention, exhibit properties sufficiently close to those of true solutions to be, for practical purposes, interchangeable with them within the context of this invention.
  • the nitrogen-free fuel detergent additives of this invention are useful as additives for fuels, in which they may function as detergents.
  • the fuel detergents of the present invention can be present in fuel compositions at 1 to 10,000 ppm (where ppm is calculated on a weight:weight basis).
  • the fuel detergent is present in fuel compositions in ranges with lower limits of 1, 5, 10, 20, 50, 100, 150 and 200 ppm and upper limits of 10,000, 5,000, 2,500, 1,000, and 500 where any upper limit may be combined with any lower limit to provide a range for the fuel detergent present in the fuel compositions.
  • the fuel detergent is present at 10 to 2500 ppm, and in another embodiment from 20-500 ppm.
  • the fuel additive composition of the present invention comprises the nitrogen-free fuel detergent additive described herein and further comprises a solvent and/or one or more additional performance additives.
  • These additive compositions also known as concentrates, may be used to prepare fuel compositions by adding the additive composition to a fuel.
  • the solvents suitable for use in the present invention include hydrocarbon solvents that provide for the additive composition's compatibility and/or homogeneity and to facilitate their handling and transfer and may include a fuel as described below.
  • the solvent can be an aliphatic hydrocarbon, an aromatic hydrocarbon, an oxygen-containing composition, or a mixture thereof.
  • the flash point of the solvent is generally about 25°C or higher.
  • the hydrocarbon solvent is an aromatic naphtha having a flash point above 62°C or an aromatic naphtha having a flash point of 40°C or a kerosene with a 16% aromatic content having a flash point above 62°C.
  • Aliphatic hydrocarbons include various naphtha and kerosene boiling point fractions that have a majority of aliphatic components.
  • Aromatic hydrocarbons include benzene, toluene, xylenes and various naphtha and kerosene boiling point fractions that have a majority of aromatic components.
  • Alcohols are usually aliphatic alcohols having about 2 to 10 carbon atoms and include ethanol, 1-propanol, isopropyl alcohol, 1-butanol, isobutyl alcohol, amyl alcohol, and 2-methyl-1-butanol.
  • the oxygen containing composition can include an alcohol, a ketone, an ester of a carboxylic acid, a glycol and/or a polyglycol, or a mixture thereof.
  • the solvent in an embodiment of the invention will be substantially free of to free of sulphur having a sulphur content in several instances that is below 50 ppm, 25 ppm, below 18 ppm, below 10 ppm, below 8 ppm, below 4 ppm, or below 2 ppm.
  • the solvent can be present in the additive concentrate composition at 0 to 99 percent by weight, and in other instances at 3 to 80 percent by weight, or 10 to 70 percent by weight.
  • the fuel addditive of the present invention and the additional performance additives taken separately or in combination can be present in the additive concentrate composition at 0.01 to 100 percent by weight, and in other instances can be present at 0.01 to 95 percent by weight, at 0.01 to 90 percent by weight, or at 0.1 to 80 percent by weight.
  • the additive concentrate may comprise the fuel detergent of the present invention and be substantially free of any additional solvent.
  • the additive concentrate containing the fuel detergent of the present invention is neat, in that it does not contain any additional solvent added to improve the material handling characteristics of the concentrate, such as its viscosity.
  • the additive concentrate containing the additive of the present invention does contain some solvent.
  • the additive concentrate composition, or a fuel composition containing the fuel detergent of the present invention may be prepared by admixing or mixing the components of the composition at ambient to elevated temperatures usually up to 60°C until the composition is homogeneous.
  • the fuel additive composition is substantially nitrogen free or nitrogen free. In other embodiments the fuel additive composition comprises the nitrogen free fuel additive described above but also comprises additional additive which may not be nitrogen free.
  • the fuel composition of the present invention comprises the fuel detergent described above and a liquid fuel, and is useful in fueling an internal combustion engine.
  • a fuel may also be a component of the additive compositions described above.
  • Fuels suitable for use in the present invention are not overly limited. Generally, suitable fuels are normally liquid at ambient conditions e.g., room temperature (20 to 30°C).
  • the liquid fuel can be a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof.
  • the hydrocarbon fuel can be a petroleum distillate, including a gasoline as defined by ASTM specification D4814, or a diesel fuel, as defined by ASTM specification D975.
  • the liquid fuel is a gasoline, and in another embodiment the liquid fuel is a non-leaded gasoline.
  • the liquid fuel is a diesel fuel.
  • the hydrocarbon fuel can be a hydrocarbon prepared by a gas to liquid process to include for example hydrocarbons prepared by a process such as the Fischer-Tropsch process.
  • the non-hydrocarbon fuel can be an oxygen containing composition, often referred to as an oxygenate, which includes an alcohol, an ether, a ketone, an ester of a carboxylic acid, a nitroalkane, or a mixture thereof.
  • the non-hydrocarbon fuel can include for example methanol, ethanol, butanol, methyl t-butyl ether, methyl ethyl ketone, transesterified oils and/or fats from plants and animals such as rapeseed methyl ester and soybean methyl ester, and nitromethane.
  • hydrocarbon and non-hydrocarbon fuels can include, for example, gasoline and methanol and/or ethanol, diesel fuel and ethanol, and diesel fuel and a transesterified plant oil such as rapeseed methyl ester and other bio-derived fuels.
  • the liquid fuel is an emulsion of water in a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof.
  • the liquid fuel can have a sulphur content on a weight basis that is 5000 ppm or less, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less.
  • the fuel composition is substantially nitrogen free or nitrogen free. In other embodiments the fuel composition comprises the nitrogen free fuel additive described above but also comprises additional additive which may not be nitrogen free.
  • the liquid fuel of the invention is present in a fuel composition in a major amount that is generally greater than 95% by weight, and in other embodiments is present at greater than 97% by weight, greater than 99.5% by weight, or greater than 99.9% by weight.
  • the additive compositions and fuel compositions of the present invention can further comprise one or more additional performance additives.
  • Additional performance additives can be added to a fuel composition depending on several factors to include the type of internal combustion engine and the type of fuel being used in that engine, the quality of the fuel, and the service conditions under which the engine is being operated.
  • the additional performance additives added are free of nitrogen.
  • the additional performance additives may contain nitrogen.
  • the additional performance additives can include: an antioxidant such as a hindered phenol or derivative thereof and/or a diarylamine or derivative thereof; a corrosion inhibitor such as an alkenylsuccinic acid; and/or a detergent/dispersant additive, other than the fuel detergent of the present invention, such as a polyetheramine or nitrogen containing detergent, including but not limited to PIB amine dispersants, quaternary salt dispersants, and succinimide dispersants.
  • an antioxidant such as a hindered phenol or derivative thereof and/or a diarylamine or derivative thereof
  • a corrosion inhibitor such as an alkenylsuccinic acid
  • a detergent/dispersant additive other than the fuel detergent of the present invention, such as a polyetheramine or nitrogen containing detergent, including but not limited to PIB amine dispersants, quaternary salt dispersants, and succinimide dispersants.
  • the additional performance additives may also include: a cold flow improver such as an esterified copolymer of maleic anhydride and styrene and/or a copolymer of ethylene and vinyl acetate; a foam inhibitor such as a silicone fluid; a demulsifier such as a polyalkoxylated alcohol; a lubricity agent such as a fatty carboxylic acid; a metal deactivator such as an aromatic triazole or derivative thereof, including but not limited to benzotriazole; and/or a valve seat recession additive such as an alkali metal sulfosuccinate salt.
  • a cold flow improver such as an esterified copolymer of maleic anhydride and styrene and/or a copolymer of ethylene and vinyl acetate
  • a foam inhibitor such as a silicone fluid
  • a demulsifier such as a polyalkoxylated alcohol
  • a lubricity agent such as a fatty carboxylic
  • the additional additives may also include a biocide; an antistatic agent, a deicer, a fluidizer such as a mineral oil and/or a poly(alpha-olefin) and/or a polyether, and a combustion improver such as an octane or cetane improver.
  • the additional performance additives which may be present in the fuel additive compositions and fuel compositions of the present invention also include di-ester, di-amide, ester-amide, and ester-imide friction modifiers prepared by reacting a dicarboxylic acid (such as tartaric acid) and/or a tricarboxyli acid (such as citric acid), with an amine and/or alcohol, optionally in the presence of a known esterification catalyst.
  • These friction modifiers often derived from tartaric acid, citric acid, or derivates thereof, may be derived from amines and/or alcohols that are branched so that the friction modifier itself has significant amounts of branched hydrocarbyl groups present within it structure. Examples of a suitable branched alcohols used to prepare these friction modifiers include 2-ethylhexanol, isotridecanol, Guerbet alcohols, or mixtures thereof.
  • the additional performance additives can each be added directly to the additive and/or the fuel compositions of the present invention, but they are generally mixed with the nitrogen-free fuel detergent additive to form an additive composition, or concentrate, which is then mixed with fuel to result in a fuel composition.
  • the additive concentrate compositions are described in more detail above.
  • the invention is useful for a liquid fuel and/or for an internal combustion engine, including either compression ignition engines or spark ignited engines.
  • the internal combustion engine includes 2-stroke or 4-stroke engines fuelled with gasoline, diesel, a natural gas, a mixed gasoline/alcohol or any of the fuels described in the sections above.
  • the compression ignition engines include both light duty and heavy duty diesel engines.
  • the spark ignited engines include direct injection gasoline engines.
  • the invention is useful in additive compositions in that the fuel detergent described above provides improved engine deposit control, allowing for improved engine performance, including but not limited to reductions in deposit-caused engine power losses, reduction in deposit-caused fuel economy losses and decreases in deposit-caused engine emissions.
  • the additive compositions of the present invention may be used in a lubricating composition such that the additives are present in the lubricating system of the engine.
  • the additives may also enter the combustion chamber of the engine during operation of the engine by the transfer of small amounts of the additive containing lubricating composition to the combustion chamber due to a phenomenon referred to as "blow by" where the lubricating composition, and in this case the additive composition, pass around the piston heads inside the cylinder, moving from the lubricating system of the engine into the combustion chamber.
  • nitrogen free is used in its ordinary sense and means that the fuel detergent additive of the present invention contains no nitrogen atoms.
  • the invention is not limited to nitrogen-free compositions, as other nitrogen-containing substances may be added to compositions that include the nitrogen-free fuel detergent described herein.
  • the nitrogen content of the additive compositions and/or the fuel compositions of the present invention are less than 100 ppm, less than 50 ppm, less than 35 ppm or less than 10 ppm (where ppm is calculated on a weight: weight basis).
  • the additive and/or fuel compositions of the present invention are free of nitrogen.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include: hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring); substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention
  • Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • substituents as pyridyl, furyl, thienyl and imidazolyl.
  • no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.
  • a commercially available nitrogen-containing additive is prepared by reacting 100 pbw mid vinylidene 1000 Mn Polyisobutylene (TPC 1105TM available from the Texas Petrochemicals LP) with with 8 pbw of an aldehyde and 11 pbw of a polyalkylamine in a reaction vessel which also contains a viscosity-controlling amount of organic solvent. The reaction is carried out below 85°C and aqueous distillate was removed from the system. The reaction product is a nitrogen-containing additive.
  • TPC 1105TM Mn Polyisobutylene
  • PiB phenol derived from mid vinylidene 1000 Mn Polyisobutylene (TPC 1105TM available from the Texas Petrochemicals LP) and phenol, is well known in the art. It is used herein as a comparative example in the testing below. This material, as the results below show, does not perform well as a fuel additive. This poor performance is expected given the lack of nitrogen, or more specifically, the lack of a polar nitrogen group, in the additive. This same result would be expected for the additives of the present invention as they too lack a polar nitrogen group.
  • a nitrogen-free fuel additive is prepared by mixing 1000 grams of mid vinylidene 1000 Mn Polyisobutylene (TPC 1105TM available from the Texas Petrochemicals LP) with 217 grams of toluene. The mixture is then charged to a reaction vessel. To the reaction vessel 281.2 grams of ortho cresol and 122 grams of toluene are charged, and the system is stirred for 15 minutes under a nitrogen blanket. Over 3 hours, 19.9 grams of boron-trifluoride etherate is added to the reaction vessel in a dropwise manner while the mixture in the reaction vessel is stirred and kept below 25°C. After the addition is complete, the mixture in the reaction vessel is stirred for 3 hours at ambient temperature.
  • TPC 1105TM available from the Texas Petrochemicals LP
  • a nitrogen-free fuel additive is prepared by mixing 165 grams of PiB cresol, derived from mid vinylidene 1000 Mn Polyisobutylene (TPC 1105TM available from the Texas Petrochemicals LP) and toluene (as described in the first part of Example 1 above), and 47.8 grams of methanol and 6.8 grams of paraformaldehyde in a reaction vessel. The reaction mixture is then stirred and heated to 55°C under a nitrogen blanket. Then 32.4 grams of a mixture of sodium methoxide at 25% actives in methanol is added to the reaction vessel subsurface over 70 minutes. After the charge is complete, the reaction mixture is heated to 60°C and then held at temperature for 150 minutes.
  • the reaction mixture is then cooled back to ambient temperature and then transferred to a rotary evaporator.
  • the material is vacuum stripped at 0.7 bar and 105°C to remove the methanol.
  • the product is then cooled and collected.
  • the collected material contains a nitrogen free additive.
  • a nitrogen-free fuel additive is prepared by mixing 250 grams of PiB cresol, derived from mid vinylidene 1000 Mn Polyisobutylene (TPC 1105TM available from the Texas Petrochemicals LP) and toluene (as described in the first part of Example 1 above), and 73.0 grams of methanol and 10.2 grams of paraformaldehyde in a reaction vessel. The reaction mixture is then stirred and heated to 55°C under a nitrogen blanket. Then 49.7 grams of a mictuxe of sodium methoxide at 25% actives in methanol is added to the reaction vessel subsurface over 70 minutes. After the charge is complete, the reaction mixture is heated to 60°C and then held at temperature for 150 minutes. The reaction mixture is then cooled back to ambient temperature and then transferred to a rotary evaporator. The material is vacuum stripped at 0.7 bar and 70°C to remove the methanol. The product is then cooled and collected. The collected material contains a nitrogen free additive.
  • TPC 1105TM available from the Texas

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Claims (9)

  1. Zusammensetzung, umfassend ein stickstofffreies Brennstoff-Detergentadditiv, das durch Formel I wiedergegeben wird:
    Figure imgb0005
     wobei:
    R1 unabhängig für Wasserstoff oder eine Hydrocarbylgruppe mit 1 bis 50 Kohlenstoffatomen steht;
    R2 unabhängig für eine Hydrocarbylgruppe mit 1 bis 10 Kohlenstoffatomen steht;
    n für 0 oder 1 steht; wobei dann, wenn n für 0 steht, R3 unabhängig für Wasserstoff oder eine Hydrocarbylgruppe mit 1 bis 50 Kohlenstoffatomen steht; und dann, wenn n für 1 steht, R3 für eine Hydrocarbylgruppe mit 1 bis 50 Kohlenstoffatomen steht;
    R4 für eine Hydrocarbylgruppe mit 1 bis 150 Kohlenstoffatomen, die von Polyisobutylen mit einem zahlenmittleren Molekulargewicht von 350 bis 5000 abgeleitet ist, steht;
    R5 jeweils unabhängig für Wasserstoff oder eine Hydroxylgruppe steht;
    R6 unabhängig für Wasserstoff oder eine Hydrocarbylgruppe mit 1 bis 50 Kohlenstoffatomen oder -(R7)m-OR8 steht, wobei R7 für eine Hydrocarbylgruppe mit 1 bis 10 Kohlenstoffatomen steht, R8 für eine Hydrocarbylgruppe mit 1 bis 50 Kohlenstoffatomen steht und m für 0 oder 1 steht; und
    wobei R1, R2, R3, R4, R5, R6, R7 und R8 frei von Stickstoff sind.
  2. Zusammensetzung nach Anspruch 1, wobei das Additiv durch Formel II wiedergegeben wird:
    Figure imgb0006
     wobei:
    R1 unabhängig für Wasserstoff oder eine Hydrocarbylgruppe mit 1 bis 6 Kohlenstoffatomen steht;
    R2 für eine Methylengruppe steht und n für 0 oder 1 steht;
    wobei dann, wenn n für 0 steht, R3 für Wasserstoff oder eine Hydrocarbylgruppe mit 1 bis 6 Kohlenstoffatomen steht; und dann, wenn n für 1 steht, R3 für eine Hydrocarbylgruppe mit 1 bis 6 Kohlenstoffatomen steht;
    R4 von Polyisobutylen mit einem zahlenmittleren Molekulargewicht von 500 bis 2500 abgeleitet ist; und
    R6 unabhängig für Wasserstoff oder eine Hydrocarbylgruppe mit 1 bis 50 Kohlenstoffatomen oder -(R7)m-OR8 steht, wobei R7 für eine Hydrocarbylgruppe mit 1 bis 10 Kohlenstoffatomen steht, R8 für eine Hydrocarbylgruppe mit 1 bis 50 Kohlenstoffatomen steht und m für 0 oder 1 steht.
  3. Zusammensetzung nach Anspruch 2, wobei das Additiv eine Mischung von zwei oder mehr Additiven aus der Gruppe bestehend aus:
    a) dem Additiv, das durch Formel II wiedergegeben wird, wobei R3 für Wasserstoff steht und R6 für Wasserstoff steht;
    b) dem Additiv, das durch Formel II wiedergegeben wird, wobei R3 für eine Hydrocarbylgruppe mit 1 bis 6 Kohlenstoffatomen steht und R6 für Wasserstoff steht;
    c) dem Additiv, das durch Formel II wiedergegeben wird, wobei R3 für Wasserstoff steht und R6 für eine Hydrocarbylgruppe mit 1 bis 6 Kohlenstoffatomen steht;
    d) dem Additiv, das durch Formel II wiedergegeben wird, wobei R3 für eine Hydrocarbylgruppe mit 1 bis 6 Kohlenstoffatomen steht und R6 für eine Hydrocarbylgruppe mit 1 bis 6 Kohlenstoffatomen steht; umfasst.
  4. Zusammensetzung nach Anspruch 2, wobei:
    R1 für Wasserstoff steht;
    R2 unabhängig für ein Methylen steht und n für 0 oder 1 steht;
    wobei dann, wenn n für 0 steht, R3 unabhängig für Wasserstoff oder eine Methylgruppe steht; und
    dann, wenn n für 1 steht, R3 für eine Methylgruppe steht;
    R6 unabhängig für Wasserstoff, eine Hydroxylgruppe oder eine Methylgruppe steht.
  5. Brennstoffadditivzusammensetzung, umfassend:
    (a) das stickstofffreie Detergentadditiv nach Anspruch 1;
    (b) ein fakultatives Lösungsmittel und
    (c) ein oder mehrere fakultative zusätzliche Performance-Additive.
  6. Brennstoffadditivzusammensetzung nach Anspruch 5, wobei Komponente (c) ein Antioxidans, einen Korrosionsinhibitor, ein anderes Detergent/Dispersant-Additiv, einen Kaltfließverbesserer, einen Schauminhibitor, einen Emulgator, ein Schmiermittel, einen Metalldesaktivator, ein Ventilüberstandsadditiv, ein Biozid, ein Antistatikum, einen Enteiser, einen Verflüssiger, einen Verbrennungsverbesserer, einen Reibungsmodifikator oder eine Kombination davon umfasst.
  7. Brennstoffzusammensetzung, umfassend:
    (a) das stickstofffreie Detergentadditiv nach Anspruch 1;
    (b) einen Brennstoff und
    (c) ein oder mehrere fakultative zusätzliche Performance-Additive.
  8. Brennstoffzusammensetzung Anspruch 7, wobei Komponente (a) in einer Menge von etwa 10 ppm bis 2500 ppm vorliegt.
  9. Verfahren zum Betreiben eines Verbrennungsmotors, bei dem man dem Motor eine Brennstoffzusammensetzung, die
    (a) das stickstofffreie Detergentadditiv gemäß Anspruch 1 und
    (b) einen Brennstoff
    umfasst, zuführt.
EP09744556.3A 2008-10-24 2009-10-23 Stickstofffreie brennstoffadditive zur bekämpfung von ablagerungen Not-in-force EP2361295B1 (de)

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CA2784747A1 (en) * 2009-12-17 2011-07-14 The Lubrizol Corporation Nitrogen-free deposit control fuel additives and one step process for the making thereof

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US5399277A (en) * 1993-10-08 1995-03-21 Exxon Chemical Patents Inc. Fuel and lubricant additives derived from dihydroxyaromatic compounds
JP2000229900A (ja) * 1999-02-09 2000-08-22 Mitsubishi Materials Corp 水酸基を有する芳香族化合物の製造方法
US20050172546A1 (en) * 2004-02-09 2005-08-11 The Lubrizol Corporation, A Corporation Of The State Of Ohio Fuel composition containing a medium substantially free of sulphur and process thereof

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US4273891A (en) * 1974-03-15 1981-06-16 The Lubrizol Corporation Hydrocarbon-substituted methylol phenols
CN1232864A (zh) * 1998-04-23 1999-10-27 李宝清 发动机燃料系统免拆清洗剂
CN1166752C (zh) * 2001-03-20 2004-09-15 中油燃料油股份有限公司 一种高硫重质燃料油脱硫剂及其应用

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US5399277A (en) * 1993-10-08 1995-03-21 Exxon Chemical Patents Inc. Fuel and lubricant additives derived from dihydroxyaromatic compounds
JP2000229900A (ja) * 1999-02-09 2000-08-22 Mitsubishi Materials Corp 水酸基を有する芳香族化合物の製造方法
US20050172546A1 (en) * 2004-02-09 2005-08-11 The Lubrizol Corporation, A Corporation Of The State Of Ohio Fuel composition containing a medium substantially free of sulphur and process thereof

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