EP2987845B1 - Verwendung von quarternären Ammoniumsalzen in Benzinbrennstoff zur Verbesserung der Brennstoffleistung - Google Patents

Verwendung von quarternären Ammoniumsalzen in Benzinbrennstoff zur Verbesserung der Brennstoffleistung Download PDF

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Publication number
EP2987845B1
EP2987845B1 EP14181490.5A EP14181490A EP2987845B1 EP 2987845 B1 EP2987845 B1 EP 2987845B1 EP 14181490 A EP14181490 A EP 14181490A EP 2987845 B1 EP2987845 B1 EP 2987845B1
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Prior art keywords
acid
fuel
engine
quaternary ammonium
additive
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French (fr)
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EP2987845A1 (de
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Xinggao Fang
Scott A. Culley
Scott D. Schwab
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Afton Chemical Corp
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Afton Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
    • 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
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • 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
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure

Definitions

  • the disclosure is directed to use of a gasoline fuel composition that exhibits reduced friction, wear, and/or corrosion.
  • the disclosure relates to an additive that reduces friction or wear in an engine and thus improves fuel economy and/or reduces the corrosiveness of a fuel in a fuel delivery system of an engine or fuel storage terminal.
  • Fuel compositions for vehicles are continually being improved to enhance various properties of the fuels in order to accommodate their use in newer, more advanced engines. Accordingly, the fuel compositions contain additives which are directed to certain properties that require improvement. For example, friction modifiers, such as fatty acid amides, are added to fuels to reduce friction and wear in the fuel delivery systems of an engine. Other additives are included in the fuel compositions to reduce the corrosiveness of the fuel compositions and/or improve the electrical conductivity of the fuel compositions. Still other additives are added to fuels to improve the fuel economy of an engine operating on the fuels. Each of the foregoing additives may improve a single property of the fuel composition and, in some instances, may adversely affect other properties of the fuel composition. Accordingly, fuel compositions typically include a complex mixture of additives that are selected to cooperate with each other to improve the fuel composition. Accordingly, there is a need for a fuel additive that is effective to improve multiple characteristics of a fuel.
  • friction modifiers such as fatty acid amides
  • US 2013/0296210 A1 discloses the use of quaternized alkylamine nitrogen compounds as a fuel additive for reduction or prevention of deposits in the injection systems of direct injection diesel engines, especially in common rail injection systems, for reduction of the fuel consumption of direct injection diesel engines, especially of diesel engines with common rail injection systems.
  • the quaternized alkylamine nitrogen compounds are also taught to be useful for minimizing power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems; and as an additive for gasoline fuels, especially for operation of DISI engines.
  • An example of a reaction product comprising a quaternized nitrogen compound is N-methyl-N-(2-hydroxypropyl)-N,N-ditallowammonium acetate which is said to be a gasoline fuel additive.
  • AU 2011 275 778 A1 discloses acid-free quaternized nitrogen compounds and the production and use thereof as diesel fuel and lubricant additives for reducing deposits in diesel engines. More specifically, the use of said acid-free quaternized nitrogen compounds as (1) fuel additives for reducing or preventing deposits in the injection systems of direct-injection diesel engines, in particular in common rail injection systems, (2) for reducing the fuel consumption of direct-injection diesel engines, in particular of diesel engines having common rail injection systems, and (3) for minimizing the power loss in direct-injection diesel engines, in particular in diesel engines having common rail injection systems, is disclosed.
  • WO 2008/027881 A2 discloses a quaternary ammonium salt detergent made from the reaction product of the reaction of: (a) Mannich reaction product having a tertiary amino group, wherein the Mannich reaction product is prepared from the reaction of a hydrocarbyl-substituted phenol, an aldehyde, and amine; and (b) a quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen, and the use of such quaternary ammonium salt detergents in a fuel composition to reduce intake valve deposits.
  • a fuel additive that is also beneficial to the engine lubricant would be desirable.
  • the properties of an engine oil of lubricating viscosity that a fuel-borne additive might affect include the corrosiveness, friction, and fuel economy of said engine oil.
  • exemplary embodiments provide use of a fuel composition for reducing wear in a fuel delivery system.
  • the invention is set out in the appended claims.
  • the fuel composition includes gasoline and from 10 to 500 ppm by weight based on a total weight of the fuel composition, of an alkoxylated quaternary ammonium salt derived from an epoxide, a tertiary amine, and an optional protonating agent.
  • the fuel composition may be essentially free of a quaternary ammonium salt of a hydrocarbyl Mannich compound such that the concentration of the quaternary ammonium salt of a hydrocarbyl Mannich compound in the fuel composition has no measurable effect on injector cleanliness or deposit formation.
  • an advantage of the method described herein is that the additive for the fuel composition may not only improve the wear properties of the fuel, but the additive may also be effective to improve fuel economy and the friction properties of the fuel
  • the fuel additive may be derived from an amido amine that is made in the substantial absence of acylating agents such as those disclosed in U.S. Patent No. 8,147,569 .
  • An advantage of the fuel additive described herein is that the additive may be used at a much lower concentration than a quaternary ammonium salt derived from an amine that is derived from an acylating agent, yet may provide better friction, and wear performance than conventional quaternary ammonium salts made from amines derived from acylating agents.
  • the additive is derived from a tertiary amine wherein the tertiary amine is an amido amine that is derived from acid having from 1 to 54 carbon atoms.
  • the additive may be derived from an ether amine such as an alkylether amine.
  • the epoxide is selected from compounds of the formula: wherein each R is independently selected from H and a C 1 to C 50 hydrocarbyl group.
  • the fuel composition contains from 60 to 180 ppm by weight, such as from 70 to 170 ppm by weight, or from 80 to 150 ppm by weight of the alkoxylated quaternary ammonium salt based on a total weight of the fuel composition.
  • each of the end points of each range disclosed herein can be combined with any of the other end points of the ranges that are disclosed herein.
  • an oil of lubricating viscosity contains from 0.05 to 5.0 wt.%, such as from 0.1 to 1.0 wt.%, or 0.15 to 0.5 wt.% of the alkoxylated quaternary ammoniuim salt based on the total weight of the oil composition.
  • FIG. 1 is a depiction of the improvement in torque efficiency for a motorized engine operated at from 500 to 3000 rpm at 115°C when using an engine lubricant containing a friction modifier.
  • the fuel additive component of the present disclosure may be used in a minor amount 10 to 500 ppm by weight in a major amount (50 wt% or more) of fuel and may be added to the fuel directly or added as a component of an additive concentrate to the fuel.
  • a suitable fuel additive component for improving the operation of internal combustion engines may be made by reacting a tertiary amine of the formula: wherein each of R 1 , R 2 , and R 3 is selected from hydrocarbyl groups containing from 1 to 200 carbon atoms, 1 to 100 carbon atoms, or 1 to 50 carbon atoms, optionally, a carboxylic acid or a phenol, and a quaternizing agent to provide an alkoxylated quaternary ammonium salt.
  • R 1 , R 2 , and R 3 contain 1 to 3 carbon atoms.
  • the reaction may be conducted in the presence of a protonating agent having an acid disassociation constant (pK a ) of less than 13, such as a carboxylic acid or an alkyl phenol.
  • the alkoxylated quaternary ammonium salt may also be derived from an amido amine and a quaternizing agent reacted in the presence of a protonating agent.
  • the protonating agent may be obtained from a carboxylic acid, an alkyl phenol, an amine or an epoxide.
  • the protonating agent may be obtained from the amido amine derived from a fatty acid wherein the reaction product containing the amido amine has an acid number ranging from 1 to 200 mg KOH/g.
  • the amine contains at least one tertiary amino group and the amido amine is made in a reaction medium that is substantially devoid of or does not contain an acylating agent.
  • hydrocarbyl group or “hydrocarbyl” 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 a molecule and having a predominantly hydrocarbon character. Examples of hydrocarbyl groups include:
  • the term “major amount” is understood to mean an amount greater than or equal to 50 wt. %, for example from 80 to 98 wt.% relative to the total weight of the composition.
  • the term “minor amount” is understood to mean an amount less than 50 wt. % relative to the total weight of the composition.
  • any suitable amine or polyamine containing at least one tertiary amino group may be used.
  • an amine including diamines and polyamines may be reacted with a C 1 to C 54 carboxylic acid to form an amido amine and the amido amine may be subsequently reacted with a quaternizing agent.
  • Suitable tertiary amido amine compounds may have a hydrocarbyl linkage, such as an ether linkage between the amido group and the amino group or the tertiary amido amine may be a compound of the formula: wherein each of R 10 , and R 11 is selected from hydrocarbyl groups containing from 1 to 50 carbon atoms, each R 9 , R 12 , R 13 and R 14 may be independently selected from hydrogen or a hydrocarbyl group, x may range from 1 to 6, y may be 0 or 1, z may be 1 to 6, and n may range from 1 to 6.
  • Each hydrocarbyl group R 9 to R 14 may be independently selected from linear, branched, substituted, cyclic, saturated, unsaturated hydrocarbyl groups, and may contain one or more hetero atoms.
  • Suitable hydrocarbyl groups may include, but are not limited to alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy groups, aryloxy groups, amino groups, and the like.
  • Particularly suitable hydrocarbyl groups may be linear or branched alkyl groups.
  • a representative example of amine reactants which may be amidized and quaternized to yield compounds disclosed herein include for example, but are not limited to, dimethyl amino propyl amine, and 2-(2-dimethylamino-ethoxy) ethylamine.
  • the amine contains solely primary or secondary amino groups, it may be desirable to alkylate at least one of the primary or secondary amino groups to a tertiary amino group prior to quaternizing the amine.
  • the primary amines and secondary amines or mixtures therof with tertiary amines may be exhaustively or partially alkylated to a tertiary amine and further alkoxylated to a quaternary salt.
  • the amine When the amine has a hydroxyl group, the amine may be converted to an ester amine by reacting the amine with a C 1 to C 54 carboxylic acid.
  • the acid may be a monoacid, a dimer acid, or a trimer acid.
  • the acid may be selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, ⁇ -linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, and the dimer and trimer acids thereof.
  • the reaction product When reacted with the amine, the reaction product may be a C 1 -C 54 -alkyl or alkenyl-substituted ester amine such as a C 1 -C 54 -alkyl or alkenyl-substituted ester propyldimethylamine.
  • the amine when it is an ether amine, it may be a hydrocarbyl ether amine or a polyamine.
  • the amine may have the formula R 15 --[O--CH 2 --CH(CH 3 )] y -NR 16 R 17 , wherein R 15 is a hydrocarbyl radical having from 8 to 18 carbon atoms and y is an integer ranging from 1 to 6, and wherein R 16 and R 17 are the same as defined for R 1 -R 3 above.
  • R 16 and R 17 contain from one to three carbon atoms, such as methyl or ethyl groups.
  • a protonating agent may be used to make the quaternary ammonium salt.
  • the protonating agent may have a pKa of less than 13 including carboxylic acids and alkyl phenols.
  • Specific examples of the organic acid are aliphatic, alkenyl or aromatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanic acid, lauric acid, tridecanic acid, myristic acid, pentacanic acid, palmitic acid, heptadecanic acid, stearic acid, nonadecanic acid, arachidic acid, isobutyric acid, isovaleric acid, isocaproic acid, ethylbutyric acid, methyl-valeric acid, isocaprylic acid, propylvaleric acid, ethyl-caproic
  • aliphatic polycarboxylic acids such as citric acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane diacid, dodecane di-acid, tridecane diacid, tetradecane diacid, pentadecane di-acid, hexadecane diacid, heptadecane diacid, octadecane diacid, noncadecane diacid, eicosane diacid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, pentylmalonic acid, hexylmalonic acid, dimethylmalonic acid, methylethylmalonic acid, diethylmalonic acid, methyl-propylmalonic acid, methylbutylmalonic acid, ethylpropyl
  • Phenols which may be used include, but are not limited to [beta]-naphthol, o-nitrophenol, p-nitrophenol, p--aminophenol, catechol, resorcinol, 4,4'-dihydroxydiphenyl-2,2-propane, C 1 -C 20 -alkyl phenols, and polyalkyl phenols or substituted Mannich bases.
  • a suitable quaternizing agents may be selected from the group consisting of hydrocarbyl epoxides of the formula: wherein each R is independently selected from H and a C 1 to C 50 hydrocarbyl group, and polyepoxides.
  • suitable epoxides that may be used as quaternizing agents may be selected from the group consisting of:
  • the alkoxylated quaternary ammonium salts from amido amines may be made in one stage or two stages.
  • the reaction may be carried out by contacting and mixing the amido amine with the olefin oxide in the reaction vessel wherein a carboxylic acid is added to the reaction mixture to provide a protonating agent.
  • the carboxylic acid may be same acid used to make the amido amine or may be selected from any of the above listed fatty acids, formic acid, acetic acid, propionic acid, butyric acid, polymeric acid and mixtures thereof, such a polyolefinic mono-or di-carboxylic acid, polymeric polyacids and mixtures thereof, and the like.
  • the mole ratio of protonating agent per mole of epoxy equivalents added to the reaction mixture may range from 1:1 to 10:1, for example from 1:1 to 5:1, or from 1:1 to 2:1 moles of acid per mole of epoxy equivalents.
  • the anion of the quaternary ammonium salt is a carboxylate anion.
  • the reaction may be carried out at temperature ranging from 30° to 90°C, for example from 45° to 70° C.
  • the reaction may be conducted by reacting any amount of tertiary amino groups to epoxy groups sufficient to provide a quaternary ammonium compound. In one embodiment a mole ratio of tertiary amino groups to epoxy groups may range from 2:1 to 1:2.
  • volatiles and unreacted reagents may be removed from the reaction product by heating the reaction product under vacuum.
  • the product may be diluted with mineral oil, diesel fuel, kerosene, alcohol, or an inert hydrocarbon solvent to prevent the product from being too viscous, if necessary.
  • the fuels may contain conventional quantities of cetane improvers, corrosion inhibitors, cold flow improvers (CFPP additive), pour point depressants, solvents, demulsifiers, lubricity additives, additional friction modifiers, amine stabilizers, combustion improvers, dispersants, antioxidants, heat stabilizers, conductivity improvers, metal deactivators, carrier fluid, marker dyes, organic nitrate ignition accelerators, cyclomatic manganese tricarbonyl compounds, and the like.
  • CFPP additive cold flow improvers
  • pour point depressants solvents
  • demulsifiers demulsifiers
  • lubricity additives additional friction modifiers
  • amine stabilizers amine stabilizers
  • combustion improvers dispersants
  • antioxidants antioxidants
  • heat stabilizers heat stabilizers
  • conductivity improvers metal deactivators
  • carrier fluid marker dyes
  • organic nitrate ignition accelerators organic nitrate ignition accelerators
  • compositions described herein may contain 10 weight percent or less, or in other aspects, 5 weight percent or less, based on the total weight of the additive concentrate, of one or more of the above additives.
  • the fuels may contain suitable amounts of conventional fuel blending components such as methanol, ethanol, dialkyl ethers, 2-ethylhexanol, and the like.
  • organic nitrate ignition accelerators that include aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic group is saturated, and that contain up to 12 carbons may be used.
  • organic nitrate ignition accelerators examples include methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate, isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl nitrate, cyclopentyl nitrate, cyclohexyl
  • metal deactivators useful in the compositions of the present application are disclosed in U.S. Pat. No. 4,482,357 issued Nov. 13, 1984.
  • Such metal deactivators include, for example, salicylidene-o-aminophenol, disalicylidene ethylenediamine, disalicylidene propylenediamine, N,N'-disalicylidene-1,2-diaminopropane, triazole, tolutriazole, and other substituted triazoles.
  • the additives may be employed in amounts sufficient to reduce or inhibit deposit formation in a fuel system or combustion chamber of an engine and/or crankcase.
  • the fuels may contain minor amounts of the above described reaction product that controls or reduces the formation of engine deposits, for example injector deposits in gasoline or diesel engines.
  • the additives of the present disclosure including the alkoxylated quaternary ammonium salt described above, and optional additives used in formulating the fuels used in this invention may be blended into the base fuel individually or in various sub-combinations.
  • the additive components of the present application may be blended into the fuel concurrently using an additive concentrate, as this takes advantage of the mutual compatibility and convenience afforded by the combination of ingredients when in the form of an additive concentrate. Also, use of a concentrate may reduce blending time and lessen the possibility of blending errors.
  • the fuels of the present disclosure may be applicable to the operation of gasoline and diesel engines.
  • the engine include both stationary engines (e.g., engines used in electrical power generation installations, in pumping stations, etc.) and ambulatory engines (e.g., engines used as prime movers in automobiles, trucks, road-grading equipment, military vehicles, etc.).
  • the fuels may include any and all middle distillate fuels, diesel fuels, biorenewable fuels, biodiesel fuel, fatty acid alkyl ester, gas-to-liquid (GTL) fuels, jet fuel, alcohols, ethers, kerosene, low sulfur fuels, synthetic fuels, such as Fischer-Tropsch fuels, liquid petroleum gas, bunker oils, coal to liquid (CTL) fuels, biomass to liquid (BTL) fuels, high asphaltene fuels, fuels derived from coal (natural, cleaned, and petcoke), genetically engineered biofuels and crops and extracts therefrom, and natural gas.
  • GTL gas-to-liquid
  • synthetic fuels such as Fischer-Tropsch fuels, liquid petroleum gas, bunker oils, coal to liquid (CTL) fuels, biomass to liquid (BTL) fuels, high asphaltene fuels, fuels derived from coal (natural, cleaned, and petcoke), genetically engineered biofuels and crops and extracts therefrom, and natural gas.
  • the biorenewable fuel can comprise monohydroxy alcohols, such as those comprising from 1 to 5 carbon atoms.
  • suitable monohydroxy alcohols include methanol, ethanol, propanol, n-butanol, isobutanol, t-butyl alcohol, amyl alcohol, and isoamyl alcohol.
  • aspects of the present disclosure are directed to methods for reducing wear in a fuel system of an engine.
  • the quaternary ammonium salts described herein or fuel containing the quaternary ammonium salt may be combined with polyhydrocarbyl-succinimides, -Mannich compounds, -acids, -amides, -esters, - amide/acids and -acid/esters.
  • the methods comprise injecting a hydrocarbon-based compression ignition fuel comprising a alkoxylated quaternary ammonium salt of the present disclosure through the injectors of the diesel engine into the combustion chamber, and igniting the compression ignition fuel.
  • the method may also comprise mixing into the diesel fuel at least one of the optional additional ingredients described above.
  • the fuels of the present disclosure may be essentially free, such as devoid, of polyhydrocarbyl-succinimides, -Mannich compounds, -acids, - amides, -esters, -amide/acids and -acid/esters.
  • the fuel is essentially free of a quaternary ammonium salt of a hydrocarbyl succinimide.
  • the term "essentially free” is defined for purposes of this application to be concentrations having substantially no measurable effect on injector cleanliness or deposit formation.
  • a mixture of oleylamido propyl dimethylamine, propylene oxide and oleic acid was used in a molar ratio of 1 to 1 to 1 and the mixture was heated 50° C. in a reaction vessel until essentially all propylene oxide was consumed. Volatiles were removed under reduced pressure to give the desired product as a brownish oil.
  • a friction test was conducted using a high frequency reciprocating rig (HFRR) under a 200 gram load with a stroke distance of 1 millimeter at 50 Hz according to diesel fuel test ASTM D6079 except that the test was conducted in gasoline fuel at 25°C.
  • the base fuel contained no additives.
  • Each of the other fuel compositions contained a typical commercial Mannich base detergent package at 280ppm.
  • the treat rate of the additive and the results are given in the following table.
  • Table 1 - Fuel HFRR data No. Additive Treat rate (ppmw) HFRR Wear (micrometer) 1 Base fuel (no additives) 0 750 2 Base fuel plus Mannich base detergent package at 280 ppm 0 755 3 No. 2 plus additive of Comparative Ex.
  • the additive of the inventive examples provided significant and unexpected wear reduction compared to the additives of comparative example nos. 3-6.
  • the greatest wear reduction in gasoline fuel was obtained by the alkoxylated quaternary ammonium salt (no. 10).
  • the comparative examples provided only slight or no reduction in wear compared to the inventive examples.
  • a friction test was conducted on a GF-5 lubricating oil that was devoid of friction modifiers using a high frequency reciprocating rig (HFRR) under a 4N load with a stroke distance of 1 millimeter at 20 Hz at 70° C, 100° C and 130° C according to ASTM D6079.
  • the base lubricating oil contained a GF-5 dispersant/inhibitor (DI) package that contained no friction modifiers.
  • DI dispersant/inhibitor
  • the inventive examples (Runs 4-6) exhibited significantly reduced friction in a lubricant composition compared to the comparative examples (Runs 2 and 3) and the base lubricant devoid of friction modifiers (Run 1).
  • the corrosion potential of various fuel compositions containing conventional additives and the inventive additives were determined using a NACE corrosion test: NACE TM0172-2001.
  • the additive treat rate was 100 ppm.
  • the NACE standard provides a procedure for conducting a test to determine the corrosive properties of gasoline and distillate fuels in preparation for transport through a pipeline.
  • the surface of a cylindrical steel test specimen was prepared by polishing with 100 grit paper and then immersed in a mixture of the test fuel and distilled water at 38°C. The mixture was stirred and was maintained at 38°C for 4 hours. The test specimen was then rated by percent of the test surface corroded according to the following rating scale:
  • inventive examples Nos. 7-10 provided unexpectedly better corrosion protection potential than the commercial friction modifier additive (No. 3) or the additives of comparative examples 2, 3, 6 and 7 (Nos. 2 and 4-6).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Lubricants (AREA)

Claims (8)

  1. Verwendung einer Kraftstoffzusammensetzung zur Verringerung des Verschleißes in einem Kraftstoffzufuhrsystem eines Motors, wobei die Kraftstoffzusammensetzung Benzin und 10 bis 500 ppm nach Gewicht, bezogen auf das Gesamtgewicht der Kraftstoffzusammensetzung, eines alkoxylierten quaternären Ammoniumsalzes umfasst, das von einem Epoxid, einem tertiären Amin und einem optionalen Protonierungsmittel abgeleitet ist.
  2. Verwendung nach Anspruch 1, wobei der Motor einen Benzinmotor mit Kraftstoffeinspritzung umfasst.
  3. Verwendung nach Anspruch 1 oder 2, wobei das tertiäre Amin ein Amidoamin umfasst, das von einer Säure oder einem Etheramin mit 1 bis 54 Kohlenstoffatomen abgeleitet ist.
  4. Verwendung nach einem der Ansprüche 1 bis 3, wobei das Epoxid ausgewählt ist aus Verbindungen der Formel:
    Figure imgb0007
     wobei jedes R unabhängig ausgewählt ist aus H und einer C1-C50-Hydrocarbylgruppe.
  5. Verwendung nach einem der Ansprüche 1 bis 3, wobei das Epoxid ausgewählt ist aus Ethylenoxid, Propylenoxid und Glycidol.
  6. Verwendung nach einem der Ansprüche 1 bis 5, einschließlich des Protonierungsmittels, und wobei das Protonierungsmittel eine Carbonsäure ist, die aus Fettsäuren, Ameisensäure, Essigsäure, Propionsäure, Buttersäure, einer Alkenyl- oder Polyalkenylbernsteinsäure, Säure/Amid oder Säure/Ester, Polymersäuren und Gemischen davon ausgewählt ist.
  7. Verwendung nach einem der Ansprüche 1 bis 6, wobei die Kraftstoffzusammensetzung 80 bis 120 ppm nach Gewicht des alkoxylierten quaternären Ammoniumsalzes, bezogen auf das Gesamtgewicht der Kraftstoffzusammensetzung, enthält.
  8. Verwendung nach einem der Ansprüche 1 bis 7, wobei die Verwendung die Reibung verringert und das Drehmoment im Motor erhöht.
EP14181490.5A 2014-08-19 2014-08-19 Verwendung von quarternären Ammoniumsalzen in Benzinbrennstoff zur Verbesserung der Brennstoffleistung Active EP2987845B1 (de)

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US20200024536A1 (en) * 2018-07-20 2020-01-23 Afton Chemical Corporation Fuel-Soluble Synergistic Cleaning Mixture for High Pressure Gasoline Engines
CN113366094A (zh) 2018-11-30 2021-09-07 道达尔销售服务公司 用作为燃料添加剂的脂肪酰氨基季胺化合物
US11390821B2 (en) 2019-01-31 2022-07-19 Afton Chemical Corporation Fuel additive mixture providing rapid injector clean-up in high pressure gasoline engines
US10947473B2 (en) * 2019-05-17 2021-03-16 Vanderbilt Chemicals, Llc Less corrosive organic compounds as lubricant additives
EP3825387A1 (de) * 2019-11-22 2021-05-26 Afton Chemical Corporation Kraftstofflöslicher kavitationsinhibitor für kraftstoffe, die in common-rail-einspritzmotoren verwendet werden
US12043808B2 (en) 2021-12-28 2024-07-23 Afton Chemical Corporation Quaternary ammonium salt combinations for injector cleanliness
US11873461B1 (en) 2022-09-22 2024-01-16 Afton Chemical Corporation Extreme pressure additives with improved copper corrosion
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