WO2013070503A1 - Additif pour carburant pour un meilleur rendement des moteurs à injection directe du carburant - Google Patents
Additif pour carburant pour un meilleur rendement des moteurs à injection directe du carburant Download PDFInfo
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- WO2013070503A1 WO2013070503A1 PCT/US2012/063189 US2012063189W WO2013070503A1 WO 2013070503 A1 WO2013070503 A1 WO 2013070503A1 US 2012063189 W US2012063189 W US 2012063189W WO 2013070503 A1 WO2013070503 A1 WO 2013070503A1
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- ammonium salt
- quaternary ammonium
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1266—Inorganic compounds nitrogen containing compounds, (e.g. NH3)
-
- 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
- C10L1/1828—Salts 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic 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
- C10L1/221—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
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
-
- 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
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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
- C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
-
- 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
Definitions
- the disclosure is directed to fuel additives and to additive and additive concentrates that include the additive that are useful for improving the performance of direct fuel injected gasoline engines (DIG),
- DIG direct fuel injected gasoline engines
- Dispersant compositions known in the art for use in fuels include compositions that may include polyalkylene succinimides, poiyalkenepolyamines, polyetheramiens, and poiyalkyl substituted Mannich compounds. Dispersants are suitable for keeping soot and sludge suspended in a fluid, however dispersants are not particularly effective for cleaning surfaces once deposits have formed on the surfaces. Hence, fuel compositions for direct fuel injected engines often produce undesirable deposits in the engines.
- compositions that can prevent deposit build up, maintaining "as new” cleanliness for the vehicle life are desired.
- the same composition that can clean up dirty fuel injectors restoring performance to the previous "as new” condition would be equally desirable and valuable in the attempt to reduce air borne exhaust emissions and to improve the power performance of the engines.
- exemplary embodiments provide a fuel composition for an internal combustion gasoline engine comprising, a method for improving performance of fuel injectors and a method for cleaning fuel injectors for an internal combustion gasoline engine,
- the fuel composition includes a major amount of fuel and a minor, effective amount of a quaternary ammonium salt having a therrnogravimetric analysis (TGA) weight loss of greater than 50 wt.% at 350° C,
- TGA therrnogravimetric analysis
- Another embodiment of the disclosure provides a method of improving the injector performance of a direct fuel injected internal combustion gasoline engine.
- the method includes operating the engine on a fuel composition containing a major amount of fuel and from about 5 to about 200 ppm by weight based on a total weight of the fuel of a quaternary ammonium salt having a therrnogravimetric analysis (TG A) weight loss of greater than 50 wt.% at 350° C.
- the quaternary ammonium salt present in the fuel may improve injector performance by providing a reduction in LTFT of at least about 30%.
- a further embodiment of the disclosure provides a method of operating a direct fuel injected gasoline engine.
- the method includes combusting in the engine a fuel composition comprising a major amount of fuel and from about 5 to about 200 ppm by weight based on a total weight of the fuel of a quaternary ammonium salt having a themiogravimetric analysis (TG A) weight loss of greater than 50 wt.% at 350° C.
- TG A themiogravimetric analysis
- the TGA weight loss is greater than 70 wt.%, such as greater than 80 wt.%, particularly greater than 90 wt.% weight loss.
- the additive concentrate includes a quaternary ammonium salt having a therrnogravimetric analysis (TGA) weight loss of greater than 50 wt.% at 350° C and at least one component selected from the group consisting of diluents, compatibilizers, octane improvers, corrosion inhibitors, solvents, demul si tiers, lubricity additives, friction modifiers, amine stabilizers, combustion improvers, dispersants, antioxidants, heat stabilizers, conductivity improvers, metal deactivators, marker dyes, and cyclomatic manganese tricarbonyl compounds.
- TGA therrnogravimetric analysis
- An advantage of the fuel additive described herein is that the additive may not only reduce the amount of deposits forming on direct fuel injectors, but the additive may also be effective to clean up dirty fuel injectors sufficient to provide improved engine performance.
- FIG. 1 is a graphical representation of the LFTF % versus time for a directed injected gasoline (DIG) engine combusting a fuel without an additive and with the additive of the disclosure.
- DIG directed injected gasoline
- the fuel additive component of the present application may be used in a minor amount in a major amount of fuel and may be added to the fuel directly or added as a component of an additive concentrate to the fuel.
- a particularly suitable fuel additive component for impro ving the operation of internal combustion gasoline engines may be made by a wide variety of well known reaction techniques with amines or polyamines.
- such additive component may be made by reacting a tertiary amine of the formula
- each of R 1 , R 2 , and R 3 is selected from hydrocarbyl groups containing from 1 to 50 carbon atoms, with a quaternizing agent to provide a compound of the formula: ' wherem each of R 1 , R "' , R and R 4 is selected from hydrocarby!
- M " is selected from the group consisting of a carbox late, a nitrate, a nitride, a nitrite, a hyponitrite, a phenate, a carbamate, a carbonate, a haiide, a sulfate, a sulfite, a sulfide, a sulfonate, a phosphate, a phosphonate, and the like.
- R 1 , R R J , and R 4 are each selected from hydrocarbyl groups containing from 1 to 20 carbon atoms, provided at least one of R 1 , R 2 , R 3 , and R 4 contains from 8 to 20 carbon atoms.
- each of R 3 ⁇ 4 , R 2 , R 3 , and R 4 is selected from an alkyl or alkenyi group.
- Suitable quaternizing agents may be selected from the group consisting of hydrocarbyl substituted carboxyiates, carbonates, cyclic-carbonates, phenates, epoxides, or mixtures thereof.
- the quaternizing agent may be derived from a hydrocarbyl (or alkyl) substituted carbonate.
- the quaternizing agent may be selected from a hydrocarbyl substituted epoxide.
- the quaternizing agent may be selected from a hydrocarbyl substituted carboxylate.
- the carboxylate quaternizing agent excludes oxalates.
- 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:
- hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyi), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and ali cyclic-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 an alicyclic radical);
- aliphatic e.g., alkyl or alkenyi
- alicyclic e.g., cycloalkyl, cycloalkenyl
- aromatic-, aliphatic-, and ali cyclic-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 an alicyclic radical);
- substituted hydrocarbon substituents that is, substituents containing non- hydrocarbon groups which, in the context of the description herein, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially chloro and iiuoro), hydroxy, alkoxy, mercapto, aikyimercapto, nitro, nitroso, amino, alkylamino, and suifoxy);
- hetero-substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this description, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
- Hetero-atoms include sulfur, oxygen, nitrogen, and encompass substituents such as pyridyl, furyi, thienyi, and imidazolyl.
- substituents such as pyridyl, furyi, thienyi, and imidazolyl.
- no more than two, or as a further example, no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; in some embodiments, there will be no non-hydrocarbon substituent in the hydrocarbyl group.
- the term “major amount” is understood to mean an amount greater than or equal to 50 wt. %, for example from about 80 to about 98 wt .% relative to the total weight of the composition. Moreo ver, as used herein, the term “minor amount” is understood to mean an amount less than 50 wt. % relative to the total weight of the composition.
- Methods for making quaternary ammonium salts include but are not limited to by ion exchange reactions, or by direct alkylation of a tertiary amine or polyamine.
- Direct alkylation may include methyiation of tertian' amines such as pyridine and isoquinoline with methyl carboxylates, or alkylation of a tertiary amine with a hydrocarbyl epoxide in a one or two step reaction.
- a tertiary amine including monoamines and poly amines may be reacted with a quaternizing agent.
- each of R 3 ⁇ 4 , R 2 , and R J is selected from hydrocarbyl groups containing from I to 50 carbon atoms may be used.
- Each hydrocarbyl group R 1 to R 3 may independently be linear, branched, substituted, cvclic, saturated, unsaturated, or contain one or more hetero atoms.
- Suitable hydrocarbyl groups may include, but are not limited to alkyl groups, aryi groups, alkylaryl groups, arylalkyl groups, alkoxy groups, aryloxy groups, and the like.
- R l, R2, R3, and R4 are each selected from hydrocarbyl groups containing from 1 to 20 carbon atoms, provided at least one of Rl, R2, R3, and R4 contains from 8 to 20 carbon atoms.
- Particularly suitable hydrocarbyl groups may be linear or branched alkyl groups.
- amine reactants which can be quatemarized to yield compounds of this invention are: trimethyl amine, triethyl amine, tri-n-propyl amine, dimethyleihyi amine, dimethyl lauryl amine, dimethyl oleyl amine, dimethyl stearyl amine, dimethyl eicosyl amine, dimethyl octadecyl amine, N-methyl piperidine, N,N'-dimethyl piperazine, N-methyl-N'-ethyl piperazine, N-methyl N-ethyi morpholine, N- hydroxyethyl morpholine, pyridine, triethanol amine, triisopropanol amine, methyl diethanol amine, dimethyl ethanol amine, lauryl diisopropanol amine, stearyl diethanol amine, dioieyl ethanol amine, dimethyl isobutanol amine, methyl diisooctanol
- the amine contains solely primary or secondary amino groups, it is necessar to alkylate at least one of the primary or secondary amino groups to a tertiary amino group prior to quaternizing the amine.
- alkylation of primary amines and secondary amines or mixtures with tertiary amines may be exhaustively or partially alkylated to a tertiary amine and further alkylated to a quaternary salt all in one step.
- alkylation up to the tertiary amine requires removal (neutralization) of the hydrogen (proton) from the product of the alkylation.
- alkylating agents such as, alkyl halides or dialkyl sulfates are used, the product of alkylation of a primary or secondary amine is a protonated salt and needs a source of base to free the amine and to proceed to the quaternary salt.
- alkylating agents require alkylation of the tertiary amine, and the product is the quaternary ammonium halide or monomethyl sulfate,
- epoxides as alkylating agents do both the alkylation and the neutralization such that the intermediate alkylation product is already the free amine.
- To proceed to the quaternary salt with epoxides it is necessary to provide an equivalent of an acid to pro vide a proton for the hydroxy group and a counter anion for the salt.
- the quatemizing agent suitable for converting the tertiary amine to a quaternary nitrogen compound may be selected from the group consisting of hydrocarbyl substituted carboxylates, carbonates, cyclic carbonates, phenates, epoxides, carbamates, halides, sulfates, sulfites, sulfides, sulfonates, phosphates, phosphonates, or mixtures thereof.
- the hydrocarbyl- substituted phenates from which the anion of the quaternary ammonium compound may be derived are of many different types. For example, hydrocarbyl-substituted phenates may be derived from phenols of the formula:
- n 1 , 2, 3, 4 or 5, where IV s may be hydrogen, or a substituted or unsubstituted, a!ky!, cycloalkyl, alkenyl, cycloalkenyl or aryl group.
- the hydrocarbon group(s) may be bonded to the benzene ring by a keto or thio-keto group. Alternatively the hydrocarbon group(s) may be bonded through an oxygen, or nitrogen atom.
- phenols examples include o-cresol; m- cresol; p-cresol; 2,3-dimethylphenol; 2,4-dimethylphenol; 2,3,4-trimethylphenol; 3-ethyl-2,4- dimethylphenol; 2,3,4,5-tetramethylphenol; 4-ethyl 2,3,5,6-tetramethylphenol; 2-ethylphenol; 3- ethylphenol; 4-ethylphenyl; 2-n-propylphenol; 2-isopropylphenol; 4-isopropylphenol; 4-isopropylphenol; 4-n- butylphenol; 4-isobutylphenol; 4-secbutylphenol; 4-t-butylphenol; 4-nonylphenol; 2- dodecylphenol; 4-dodecyiphenoi; 4-octadecylphenol; 2-cyclohexylphenol: 4-cyclohexylphenol: 2-allylphenol; 4-aSiylphenoi; 2-hydroxydiphenyl; 4-hydroxydi
- R and R" which may be the same or different are as defined above for R and m and n are integers and for each m or n greater than 1 each R 20 and R "' 1 may be the same or different.
- phenols examples include 2,2-dihydroxy-5,5-dimethyldiphenylmethane
- the hydrocarbyl (or alkyl) groups of the hydrocarbyl substituted carbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atoms per group.
- the hydrocarbyl substituted carbonates contain two hydrocarbyl groups that may be the same or different.
- suitable hydrocarbyl substituted carbonates include dimethyl, diethyl, ethylene, and propylene carbonates and mixtures thereof.
- the quatemizing agent can be a hydrocarbyl epoxide, as represented by the following formula, in combination with an acid:
- R: ⁇ R 6 , R' and R 8 may be independently H or a CMS hydrocarbyl group.
- hydrocarbyl epoxides may include, but are not limited to: styrene oxide, ethylene oxide, propylene oxide, butylene oxide, epoxyhexane, oct-l l-ene oxide, stilbene oxide and C2-50 epoxide,
- the quaternary ammonium salts may be made in one stage or two stages.
- Aikyiation of a tertiary amine with alkyl epoxide may be conducted in a one step reaction with acid present as set forth in U.S. Patent No. 4,814,108, 4,675,180 or in a two step process that includes aikyiation of the tertiary amine in polar medium then mixing the alkylated product with an acid.
- 1 mole of the amine may be treated with X moles of the olefin oxide (where X is the number of tertiary nitrogens in the amine molecule) in the presence of an excess of water over that required by the stoichiometry of the reaction,
- pyridine (1 mole) may be treated with an olefin oxide
- Triethylenediamine (1 mole) may be treated with an olefin oxide (2 moles) in water (>2 mole).
- Hex amine (1 mole) may be treated with an olefin oxide (4 moles) in water (>4 moles).
- the olefin oxide may be used in excess if required, or desired, the excess olefin oxide then reacting with the quaternary ammonium hydroxide.
- any quantity of water may be used as long as it represents an excess over that required by the stoichiometry of the reaction.
- the reaction may be carried out by contacting and mixing the amine with the olefin oxide in the reaction vessel wherein water is added to the reaction mixture.
- the rate of addition of the water does not affect the quality of the final product but slow addition of water may be used to control an exothermic reaction.
- the amine may be mixed with water in the reaction vessel and the olefin oxide then added to the stirred reaction mixture.
- the olefin oxide may be added as a gas either pure or diluted with an inert carrier (e.g., nitrogen); a liquid; a solution in water; or a solution in a water miscible organic solvent (e.g., methyl or ethyl alcohol).
- an inert carrier e.g., nitrogen
- a liquid e.g., a solution in water
- a water miscible organic solvent e.g., methyl or ethyl alcohol
- the olefin oxide may be mixed with the water in the reaction vessel and the amine added to the reaction mixture.
- the amine may be added as a pure gas, liquid or solid; a solution in water; a solution in a water soluble organic solvent.
- slow addition of the amine may be used to control an exothermic reaction
- the mixed reactants may be heated together at a given temperature while the third reactant is added at a rate sufficient to maintain a steady reaction rate and controllable reaction temperature.
- the reactants may be heated in a pressure vessel but, when heating the reactants to promote the reaction, a temperature greater than 100° C. is desirably avoided to prevent decomposition of the quaternary ammonium hydroxide.
- the second stage of the reaction sequence comprises neutralization of the quaternary ammonium hydroxide formed in the first stage with the organic acid.
- the neutralization reaction may be carried out in the absence of any solvent; in the presence of an alcohol, e.g., methanol, ethanol, isopropanol, 2-ethoxyethanol, 2-ethylhexanol, or ethylene glycol; in the presence of any other polar organic solvent, e.g., acetone, methyl ethyl ketone, chloroform, carbon tetrachloride, or tetrachloroetbane; in the presence of a hydrocarbon solvent, e.g., hexane, heptane, white spirit, benzene, toluene or xylene; or in the presence of a mixture of any of the above solvents,
- an alcohol e.g., methanol, ethanol, isopropanol, 2-ethoxyethanol, 2-ethylhexanol, or ethylene glycol
- any other polar organic solvent e.g., acetone, methyl e
- the organic acid which may be used in the second stage of the reaction and hence forms the anion in the quaternary ammonium salt may be, for example, a carboxylic acid, phenol, sulfurized phenol, or sulphonic acid.
- the neutralization reaction may be canied out at ambient temperature but generally an elevated temperature is used. When the reaction is completed the water and any solvents used may be removed by heating the reaction product under vacuum.
- the product is generally diluted with mineral oil, diesel fuel, kerosene, or an inert hydrocarbon solvent to prevent the product from being too viscous.
- the quateraizing agent may be a hydrocarbyl-substituted carboxylate, also known as an ester of a carboxylic acid.
- the corresponding acids of the carboxylates may be selected from mono-, di-, and poly-carboxylic acids.
- the mono-carboxylic acids may include an acid of the formula:
- R-COOH wherein R is hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, or aryl group containing from 1 to 50 carbon atoms.
- acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, palmitic acid, stearic acid, cyclohexanecar- boxylic acid, 2-methylcyclohexane carboxylic acid, 4-methylcyclohexane carboxylic acid, oleic acid, linoleic acid, linolenic acid, cyclohex-2-eneoie acid, benzoic acid, 2-methyibenzoic acid, 3- methylbenzoic acid, 4-methylbeiizoic acid, salicylic acid, 2 iyd.roxy-4-niethylbenzoic acid, 2- hydroxy-4-ethylsalicylic acid, p-hydroxybenzo
- the dicarboxylic acids may include an acid of the formula:
- n is zero or an integer, including e.g. oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeiic acid and suberic acid. Also included are acids of the formula
- x is zero or an integer
- y is zero or an integer and x and y may be equal or different and R is hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, or a d group containing from 1 to 50 carbon atoms as described above.
- Such acids include the alkyl or alkenyl succinic acids, 2-methylbutanedioic acid, 2-ethylpentanedioic acid, 2-n- dodecylbutanedioic acid, 2-n-dodecenylbutanedioic acid, 2-phenylbutanedioic acid, and 2-(p- methylphenyl)butanedioic acid.
- polysubstituted alkyl dicarboxylic acids wherein other R groups as described above may be substituted on the alkyl chain.
- Examples include 2,2-dimethylbutanedioic acid; 2,3-dimethylbutanedioic acid; 2,3,4-trimethylpentanedioic acid; 2,2,3-trimethylpentanedioic acid; and 2-ethyl-3-methylbutanedioic acid.
- the dicarboxylic acids also include acids of the formula:
- r is an integer of 2 or more.
- examples include maleic acid, fumaric acid, pent-2- enedioic acid, hex-2-enedioic acid; hex-3-enedioic acid, 5-methylhex-2-enedioic acid; 2,3-di- methylpent-2-enedioic acid; 2-methylbut-2-enedioic acid; 2-dodecylbut-2-enedioic acid; and 2- polyisobutylbut-2-enedioic acid.
- the dicarboxylic acids also include aromatic dicarboxylic acids e.g. phthalic acid, isophthalic acid, terephthalic acid and substituted phthalic acids of the formula:
- examples of such acids include 3-methylbenzene- 1 ,2-dicarboxylic acid; 4- phenylbenzene-l ,3-dicarboxylie acid; 2-(l -propenyl)benzene-l ,4-dicarboxylic acid, and 3,4- dimethyibenzene- 1 ,2-dicarboxylic acid.
- the correspondmg acid of the carboxyiate may have a pKa of less than 4,2.
- the corresponding acid of the carboxyiate may have a pKa of less than 3.8, such as less than 3.5, with a pKa of less than 3.1 being particularly desirable.
- suitable carboxvlates may include, but not limited to, maleate, citrate, fumarate, phthalate, 1 ,2,4-benzenetricarboxylate, 1 ,2,4,5- benzenetetracarboxylate, nitrobenzoate, nicotinate, oxalate, aminoacetate, and salicylate.
- the quaternary ammonium salt may be prepared by ion exchange reactions such as
- X is a halide
- R is defined above and Ar is an aromatic group.
- the quat may also be prepared by direct alkylation of a tertiary amine or polyamine.
- Alkylating agents include but not limited to alkyl halide, alkyl carbonate, aikyi sulfate, cyclic carbonate, alkyl epoxide, alkyl carboxylate, and alkyl carbamate.
- the quaternary ammonium salt compositions of this disclosure may be used in combination with a fuel soluble carrier.
- a fuel soluble carrier may be of various types, such as liquids or solids, e.g., waxes.
- liquid carriers include, but are not limited to, mineral oil and oxygenates, such as liquid polyalkoxylated ethers (also known as polyalkylene glycols or polyaikyiene ethers), liquid polyalkoxylated phenols, liquid polyalkoxylated esters, liquid polyalkoxylated amines, and mixtures thereof.
- oxygenate carriers may be found in U.S. Pat, No.
- oxygenate carriers include alkyl-substituted aryl polyalkoxylates described in U.S. Patent Publication No. 2003/0131527, published Jul. 17, 2003 to Colucci et. al., the description of which is herein incorporated by reference in its entirety.
- the quaternary ammonium salt compositions may not contain a carrier.
- some compositions of the present disclosure may not contain mineral oil or oxygenates, such as those oxygenates described above.
- the fuels may contain conventional quantities of octane improvers, corrosion inhibitors, cold flow improvers (CFPP additive), pour point depressants, solvents, demulsifiers, lubricity additives, friction modifiers, amine stabilizers, combustion improvers, dispersants, antioxidants, heat stabilizers, conductivity improvers, metal deactivators, marker dyes, cyciomatic manganese tricarbonyl compounds, and the like.
- CFPP additive cold flow improvers
- pour point depressants solvents
- demulsifiers demulsifiers
- lubricity additives friction modifiers
- amine stabilizers amine stabilizers
- combustion improvers dispersants
- antioxidants antioxidants
- heat stabilizers heat stabilizers
- conductivity improvers metal deactivators
- marker dyes cyciomatic manganese tricarbonyl compounds, and the like.
- compositions described herein may contain about 10 weight percent or less, or in other aspects, about 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, and the like.
- metal deactivators useful in the compositions of the present application are disclosed in U.S. Pat. No. 4,482,357 issued Nov. 13, 1984, the disclosure of which is herein incorporated by reference in its entirety.
- metal deactivators include, for example, salicylidene-o-aminophenol, disalicylidene ethylenediamine, disahcylidene propylenediamine, and ⁇ , ⁇ '-disalicylidene- 1 ,2-diaminopropane.
- Suitable optional cvclomatic manganese tricarbonyl compounds which may be employed in the compositions of the present application include, for example, cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, indenyl manganese tricarbonyl, and ethylcyclopentadienyl manganese tricarbonyl.
- suitable cvclomatic manganese tricarbonyl compounds are disclosed in U.S. Pat. No. 5,575,823, issued Nov. 19, 1996, and U.S. Pat. No. 3,015,668, issued Jan. 2, 1962, both of which disclosures are herein incorporated by reference in their entirety.
- 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 engines.
- the gasoline fuels of this application may contain, on an active ingredient basis, an amount of the quaternary ammonium salt in the range of about 5 mg to about 200 mg of reaction product per Kg of fuel, such as in the range of about 10 mg to about 150 mg of per Kg of fuel or in the range of from about 30 mg to about 100 mg of the quaternary ammonium salt per Kg of fuel, in aspects, where a carrier is employed, the fuel compositions may contain, on an active ingredients basis, an amount of the carrier in the range of about 1 mg to about 100 mg of carrier per Kg of fuel, such as about 5 mg to about 50 mg of earner per Kg of fuel.
- the active ingredient basis excludes the weight of (i) unreacted components associated with and remaining in the product as produced and used, and (ii) solvent(s), if any, used in the manufacture of the product either during or after its formation but before addition of a carrier, if a carrier is employed.
- the additives of the present application including the reaction product described above, and optional additi ves used in formulating the fuels of 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 concen trate may reduce blending time and lessen the possibility of blending errors.
- the fuels of the present application may be applicable to the operation of gasoline engines.
- the engine include both stationary engines (e.g., engines used in electrical power generation installations, in pumping stations, etc.) and ambulator ⁇ ' engines (e.g., engines used as prime movers in automobiles).
- the fuels may include any and all gasoline fuels, biorenewable fuels, gas-to-liquid (GTL) fuels, synthetic fuels, such as Fischer-Tropsch fuels, biomass to liquid (BTL) fuels, "Biorenewable fuels" as used herein is understood to mean any fuel which is derived from resources other than petroleum.
- the biorenewable fuel can comprise monohydroxy alcohols, such as those comprising from 1 to about 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 application are directed to methods for reducing the amount of injector deposits of engines having at least one combustion chamber and one or more direct fuel injectors in fluid connection with the combustion chamber.
- the quaternary ammonium salts described herein may be combined with relatively high molecular weight quaternary ammonium salts having one or more polyolefin groups; such as quaternary ammonium salts of polymono-olefins, polyhydrocarbyl succinimides; polyhydrocarbyl Mannich compounds: polyhydrocarbyl amides and esters, wherein "relatively high molecular weight” means having a number average molecular weight of greater than 600 Daltons.
- the methods comprise injecting a hydrocarbon-based fuel comprising the quaternary ammonium salt of the present disclosure through the injectors of the engine into the combustion chamber, and igniting the fuel.
- the method may also comprise mixing into the fuel at least one of the optional additional ingredients described above.
- the fuels of the present application may be essentially free, such as devoid, of conventional succinimide dispersant compounds.
- the fuel is essentially free of a quaternary ammonium salt of a hydrocarbyl succinimide or quaternary ammonium salt of a hydrocarbyl Mamiich compound having a number average molecular weight of greater than 600 Daltons.
- 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.
- PIBSI is prepared as in comparative example 1 except that dimethyl aminopropyl- amine (DMAPA) was used in place of ⁇ .
- DMAPA dimethyl aminopropyl- amine
- the resulting PIBSI (PD, about 21 Og ) was reacted with 36.9 grams of 1,2-epoxyhexane (E6), 18.5 grams of acetic acid, (18.5g) and 82 grams of 2-ethylhexanol up to 90°C for 3 hours. Volatiles were removed under reduced pressure to give the desired quaternary salt (quat).
- PIBSI from comparative example 2 (146g) was reacted with 13.3 grams of dimethyl oxalate in 50 grams of aromatic solvent 150 at 1 0°C for about 2 hours, The resulting product was a brownish oil.
- Trioctyimethylammonium chloride 70grams was mixed with 130 grams of heptane. The mixture was extracted five times with 70 grams of sodium acetate (about 16% wt. in water). Volatiles from the resulting organic layer were removed under reduced pressure to give a quat acetate. FTIR showed strong peaks at 1578 and 1389cm "1 , characteristic of a carboxylate salt.
- Salicylate (MS 14, 103 g) was heated at 160° C. for 4 hours to give a quaternary ammonium reaction product without further purification. There was about 90% wt. of nonvolatile materials in die reaction product.
- TGA thermogravimetric analysis
- DIG test An engine test measuring fuel injector deposit (referred to as "DIG test") was performed following a procedure disclosed in Society of Automotive Engineer (SAE) International publication 2009-01-2641 "Test and Control of Fuel Injector Deposits in Direct Injected Spark Ignition Vehicles".
- SAE Society of Automotive Engineer
- a mathematical value of Long Term Fuel Trim (LTFT) was used to gauge the ability of additive to keep deposit from accumulating in the injectors, or to keep injectors clean. The higher the LTFT, the more deposit in the injectors and the less effective is the additive in keeping injectors clean.
- the test may also be used to gauge the effectiveness of additives to clean up the injectors in a gasoline engine by running a standard 48 hour dirty up phase followed by a 48 hour clean up phase.
- Run 1 shows the effects of gasoline with no additive on injectors in a directed injected gasoline engine.
- Run 2 containing the quaternar ammonium salt of the disclosure showed a significant clean up dirty injectors for a DIG engine at a relatively low treat rate.
- FIG. 1 The advantages of the quaternar ammonium salt of the disclosure are further illustrated by FIG. 1 .
- a gasoline fuel containing no additive (Arrow A) is used in a directed injected gasoline engine for the first 48 hours.
- the additive of inventive Example 2 (Arrow C) is added to the gasoline and the resulting LTFT % decreased rapidly and maintained a low LTFT % for the remainder of the test.
- the following test method is a bench test procedure that was used to evaluate the tendency of automotive spark-ignition engine fuels to foul electronic port fuel injectors (PFI) in a spark ignition engine.
- the test method used a bench apparatus equipped with Bosch injectors specified for use in a 1985-1987 Chrysler 2,2-L turbocharged engine.
- the test method was based on a test procedure developed by the Coordinating Research Council (CRC Report No. 592) for predicting the tendency of spark-ignition engine fuel to form deposits in small metering clearances of fuel injectors in a port fuel injection engine.
- Fuel injector fouling was calculated according to the following equation:
- F 0 is the percent fouling
- F? is an initial flow mass in tenths of a gram
- F 2 is a flow mass at the end of the test in tenths of a gram. The percent fouling was calculated for each injector for three flow mass readings and the average of four injectors was reported in percent.
- Examples 4 and 5 provided significant improvement in injector fouling in a port fuel injected gasoline engine as compared to the base fuel without any detergent and as compared to the same base fuel containing a conventional Mannich detergent even at a lower treat rate of the Inventive compound.
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Abstract
La présente invention se rapporte à une composition de carburant pour un moteur diesel à injection directe du carburant, à un procédé permettant d'améliorer le rendement des injecteurs de carburant et à un procédé permettant de nettoyer les injecteurs de carburant dans un moteur diesel à combustion interne. La composition de carburant comprend une grande quantité de carburant et une petite quantité efficace d'un sel d'ammonium quaternaire qui présente une perte de poids par analyse thermogravimétrique inférieure ou égale à 50 % en poids à une température égale à 350 °C. La quantité de sel d'ammonium quaternaire présente dans le carburant est suffisante pour améliorer le rendement du moteur à injection directe du carburant qui a brûlé la composition par comparaison avec le rendement d'un tel moteur qui a brûlé une composition de carburant qui ne contient pas le sel d'ammonium quaternaire.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12847646.2A EP2776691B1 (fr) | 2011-11-11 | 2012-11-02 | Utilisation d'une composition de combustible |
US14/270,738 US9458400B2 (en) | 2012-11-02 | 2014-05-06 | Fuel additive for improved performance in direct fuel injected engines |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161558779P | 2011-11-11 | 2011-11-11 | |
US61/558,779 | 2011-11-11 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US14/270,738 Continuation-In-Part US9458400B2 (en) | 2012-11-02 | 2014-05-06 | Fuel additive for improved performance in direct fuel injected engines |
Publications (1)
Publication Number | Publication Date |
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WO2013070503A1 true WO2013070503A1 (fr) | 2013-05-16 |
Family
ID=48290464
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2012/063189 WO2013070503A1 (fr) | 2011-11-11 | 2012-11-02 | Additif pour carburant pour un meilleur rendement des moteurs à injection directe du carburant |
Country Status (3)
Country | Link |
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EP (1) | EP2776691B1 (fr) |
CA (1) | CA2789907A1 (fr) |
WO (1) | WO2013070503A1 (fr) |
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EP2776691A1 (fr) | 2014-09-17 |
EP2776691B1 (fr) | 2018-10-10 |
CA2789907A1 (fr) | 2013-05-11 |
EP2776691A4 (fr) | 2015-07-08 |
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