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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • 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
  • C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
• • 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
  • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
• • 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
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
• • 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
  • C10L1/1985—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 polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

• This invention involves fuel additive compositions, fuel compositions that include the fuel additive compositions, and a method of operating internal combustion engines with the fuel compositions.
• the compositions of the present invention are effective in reducing deposits in fuel intake systems of internal combustion engines.
• U.S. Patent 5,925,151 filed September 19, 1996 disclose a detergent additive composition comprising the combination of a monosuccinimide, derived from polyisobutylene and a polyethylene polyamine, and an aromatic hydrocarbon diluent that may be used in diesel fuel to remove or prevent deposits.
• succinimides of the present invention prepared by thermal condensation of a highly reactive polyolefin with maleic anhydride or a reactive equivalent thereof followed by amination of the thermal condensate with a polyamine under conditions that increase imide content and decrease water content, provide improved performance in fuel compositions in reducing deposits in fuel intake systems of internal combustion engines.
• the succinimides of the present invention also have the environmental feature of a low chlorine content.
• the fuel additive composition of the present invention comprises a reaction product of an aliphatic hydrocarbon substituted succinic acylating agent and a polyamine having at least one condensable primary amine group represented by the formula -NH 2 wherein said reaction product has a ratio of the imide to amide infrared carbonyl absorption peak areas of about 1:0.0-0.6 and a water content of about 0.3% or less by weight, and wherein the aliphatic hydrocarbon substituted succinic acylating agent is prepared by thermal condensation of a highly reactive polyolefin with maleic anhydride or a reactive equivalent thereof.
• a further embodiment of the present invention is a fuel composition comprising a major amount of a normally liquid fuel that is a gasoline or a diesel fuel; and the above-described fuel additive composition.
• Another aspect of the present invention is a method of reducing deposits in the fuel intake system of an internal combustion engine by operating the engine with the above-described fuel composition.
• the fuel additive compositions of the present invention comprise a reaction product of an aliphatic hydrocarbon substituted succinic acylating agent and polyamine.
• the aliphatic hydrocarbon substituent of the succinic acylating agent can be a straight- or branched-chain hydrocarbon group, and can be saturated, olefinic with one or more carbon-to-carbon double bonds, or acetylenic with a carbon-to-carbon triple bond.
• the aliphatic hydrocarbon substituent is usually a branched-chain, olefinic group.
• the polyamine contains two or more amine groups where at least one of the amine groups is a condensable primary amine group represented by the formula - NH 2 .
• the reaction product of the present invention of the succinic acylating agent and polyamine has a ratio of the imide to amide infrared carbonyl absorption peak areas of about 1:0.0-0.6 and a water content of about 0.3% or less by weight.
• the reaction of the succinic acylating agent and polyamine can result in a reaction product that contains several components including the succinate derivatives imide, amide and ammonium carboxylate salt.
• the reaction of the succinic acylating agent and polyamine is run under conditions detailed herein that increases the amount of the imide relative to the amide and ammonium carboxylate salt and that decreases the water content of the reaction product.
• the succinic acylating of the present invention is usually a succinic anhydride, but can be a reactive equivalent to include the bisacid, bisesters, and acid-esters and bis acyl halides.
• the succinic acylating agent is prepared by a thermal condensation of a highly reactive polyolefin with maleic anhydride or a reactive equivalent thereof to include maleic acid, bis acyl halides, bisesters and acid-esters. Maleic anhydride is generally used.
• the highly reactive polyolefin can contain about 30 to about 180 carbon atoms, and in another instance about 40 to about 130 carbon atoms.
• the polyolefin usually contains about 55 to about 90 carbon atoms.
• the highly reactive polyolefin can be derived from homopolymerized or interpolymerized 1-olefins having 2 to 18 carbon atoms.
• the 1-olefins include ethylene, propylene, the butene isomers 1-butene, 2-butene and isobutylene, and mixtures of 1-olefins.
• polyolefins examples include polyethylenes, polypropylenes, polyisobutylenes, especially those derived from refinery streams, copolymers of ethylene and 1-olefins such as ethylene-propylene copolymers, and terpolymers of ethylene with 1-olefins and dienes such as ethylene-propylene-diene terpolymers.
• a preferred highly reactive polyolefin is a polyisobutylene having a high vinylidene content of 70% or more.
• the polyisobutylene can have a number average molecular weight of about 400 to about 2,500, while about 600 to about 1,800 is more preferred, and about 800 to about 1,200 is most preferred.
• Well known procedures involving gel phase chromatography and vapor phase osmometry are used to determine the number average molecular weights of polyolefins such as polyisobutylene.
• Polyisobutylene having a high vinylidene content is commercially available from BASF under the tradename Glissopal ® '
• the succinic acylating agents of the present invention are prepared by thermally condensing a highly reactive polyolefin with maleic anhydride or a reactive equivalent thereof. Procedures for the thermal condensation are well known and usually involve temperatures above 200°C at an elevated pressure. U.S. Application Serial No. 60/219,791 filed July 19, 2000 (Duncan et al.) describe the procedure for a thermal condensation of a polyisobutylene having a high vinylidene content with maleic anhydride, the disclosure of which is incorporated herein by reference.
• the polyamines of the present invention include polyethylene polyamines as well as other types of polyamines.
• Polyethylene polyamines are available from Dow and Union Carbide and include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and polyethylene polyamine bottoms.
• Other types of polyamines include polyalkylene polyamines in addition to polyethylene polyamines described above, heterocyclic polyamines, aromatic heterocyclic polyamines, polyamines containing one or more hydroxyl groups and ether or polyether containing polyamines.
• Examples of other types of polyamines are tris(2-aminoethyl)amine, propylenediamine, dipropylenetriamine, N-(2-aminoethyl)- 1 ,3-propanediamine, N,N'-bis(2-aminoethyl)- 1,3-propanediamine, dimethylaminopropylamine, diethylaminopropylamine, l-(3- aminopropyl) imidazole and 4-(3-aminopropyl) morpholine.
• the succinic acylating agent and polyamine of the present invention can be reacted using various molar ratios of the two reactants.
• a preferred molar ratio of succinic acylating agent to polyamine is about 1:0.3-1.1, more preferred is about 1:0.5-1, and most preferred is about 1:0.74-1.
• the present invention involves the reaction product of a succinic acylating agent, derived from thermally condensing a highly reactive polyolefin and maleic anhydride or a reactive equivalent thereof, and a polyamine under reaction conditions wherein the reaction product has an increased imide content and decreased water content relative to analogous materials prepared under conditions less selective for increased imide and decreased water content. It has been found that increasing the level of imide relative to amide and ammonium carboxylate salt in the reaction product provides a fuel additive composition with improved deposit reduction performance in the fuel intake system of an internal combustion engine. Additionally, it has been found that decreasing the level of water in the reaction product provides a fuel additive composition that is much more stable and retains a nearly constant imide level for a long period of time.
• analogous materials prepared under conditions less selective for increased imide level and decreased water level provide a reduced level of deposit reduction as fuel additives and also show a much greater decrease in imide content with time.
• the additive composition of the present invention provides improved deposit reduction performance due to the increased imide content. Additionally, this improved performance is deliverable even after a lengthy storage period due to the decreased water content which results in a more stable imide content with time.
• the reaction products of the present invention have an increased level of imide relative to amide and ammonium carboxylate salt compared to analogous materials prepared under conditions less favorable to forming imide such as current commercial materials.
• the reaction products of the present invention have a ratio of the imide to amide to ammonium carboxylate salt infrared carbonyl absorption peak areas of about 1:0.0-0.6:0.0-0.3, more preferably of about 1:0.0-0.4:0.0-0.2, and most preferably of about 1:0.0-0.3:0.0-0.1.
• the infrared carbonyl absorption peak areas were obtained using a Perkin-Elmer "Spectrum One" program for imide at about 1,705cm "1 , for amide at about 1,660cm "1 and for ammonium carboxylate salt at about 1,550cm "1 .
• Samples of an analogous commercial material prepared under conditions less selective for imide formation had a ratio of the imide to amide to ammonium carboxylate salt infrared carbonyl absorption peak areas of about 1:0.8-1.4:0.3-0.5.
• This commercial material also provided less deposit reduction performance compared to reaction products of the present invention as detailed in examples that follow herein.
• the reaction products of the present invention have a decreased level of water that provides a fuel additive composition that is more stable in having a nearly constant level of imide for several months. This enhanced stability of the imide level ensures delivery of improved performance from the increased level of imide even after a lengthy storage period.
• reaction products of the present invention have a nearly constant level of imide for about 3 months with the imide level only slowly decreasing over extended periods when the water content of the reaction products as determined by Karl Fischer titration is about 0.3% or less by weight, more preferably about 0.25% or less by weight, and most preferably about 0.2% or less by weight. Examples that follow illustrate the stability of the imide content when water content is decreased.
• reaction products of the succinic acylating agents and polyamines of the present invention are prepared under reaction conditions that result in products having a ratio of the imide to amide infrared carbonyl absorption peak areas of about 1:0.0- 0.6 and a water content of about 0.3% or less by weight.
• the reaction conditions that can increase imide content and decrease water content are temperatures of about 140°C or higher for an extended period of time, use of an inert gas sparge, use of reduced pressure, use of a solvent that forms an azeotrope with water, and combinations of two or more thereof.
• the following examples are illustrative of reaction conditions that result in reaction products of the present invention which have increased imide content and decreased water content.
• Example A A commercial succinimide, Komad 303 available from MOL of Hungary, has a ratio of imide to amide to ammonium carboxylate salt infrared carbonyl absorption peak areas of 1:1.39:0.5.
• Komad 303 is 60% active chemical in a 350 neutral mineral oil.
• Komad 303 is prepared by thermal condensation of a high vinylidene 1,000 molecular weight polyisobutene (BASF Glissopal ® 1000) and a maleic anhydride followed by amination with tetraethylenepentamine in a molar ratio of about 1:0.87.
• Example B Comparative
• a commercial succinimide Komad 303 from a batch different from that of Example A, has a ratio of imide to amide to ammonium carboxylate salt infrared carbonyl absorption peak areas of 1:0.78:0.3.
• Example C
• Example D A sample (1003.5 g) of the commercial succinimide of Example A was placed in a flask fitted for distillation and heated with stirring to 180°C. Some foaming was observed. A vacuum was gradually applied, and the sample was held at 180° and a reduced pressure of 49mm Hg for 1 hour. The product residue weighed 986.1 g, and the distillate was a yellow liquid weighing 7.25g. The product had a nitrogen content of 2.71%, a total base number of 74 (where base equivalents are expressed in terms of mg of KOH per g of sample), and a ratio of imide to amide to ammonium carboxylate salt infrared carbonyl absorption peak areas of 1:0.46:0.09.
• Example D A sample (1003.5 g) of the commercial succinimide of Example A was placed in a flask fitted for distillation and heated with stirring to 180°C. Some foaming was observed. A vacuum was gradually applied, and the sample was held at 180° and a reduced pressure of 49mm Hg for 1 hour
• a sample (300g) of the commercial succinimide of Example B was placed in a flask fitted for distillation, heated with stirring to 175°C, and held at 175°C for 3 hours.
• the sample was heated to 200°C, and 60ml of 2-ethyl-l-hexanol was added.
• a vacuum was applied, and the sample and alcohol were held at 200°C and a reduced pressure of 49mm Hg for 1 hour.
• the product residue weighed 286.5g.
• the distillate collected was 60ml of the alcohol and 3ml of water.
• the product had a nitrogen content of 2.51%, a total base number of 60 (as mg KOH per g of sample), a water content of 0.05%, and a ratio of imide to amide to ammonium carboxylate salt infrared carbonyl absorption peak areas of 1:0.21:0.02.
• a sample (3.5 Kg) of an unfiltered polyisobutenylsuccinic anhydride, derived from a thermal condensation of a high vinylidene 1,000 molecular weight polyisobutene (BASF Glissopal ® 1000) and maleic anhydride, and 2.333 Kg of a 330 neutral mineral oil were blended together at 50°C for 0.5 hour. The blend was then filtered through diatomaceous earth. A sample of the filtrate (5 Kg) was placed in a flask fitted for distillation and heated with stirring under a nitrogen purge to 175°C. Tetraethylenepentamine (567.9g at a molar ratio of succinic anhydride to polyamine of 1:0.87) was added dropwise over 95 minutes.
• the reaction mixture was held at 175°C for 3 hours. Vacuum was applied, and the mixture was held at 175°C and a reduced pressure of 49mm Hg for 0.5 hour. Next 580ml of 2-ethyl-l-hexanol was added, and the mixture was heated to 190°C and held at 190°C for 2.5 hours. A vacuum was applied, and the mixture held at 190°C and a reduced pressure of 49mm Hg to remove the alcohol and additional water. The distillate consisted of 580ml of the alcohol and 18ml of water.
• the product residue had a nitrogen content of 3.0%, a total base number of 83 (as mg KOH per g of sample), a water content of 0.25%, and a ratio of imide to amide to ammonium carboxylate salt infrared carbonyl absorption peak areas of 1:0.44:0.06.
• the product had a nearly constant imide level over a period of 98 days.
• Example F A sample (180 parts by weight) of an unfiltered polyisobutenylsuccinic anhydride, derived from a thermal condensation of a high vinylidene 1,000 molecular weight polyisobutene (BASF Glissopal ® 1000) and maleic anhydride, and 120 parts by weight of a 330 neutral mineral oil were blended together at 50°C for 0.5 hr. The blend was then filtered through diatomaceous earth. The filtrate was placed in a reactor fitted for distillation and heated with stirring to 110°C. Tetraethylenepentamine (31.8 parts at a molar ratio of succinic anhydride to polyamine of 1:0.72) was added over 3 hours at 110-120°C.
• BASF Glissopal ® 1000 high vinylidene 1,000 molecular weight polyisobutene
• maleic anhydride 120 parts by weight of a 330 neutral mineral oil were blended together at 50°C for 0.5 hr. The blend was then filtered through diatomaceous earth
• the reaction mixture was heated to 175°C over 6 hours, and was nitrogen sparged at 175°C for 4 hours.
• the aqueous distillate was 4.6 parts.
• the product residue was 320.6 parts.
• the product had a nitrogen content of 3.36%, a total base number of 85.5 (as mg KOH per g of sample), a water content of 0.1%, and a ratio of imide to amide to ammonium carboxylate salt infrared carbonyl absorption peak areas of 1:0.23:0.03.
• the product had a nearly constant imide level over a period of 70 days.
• Example G A sample (180g) of an unfiltered polyisobutenylsuccinic anhydride, derived from a thermal condensation of a high vinylidene 1,000 molecular weight polyisobutene (BASF Glissopal ® 1000) and maleic anhydride, and 120g of Solvesso 150 (high boiling aromatic solvent from Exxon Chemicals) were blended together for 0.5 hour. The blend was filtered through diatomaceous earth. The filtrate was placed in a flask fitted for distillation, and heated with stirring to 175°C. Tetraethylenepentamine (34.
• the fuel additive compositions of the present invention can include a carrier fluid.
• Suitable carrier fluids are alkylphenols including alkoxylated alkylphenols, esters of carboxylic acids including polyol esters and vegetable oils, alkoxylated alcohols including polyols, polyalkylene glycols, and mineral oils. Mineral oils having a viscosity ranging from about 100 to about 400 centistokes at 40°C are especially useful.
• the fuel additive compositions can include a solvent. Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, glycol ethers, alcohols, and mixtures thereof.
• the fuel additive compositions in a further embodiment of the present invention can include additional fuel additives such as cold flow improvers, pour point depressants, storage stabilizers, corrosion inhibitors such as alkenylsuccinic acids, cetane improvers, anti-knock additives, anti-static agents, biocidal additives, smoke suppressants, other types of detergents, antifoam agents including silicone fluids, lubricity additives such as tall oil fatty acid, and demulsifiers such as alkoxylated alkylphenols.
• additional fuel additives such as cold flow improvers, pour point depressants, storage stabilizers, corrosion inhibitors such as alkenylsuccinic acids, cetane improvers, anti-knock additives, anti-static agents, biocidal additives, smoke suppressants, other types of detergents, antif
• the normally liquid fuel can be a gasoline or a diesel fuel.
• the gasoline can be one or more hydrocarbon fractions generally boiling in the range from 30°C to 230°C.
• the gasoline can contain oxygenates, oxygen-containing compounds, including alcohols such as ethanol and ethers such as methyl t-butyl ether.
• the diesel fuel can be a hydrocarbon diesel fuel from one or more hydrocarbon fractions generally boiling in the range from 140°C to 400°C, for example, from 170 to 350°C.
• the hydrocarbon diesel fuel usually contains several hydrocarbon fractions.
• the hydrocarbon diesel fuel has at least 90% by volume hydrocarbon fraction boiling at 350°C, in a second embodiment greater than 95% by volume fraction boiling at 350°C, in a third embodiment at least 10% by volume fraction boiling at 180°C, and in a fourth embodiment at least 15% by volume fraction boiling at 180°C.
• the aromatic content of the hydrocarbon diesel fuel is typically less than 40% by volume, in another instance less than 30%, and in a further instance less than 20%.
• the cetane number of the hydrocarbon diesel fuel is usually greater than 40, in another embodiment greater than 45, and in a further embodiment greater than 50.
• the sulfur content of the hydrocarbon diesel fuel can be 0.5 wt% or less, in a second instance 0.2 wt% or less , and in a third instance 0.05 wt% or less, and in a fourth instance 0.0010 wt% or less.
• the diesel fuel can be a biodiesel fuel.
• the biodiesel fuel includes esters of naturally occurring fatty acids which can be prepared by the transesterification of triglycerides of natural fats and oils with lower aliphatic alcohols to include methyl, ethyl, propyl and butyl alcohol. Natural fats and oils include sunflower oil, rapeseed oil, coriander oil, castor oil, soybean oil, cottonseed oil, peanut oil, coconut oil, and beef tallow.
• the diesel fuel can be a mixture of a hydrocarbon diesel fuel and a biodiesel fuel such as the methyl ester of rapeseed oil.
• Fuel compositions of the present invention that include a diesel fuel are especially useful in compression ignition engines to reduce deposits in the fuel intake system.
• Fuel compositions of the present invention include the reaction products of the succinic acylating agents and the polyamines at a level sufficient to provide deposit reduction performance.
• the level of the reaction product in the fuel composition can range from about 10 ppm to about 1,000 ppm based on the weight of the fuel composition, in another instance from about 20 ppm to about 600 ppm, and also from about 30 ppm to about 300 ppm.
• the fuel additive compositions and fuel compositions of the present invention are prepared by mixing components at ambient temperatures or at somewhat elevated temperatures ranging from about 40°C to 60°C until the mixture is homogeneous.
• the components can include the reaction products of the succinic acylating agents and polyamines, carrier fluids, solvents, additional fuel additives, and normally liquid fuels.
• a further embodiment of the present invention is a method of reducing deposits in the fuel intake system of an internal combustion engine by operating the engine with the fuel composition of the present invention. This method is especially effective in compression ignition engines fueled with diesel fuels in reducing deposits in and around fuel injector nozzles.
• This deposit reduction performance includes both preventing deposits from forming as well as removing or cleaning up deposits that have formed.
• the following examples show the benefit of the present invention in providing improved deposit reduction performance in the fuel intake system of an internal combustion engine.
• the Peugeot XUD-9 diesel engine 10 hour test is used to evaluate the effectiveness of a detergent that is added to a diesel fuel as part of a diesel fuel additive package.
• the test evaluates deposit reduction performance of the detergent by measuring the average % flow remaining for the fuel injectors at the end of test. Detergents having larger % flow remaining values are more effective.
• the detergents are the succinimide compositions of Examples A-G that were described in detail earlier in the detailed description.
• Examples A and B are comparative while Examples C-G are embodiments of the present invention showing improved deposit reduction performance.
• Ratios are determined as the ratio of infrared carbonyl abso ⁇ tion peak areas for the imide at about
• the treat levels are active chemical levels of the detergents in the diesel fuel.
• Komad 303 is a commercial succinimide available from MOL of Hungary.
• the fuel consisted of 70% by volume of a standard hydrocarbon diesel fuel and 30% by volume of a biodiesel fuel which was the methyl ester of rapeseed oil. - - configuration with one engine operated to drive the second nonoperated engine in a test cycle capable of producing injector deposits.
• U.S. Patent No. 6,042,626 further describes the procedure, and test details are available from Engineering Test Services, a division of the Cummins Engine Co., Charleston, S.C, U.S.A. In the test standard hydrocarbon diesel fuel was treated with each detergent at the same commercial treat level on an active chemical basis.
• Ratios are determined as the ratio of infrared carbonyl absorption peak areas for imide at about 1,705cm "1 and for the amide at about 1,660 cm “1 using a Perkins-Elmer "Spectrum One" program. 3 An average deposit rating of 10 or lower for the fuel injectors is a good, desirable result.
• Komad 303 is a commercial succinimide available from MOL of Hungary. 5 Infrared analyses of the detergent were available for dates that bracketed the test date.

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