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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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)
  • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
  • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
  • C10L1/306—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond) organo Pb compounds

Definitions

• the present invention relates in general to internal combustion engine fuel compositions.
• the invention relates to the use of nitrogen-containing compounds as dispersants in the aforesaid fuel compositions.
• Nitrogen-containing compounds which have long been used as dispersant/detergent additives in lubricating oils include the hydrocarbyl-substituted succinimides.
• the preparation of succinimides and their use as lubricating oil additives is described in, for example, US-A-3,024,237; US-A-3,202,678; US-A-3,219,666 and US-A-3,275,554.
• Hydrocarbon fuels generally contain numerous deposit-forming substances. When used in internal combustion engines, deposits tend to form on and around constricted areas of the engine in contact with the fuel. In diesel engines, deposits tend to accumulate in the fuel injection system, thereby hampering good performance of the engine. In automobile engines deposits can build up on engine intake valves leading to progressive restriction of gaseous fuel mixture flow into the combustion chamber and also to valve sticking. It is common practice to incorporate a detergent in the fuel composition for the purpose of inhibiting the formation, and facilitating the removal, of engine deposits, thereby improving engine performance. Nitrogen-containing compounds commonly used as additives in hydrocarbon fuels include polyisobutene amines.
• US-A-3,236,613 discloses petroleum distillate hydrocarbon fuels containing from between about 1 to about 100 pounds, per thousand barrels of fuel, of a compound of the following formula: wherein R is the aliphatic residue of an aliphatic dicarboxylic acid, R' is an aliphatic hydrocarbon group, R'' is a member from the group consisting of and x is an integer from 1 to 6.
• Such compounds can be prepared by heating at 75 to 100 o C for about 2 hours a mole to mole mixture of an aliphatic dicarboxylic acid anhydride and aliphatic primary amine to form the amic acid, ie subjecting the amic acid (A) to condensation reaction at 95 o C to 150 o C for 2 to 5 hours with a polyamine of the following formula: (R'') x NH2 in substantially molar amounts to provide the following condensation reaction product: and further condensing product (B) in mole to mole ratio with salicyladehyde at 125 to 175 o C for 2 to 5 hours.
• the compounds function as anti-screen clogging and sediment stabilising addiion agents for petroleum hydrocarbon distillate fuel oils and, as antioxidants and metal deactivators in both fuel oils and gasolines.
• Other publications, eg US-A-4,698,169 and EP-A-191967 disclose a reaction product useful as either a fuel or lubricant additive which is obtained by the reaction of an alkenyl succinic anhydride or acid with an aromatic secondary amine to form an intermediate product and thereafter reacting the intermediate product with either an alkanolamine, an aminomethane or a hindered alcohol.
• hydrocarbyl-substituted succinic diamides obtainable as described hereinafter are particularly useful as dispersants in fuel compositions.
• the present invention provides a hydrocarbon fuel composition
• a hydrocarbon fuel composition comprising a hydrocarbon fuel and an amount sufficient to provide dispersancy of a hydrocarbyl-substituted succinic diamide, wherein the hydrocarbyl substituent is of a size sufficient to render the diamide soluble in the fuel, the diamide being obtainable by reacting at elevated temperature a secondary amine with either a hydrocarbyl-substituted succinic acid or an anhydride, ester or monoamide derivative thereof.
• the hydrocarbyl substituent of the succinic diamide is of a size sufficient to render the diamide soluble in the hydrocarbon fuel. Typically this may be achieved with a hydrocarbyl substituent having at least 25 carbon atoms, preferably greater than 35 carbon atoms, and up to about 500 carbon atoms, preferably up to about 300 carbon atoms.
• the hydrocarbyl substituent may be derived from a suitable polyalkene or mixture of polyalkenes selected from, for example, polyethylene, polypropylene and polybutenes.
• a preferred hydrocarbyl substituent is derived from a polyisobutene.
• Polyisobutene succinic anhydrides (PIBSAs) suitable for use in the reaction may be obtained commercially.
• Polyisobutene succinic acids suitable for use in the reaction may be obtained by hydrolysis of PIBSAs, suitably using water as the hydrolysing agent, and at elevated temperature.
• Polyisobutene succinic acid esters may suitably be obtained by esterification of either a PIBSA or a polyisobutene succinic acid.
• Polyisobutene succinic monoamides may suitably be obtained by reacting a PIBSA or a polyisobutene succinic acid salt with up to 1 mole per mole of a secondary amine.
• the secondary amine there may be used a secondary mono-, di- or poly-amine.
• a secondary mono-amine having the formula:- wherein R1 and R2 are independently C1-C15 hydrocarbyl groups, suitably alkyl groups, preferably C1 to C4 alkyl groups.
• a secondary diamine having the formula:- wherein X is a divalent hydrocarbyl group, suitably an alkylene group, having up to 15 carbon atoms, preferably up to 6 carbon atoms; and R1 and R2 are independently C1 to C15 hydrocarbyl groups, suitably alkyl groups, preferably C1 to C4 alkyl groups.
• a secondary polyamine having the formula:- wherein X is a C1 to C15 divalent hydrocarbyl group, suitably a C1 to C6 alkylene group, preferably an ethylene or propylene group, which may be substituted with, for example, hydroxyl groups; R1 and R2 are independently C1 to C15 hydrocarbyl groups, suitably alkyl groups, preferably C1 to C4 alkyl groups; and n is an integer in the range from 1 to 6, preferably from 1 to 4.
• N-alkyl piperazines are preferred because they eliminate the possibility of the diamide product being contaminated with esters, unlike compounds of the formulae (IV) and (V).
• a preferred secondary amine reactant is N-methyl piperazine.
• the hydrocarbyl-sutstituted succinic diamide is obtainable by reacting at elevated temperature a hydrocarbyl-substituted succinic acid or an anhydride, ester or monoamide derivative thereof with a secondary amine. The reactants are reacted in proportions such that there is formed a diamide. Using a hydrocarbyl-substituted succinic acid or anhydride it is preferred to react at least 2 moles of the secondary amine for each mole of acid or anhydride. Using a hydrocarbyl-substituted succinic acid monoamide it is preferred to react at least 1 mole of the secondary amine for each mole of monoamide.
• hydrocarbyl substituted succinic acid or anhydride it is preferred to react a hydrocarbyl substituted succinic acid or anhydride with at least 2 moles of the secondary amine for each mole of acid or anhydride.
• a hydrocarbyl-substituted succinic acid monoamide as the starting material for the reaction with the secondary amine it is possible to produce diamides having different amido substituents by employing a secondary amine different to that used in the formation of the monoamide. Otherwise mixtures of diamides may be obtainable by using mixtures of at least two secondary amines in the diamide forming reaction.
• the reaction may be accomplished in the presence or absence of a solvent.
• Suitable solvents include liquid hydrocarbons, for example xylene or cyclohexane.
• reaction of the acid or derivative thereof with the secondary amine may suitably be effected at elevated temperatures, suitably below 250°C, for example from about 90 to 180°C.
• reaction of a PIBSA with diethanolamine for example, may suitably be represented as follows:-
• reaction of a polyisobutene succinic acid with N-methyl piperazine may suitably be represented as follows:
• the hydrocarbon fuel may suitably comprise a hydrocarbon fraction boiling in the gasoline range or a hydrocarbon fraction boiling in the diesel range.
• Such gasolines may comprise mixtures of saturated, olefinic and aromatic hydrocarbons. They may be derived from straight-run gasoline, synthetically produced aromatic hydrocarbon mixtures, thermally or catalytically cracked hydrocarbon feedstocks, hydrocracked petroleum fractions or catalytically reformed hydrocarbons.
• the octane number of the base fuel is not critical and will generally be above 65.
• hydrocarbons may be replaced in part by alcohols, ethers, ketones or esters, typically in an amount up to 20% by weight.
• liquid hydrocarbon fuel there may be used any fuel suitable for operating spark compression engines, such as those which may be found in road vehicles, ships and the like.
• a diesel fuel will boil in the range from about 140°C to about 400°C (at atmospheric pressure), particularly in the range from about 150 to 390°C, especially from about 175 to 370°C.
• Such fuels may be obtained directly from crude oil (straight-run) or from a catalytically or thermally cracked product or a hydrotreated product, or from a mixture of the aforesaid.
• a biofuel for example rape seed methyl ester.
• the cetane number will typically be in the range from 25 to 60.
• the fuel composition contains the hydrocarbyl substituted succinic diamide in an amount sufficient to provide dispersancy. Typically in a gasoline fuel this amount will be in the range from 20 to 1000 ppm w/w based on the total weight of the composition. Typically in a diesel fuel this amount will be in the range from 10 to 500 ppm w/w based on the total weight of the composition.
• the fuel composition may suitably be prepared by blending a concentrate composition comprising a fuel compatible hydrocarbon solvent and the hydrocarbyl-substituted succinic diamide with the hydrocarbon fuel.
• the fuel composition in addition to the hydrocarbyl-substituted succinic diamide may contain known additives.
• the nature of the additives will depend to some extent on the end-use of the fuel composition.
• Diesel fuel compositions may contain nitrates or nitrites as a cetane improver, or copolymers of ethylene and/or vinylesters, eg vinylacetate, as a pour point depressant.
• Gasoline fuel compositions may contain a lead compound as an anti-knock additive and/or an antioxidant, eg 2,6-di-tert-butyl phenol, and/or an anti-knock compound other than a lead compound, and/or an additional dispersant, for example a PIB polyamine.
• the other additives (if any) may be blended directly into the fuel composition or may be incorporated by way of a concentrate composition.
• PIBSA polyisobutene (PIB) of number average molecular weight (M n ) of about 1000)
• M n number average molecular weight
• n-heptane was subsequently removed on a rotary evaporator at 110 o C/28 inches Hg over one hour.
• N-methyl piperazine (NMP)(25 g), the "clean” PIBSA of Example A (200 g) and xylene (100 g) were mixed and the mixture heated to reflux at 165-170 o C. The mixture was held at the reflux temperature for 3 hours.
• the product was stripped on a rotary evaporator at 130 o C/29.5 inches Hg.
• the product was stripped on a rotary evaporator at 130 o C/28 inches Hg.
• Example 2 was repeated except that instead of using xylene (100 g) there was used cyclohexane (100 g). In this preparation vigorous reflux occurred initially. A temperature of 107 o C was attained. After removal of 16.8 g cyclohexane a reflux temperature of 140 o C was attained.
• the product was stripped on a rotary evaporator at 130 o C/28 inches Hg.
• a "clean" PIBSA derived from a commercially available more reactive, ie higher vinylidene content (about 60%) PIB of M n about 1300 was obtained by blending the PIBSA (715 g) and n-heptane (185 g) followed by filtering through a diatomaceous earth filter aid and removing the n-heptane solvent by rotary evaporation at 130 o C/28 inches Hg (425 g blend charged; 400.1 g product recovered).
• NMP N-methylpiperazine
• Example 5 A mixture of a PIBSA identical to that used in Example 5 (400 g), xylene (230 g) and water (6.2 g) was charged to a one litre 5-necked flange pot reactor equipped with Eurotherm, agitator and Dean and Stark trap. The contents were then heated to 95 o C to effect hydrolysis. Subsequently N-methyl piperazine (NMP) (64.8 g; b.pt. 138 o C) was added.
• NMP N-methyl piperazine
• the product was stripped at 150 o C/28.5 inches Hg to remove solvents.
• the product was stripped at 150°C/28.5 inches Hg.
• Results were generated in an Opel Kadett engine test run on fuel treated with either 500 or 1000 ppm w/w of an additive package.
• the additive package was based on a commercial formulation modified in the respect that the customary dispersant actives component was replaced on a weight/weight basis in turn by a dispersant according to the invention and prior art succinimide dispersants as indicated in Table 2 below.
• succinimides 1 and 2 These materials are characterised as follows:-

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=10731407

Family Applications (1)

Country Status (4)

Cited By (51)

Families Citing this family (2)

Citations (9)

• 1993
  • 1993-03-03 GB GB939304350A patent/GB9304350D0/en active Pending
• 1994
  • 1994-02-24 DE DE69411784T patent/DE69411784T2/de not_active Expired - Fee Related
  • 1994-02-24 EP EP94301303A patent/EP0613938B1/de not_active Expired - Lifetime
  • 1994-03-01 JP JP6031583A patent/JPH06299170A/ja active Pending

Patent Citations (9)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events