DE60109936T2 - ADDITIVE COMPOSITION FOR MIDDESTILLATE FUELS AND MIDDLE DISTILLATE FUEL COMPOSITIONS CONTAINING THEREOF - Google Patents

Abstract

Additive compositions for improving middle distillate fuel oils comprise (A) from about 35 to about 55 parts by weight of a hydrocarbyl substituted monosuccinimide dispersant containing from about 30 to about 200 carbon atoms in the hydrocarbyl group and (B) from about 75 to about 40 parts by weight of an oil having viscosity ranging from about 100 to about 400 centistokes at 40 DEG C, fuel compositions comprising a major amount of a middle distillate fuel oil and a sufficient amount of the additive composition to provide from about 35 to about 55 parts by weight of (A) a hydrocarbyl substituted monosuccinimide dispersant containing from about 30 to about 200 carbon atoms in the hydrocarbyl group and from about 75 to about 40 parts by weight of (B) an oil having viscosity ranging from about 100 to about 400 centistokes at 40 DEG C, per million parts by weight of fuel oil, a method for reducing fouling of fuel oil injectors comprising fueling a device equipped with said injectors with the fuel composition of the invention, and a method of operating a compression-ignition engine comprising providing as the fuel the fuel oil composition of this invention thereby reducing fouling of fuel oil injectors of said engine.

Description

AREA OF INVENTION

The This invention relates to middle distillate fuel additive compositions and middle distillate fuel compositions, the tendencies thereto significantly increase the formation of fuel injector deposit Reduce.

BACKGROUND THE INVENTION

Middle distillate fuels are used in a number of applications such as heating equipment and in engines, e.g. Aircraft engines and diesel engines. The fuels become common the combustion chamber over Fuel injectors supplied. Since the injectors are very close to the combustion chamber, they are exposed to high temperatures. Deposits can be made a degradation of the fuel arise exposed to elevated temperatures becomes.

fuel additives are used to improve performance. A great variety of additives is known, including cetane number improvers, the quality of ignition of the fuel improve, stabilizers, smoke-reducing additives, corrosion inhibitors and detergents / dispersants.

diesel engines are compression-ignition engines. A compression of the air / fuel mixture within the combustion chamber generates the heat, which needed is to ignite the fuel. In the diesel combustion process are a fuel treatment and effective mixing with available air while ensuring effective combustion is essential. The fuel injection equipment provides the mechanical means for it ready to achieve this, and their performance is crucial in controlling the speed of fuel injection and atomization. A optimum performance is only achieved when the fuel injection system is free of deposits and consistent adjusted with the specifications of the manufacturer. As described, is there a tendency for Fuels that they deposit during a distribution and Form combustion. These deposits can be the combustion process noticeably influence.

critical Deposits can form in two basic areas. A formation of rubber or resinous degradation products can occur in the injection system. Problems often occur on isolated cylinders of an engine, wherein the resulting misfire causes a loss of performance and increased exhaust gas smoke. Carbon deposits on parts of injectors, the hot combustion gases exposed to influence both a fuel flow as well the fuel atomization. A loss of performance, increased exhaust fumes and a bad start are significant engine performance problems.

deposits can form in other areas exposed to fuel are.

One Fouling of diesel fuel injector nozzles by fuel and oil degradation products leads to a poor provision in terms of quantity and spray direction of the fuel supplied to the combustion chamber. Driveability problems, a reduced fuel economy, adverse emission performance and wear of the piston skirt are some of the possible Consequences of such a fouling.

Dry Additives were used to control the formation of deposits. traditionally, these are ashless-type dispersants, i. you are essentially free of metals. In general, the additives were numerous nitrogenous compounds.

The Costs are a major consideration, if materials as performance-enhancing additives for fuels be considered. Dispersants are generally included Minimum amounts used to provide acceptable performance. Oil and others thinner become common in minimum quantities as diluent for dispersants used to facilitate the handling thereof, e.g. to reduce the viscosity, etc. These diluents are typically light oil fractions, e.g. 100 solvent neutral oils. The as a diluent used oils are not usually considered to be any significant effect on detergency or dispersing properties exhibit.

Sugimoto, U.S. Patent 6,051,039 U.S. Patent Nos. 3,199,074, 5,260,642, 4,260,199 and 5,422,160 describe diesel fuel compositions containing an additive composition obtained by mixing or reacting A) at least one dicarboxylic acid having about 8 to 500 carbon atoms or a reactive equivalent thereof and b) at least one amine having from about 6 to about 80 carbon atoms and optionally at least one monocarboxylic acid at about From 8 to about 28 carbon atoms or a reactive equivalent thereof.

Dorer, U.S. Patent 3,658,494 US-A-5,642,642 describes fuel compositions comprising a major amount of a normally liquid fuel and a minor amount of an additive combination comprising at least one oxy-compound selected from monoethers of glycols and polyglycols and at least one fuel-soluble dispersant including, inter alia, imides of substantially saturated carboxylic acids characterized by the presence within the acyl group of at least 30 aliphatic carbon atoms.

We have now found that mixtures of monosuccinimide-like Dispersants and oils within a certain viscosity range, which in specific Unexpectedly an improved Cleanliness of injectors in diesel engines and other middle distillate supplies Provide devices.

SUMMARY THE INVENTION

The The invention relates to an additive composition for improving Middle distillate fuel oils which (A) 35 to 55 parts by weight of a hydrocarbyl-substituted monosuccinimide dispersant having 30 to 200 carbon atoms in the hydrocarbyl group and (B) 75 to 40 parts by weight of an oil, the one viscosity of 300 to 350 centistokes at 40 ° C comprises. In one embodiment The invention relates to a fuel composition comprising a Main amount of a middle distillate fuel oil and a sufficient amount of the additive composition comprises from 35 to 55 parts by weight of (A) a hydrocarbyl-substituted monosucine cinimide dispersant with 30 to 200 carbon atoms in the hydrocarbyl group and 75 up to 40 parts by weight of (B) an oil, the one viscosity from 300 to 350 centistokes at 40 ° C, each per million Parts by weight of fuel oil, provide. In a further embodiment, the invention relates a method for reducing fouling of fuel oil injectors, the supplying a device equipped with the injectors is, with the fuel composition of the invention includes. In a further embodiment The invention relates to a method for operating an engine with compression ignition, providing the fuel oil composition of the invention as the fuel comprises, resulting in fouling of fuel oil injectors of the engine is reduced.

PRECISE DESCRIPTION THE PREFERRED EMBODIMENTS

As As used herein, the term "hydrocarbon" refers to a group that is a pure hydrocarbon is, i. a compound of hydrogen and carbon atoms, which contains no heteroatoms. The The terms "hydrocarbyl group" or "hydrocarbon-based" mean that the group described a predominantly hydrocarbon character within the context of the invention. hydrocarbyl and hydrocarbon-based groups include groups that are pure Hydrocarbons are, i. they contain only carbon and hydrogen atoms. You can also include groups which are non-hydrocarbon substituents or atoms containing the predominantly hydrocarbon character do not change the group. Such substituents can Halogen, alkoxy, nitro groups, etc. include. These groups can also contain heteroatoms. Suitable heteroatoms will be apparent to those skilled in the art be known and include e.g. Sulfur, nitrogen and oxygen atoms. Consequently, you can these groups while they predominantly hydrocarbons in character remain in the context of the invention, of carbon atoms contain different atoms in a chain or a ring which are otherwise composed of carbon atoms is. Thus, the terms "hydrocarbyl group" and "hydrocarbon-based" are broader than that Term "hydrocarbon", since all hydrocarbon groups also hydrocarbyl groups or hydrocarbon-based groups are while the hydrocarbyl groups or hydrocarbon-based groups, which contain heteroatoms, are not hydrocarbon groups.

in the Generally not more than about three non-hydrocarbon substituents or heteroatoms, and preferably not more than one non-hydrocarbon substituent or Heteroatom for every 10 carbon atoms in the hydrocarbyl groups or groups be present on a hydrocarbon basis. Most preferred the groups are pure hydrocarbons, i. they are essentially free of atoms different from carbon and hydrogen atoms.

The Hydrocarbyl groups and hydrocarbon-based groups are preferred free of acetylenic unsaturation. Ethyleneic unsaturation, if any, will generally be such that nothing more as an ethylenic bond for each 10 carbon-carbon bonds is present. The groups are often complete saturated and therefore do not contain ethylenic unsaturation.

As used in the description and in the appended claims the singular forms "one / one" and "the / the" the plural, if not the context clearly indicates otherwise. Consequently, it includes e.g. a reference to a polymer blends of polymers, a reference an acylating agent includes mixtures of acylating agents, Etc.

Hydrocarbyl substituted Succinimide dispersant

dargestellt werden, worin R der Hydrocarbylsubstituent ist und X ausgewählt ist aus der Gruppe bestehend aus H, Hydrocarbylgruppen mit 1 bis 30 Kohlenstoffatomen, vorzugsweise aliphatischen Hydrocarbylgruppen, -Alkylen-OR³-Gruppen, worin R³ H oder eine Hydrocarbylgruppe, vorzugsweise H oder eine Niederalkylgruppe ist, und Gruppen der Formel

worin n einen durchschnittlichen Wert von 1 bis 10 aufweist, die "Alkylen"-Gruppe 1 bis 10 Kohlenstoffatome aufweist und jede Gruppe R₅ unabhängig ein Wasserstoffatom oder eine aliphatische Gruppe oder eine Hydroxy-substituierte oder eine amino-aliphatische Gruppe mit bis zu 30 Kohlenstoffatomen ist. Vorzugsweise ist die "Alkylen"-Gruppe eine Ethylen- oder Propylengruppe.As described herein, the compositions of the invention comprise a hydrocarbyl-substituted monosuccinimide dispersant having from 30 to 200 carbon atoms in the hydrocarbyl group. These can be explained by the general formula

wherein R is the hydrocarbyl substituent and X is selected from the group consisting of H, hydrocarbyl groups having from 1 to 30 carbon atoms, preferably aliphatic hydrocarbyl groups, alkylene-OR ³ groups, wherein R ^{3 is} H or a hydrocarbyl group, preferably H or one Lower alkyl group, and groups of the formula

wherein n has an average value of 1 to 10, the "alkylene" group has 1 to 10 carbon atoms, and each group R ₅ independently represents a hydrogen atom or an aliphatic group or a hydroxy-substituted or an amino-aliphatic group having up to 30 carbon atoms is. Preferably, the "alkylene" group is an ethylene or propylene group.

Used according to the invention Monosuccinimides are prepared by known methods. you will be typically prepared by a hydrocarbyl group-substituted succinic with ammonia or at least one amine with at least one condensable H-N <group implemented becomes.

Hydrocarbyl-substituted succinic, in the preparation of the monosuccinimide dispersants used in the invention are hydrocarbyl group-substituted succinic acids and reactive equivalents from that. A reactive equivalent is a reactant that will react in a similar way to which is a hydrocarbyl group-substituted succinic acid, to form derivatives that are essentially the same as those obtained from succinic acid. For example Anhydrides, lower alkyl esters, lower alkyl esters and acyl halides to react with amines to substantially similar products as the corresponding ones acids to build. Anhydrides, lower alkyl esters, lower alkyl esters and acyl halides are all considered to be reactive equivalents to the corresponding succinic acid are.

The group "R" is a hydrocarbyl group, preferably a hydrocarbon-based group. More preferably, the group "R" is an aliphatic group. The hydrocarbyl group "R" contains 30 to 200 carbon atoms, often 30, more often 50 to 100 carbon atoms. The hydrocarbyl group is most preferably an aliphatic group derived from homopolymerized and copolymerized polyolefins wherein the olefins, usually 1-olefins, contain from 2 to 18 carbon atoms. Often the olefins are never preferably olefins, preferably ethylene, propylene and butenes, typically 1-butene and isobutylene and mixtures thereof, in particular isobutylene.

As As used herein, the term "polyolefin" defines a polymer derived from olefins derives.

In a further preferred embodiment R is derived from polypropylene. In a further preferred embodiment R is derived from ethylene-alpha-olefin polymers including, Ethylene-α-olefin-diene polymers, especially those in which the diene is an unconjugated Diene is. examples for such polymers are the ethylene-propylene copolymers and ethylene-propylene-diene terpolymers.

A preferred source of hydrocarbyl groups R are polybutenes obtained by polymerizing a C ₄ refining stream having a butene content of 35 to 75% by weight and an isobutylene content of 15 to 60% by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or Boron trifluoride can be obtained. These polybutenes contain predominantly (greater than 80% of the total repeating units) repeating isobutylene units of the configuration

These Polybutenes are typically monoolefinic, i. they contain only one olefinic bond per molecule.

insbesondere diejenigen der Formel

obwohl die Polybutene auch andere olefinische Konfigurationen umfassen können.In one embodiment, the monoolefinic groups are predominantly vinylidene groups, ie, groups of the formula

especially those of the formula

although the polybutenes may also include other olefinic configurations.

In one embodiment, the polybutene is substantially monoolefinic, comprising at least 30 mole%, preferably at least 50 mole% vinylidene groups, more often at least 70 mole% vinylidene groups. Such materials and methods of making the same are described in U.S. Patent Nos. 5,071,919, 5,137,978, 5,137,980, 5,286,823 and 5,408,018, and published EP Patent Application 646103-A1. They are for example commercially available under the trade names ULTRAVIS ^® (BP Chemicals) and GLISSOPAL ^® (BASF).

In one embodiment, the hydrocarbyl substituent is a polyisobutenyl group having M ¯ _n ranging from 400 to 2500, often 800 to 1200.

Molecular weights of the polymers are determined using known methods described in the literature. Examples of methods for determining molecular weights are gel permeation chromatography (GPC) (also known as size exclusion chromatography), light scattering and vapor phase osmometry (VPO). The GPC technique uses standard materials against which the samples are compared. For best results, standards are used which are chemically similar to those of the sample. For example, for polystyrene polymers, a polystyrene standard, preferably of similar molecular weight, is used. If the standards are not similar to the samples, relative molecular weights of related polymers can generally be determined. For example, using a polystyrene standard, relative, but not absolute, molecular weights can be determined for a variety of polymethacrylates. These and other methods are described in numerous publications, including:
PJ Flory, "Principles of Polymer Chemistry", Cornell University Press (1953), Chapter VII, pages 266-316,
"Macromolecules, to Introduction to Polymer Science," FA Bovey and FH Winslow, Editors, Academic Press (1979), pages 296-312, and
WW Yau, JJ Kirkland and DD Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.

Succinic acylating agents and the preparation thereof are each known to those skilled in the art. They are conveniently prepared by reacting a polyolefin with maleic acid or a reactive equivalent thereof. Reactive equivalents are acyl halides, esters, especially lower alkyl esters, acid esters and maleic anhydride. Maleic anhydride is preferred. The reaction can be carried out thermally, ie by simply combining and heating the reactants, or with the addition of chlorine during the reaction. Alternatively, the maleic reactant may be reacted with a halogenated, usually chlorinated, polyolefin. Monosuccinating the polyolefin is desired. Accordingly, typically about 0.95 to about 1.1, most preferably 1 mole of maleic acid or reactive equivalent thereof with 1 mole of reacted based on the M _n of the polyolefin. Examples of hydrocarbyl group-substituted succinic acylating agents and methods for their preparation are described in numerous patents, including U.S. Patents 3,172,892, 3,454,607, 3,215,707 and 6,051,039.

Monosuccinimide dispersant are derived from the reaction of succinic acylating agents with ammonia or at least one amine having at least one condensable primary Amino group.

The Amines can Monoamines or polyamines, typically polyamines, preferably Ethylene polyamines, amine bottoms or amine condensates. The amines can be aliphatic, cycloaliphatic, be aromatic or heterocyclic, including aliphatic-substituted cycloaliphatic, aliphatic-substituted aromatic, aliphatic-substituted heterocyclic, cycloaliphatic-substituted aliphatic, cycloaliphatic-substituted heterocyclic, aromatic-substituted aliphatic, aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic, heterocyclic-substituted aliphatic, heterocyclic-substituted alicyclic and heterocyclic-substituted aromatic amines, and you can saturated or unsaturated be.

Usable according to the invention Monoamines generally contain 1 to 24 carbon atoms, preferably 1 to 12 and more preferably 1 to 6 carbon atoms. Examples for primary monoamines, the invention suitable include methylamine, propylamine, butylamine, cyclopentylamine, Dodecylamine, allylamine, cocoamine and stearylamine.

The monoamine can be an alkanolamine of the formula: H ₂ N-R'-OH wherein R 'is a divalent hydrocarbyl group of about 2 to 18 carbon atoms, preferably 2 to 4 carbon atoms. The group -R'-OH in such formulas corresponds to the hydroxyhydrocarbyl group. R 'may be an acyclic, alicyclic or aromatic group. Typically, R 'is an acyclic straight or branched alkylene group such as ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc.

Examples for alkanolamines include monoethanolamine, propanolamine, etc.

The hydroxyamines may also be ether N- (hydroxyhydrocarbyl) amines. These are hydroxypoly (hydrocarbyloxy) analogs of the hydroxyamines described above (these analogs also include hydroxyl-substituted oxyalkylene analogs). Such N- (hydroxyhydrocarbyl) amines may conveniently be prepared, for example, by reacting epoxides with ammonia and may be represented by the formula: H ₂ N- (R'O) _x -H where x is a number from 2 to 15 and R 'is as described above.

Other suitable amines include etheramines of the general formula R ₆ OR ¹ NH ₂ wherein R _{6 is} a hydrocarbyl group, preferably an aliphatic group, more preferably an alkyl group having 1 to 24 carbon atoms, R ^{1 is} a divalent hydrocarbyl group, preferably an alkylene group, with 2 to 18 carbon atoms, more preferably 2 to 4 carbon atoms. Especially preferred ether amines are those available under the name SURFAM ^®, manufactured and marketed by Sea Land Chemical Co., Westlake, Ohio.

The Amine can also be a polyamine. The polyamine can be aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples for suitable Polyamines include alkylene polyamines, hydroxy-containing polyamines, Polyoxyalkylenepolyamines, arylpolyamines and heterocyclic polyamines.

dargestellt, worin n einen durchschnittlichen Wert von 1 bis 10, vorzugsweise 2 bis 7, mehr bevorzugt 2 bis 5 aufweist und die "Alkylen"-Gruppe 1 bis 10 Kohlenstoffatome, vorzugsweise 2 bis 6, mehr bevorzugt 2 bis 4 Kohlenstoffatome aufweist. Jede Gruppe R₅ ist unabhängig ein Wasserstoffatom, eine aliphatische Gruppe oder eine Hydroxy-substituierte oder Amino-substituierte aliphatische Gruppe mit bis zu 30 Kohlenstoffatomen. Vorzugsweise ist R₅ H oder eine Niederalkylgruppe, am meisten bevorzugt H.Alkylenepolyamines are represented by the formula

wherein n has an average value of 1 to 10, preferably 2 to 7, more preferably 2 to 5, and the "alkylene" group has 1 to 10 carbon atoms, preferably 2 to 6, more preferably 2 to 4 carbon atoms. Each group R ₅ is independently a hydrogen atom, an aliphatic group or a hydroxy-substituted or amino-substituted aliphatic group having up to 30 carbon atoms. Preferably, R _{5 is} H or a lower alkyl group, most preferably H.

alkylene include methylene, ethylene, butylene, propylene, pentylene and other polyamines. higher Homologous and related heterocyclic amines such as N-aminoalkyl-substituted Piperazines are also included. Specific examples of such Polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, Tris (2-aminoethyl) amine, propylenediamine, N, N-dimethylaminopropylamine, Trimethylenediamine, tripropylenetetramine, tetraethylenepentamine, hexaethyleneheptamine, Pentaethylenehexamine, aminoethylpiperazine, etc.

Higher homologues, by condensing two or more of the alkylene amines described above are obtained in similar Way suitable and mixtures of two or more of the above described polyamines, with the proviso that the resulting condensed amine contains at least one primary amino group.

Ethylene polyamines such as some of those described above are preferred. They are published under the heading "Diamines and Higher Amines" in Kirk Othmer's "Encyclopedia of Chemical Technology", 4th Edition, Volume 8, pages 74-108, John Wiley and Sons, New York (1993), and Meinhardt et al ., U.S. Patent 4,234,435 , both of which are hereby incorporated herein by reference for their description of suitable polyamines. Such polyamines are most conveniently prepared by the reaction of ethylene dichloride with ammonia or by reacting an ethyleneimine with a ring-opening reagent such as water, ammonia, etc. These reactions result in the preparation of a complex mixture of polyalkylene polyamines, including cyclic condensation products such as the piperazines described above. Ethylene polyamine mixtures are suitable. Heavy polyamines, like those in the U.S. Patent 5,936,041 are also suitable.

Other suitable types of polyamine mixtures are those that are from stripping of the polyamine mixtures described above yield, as a backlog leave, what is often referred to as "polyamine bottoms". In general, you can alkylene polyamine be characterized in that they are less than two, usually less 1% (by weight) of material boiling below about 200 ° C. A typical sample of such ethylene-polyamine bottoms available from Dow Chemical Company from Freeport, Texas, and referred to as "E-100", has a specific one Density at 15.6 ° C of 1.0168, a nitrogen content of 33.15% and a viscosity at 40 ° C of 121 Centistokes. A gas chromatographic analysis of such a sample shows that it is about 0.93% "Light Ends "(most likely Diethylenetriamine), 0.72% triethylenetetramine, 21.74% tetraethylenepentamine and 76.61% pentaethylenehexamine and higher (by weight). These alkylene polyamine include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetramine and the like.

Another suitable polyamine is a condensation product obtained by reacting at least one hydroxy compound with at least one polyamine reactant containing at least one primary or secondary amino group. The hydroxy compounds are preferably polyhydric alcohols and amines having multiple alcohol groups. Preferably, the hydroxy compounds are amines having multiple alcohol groups. Amines having multiple alcohol groups include any of the monoamines described above which are reacted with an alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) having 2 to 20 kos lenstoffatomen, preferably two to four carbon atoms are reacted. Examples of amines having multiple alcohol groups include tri (hydroxypropyl) amine, tris (hydroxymethyl) aminomethane, 2-amino-2-methyl-1,3-propanediol, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine and N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine.

polyamine, with the polyhydric alcohol or the amine with several Alcohol groups convert to the condensation products or condensed Amines are described above. Preferred polyamine reactants include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), Pentaethylenehexamine (PEHA) and mixtures of polyamines, such as previously described "amine bottoms".

The Condensation reaction of the polyamine reactant with the hydroxy compound takes place at an elevated Temperature, usually at 60 ° C up to 265 ° C, in the presence of an acid catalyst.

The Amine condensates and methods for making the same are in Steckel (U.S. Patent 5,053,152) described.

The Polyamines can hydroxy containing polyamines, with the proviso that they are at least a condensable primary Contain amino group. These include hydroxy containing polyamine analogs of hydroxymonoamines, in particular alkoxylated alkylene polyamines. Such polyamines can be prepared by the above-described Alkylenamine with one or more of the alkylene oxides described above be implemented.

specific examples for alkoxylated alkylene polyamines include N- (2-hydroxyethyl) ethylenediamine, N, N-di (2-hydroxyethyl) ethylenediamine, Mono (hydroxypropyl) substituted tetraethylenepentamine, N- (3-hydroxybutyl) tetramethylenediamine, etc. Higher Homologs obtained by condensation of the hydroxy-containing polyamines described above via amino groups or over Hydroxy groups are also suitable. A condensation via amino groups leads to a higher one Amin, accompanied by a removal of ammonia, while a Condensation over the hydroxy group leads to products containing ether bonds, accompanied by a removal of water. Mixtures of two or more of any of the polyamines described above also suitable.

The polyamines may be polyoxyalkylene polyamines, including polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights of 200 to 2000. Polyoxyalkylenepolyamines including polyoxyethylene-polyamines, for example, under the trade name JEFFAMINE ^® commercially available from Texaco Chemical Co.. U.S. Patents 3,804,763 and 3,948,800 contain descriptions of polyoxyalkylene polyamines.

In a further embodiment For example, the polyamine may be a heterocyclic polyamine. The heterocyclic Polyamines include aminoalkyl-substituted heterocyclic polyamines such as N-aminoalkylthiomorpholines, N-aminoalkylmorpholines, N-aminoalkylpiperazines, N, N'-bisaminoalkyl and mixtures of two or more of these heterocyclic amines. Preferred heterocyclic amines are the saturated 5- and 6-membered heterocyclic amines containing only nitrogen or nitrogen Contain oxygen and / or sulfur atoms in the hetero ring, in particular the piperidines, piperazines, thiomorpholines, morpholines, Pyrrolidines and the like. Aminoalkyl-substituted piperidines, Aminoalkyl-substituted piperazines, aminoalkyl-substituted morpholines, Pyrrolidine and aminoalkyl-substituted pyrrolidines are especially prefers. Usually the aminoalkyl substituents are substituted on a nitrogen atom, that forms part of the hetero ring. Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine and N, N'-diaminoethylpiperazine.

hydrazine and substituted hydrazine also be used to nitrogen-containing carboxylic dispersants to build. At least one of the nitrogen atoms in the hydrazine must contain two hydrogen atoms directly attached to it. The substituents which may be present on the hydrazine include Alkyl, alkenyl, aryl, aralkyl, alkaryl groups and the like. Usually the substituents are alkyl groups, in particular lower alkyl groups, Phenyl and substituted phenyl groups such as lower alkoxy-substituted Phenyl groups or lower alkyl-substituted phenyl groups. specific examples for substituted hydrazines are methylhydrazine, N, N-dimethylhydrazine, Phenylhydrazine, N- (para-nitrophenyl) hydrazine, N- (para-nitrophenyl) -N-methylhydrazine, Aminoguanidine bicarbonate and the like.

During a reaction of the hydrocarbyl-substituted succinic acylating agent with the primary amine reactants may form a non-monosuccinimide along with monosuccinimide products. These include amine salts, amides and imidazolines, as well as mixtures thereof. Desirably, at least 50 mole percent of the succinic acylating agent is converted to monosuccinimide, more preferably at least 75 percent is converted to monosuccinimide.

Around to produce the monosuccinimide from the amines become one or more of the hydrocarbyl-substituted succinic acylating agents and one or more amines heated, optionally in the presence of a normally liquid, substantially inert organic liquid solvent / diluent, at temperatures of 50 ° C to the decomposition point of any of the reactants or of the product, but usually at temperatures of 100 to 300 ° C, with the proviso that 300 ° C does not exceed the decomposition point of a reactant or product. Temperatures of 100 ° C, often 125 ° C to 250 ° C normally used. The succinic acylating agent and the Amine are reacted in an amount sufficient to about one half mol to about 1.1 moles of primary amine per mole of succinic acylating agent provide.

A Succinimide production, including monosuccinimide production, is e.g. in the following patents: U.S. Patents 2,992,708, 3,018,291, 3,024,237, 3,100,673, 3,172,892, 3,219,666 and 3,272,746. These patents describe the manufacture of a wide variety Succinimide-type dispersants.

The Examples below illustrate several succinimide compounds. The products of Examples 1 and 4 illustrate the additive compositions of the invention as well as means for producing the same. It should be understood that these examples are not intended to limit the scope of the invention. Unless otherwise indicated, all parts are parts by weight and that Temperatures are given in degrees Celsius. If the quantities in Volumes are given is the relationship between parts by weight and parts by volume, such as grams to milliliters. Reactions take place under Nitrogen. Any filtrations are done using a Diatomaceous earth filter aid. Analytical values are determined by actual analysis receive.

example 1

A succinimide is prepared by reacting polyisobutylene (M _n value of about 1000 with about 90% terminal vinylidene groups (Glissopal 1000, BASF)) succinate with 0.87 moles of tetraethylenepentamine (Union Carbide) per succinate group (2.2 N per C = O) as a 60% by weight active solution in SN350 mineral oil.

Example 2

Part A

A 316 stainless steel jar is filled with 21 parts of polyisobutylene containing one M _n value of about 1000 and containing about 83 to 85 mole% of terminal vinylidene groups (Ultravis 10, BP Chemicals), charged and heated to 170 ° C. The pressure is set at 200 kilopascals (kPa) and the temperature is increased to 220 ° C as maleic anhydride is introduced. A total of 4 parts (2 moles per mole of polyisobutylene) are added, the first part over 0.25 hours, the remainder over 1.5 hours. The reaction is then heated at 228 ° C / 200 kPa for 2 hours. Highly reduced pressure is then applied and an excess of maleic anhydride (1.6 parts) is removed. The reactor is depressurized with nitrogen and cooled to 150 ° C and a sample is removed. This sample (0.1 part) is identified as "pure PIBSA with a molecular weight of 1000, unfiltered". The remainder of the material is then transferred to a filter feed vessel and 10 parts of hydrocarbon solvent (80% high boiling aromatic solvent / 20% aliphatic solvent, CAROMAX 26, available from Carless Refining and Marketing, UK) and 30 parts filter aid are added. The solution is filtered, yielding 33 parts of filtrate having a saponification number of 99.

part B

10 Portions of the filtrate of Part A of this example are placed in a 316 stainless steel reactor given and at 175 ° C heated. 1.8 parts of HPAX (polyethylene distillate bottoms, Union Carbides, 0.87 moles of HPAX, 2.6 N per C = O) are added over 4 hours. The exothermic reaction is at 165 ° C cooled, for an overcooking over of the solvent shortstop. The collected distillate is 110 parts water and 480 Parts of solvent, the with fresh solvent be replaced in the product to constant the concentration hold. The reaction is at 165 ° C 2 hours, giving 11.7 parts of product at 5.4% N.

Example 3

One 1 liter wide-necked round bottom flask is charged with 400 parts of the filtrate from Part A of Example 2 fed. The contents of the piston will sink stir to 175 ° C heated under a positive pressure of nitrogen, and at this Point is tetraethylenepentamine (52.8 parts, 0.87 moles of TEPA per succinic anhydride headgroup, 2.2 N per C = O) dropwise over added a pressure equalizing dropping funnel over 0.5 hours. An exotherm of 20 ° C is determined. The reaction mixture is then kept at 175 ° C with stirring and the nitrogen flow is increased, about the removal of water over To support 3 hours, which gives 428.8 parts product with 4.4% N. The amount of collected Distillate are 5 parts water and 9.9 parts solvent.

Example 4

One Vessel is with 1014.4 parts of the sample called "pure PIBSA with a molecular weight from 1000, unfiltered " and Part A of Example 2 and 434.7 parts of SN350 mineral oil (Total) charged. The materials are stirred by 0.5 Hours at 50 ° C mixed. The resulting 60% solution is then filtered. A 1 liter round bottom flask is charged with 400 parts of the filtrate. The contents of the flask are then stirred at 175 ° C and a heated to positive pressure of nitrogen, and at this point will Tetraethylenepentamine (TEPA) (51.7 parts, 0.87 moles of TEPA per succinic anhydride headgroup, 2.2 N per C = O) dropwise over a pressure equalizing dropping funnel over a period of 0.5 Hours added. An exotherm of 20 ° C is detected. The reaction mixture then at 175 ° C with stirring held, and the nitrogen flow is increased to the removal of water To support 3 hours, giving 436.7 parts of 3.9% N product. The amount of collected Distillate is 1.6 parts.

Example 5

One Succinimide is prepared as in Example 1, with the exception that an amine reactant is used to provide 1.81 N per C = O.

Example 6

One Succinimide is prepared as in Example 1, with the exception that that the mineral oil 150 N is.

The oil

Oils that usable according to the invention are, can mineral oils, synthetic oils or vegetable oils. Most frequently they are mineral oils. The oils have a viscosity at 40 ° C from 300 cSt to 350 cSt.

thermal more stable oils are preferred. Particularly preferred are hydrogen-treated oils and solvent-neutral oils.

The inventive additive compositions contain 75 to 40 wt .-% of the oil per 35 to 55 parts by weight of the succinimide dispersant.

Middle distillate fuels

Middle distillate fuels may be derived from petroleum or from plant sources or mixtures thereof. More often, they are derived from petroleum derived materials for the purposes of this invention. Middle distillate fuel oils typically have boiling points of 80 to 500 ° C. These include fuel oils, kerosene, jet fuels and diesel fuels. All of these types of fuels are contemplated to be within the scope of the invention, but diesel fuels are particularly preferred. These are fuel oils boiling in the range of 160 ° C up to between 290 ° C and 360 ° C. Such materials are in the U.S. Patent 5,997,592 , Shell Oil Co., described.

Properties of diesel oils and specifications for various grades thereof are described in the publication "Ready Reference for Lubricant and Fuel Performance", Publication no. 240-94R ₅ (August, 1998) The Lubrizol Corporation, pages 84-92.

Other materials conventionally used as performance enhancing additives for middle distillate fuels and in particular diesel fuels can be incorporated into the compositions of the invention in conventional amounts. These other materials include cold flow improvers, pour point depressants, storage stabilizers, corrosion inhibitors, cetane improvers, antistatic agents, biocidal additives, smoke suppressants. These additives are known to the person skilled in the art. Examples of several types of these additives are in the U.S. Patent 4,943,303 specified.

Inventive additive compositions are prepared by mixing components (A) and (B) become. In one embodiment For example, the mixing may take place in the fuel after each component the additive composition was added individually to the fuel. In a further embodiment the components of the additive compositions are mixed first, together with other additives, if desired, the additive composition to form that subsequently is combined with the fuel. In a still further embodiment is at least something of the oil (B) present in the reaction mixture, acting as a diluent while a preparation of the dispersant (A).

The Additive composition comprises 35 to 55 percent by weight of the dispersant (A) and 30 to 200 parts by weight of the oil (B). In a preferred embodiment For example, the additive composition comprises 35 to 40 parts by weight of (A) and 60 to 90 parts by weight (B).

Inventive additive compositions are used in the fuel in amounts sufficient to 35 to 55 parts by weight of (A) a hydrocarbyl-substituted succinimide dispersant with 30 to 200 carbon atoms in the hydrocarbyl group and 75 Up to 40 parts by weight (B) of an oil with a viscosity from 300 to 350 cSt at 40 ° C, each per million parts by weight of fuel oil.

The the following examples illustrate fuel compositions, including a "good" baseline composition, Comparison fuel compositions and fuel compositions of the invention. The basic fuel used is Cat 1K reference fuel. The specified products and the added oil, if used mixed in the basic fuel. The amounts of dispersant on an undiluted, solventless Base and total oil or solvent are for each composition listed. Amounts of dispersant (A), oil (B) and solvent are in parts per million parts (ppm) of fuel.

The Effectiveness of the additive compositions according to the invention, To improve diesel engine fuel injectors is used Cummins (Cummins Corp., Columbus, IN) -L-10 Injector Deposition Tests certainly. This test uses two Cummins L-10 engines running in a tandem configuration, front to back, fixed, and wherein the flywheel to the front pulley adapter of the crankshaft via a Drive shaft is connected. The operating conditions are cyclic, one motor driving the other at measured intervals. The maximum power generated by the powered engine is the friction horsepower the non-running engine. The test runs for a total of 125 hours. Test results include fuel flow data and deposit ratings from every fuel injector. A deposit rating of 10 or lower is desired.

The test is in the U.S. Patent 6,042,626 described. Specific details of this test are available from Engineering Test Services, a division of Cummins Engine Co., Charleston, SC, USA.

It It is known that some of the materials described above in the final formulation can interact so that the components the final formulation of those added initially are different. For example, you can Metal ions (from, for example, a detergent) to other acidic sites other molecules hike. The products formed thereby, including the Products made using the composition of the invention in their intended use can be a simple description inaccessible be. Nevertheless, all such modifications and reaction products included within the scope of the invention. The invention comprises the composition obtained by mixing the above described components is produced.

If not stated otherwise, is any chemical or composition, referred to herein as a material for sale Goodness viewed which are the isomers, by-products, derivatives and other such Contain materials that are normally understood to be that they are in the commercial Goodness available are. However, the amount of each chemical component is exclusive of any solvent or dilution oil, this conventionally in the commercial Material may be present unless otherwise specified. It should be understood that the upper and lower mentioned herein Quantity, range and ratio limits independently can be combined from each other. As used herein, the term "consisting essentially of" allows the uptake of Substances that underlie the basic and new properties of Do not materially affect the composition considered.

Even though the invention with reference to its preferred embodiments explained It should be understood that various modifications thereof will be apparent to those skilled in the art upon reading the description. Thus, it should be understood that the invention described herein Such modifications are intended to fall within the scope of the appended claims.

Claims (14)

An additive composition for improving middle distillate fuel oils which includes: (A) 35 to 55 parts by weight of a hydrocarbyl-substituted Succinimide dispersant having 30 to 200 carbon atoms in the hydrocarbyl group and (B) 75 to 40 parts by weight of an oil which a viscosity from 300 to 350 centistokes at 40 ° C. An additive composition according to claim 1, wherein the Hydrocarbyl group is an aliphatic hydrocarbyl group. An additive composition according to claim 2 wherein the hydrocarbyl group contains from 30 to 100 carbon atoms derived from homopolymerized and copolymerized C _2-18 olefins. An additive composition according to claim 3, wherein the polymerized olefins are 1-olefins. An additive composition according to claim 4, wherein the 1-olefins selected are selected from the group consisting of ethylene, propylene, 1-butene, isobutylene and mixtures thereof. An additive composition according to claim 2, wherein the hydrocarbyl group is a polyisobutenyl group having an M _n value of 400 to 2,500. An additive composition according to claim 1 wherein the succinimide is the general formula

wherein R is a hydrocarbyl group having 30 to 200 carbon atoms and wherein the group X is selected from the group consisting of H, an aliphatic hydrocarbyl group having 1 to 30 carbon atoms and

wherein n has an average value of 1 to 10, the "alkylene" group has 1 to 10 carbon atoms, and each R ⁵ group is independently a hydrogen atom or an aliphatic or aminoaliphatic group having up to 30 carbon atoms. An additive composition according to claim 7, wherein the "alkylene" group is an ethylene or propylene group. An additive composition according to claim 1, wherein the oil is (B) a mineral oil is. Fuel composition, which is a major amount of a Middle distillate fuel oil and a sufficient amount of the additive composition of claim 1 to 35 to 55 parts by weight of (A) of a hydrocarbyl-substituted one Succinimide dispersant having 30 to 200 carbon atoms in the hydrocarbyl group; and (B) 75 to 40 parts by weight of an oil which a viscosity from 300 to 350 centistokes at 40 ° C, each per million Parts by weight of fuel oil, provide. A fuel composition according to claim 10, which 75 to 130 parts by weight of the additive composition according to claim 1 per million parts by weight of fuel oil. A fuel composition according to claim 10, wherein the middle distillate fuel oil a diesel is. Method for reducing fouling of fuel oil injectors, the supplying a device equipped with the injectors is included with the fuel composition of claim 10. A method of operating a compression ignition engine, the providing the fuel oil composition according to claim 10 as the fuel, whereby a fouling of fuel oil injectors of the engine is reduced.