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EP1303577B1 - Composition additive pour combustibles de distillat moyen et compositions de combustibles de distillat moyen les contenant - Google Patents

Composition additive pour combustibles de distillat moyen et compositions de combustibles de distillat moyen les contenant Download PDF

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Publication number
EP1303577B1
EP1303577B1 EP01961656A EP01961656A EP1303577B1 EP 1303577 B1 EP1303577 B1 EP 1303577B1 EP 01961656 A EP01961656 A EP 01961656A EP 01961656 A EP01961656 A EP 01961656A EP 1303577 B1 EP1303577 B1 EP 1303577B1
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Prior art keywords
fuel
group
parts
oil
weight
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German (de)
English (en)
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EP1303577A1 (fr
Inventor
David A. Duncan
Glen A. Blythe
David J. Moreton
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Lubrizol Corp
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Lubrizol Corp
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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
    • C10L1/143—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
    • C10L1/22—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)

Definitions

  • This invention relates to additive compositions for middle distillate fuels and middle distillate fuel compositions which exhibit markedly reduced fuel injector deposit forming tendencies.
  • Middle distillate fuels are used in a number of applications such as in heating equipment and in engines, for example jet engines and diesel engines.
  • the fuels are frequently supplied to the combustion chamber via fuel injectors. Since the injectors are in close proximity to the combustion chamber, they are exposed to high temperatures. Deposits can form arising from degradation of the fuel being exposed to elevated temperatures.
  • Fuel additives are employed to improve performance.
  • a wide variety of additives are known, including cetane number improvers which improve the ignition quality of the fuel, stabilizers, smoke reducing additives, corrosion inhibitors and detergents/dispersants.
  • Diesel engines are compression ignition engines. Compression of the air/fuel mixture within the combustion chamber generates the heat required to ignite the fuel. In the diesel combustion process, fuel vaporization and efficient mixing with available air are essential in insuring efficient combustion.
  • the fuel injection equipment provides the mechanical means of achieving this and its performance is critical in controlling rate of fuel injection and atomization. Optimum performance is only achieved when the fuel injection system is free from deposits and is adjusted in accordance with the manufacturer's specifications. As noted, there is a tendency for fuels to form deposits during distribution and combustion. These deposits can markedly affect the combustion process.
  • Deposits can form in other areas exposed to the fuel.
  • Fouling of diesel fuel injector nozzles by fuel and oil decomposition products leads to imperfect fuelling in terms of amount and spray direction of fuel delivered to the combustion chamber. Driveability difficulties, reduced fuel economy, adverse emissions performance and cylinder liner wear are some of the possible consequences of such fouling.
  • Chemical additives have been used to control formation of deposits. Commonly, these are dispersants of the ashless type, that is, they are essentially free of metal. Generally, the additives have been various nitrogen-containing compounds.
  • Dispersants are generally used at minimal levels to provide acceptable performance. Oil and other diluents are frequently used in minimum amounts, as diluents for dispersants to facilitate handling thereof, e.g., reduce viscosity, etc. These diluents are typically light oil fractions, for example 100 solvent neutral oils. The oils used as diluents normally are not considered as having any significant effect on detergency or dispersancy.
  • U.S. Patent 6,051,039 describes diesel fuel compositions containing an additive composition made by mixing or reacting A) at least one dicarboxylic acid having about 8-500 carbon atoms or a reactive equivalent thereof and B) at least one amine having about 6 to about 80 carbon atoms and optionally, at least one monocarboxylic acid of about 8 to about 28 carbon atoms or a reactive equivalent thereof.
  • U.S. Patent 3,658,494 teaches 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 radical of at least 30 aliphatic carbon atoms.
  • This invention is directed to an additive composition for improving middle distillate fuel oils comprising (A) from 35 to 55 parts by weight of a hydrocarbyl substituted monosuccinimide dispersant containing from 30 to 200 carbon atoms in the hydrocarbyl group and (B) from 75 to 40 parts by weight of an oil having viscosity ranging from 300 to 350 centistokes at 40°C.
  • the invention is directed to a fuel composition comprising a major amount of a middle distillate fuel oil and a sufficient amount of the additive composition to provide from 35 to 55 parts by weight of (A) a hydrocarbyl substituted monosuccinimide dispersant containing from 30 to 200 carbon atoms in the hydrocarbyl group and from 75 to 40 parts by weight of (B) an oil having viscosity ranging from 300 to 350 centistokes at 40°C, each per million parts by weight of fuel oil.
  • the invention is directed to a method for reducing fouling of fuel oil injectors comprising fueling a device equipped with said injectors with the fuel composition of the invention.
  • the invention is directed to 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.
  • hydrocarbon means a group which is purely hydrocarbon, that is, a compound of hydrogen and carbon containing no hetero atoms.
  • hydrocarbyl or “hydrocarbon based” mean that the group being described has predominantly hydrocarbon character within the context of this invention.
  • Hydrocarbyl groups and hydrocarbon based groups include groups that are purely hydrocarbon in nature, that is, they contain only carbon and hydrogen. They may also include groups containing non-hydrocarbon substituents or atoms which do not alter the predominantly hydrocarbon character of the group. Such substituents may include halo-, alkoxy-, nitro-, etc. These groups also may contain hetero atoms.
  • Suitable hetero atoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen and oxygen. Therefore, while remaining predominantly hydrocarbon in character within the context of this invention, these groups may contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. Thus, the terms “hydrocarbyl” and “hydrocarbon based” are broader than the term “hydrocarbon” since all hydrocarbon groups are also hydrocarbyl or hydrocarbon based groups while the hydrocarbyl or hydrocarbon based groups containing hetero atoms are not hydrocarbon groups.
  • the groups are purely hydrocarbon in nature, that is they are essentially free of atoms other than carbon and hydrogen.
  • the hydrocarbyl and hydrocarbon based groups are preferably free from acetylenic unsaturation; ethylenic unsaturation, when present will generally be such that there is no more than one ethylenic linkage present for every ten carbon-to-carbon bonds.
  • the groups are often completely saturated and therefore contain no ethylenic unsaturation.
  • compositions of this invention comprise a hydrocarbyl substituted monosuccinimide dispersant containing from 30 to 200 carbon atoms in the hydrocarbyl group.
  • R is the hydrocarbyl substituent and X is selected from the group consisting of H, hydrocarbyl containing from 1 to 30 carbon atoms, preferably aliphatic hydrocarbyl, -alkylene-OR 3 wherein R 3 is H or hydrocarbyl, preferably H or lower alkyl, and groups of the formula wherein n has an average value between 1 and 10, the "Alkylene” group has from 1 to 10 carbon atoms, and each R 5 is independently hydrogen or an aliphatic group or a hydroxy substituted or an amino aliphatic group containing up to 30 carbon atoms.
  • the "Alkylene” group is an ethylene or propylene group.
  • Monosuccinimides used in this invention are prepared by methods well known in the art. They are typically prepared by reacting a hydrocarbyl group substituted succinic acylating agent with ammonia or at least one amine having at least one condensable H-N ⁇ group.
  • Hydrocarbyl group substituted succinic acylating agents used in the preparation of the monosuccinimide dispersants used in this invention are hydrocarbyl group substituted succinic acids and reactive equivalents thereof.
  • a reactive equivalent is a reactant that will react in a fashion similar to a hydrocarbyl group substituted succinic acid to form derivatives that are essentially the same as those obtained from the succinic acid.
  • anhydrides, lower alkyl esters, acid-lower alkyl ester and acyl halides will react with amines to form substantially similar products as the corresponding acids.
  • Anhydrides, lower alkyl esters, acid-lower alkyl esters and acyl halides are all considered to be reactive equivalents to the corresponding succinic acid.
  • 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 from 30 to 200 carbon atoms, often from 30, more often from 50 up to 100 carbon atoms.
  • the hydrocarbyl group is most preferably an aliphatic group derived from homopolymerized and interpolymerized polyolefins, wherein the olefins, usually 1-olefins, contain from 2 to 18 carbon atoms. Often the olefins are lower olefins, preferably ethylene, propylene and butenes, typically 1-butene and isobutylene and mixtures thereof, particularly, isobutylene.
  • polyolefin defines a polymer derived from olefins.
  • R is derived from polypropylene.
  • R is derived from ethylene-alpha olefin polymers, including ethylene- ⁇ -olefin-diene polymers, especially those wherein the diene is a non-conjugated diene. Representative of such polymers are the ethylene-propylene copolymers and ethylene-propylene-diene terpolymers.
  • a preferred source of hydrocarbyl groups R are polybutenes obtained by polymerization of a C 4 refinery stream having a butene content of 35 to 75 weight percent and isobutylene content of 15 to 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than 80% of total repeating units) isobutylene repeating units of the configuration These polybutenes are typically monoolefinic, that is they contain but one olefinic bond per molecule.
  • the monoolefinic groups are predominantly vinylidene groups, i.e., groups of the formula especially those of the formula although the polybutenes may also comprise other olefinic configurations.
  • 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 for preparing them are described in U.S. Patents 5,071,919; 5,137,978; 5,137,980; 5,286,823 and 5,408,018, and in published European patent application EP 646103-A1. They are commercially available, for example under the tradenames ULTRAVIS® (BP Chemicals) and GLISSOPAL® (BASF).
  • the hydrocarbyl substituent is a polyisobutenyl group having M n ranging from 400 to 2,500, more often from 800 to 1200.
  • Molecular weights of the polymers are determined using well known methods described in the literature. Examples of procedures for determining the molecular weights are gel permeation chromatography (GPC) (also known as size-exclusion chromatography), light scattering, and vapor phase osmometry (VPO).
  • GPC gel permeation chromatography
  • VPO vapor phase osmometry
  • the GPC technique employs standard materials against which the samples are compared. For best results, standards that are chemically similar to those of the sample are used. For example, for polystyrene polymers, a polystyrene standard, preferably of similar molecular weight, is employed. When standards are dissimilar to the sample, generally relative molecular weights of related polymers can be determined. For example, using a polystyrene standard, relative, but not absolute, molecular weights of a series of polymethacrylates may be determined.
  • Succinic acylating agents and the production thereof are both well 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, particularly lower alkyl esters, acid-esters, and maleic anhydride. Maleic anhydride is preferred. The reaction can be conducted thermally, i.e., by simply combining and heating the reactants or with the addition of chlorine during the reaction. Alternatively, the maleic reactant can be reacted with a halogenated, usually chlorinated, polyolefin. Monosuccination of the polyolefin is desired.
  • Monosuccinimide dispersants are derived by reacting the succinic acylating agents with ammonia or at least one amine having at least one condensable primary amino group.
  • the amines may be monoamines or polyamines, typically polyamines, preferably ethylene polyamines, amine bottoms or amine condensates.
  • the amines can be aliphatic, cycloaliphatic, 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 aliphatic, heterocyclic-substituted aliphatic, heterocyclic-substituted aliphatic, heterocyclic-substituted aliphatic, heterocyclic-sub
  • Monoamines useful in this invention generally contain from 1 to 24 carbon atoms, preferably 1 to 12, and more preferably 1 to 6.
  • Examples of primary monoamines useful in the present invention include methylamine, propylamine, butylamine, cyclopentylamine, dodecylamine, allylamine, cocoamine and stearylamine.
  • the monoamine may be an alkanol amine represented by the formula: H 2 N ⁇ R' ⁇ OH wherein R' is a divalent hydrocarbyl group of about two to 18 carbon atoms, preferably two to four carbon atoms.
  • the group -R'-OH in such formulae represents the hydroxyhydrocarbyl group.
  • R' can be an acyclic, alicyclic or aromatic group. Typically, R' is an acyclic straight or branched alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc. group.
  • alkanolamines examples include monoethanolamine, propanolamine, etc.
  • the hydroxyamines can also be ether N-(hydroxyhydrocarbyl) amines. These are hydroxy poly(hydrocarbyloxy) analogs of the above-described hydroxy amines (these analogs also include hydroxyl-substituted oxyalkylene analogs).
  • N-(hydroxyhydrocarbyl) amines can be conveniently prepared, for example, by reaction of epoxides with ammonia and can be represented by the formula: H 2 N ⁇ (R'O) x ⁇ H, wherein x is a number from 2 to 15 and R' is as described above.
  • ether amines 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, containing from 1 to 24 carbon atoms, R 1 is a divalent hydrocarbyl group, preferably an alkylene group, containing from two to 18 carbon atoms, more preferably two to 4 carbon atoms.
  • R 6 is a hydrocarbyl group, preferably an aliphatic group, more preferably an alkyl group, containing from 1 to 24 carbon atoms
  • R 1 is a divalent hydrocarbyl group, preferably an alkylene group, containing from two to 18 carbon atoms, more preferably two to 4 carbon atoms.
  • Especially preferred ether amines are those available under the name SURFAM® produced and marketed by Sea Land Chemical Co., Westlake, Ohio.
  • the amine may also be a polyamine.
  • the polyamine may be aliphatic, cycloaliphatic, heterocyclic or aromatic.
  • useful polyamines include alkylene polyamines, hydroxy containing polyamines, polyoxyalkylene polyamines, arylpolyamines, and heterocyclic polyamines.
  • Alkylene polyamines are represented by the formula wherein n has an average value between 1 and 10, preferably 2 to 7, more preferably 2 to 5, and the "Alkylene" group has from 1 to 10 carbon atoms, preferably 2 to 6, more preferably 2 to 4.
  • Each R 5 is independently hydrogen, an aliphatic group or a hydroxy-substituted- or amino-substituted- aliphatic group of up to 30 carbon atoms.
  • R 5 is H or lower alkyl, most preferably, H.
  • Alkylene polyamines include methylene-, ethylene-, butylene-, propylene-, pentylene- and other polyamines. Higher homologs and related heterocyclic amines such as N-amino alkyl-substituted piperazines are also included. Specific examples of such polyamines are ethylene diamine, diethylene triamine, triethylene tetramine, tris-(2-aminoethyl)amine, propylene diamine, N,N-dimethylaminopropylamine, trimethylene diamine, tripropylene tetramine, tetraethylene pentamine, hexaethylene heptamine, pentaethylenehexamine, aminoethyl piperazine, etc.
  • Ethylene polyamines such as some of those mentioned above, are preferred. They are described in detail under the heading "Diamines and Higher Amines” in Kirk Othmer's “Encyclopedia of Chemical Technology", 4th Edition, Vol. 8, pages 74-108, John Wiley and Sons, New York (1993) and in Meinhardt, et al, U.S. 4,234,435, both of which are hereby incorporated herein by reference for disclosure of useful polyamines.
  • Such polyamines are most conveniently prepared by the reaction of ethylene dichloride with ammonia or by reaction of an ethylene imine with a ring opening reagent such as water, ammonia, etc.
  • alkylene polyamine bottoms can be characterized as having less than two, usually less than 1% (by weight) material boiling below about 200°C.
  • a typical sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company of Freeport, Texas, designated “E-100” has a specific gravity at 15.6°C of 1.0168, % nitrogen of 33.15 and a viscosity at 40°C of 121 centistokes.
  • Another useful polyamine is a condensation product obtained by reaction of 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.
  • Preferably the hydroxy compounds are polyhydric amines.
  • Polyhydric amines include any of the above-described monoamines reacted with an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) having two to 20 carbon atoms, preferably two to four.
  • polyhydric amines examples include tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane, 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 reactants which react with the polyhydric alcohol or amine to form 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 the above-described "amine bottoms”.
  • the condensation reaction of the polyamine reactant with the hydroxy compound is conducted at an elevated temperature, usually 60°C to 265°C in the presence of an acid catalyst.
  • the polyamines may be hydroxy-containing polyamines provided that they contain at least one condensable primary amino group. These include hydroxy-containing polyamine analogs of hydroxy monoamines, particularly alkoxylated alkylenepolyamines. Such polyamines can be made by reacting the above-described alkylene amines with one or more of the above-described alkylene oxides.
  • alkoxylated alkylenepolyamines include N-(2-hydroxyethyl) ethylenediamine, N,N-di-(2-hydroxyethyl)-ethylenediamine, mono-(hydroxypropyl)-substituted tetraethylene-pentamine, N-(3-hydroxybutyl)-tetramethylene diamine, etc.
  • Higher homologs obtained by condensation of the above illustrated hydroxy-containing polyamines through amino groups or through hydroxy groups are likewise useful. Condensation through amino groups results in a higher amine accompanied by removal of ammonia while condensation through the hydroxy groups results in products containing ether linkages accompanied by removal of water. Mixtures of two or more of any of the aforesaid polyamines are also useful.
  • the polyamines may be polyoxyalkylene polyamines, including polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from 200 to 2000.
  • Polyoxyalkylene polyamines, including polyoxyethylene-polyoxypropylene polyamines, are commercially available, for example under the tradename JEFFAMINE® from Texaco Chemical Co.
  • U.S. Patent numbers 3,804,763 and 3.948,800 contain disclosures of polyoxyalkylene polyamines.
  • the polyamine may be a heterocyclic polyamine.
  • the heterocyclic polyamines include aminoalkyl substituted heterocyclic polyamines such as N-aminoalkyl-thiomorpholines, N-aminoalkylmorpholines, N-aminoalkyl-piperazines, N,N'-bisaminoalkyl piperazines, 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 with oxygen and/or sulfur in the hetero ring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the like.
  • aminoalkylsubstituted piperidines aminoalkylsubstituted piperazines, aminoalkylsubstituted morpholines, pyrrolidine, and aminoalkyl-substituted pyrrolidines, are especially preferred.
  • aminoalkyl substituents are substituted on a nitrogen atom forming part of the hetero ring.
  • heterocyclic amines include N-aminopropylmorpholine, N-amino-ethylpiperazine, and N,N'-diaminoethyl-piperazine.
  • Hydrazine and substituted-hydrazine can also be used to form nitrogen-containing carboxylic dispersants. At least one of the nitrogens in the hydrazine must contain two hydrogens directly bonded thereto.
  • the substituents which may be present on the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, the substituents are alkyl, especially lower alkyl, phenyl, and substituted phenyl such as lower alkoxy-substituted phenyl or lower alkyl-substituted phenyl.
  • substituted hydrazines are methylhydrazine, N,N-dimethylhydrazine, phenylhydrazine, N-(para-nitrophenyl)-hydrazine, N-(para-nitrophenyl)-N-methyl-hydrazine, amino guanidine bicarbonate, and the like.
  • non-monosuccinimide may be formed along with monosuccinimide products.
  • monosuccinimide products include amine salts, amides, and imidazolines as well as mixtures thereof.
  • at least 50 mole % of the succinic acylating agent is converted to monosuccinimide, more preferable at least 75% is converted to monosuccinimide.
  • one or more of the hydrocarbyl substituted succinic acylating agents and one or more amines are heated, optionally in the presence of a normally liquid, substantially inert organic liquid solvent/diluent, at temperatures in the range of from 50°C up to the decomposition point of any of the reactants or the product, but normally at temperatures in the range of from 100°C up to 300°C, provided 300°C does not exceed the decomposition point of a reactant or the product. Temperatures of 100°C, frequently of 125°C to 250°C are normally used.
  • the succinic acylating agent and the amine are reacted in an amount sufficient to provide from about one-half mole up to about 1.1 moles of primary amine per mole of the succinic acylating agent.
  • Succinimide production including monosuccinimide production, is described in, for example, the following patents: U.S. 2,992,708; U.S. 3,018,291; U.S. 3,024,237; U.S. 3,100,673; U.S. 3,172,892; U.S. 3,219,666 and U.S. 3,272,746. These patents describe the production of a wide variety of succinimide type dispersants.
  • a 316 stainless steel vessel is charged with 21 parts polyisobutylene having M n about 1,000 and containing about 83-85 mole percent terminal vinylidene groups (Ultravis 10, BP Chemicals), and heated to 170°C. Pressure is set to 200 kilopascal (kPa) and temperature is ramped to 220°C as maleic anhydride introduced. A total of 4 parts (2 moles per mole of polyisobutylene) is added, the first part over 0.25 hour, the remainder over 1.5 hour. The reaction is then heated for 2 hours at 228°C/200 kPa. Full vacuum is then applied and excess maleic anhydride (1.6 part) is removed. The reactor is depressurized with nitrogen and cooled to 150°C and sampled.
  • polyisobutylene having M n about 1,000 and containing about 83-85 mole percent terminal vinylidene groups (Ultravis 10, BP Chemicals)
  • Pressure is set to 200 kilopascal (kPa) and temperature is ramped to
  • a 1-liter round-bottomed wide necked flask is charged with 400 parts of the filtrate of Part A of Example 2.
  • the reaction mixture is then maintained at 175°C with stirring and the nitrogen flow increased to aid removal off water for a 3 hours yielding 428.8 parts product containing 4.4%N.
  • the amount of distillate collected is 5 parts water and 9.9 parts solvent..
  • TEPA
  • Oils that are useful in this invention may be mineral oils, synthetic oils or vegetable oils. Most often they are mineral oils. The oils have viscosity at 40°C ranging from 300 cSt to 350 cSt.
  • thermally stable oils are preferred. Particularly preferred are hydrotreated oils and solvent neutral oils.
  • the additive compositions of this invention contain from 75 to 40 parts by weight of the oil per 35 to 55 parts by weight of the succinimide dispersant.
  • Middle distillate fuels may be derived from petroleum or from vegetable sources or mixtures thereof. More often, for the purposes of this invention they are petroleum derived materials. Middle distillate fuel oils typically have boiling points ranging from 80°C to 500°C. These include heating oils, kerosene, jet fuels and diesel fuels. All of these types of fuels are contemplated as being within the scope of this invention, but diesel fuels are particularly preferred. These are fuel oils boiling in the range from 160°C up to between 290°C and 360°C. Such materials are described in U.S. Patent 5,997,592 issued to Shell Oil Co.
  • compositions of this invention may be incorporated into the compositions of this invention in conventional amounts.
  • these other materials include cold flow improvers, pour point depressants, storage stabilizers, corrosion inhibitors, cetane improvers, anti-static agents, biocidal additives, smoke suppressants.
  • cold flow improvers pour point depressants
  • storage stabilizers corrosion inhibitors
  • cetane improvers anti-static agents
  • biocidal additives smoke suppressants.
  • smoke suppressants are well known to those of skill in the art. Examples of several types of these additives are given in U.S. Patent 4,943,303.
  • Additive compositions of the present invention are made by mixing components (A) and (B).
  • the mixing may take place in the fuel after each component of the additive composition is added separately to the fuel.
  • the components of the additive composition are first mixed, together with other additives if desired, to form the additive composition which is subsequently combined with the fuel.
  • at least some of the oil (B) is present in the reaction mixture, serving as a diluent during preparation of the dispersant (A).
  • the additive composition comprises from 35 to 55 parts by weight of the dispersant (A) and from 30 to 200 parts by weight of the oil (B). In a preferred embodiment, the additive composition comprises from 35 to 40 parts by weight of (A) and from 60 to 90 parts by weight of (B).
  • Additive compositions of this invention are used in the fuel in amounts sufficient to provide from 35 to 55 parts by weight of (A) a hydrocarbyl substituted succinimide dispersant containing from 30 to 200 carbon atoms in the hydrocarbyl group and from 75 to 40 parts by weight of (B) an oil having viscosity ranging from 300 to 350 centistokes at 40°C, each per million parts by weight of fuel oil.
  • A a hydrocarbyl substituted succinimide dispersant containing from 30 to 200 carbon atoms in the hydrocarbyl group and from 75 to 40 parts by weight of (B) an oil having viscosity ranging from 300 to 350 centistokes at 40°C, each per million parts by weight of fuel oil.
  • the following examples illustrate fuel compositions, including a "good" baseline composition, comparative fuel compositions and fuel compositions of this invention.
  • the base fuel used is Cat 1K Reference Fuel.
  • the indicated products and added oil, if used are blended into the base fuel.
  • the amounts of dispersant on a neat, diluent free basis and total oil or solvent are listed for each composition.
  • Amounts of Dispersant (A), Oil (B) and Solvent are in parts per million parts (ppm) of fuel.
  • the effectiveness of the additive compositions of this invention to improve diesel engine fuel injectors is determined using the Cummins (Cummins Corp., Columbus, IN, USA) L-10 injector depositing test.
  • Cummins Cummins Corp., Columbus, IN, USA
  • This test utilizes two Cummins L-10 engines mounted in a tandem configuration, front to rear, connected flywheel to front crankshaft pulley adapter by a driveshaft. The operating conditions are cyclic, with one engine driving the other in measured intervals. The maximum power generated by the operating engine is the frictional horsepower of the non-running engine.
  • the test operates for a total of 125 hours. Test results include fuel flow data and deposit ratings from each fuel injector. A deposits rating of 10 or lower is desired.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
  • the amount of each chemical component is presented exclusive of any solvent or diluent oil which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined.
  • the expression “consisting essentially of” permits the inclusion of substances which do not materially affect the basic and novel characteristics of the composition under consideration.

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  • 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)
  • Lubricants (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (14)

  1. Composition d'additif permettant d'améliorer des combustibles de distillat moyen comprenant
    (A) de 35 à 55 parties en poids d'un dispersant de type succinimide substitué par un groupe hydrocarbyle qui renferme de 30 à 200 atomes de carbone et
    (B) de 75 à 40 parties en poids d'une huile dont la viscosité varie de 300 à 350 centistokes à 40°C.
  2. Composition d'additif selon la revendication 1, dans laquelle le groupe hydrocarbyle est un groupe hydrocarbyle aliphatique.
  3. Composition d'additif selon la revendication 2, dans laquelle le groupe hydrocarbyle renferme de 30 à 100 atomes de carbone et dérive d'alcènes en C2-18 homopolymérisés et interpolymérisés.
  4. Composition d'additif selon la revendication 3, dans laquelle les alcènes polymérisés sont des 1-alcènes.
  5. Composition d'additif selon la revendication 4, dans laquelle les 1-alcènes sont choisis dans le groupe comprenant l'éthylène, le propylène, le 1-butène, l'isobutylène, et les mélanges de ces composés.
  6. Composition d'additif selon la revendication 2, dans laquelle le groupe hydrocarbyle est un groupe polyisobutènyle dont la masse moléculaire moyenne en nombre varie de 400 à 2 500.
  7. Composition d'additif selon la revendication 1, dans laquelle le succinimide a la formule générale
    Figure 00260001
    dans laquelle R représente un groupe hydrocarbyle renfermant de 30 à 200 atomes de carbone, et dans laquelle le groupe X est choisi parmi un atome d'hydrogène, un groupe hydrocarbyle aliphatique renfermant de 1 à 30 atomes de carbone et un groupe
    Figure 00270001
    dans lequel la valeur moyenne de n varie de 1 à 10, le groupe « alkylène » possède de 1 à 10 atomes de carbone, et chaque groupe R5 représente indépendamment un atome d'hydrogène, un groupe aliphatique ou un groupe amino aliphatique renfermant jusqu'à 30 atomes de carbone.
  8. Composition d'additif selon la revendication 7, dans laquelle le groupe « alkylène » représente un groupe éthylène ou propylène.
  9. Composition d'additif selon la revendication 1, dans laquelle l'huile (B) représente une huile minérale.
  10. Composition de combustible comprenant une quantité importante d'un combustible de distillat moyen et une quantité suffisante de la composition d'additif selon la revendication 1 afin d'obtenir
    (A) de 35 à 55 parties en poids d'un dispersant de type succinimide substitué par un groupe hydrocarbyle qui renferme de 30 à 200 atomes de carbone et
    (B) de 75 à 40 parties en poids d'une huile dont la viscosité varie de 300 à 350 centistokes à 40°C, chacun par million de parties en poids de combustible.
  11. Composition de combustible selon la revendication 10, comprenant de 75 à 130 parties en poids de la composition d'additif selon la revendication 1, par million de parties en poids de combustible.
  12. Composition de combustible selon la revendication 10, dans laquelle le combustible de distillat moyen est un combustible diesel.
  13. Procédé permettant de réduire l'encrassement des injecteurs de combustible qui comprend l'alimentation en combustible d'un dispositif équipé desdits injecteurs avec la composition de combustible selon la revendication 10.
  14. Procédé permettant de faire fonctionner un moteur diesel comprenant le fait de fournir, en tant que combustible, la composition de combustible selon la revendication 10 de manière à réduire l'encrassement des injecteurs de combustible dudit moteur.
EP01961656A 2000-07-19 2001-07-18 Composition additive pour combustibles de distillat moyen et compositions de combustibles de distillat moyen les contenant Expired - Lifetime EP1303577B1 (fr)

Applications Claiming Priority (3)

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US21979100P 2000-07-19 2000-07-19
US219791P 2000-07-19
PCT/US2001/022520 WO2002006428A1 (fr) 2000-07-19 2001-07-18 Composition additive pour combustibles de distillat moyen et compositions de combustibles de distillat moyen les contenant

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AT (1) ATE292665T1 (fr)
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EP1819739B1 (fr) * 2004-12-09 2019-07-24 The Lubrizol Corporation Procédé de préparation d'un additif
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US12187970B2 (en) 2020-11-13 2025-01-07 Ecolab Usa Inc. Synthetic lubricity additives for hydrocarbon fuels

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EP1303577A1 (fr) 2003-04-23
ATE292665T1 (de) 2005-04-15
DE60109936D1 (de) 2005-05-12
DE60109936T2 (de) 2006-02-02
WO2002006428A1 (fr) 2002-01-24

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