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
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
• • 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
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
  • C10L10/16—Pour-point depressants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
  • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1888—Carboxylic acids; metal salts thereof tall oil
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • 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 improvements in fuel oil compositions, and more especially to fuel oil compositions containing detergent species and susceptible to wax formation at low temperatures.
• Fuel oils whether derived from petroleum or from vegetable sources, contain components, e.g., n-alkanes or methyl n-alkanoates, that at low temperature tend to precipitate as large, plate-like crystals or spherulites of wax in such a way as to form a gel structure which causes the fuel to lose its ability to flow.
• the lowest temperature at which the fuel will still flow is known as the pour point.
• WASA wax anti-settling additives
• UK Patent specification No 960,493 describes the incorporation of metal-free detergents, in the form of polyolefin-substituted succinimides of tetraethylene pentamine, in base fuels for internal combustion engines.
• metal-free detergents are now widespread.
• polyisobutylene substituted succinimides which are the reaction products of polyisobutylene substituted acylating agents such as succinic acid or anhydride with polyamines.
• Such materials and their methods of production will be known to those skilled in the art.
• the present invention is based on the discovery that the additional presence of a third co-additive species can restore the low temperature properties of the fuel containing a wax anti-settling additive and a polyamine detergent.
• WO95/03377 describes that certain fuel additives not known for providing improvements in low temperature properties can nevertheless be beneficial to such properties when combined with copolymeric ethylene flow improvers.
• Oil soluble ashless dispersants are disclosed as one such class of fuel additives. Further additives including wax anti-settling additives may additionally be incorporated.
• EP 0 104 015 A describes that certain carboxylic acids, preferably aromatic acids such as benzoic acid, can be used to improve the solubility of certain wax anti-settling additives when they are combined together in a fuel additive concentrate. At least one mole of acid is required per mole of wax anti-settling additive.
• the present invention provides a method of improving the low temperature properties of a fuel oil composition
• a fuel oil composition comprising a major amount of a fuel oil and minor amounts of (a) at least one polar nitrogen compound effective as a wax anti-settling additive and (b) at least one polyamine detergent, the method comprising adding to the composition (c) at least one acidic organic species.
• the present invention provides the use of (c) at least one acidic organic species to improve the low temperature properties of a fuel oil composition; wherein the fuel oil composition comprises a major amount of a fuel oil and minor amounts of (a) at least one polar nitrogen compound effective as a wax anti-settling additive and (b) at least one polyamine detergent.
• the present invention provides the use of (e) at least one acidic organic species to substantially restore a loss in low temperature properties of a fuel oil comprising (a) at least one polar nitrogen compound effective as a wax anti-settling additive, such loss being attributable to the presence of (b) at least one polyamine detergent in the fuel oil.
• the present invention provides a process of ameliorating a negative interaction on the low temperature performance of (a) a polar nitrogen compound effective as a wax anti-settling additive attributable to its use in combination with (b) at least one polyamine detergent, the process comprising:
• an improvement in the low temperature properties can refer to an improvement in terms of either wax anti-settling performance, an improvement in CFPP or preferably an improvement in both properties.
• the invention requires that eider or both, preferably both, of the wax anti-settling behaviour and the CFPP of the fuel oil is improved when (c) is present compared to the situation where (c) is absent. It should be noted that it is not required that either property necessarily reaches the level which would be expected without the presence of (b).
• the use of (c) should return either or both, preferably both, of the wax anti-settling behaviour and the CFPP of the fuel oil to the level which would be expected without the presence of (b).
• the use of the term ‘substantially restore’ should be taken to include the situation where, although the precise numerical value of the property may not be regained, the difference is not practically significant.
• the situation where the use of (c) leads to better low temperature properties than would be expected without the presence of (b) is also included in the scope of the third aspect.
• the fourth aspect should be taken in the same context as the first and second aspects. That is, it is not required that either the wax anti-settling performance or the CFPP of the fuel oil composition manufactured in step (iii) necessarily reaches the level which would be expected without the presence of (b), but simply that at least one property, preferably both, are improved relative to those determined in step (i).
• oil-soluble polar nitrogen compounds carrying one or more, preferably two or more, substituents of the formula >NR 13 , where R 13 represents a hydrocarbyl group containing 8 to 40 atoms, which substituent or one or more of which substituents may be in the form of a cation derived therefrom.
• the oil soluble polar nitrogen compound is generally one capable of acting as a wax crystal growth inhibitor in fuels. It comprises for example one or more of the following compounds:
• An amine salt and/or amide formed by reacting at least one molar proportion of a hydrocarbyl-substituted amine with a molar proportion of a hydrocarbyl acid having from 1 to 4 carboxylic acid groups or its anhydride, the substituent(s) of formula >NR 13 being of the formula —NR 13 R 14 where R 13 is defined as above and R 14 represents hydrogen or R 13 , provided that R 13 , and R 14 may be the same or different, said substituents constituting part of the amine salt and/or amide groups of the compound.
• Ester/amides may be used, containing 30 to 300, preferably 50 to 150, total carbon atoms. These nitrogen compounds are described in U.S. Pat. No. 4,211,534. Suitable amines are predominantly C 12 to C 40 primary, secondary, tertiary or quaternary amines or mixtures thereof but shorter chain amines may be used provided the resulting nitrogen compound is oil soluble, normally containing about 30 to 300 total carbon atoms. The nitrogen compound preferably contains at least one straight chain C 8 to C 40 , preferably C 14 to C 24 , alkyl segment.
• Suitable amines include primary, secondary, tertiary or quaternary, but are preferably secondary. Tertiary and quaternary amines only form amine salts. Examples of amines include tetradecylamine, cocoamine, and hydrogenated tallow amine. Examples of secondary amines include di-octadecylamine, di-cocoamine, di-hydrogenated tallow amine and methylbehenyl amine. Amine mixtures are also suitable such as those derived from natural materials.
• a preferred amine is a secondary hydrogenated tallow amine, the alkyl groups of which are derived from hydrogenated tallow fat composed of approximately 4% C 14 , 31% C 16 , and 59% C 18 .
• carboxylic acids and their anhydrides for preparing the nitrogen compounds include ethylenediamine tetraacetic acid, and carboxylic aids based on cyclic skeletons, e.g., cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid and naphthalene dicarboxylic acid, and 1,4-dicarboxylic acids including dialkyl spirobislactones. Generally, these acids have about 5 to 13 carbon atoms in the cyclic moiety.
• Preferred acids useful in the present invention are benzene dicarboxylic acids, e.g.
• phthalic acid isophthalic acid, and terephthalic acid.
• Phthalic acid and its anhydride are particularly preferred.
• the particularly preferred compound is the amide-amine salt formed by reacting 1 molar portion of phthalic anhydride with 2 molar portions of dihydrogenated tallow amine.
• long chain alkyl or alkylene substituted dicarboxylic acid derivatives such as amine salts of monoamides of substituted succinic acids, examples of which are known in the art and described in U.S. Pat. No. 4,147,520, for example.
• Suitable amines may be those described above.
• polar nitrogen compounds are compounds containing a ring system carrying at least two substituents of the general formula below on the ring system
• A is a linear or branched chain aliphatic hydrocarbylene group optionally interrupted by one or more hetero atoms
• R 15 and R 16 are the same or different and each is independently a hydrocarbyl group containing 9 to 40 atoms optionally interrupted by one or more hetero atoms, the substituents being the same or different and the compound optionally being in the form of a salt thereof.
• A has from 1 to 20 carbon atoms and is preferably a methylene or polymethylene group.
• Suitable amines including primary, secondary tertiary or quaternary, but are preferably secondary.
• amines include tetradecylamine, cocoamine, and hydrogenated tallow amine.
• secondary amines include di-octadecylamine, di-cocoamine, di-hydrogenated tallow amine and methylbehenyl amine, Amine mixtures are also suitable such as those derived from natural materials.
• a preferred amine is a secondary hydrogenated tallow amine, the alkyl groups of which are derived from hydrogenated tallow fat composed of approximately 4% C 14 , 31% C 16 , and 59% C 18 .
• a preferred class of polyamine detergents are those made by reacting an acylating agent having a hydrocarbyl substituent of at least 10 carbon atoms and a nitrogen compound characterized by the presence of at least one —NH— group.
• the acylating agent will be a mono- or polycarboxylic acid (or reactive equivalent thereof) such as a substituted succinic or propionic acid and the amino compound will be a polyamine or mixture of polyamines, most typically, a mixture of ethylene polyamines.
• the amine also may be a hydroxyalkyl-substituted polyamine.
• the hydrocarbyl substituent in such acylating agents preferably averages at least about 30 or 50 and up to about 200 carbon atoms.
• hydrocarbyl substituent groups containing at least 10 carbon atoms are n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, chlorooctadecyl, triicontanyl, etc.
• the hydrocarbyl substituents are made from homo- or interpolymers (e.g. copolymers, terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc.
• these olefins are 1-monoolefins.
• This substituent can also be derived from the halogenated (e.g. chlorinated or brominated) analogs of such homo- or interpolymers.
• the hydrocarbyl substituents are predominantly saturated.
• the hydrocarbyl substituents are also predominantly aliphatic in nature, that is they contain no more than one non-aliphatic moiety (cycloalkyl, cycloalkenyl or aromatic) group of 6 or less carbon atoms for every 10 carbon atoms in the substituent.
• the substituents contain no more than one such non-aliphatic group for every 50 carbon atoms, and in many cases, they contain no such non-aliphatic groups at all; that is, the typically substituents are purely aliphatic.
• these purely aliphatic substituents are alkyl or alkenyl groups.
• a preferred source of the substituents are poly(isobutene)s obtained by polymerization of a C 4 refinery stream having a butene content of 35 to 75 weight percent and isobutene content of 30 to 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes predominantly contain monomer repeating units of the configuration —C(CH 3 ) 2 CH 2 —.
• hydrocarbyl substituent is attached to the succinic acid moiety or derivative thereof via conventional means, for example the reaction between maleic anhydride and an unsaturated substituent precursor such as a polyalkene, as described for example in EP-B-0 451 380.
• One procedure for preparing the substituted succinic acylating agents involves first chlorinating the polyalkene until there is an average of at least about one chloro group for each molecule of polyalkene. Chlorination involves merely contacting the polyalkene with chlorine gas until the desired amount of chlorine is incorporated into the chlorinated polyalkene. Chlorination is generally carried out at a temperature of about 75° C. to about 125° C. If desired, a diluent can be used in the chlorination procedure. Suitable diluents for this purpose include poly- and perchlorinated and/or fluorinated alkanes and benzenes.
• the second step in the procedure is to react the chlorinated polyalkene with the maleic reactant at a temperature usually within the range of about 100° C. to about 200° C.
• the mole ratio of chlorinated polyalkene to maleic reactant is usually about 1:1.
• a stoichiomeic excess of maleic reactant can be used, for example, a mole ratio of 1:2. If an average of more than about one chloro group per molecule of polyalkene is introduced during the chlorination step, then more than one mole of maleic reactant can react per molecule of chlorinated polyalkene. It is normally desirable to provide an excess of maleic reactant; for example, an excess of about 5% to about 50%, for example 25% by weight. Unreacted excess maleic reactant may be stripped from the reaction product, usually under vacuum.
• Another procedure for preparing substituted succinic acid acylating agents utilizes a process described in U.S. Pat. No. 3,912,764 and U.K. Pat. No. 1,440,219.
• the polyalkene and the maleic reactant are first reacted by heating them together in a direct alkylation procedure.
• chlorine is introduced into the reaction mixture to promote reaction of the remaining unreacted maleic reactants.
• 0.3 to 2 or more moles of maleic anhydride are used in the reaction for each mole of polyalkene.
• the direct alkylation step is conducted at temperatures to 180° C. to 250° C. During the chlorine-introducing stage, a temperature of 160° C. to 225° C. is employed.
• the attachment of the hydrocarbyl substituent to the succinic moiety may alternatively be achieved via the thermally-driven ‘ene’ reaction, in the absence of chlorine.
• Use of such a material a the acylating agent leads to products having particular advantages; for example, chlorine-free products having excellent detergency and lubricity properties.
• the reactant is preferably formed from a polyalkene having at least 30% preferably 50% or more such as 75% of residual unsaturation in the form of terminal, e.g. vinylidene, double bonds.
• Suitable polyamines are those comprising amino nitrogens linked by alkylene bridges, which amino nitrogens may be primary, secondary and/or tertiary in nature.
• the polyamines may be straight chain, wherein all the amino groups will be primary or secondary groups, or may contain cyclic or branched regions or both, in which case tertiary amino groups may also be present.
• the alkylene groups are preferably ethylene or propylene groups, with ethylene being preferred.
• Such materials may be prepared from the polymerization of lower alkylene diamines such as ethylene diamine, a mixture of polyamines being obtained, or via the reaction of dichloroethane and ammonia.
• polyalkylene polyamines (1) are ethylene diamine, tetra(ethylene)pentamine, tri-(trimethylene)tetramine and 1,2-propylene diamine.
• hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl)ethylene diamine, N,N 1 -bis-(2-hydroxyethyl)ethylene diamine, N-(3-hydroxybutyl) tetramethylene diamine, etc.
• heterocyclic-substituted polyamines (2) are N-2-aminoethyl piperazine, N-2 and N-3 amino propyl morpholine, N-3-(dimethylamino) propyl piperazine, 2-heptyl-3-(2-aminopropyl) imidazoline, 1,4-bis(2-aminoethyl)piperazine, 1-(2-hydroxy ethyl)piperazine, and 2-heptadecyl-1-(2-hydroxyethyl)-imidazoline, etc.
• aromatic polyamines (3) are the various isomeric phenylene diamines, the various isomeric naphthalene diamines, etc.
• a typical and preferred compound of this class is that made by reacting a poly(isobutylene)-substituted succinic anhydride acylating agent (e.g.
• poly(isobutene) substituent has between about 50 to about 200 carbon atoms with a mixture of ethylene polyamines having 3 to about 10 amino nitrogen atoms per ethylene polyamine and about 1 to about 6 ethylene groups.
• the polyamine component may be defined by the average numrber of nitrogen atoms per molecule of the component, which may preferably be in the range of 4 to 8.5, more preferably 6.8 to 8, especially 6.8 to 7.5 nitrogens per molecule.
• amine mixtures comprising polyamines having seven and eight, and optionally nine, nitrogen atoms per molecule (so-called ‘heavy’ polyamines).
• the polyamine mixture comprises at least 45% and preferably 50% by weight of polyamines having seven nitrogen atoms per molecule, based on the total weight of polyamines.
• single species may also be used, for example TEPA and TETA.
• a preferred polyamine detergent comprises the reaction product between a poly(isobutene) substituted succinic anhydride acylating agent with a polyamine or mixture of polyamines as hereinbefore described.
• the poly(isobutene) has a number average molecular weight (Mn) of about 400-2500, preferably 400-1300, such as about 950.
• a range of acidic organic species have been found to be effective in the present invention.
• One class of species are unsaturated, monocarboxylic acids, particularly aliphatic acids having between 8 and 30 carbon atoms.
• Preferred in this class are the fatty acids, preferably fatty acids with 12 to 22 carbon atoms. Examples include lauric acid, palmitoleic acid, oleic acid, elaidic acid, petroselic acid, ricinoleic acid, elaeostearic acid, linoleic acid, linolenic acid, gadoleic acid, or erucic acid.
• Mixtures of fatty acids such as those obtained from natural sources are also suitable. Examples include rape-seed oil fatty acid, soya fatty acid and tall oil fatty acid.
• Saturated carboxylic acids are also suitable with the proviso that saturated acids containing straight-chains of 10 or more carbon atoms have been found not to be effective.
• Non-limiting examples include acetic acid, propionic acid, butyric acid,
• Acids if unsaturated, may be linear or branched. Saturated acids, provided that the proviso above is applied may be linear, or they may be branched. Non-limiting examples of branched acids include neodecanoic acid and neo-tridecoanoic acid.
• Polycarboxylic acids are also suitable, for example hydrocarbyl-substituted succinic acids or dimer, trimer and higher oligomer acids derived from fatty acids.
• Acids comprising aromatic ring systems are also suitable.
• Non-limiting examples include benzoic acid, salicylic acid and similar.
• Non-aromatic, cyclic acids may be used. These may be single rings or used ring structures and may contain unsaturation. Non-limiting examples include naphthenic acids and resin acids such as abietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, levopimaric acid, parastrinic acid and similar.
• the acidic organic species comprises an unsaturated, monocarboxylic acid having between 8 and 30 carbon atoms, preferably between 12 and 22 carbon atoms.
• the fuel oil may be, e.g., a petroleum-based fuel oil, especially a middle distillate fuel oil.
• Such distillate fuel oils generally boil within the range of from 110° C. to 500° C., e.g., 150° C. to 400° C.
• the invention is applicable to middle distillate fuel oils of all types, including the broad-boiling distillates, i.e., those having a 90%-20% boiling temperature difference, as measured in accordance with ASTM D-86, of 50° C. or more.
• the fuel oil may comprise atmospheric distillate or vacuum distillate, cracked gas oil, or a blend in any proportion of straight run and thermally and/or catalytically cracked distillates.
• the most common petroleum distillate fuels are kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils.
• the heating oil may be a straight atmospheric distillate, or may also contain vacuum gas oil or cracked gas oil or both.
• the fuels may also contain major or minor amounts of components derived from the Fischer-Tropsch process.
• Fischer-Tropsch fuels also known as FT fuels, include those that are described as gas-to-liquid fuels, coal and/or biomass conversion fuels.
• syngas CO+H 2
• the normal paraffins may then be modified by processes such as catalytic cracking/reforming or isomerisation, hydrocracking and hydroisomerisation to yield a variety of hydrocarbons such as iso-paraffins, cyclo-paraffins and aromatic compounds.
• the resulting FT fuel can be used as such or in combination with other fuel components and fuel types such as those mentioned in this specification.
• the above mentioned low temperature flow problem is most usually encountered with diesel fuels and with heating oils.
• the invention is also applicable to fuel oils containing fatty acid methyl esters derived from vegetable oils, for example, rapeseed methyl ester, either used alone or in admixture with a petroleum distillate oil.
• the fuel oil is preferably a low sulphur content fuel oil.
• the sulphur content of the fuel oil will be less than 500 ppm (parts per million by weight).
• the sulphur content of the fuel will be less than 100 ppm, for example, less than 50 ppm.
• Fuel oils with even lower sulphur contents, for example less that 20 ppm or less than 10 ppm are also suitable.
• each component present in the fuel oil will depend on the nature of the species used, the properties of the fuel oil and the low temperature performance required. As discussed hereinabove, the present invention is based on the observation of a negative impact on the low temperature behaviour of the wax anti-settling additive when present in premium diesel fuels which contain relatively high levels of polyamine detergent.
• the amount of (b) at least one polyamine detergent in the fuel oil composition will be in excess of 50 ppm by weight based on the weight of the fuel oil, for example in excess of 75 ppm by weight or 100 ppm by weight.
• Some premium diesel fuels may contain up to 500 ppm by weight of polyamine detergent. This can be compared to a treat rate of around 10-75 ppm for more conventional, non-premium diesel fuels.
• the amount of (a) at least one polar nitrogen compound effective as a wax anti-settling additive will typically be in the range of 10-300 ppm, preferably 10-100 ppm by weight based on the weight of the fuel oil.
• the amount of (c) used will typically be in the range of 5-200, preferably, 5-150, more preferably 5-100, for example 10-50 ppm by weight based on the weight of the fuel oil.
• the fuel oil further comprises an ethylene-unsaturated ester copolyner.
• the method of the first aspect, the uses of the second and third aspects and the process of the fourth aspect all require that the low temperature properties of the fuel oil composition be measured.
• the low temperature properties are as determined by measuring ⁇ CP, CFPP, or both.
• the low temperature properties improved in all aspects of the present invention are ⁇ CP, CFPP, or both.
• ⁇ CP is a measurement of the propensity of the wax content of a fuel oil to settle and thus a determination of the effectiveness of a wax anti-settling additive.
• CP cloud point
• the wax anti-settling additive under study is then added to the base fuel and the sample cooled to a temperature below the measured CP. This temperature may vary, in Germany a temperature of ⁇ 13° C. is commonly used, in South Korea it may be ⁇ 15 or ⁇ 20° C. and a value of ⁇ 18° C. is also often used.
• the CP of the bottom 20% by volume of the sample is measured. The difference between this measurement and the value obtained for the base fuel is ⁇ CP.
• a small value, preferably around zero, of ⁇ CP indicates good wax dispersancy.
• CFPP is a standard industry test to evaluate the ability of a fuel oil sample to flow through a filter at reduced temperature.
• the test which is carried out by the procedure described in detail in “ Jn. Of the Institute of Petroleum ”, vol. 52, No. 510 (1996), pp 173-285, is designed to correlate with the cold flow of a middle distillate in automotive diesels.
• a sample of the oil to be tested (40 cm 3 ) is cooled in a bath which is maintained at about ⁇ 34° C. to give linear cooling at about 1° C./min.
• the oil Periodically (at each one degree centigrade starting from above the cloud point), the oil is tested for its ability to flow through a fine screen in a prescribed time period using a test device which is a pipette to whose lower end is attached an inverted funnel which is positioned below the surface of the oil to be tested. Stretched across the mouth of the funnel is a 350 mesh screen having an area defined by a 12 mm diameter.
• the periodic tests are initiated by applying a vacuum to the upper end of the pipette whereby oil is drawn through the screen up into the pipette to a mark indicating 20 cm 3 of oil. After each successful passage, the oil is returned immediately to the CFPP tube. The test is repeated with each one degree drop in temperature until the oil fails to fill the pipette within 60 seconds, the temperature at which failure occurs being reported as the CFPP temperature.
• the present invention encompasses a method for improving the low temperature properties of a fuel oil composition
• a method for improving the low temperature properties of a fuel oil composition comprising adding at least one acidic organic species to a fuel oil composition; wherein the fuel oil composition comprises a major amount of a fuel oil and minor amounts of (a) at least one polar nitrogen compound effective as a wax anti-settling additive and (b) at least one polyamine detergent.
• the present invention encompasses a method for restoring a loss in low temperature properties of a fuel oil comprising adding at least one acidic organic species comprising at least one polar nitrogen compound to a faet oil.
• the polar nitrogen compound effective as a wax anti-settling used was an N,N-dialkylammonium salt of 2-N′,N′dialkylamidobenzoate, the product of reacting one mole of phthalic hydride and two moles of di(hydrogenated tallow) amine.
• the polyamine detergent used was a PIBSA-PAM detergent, the product of reacting a polyisobutylene-substituted succinic anhydride, the polyisobutylene group having a molecular weight of ca. 1000, with a polyamine mixture predominating in species having at least seven nitrogen atoms per molecule.
• the diesel fuel also contained fixed amounts of additional cold-flow additives. These are typical of additives routinely used in commercial diesel fuels and were mainly ethylene-unsaturated ester co-polymers and fumarate vinyl acetate co-polymers. All amounts are given in ppm of active ingredient (i.e. ingredient which is not solvent or carrier) by weight, based on the weight of the fuel.
• the fuel was cooled to ⁇ 18° C.
• Table 1 gives results showing the effect of an acidic organic species comprising a mixture of fatty acids predominating in straight-chain C18 mono- and di-unsaturated mono-carboxylic acids.
• Table 3 shows the results for several other organic acids. As with Tables 1 and 2, all show an improvement in either CFPP, ⁇ CP or both compared to Comparative Examples 1-4.

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• 2007
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