EP0255345B1 - Compositions de combustibles liquides - Google Patents

Compositions de combustibles liquides Download PDF

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Publication number
EP0255345B1
EP0255345B1 EP87306670A EP87306670A EP0255345B1 EP 0255345 B1 EP0255345 B1 EP 0255345B1 EP 87306670 A EP87306670 A EP 87306670A EP 87306670 A EP87306670 A EP 87306670A EP 0255345 B1 EP0255345 B1 EP 0255345B1
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EP
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Prior art keywords
wax
fuel
copolymer
ethylene
distillate
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EP87306670A
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German (de)
English (en)
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EP0255345A1 (fr
Inventor
June Kathleen Costello
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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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
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1691—Hydrocarbons petroleum waxes, mineral waxes; paraffines; alkylation products; Friedel-Crafts condensation products; petroleum resins; modified waxes (oxidised)
    • 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
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • 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
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides

Definitions

  • This invention relates to distillate fuel compositions containing a flow improver.
  • Heating oils and other distillate petroleum fuels e.g. diesel fuels
  • the lowest temperature at which the fuel will still flow is generally known as the pour point.
  • Effective wax crystal modification (as measured by CFPP and other operability tests, as well as simulated and field performance) can be achieved by flow improvers, mostly ethylene-vinyl acetate copolymer (EVA) based, in distillates containing up to 4 wt%-n-alkanes at 10°C below cloud point, as determined by gravimetric or DSC methods. Additive response in these distillates is normally stimulated by the refiner adjusting ASTM D-86 distillation characteristics of the distillates to increase the tail 90% to Final Boiling Point to deltas between 20°C and 25°C.
  • EVA ethylene-vinyl acetate copolymer
  • US-A-3640691 proposes that the response of the same types of middle distillate to similar additives may be improved by the addition of a paraffinic distillate fraction containing normal alkanes higher than n-nexacosane and as high as n-tetracontane to provide from 0.1 to 2 wt.% of normal alkanes of C24 and higher.
  • a paraffinic distillate fraction containing normal alkanes higher than n-nexacosane and as high as n-tetracontane to provide from 0.1 to 2 wt.% of normal alkanes of C24 and higher.
  • a paraffinic distillate fraction containing normal alkanes higher than n-nexacosane and as high as n-tetracontane to provide from 0.1 to 2 wt.% of normal alkanes of C24 and higher.
  • the most difficult to treat are those fuels obtained from high wax crudes such as those from the crudes in Australia and the Far East where the total n alkane content of the distillate can be greater than 20%, the total content being C12 and higher n-alkanes as measured by Gas Liquid Chromatography.
  • a middle distillate responsive to flow improvers may be obtained by adjusting the total wax content of the fuel to between 5.5 and 12 wt.%, preferably by blending of high and low wax content fuels, the wax content being that precipitated with methyl ethyl ketone from a 1 gram of the fuel at -20°C.
  • This technique is not a satisfactory indication of the wax content of the fuel to be treated by the additives since it is the wax precipitated between the cloud point of the fuel and its operability point which is treated by the additive and which is important to the low temperature characteristics of the fuel.
  • the ability of these fuels to respond to flow improvers is not dependent on the total wax content of the fuel.
  • a typical hard to treat distillate fuel containing 5 to 10 wt.% wax at 10°C below its cloud point and/or greater than 20 wt.% n-alkanes C 12+ has the following ASTM D-86 characteristics: Initial Boiling Point 212°C 5% 234°C 10% 243°C 20% 255°C 30% 263°C 40% 279°C 50% 288°C 60% 298°C 70% 303°C 80% 321°C 90% 334°C 95% 343°C Final Boiling Point 361°C
  • a liquid fuel composition comprises a major proportion by weight of a distillate fuel containing between 4 and 10 wt.% wax at 10°C below cloud point and having a narrow n-alkane distribution, i.e. containing substantially no paraffins longer than n-triacontane (C30), 0.001 to 2.0 wt.% based on the weight of the distillate fuel of a copolymer of ethylene and at least one second unsaturated monomer and 0.1 to 0.5 wt.% of a hydrocarbon wax.
  • Also according to this invention is the use as a cold flow improver for a distillate fuel containing between 4 and 10 wt.% of wax at 10°C below cloud point and having a narrow carbon distribution, i.e. containing substantially no paraffins longer than n-triacontane (C30) of a mixture of 0.1 to 0.5 wt % of a hydrocarbon wax and 0.001 to 2.0 wt % of a copolymer of ethylene and at least one second unsaturated monomer.
  • n-triacontane C30
  • the second unsaturated monomer can be another monoolefin, e.g. a C3 to C18 alpha-monoolefin or it can be an unsaturated ester, as for example, vinyl acetate, vinyl butyrate, vinyl propionate, lauryl methacrylate, ethyl acrylate or the like.
  • the second monomer can also be a mixture of an unsaturated mono or diester and a branched or straight chain alpha monoolefin.
  • Mixtures of copolymers can also be used, as for example mixtures of a copolymer of ethylene and vinyl acetate with an alkylated polystyrene or with an acylated polystyrene.
  • Alternative materials are the amino succinic acid derivatives, esters such as polyacrylates and esterified maleic anhydride copolymers, polyalpha olefins, etc.
  • the preferred copolymer useful in this invention consists of 1 to 40, and preferably 1 to 20, more preferably 3 to 20 molar proportions of ethylene per molar proportion of the ethylenically unsaturated monomer, which latter monomer can be a single monomer or a mixture of such monomers in any proportion, said polymer being oil soluble and having a number average molecular weight in the range of about 1,000 to 50,000, preferably about 1,000 to about 5,000.
  • Molecular weights can be measured by cryoscopic methods or by vapor phase osmometry, for example by using a Mechrolab Vapor Phase OsmometerModel 310A.
  • the unsaturated monomers which may be homopolymerised or copolymerised with ethylene or with each other include unsaturated acids, acid anhydrides, and mono and diesters of the general formula: wherein R1 is hydrogen or methyl; R3 is a -OOCR4 or -COOR4 group wherein R4 is hydrogen or a C1 to C16, preferably C1 to C4 straight or branched chain alkyl group and R3 is hydrogen or -COOR4.
  • the monomer, when R1 to R3 are hydrogen and R2 is -OOCR4 includes vinyl alcohol esters of C2 to C17 monocarboxylic acids.
  • esters examples include vinyl acetate, vinyl isobutyrate, vinyl laurate, vinyl myristate, vinyl palmitate, etc.
  • R2 is -COOR4
  • esters include C8 oxo alcohol acrylate, methyl-acrylate, methyl methacrylate, lauryl acrylate, isobutyl methacrylate, palmityl alcohol ester of alpha-methacylic acid, C13 oxo alcohol esters of methacrylic acid, etc.
  • Examples of monomers wherein R1 is hydrogen and R2 and R3 are-OOCR4 groups include mono C12 oxo alcohol fumarate, di-isopropyl maleate; di-lauryl fumarate; ethyl methyl fumarate; fumaric acid, maleic acid, etc.
  • R2 is H and R1 is COOR4 and R3 is CH2 COOR4 such as the itaconates.
  • unsaturated monomers copolymerizable with ethylene to prepare copolymer useful in this invention include C3 to C16 branched chain or straight-chain alpha monoolefins, as for example, propylene, n-octene-1, 2-ethyl decene-1, n-decene-1, etc.
  • a C2 to C16 branched or straight-chain alpha monoolefin e.g. propylene, n-octene-1, n-decene-1, etc.
  • copolymers of 3 to 40 moles of ethylene with one mole of a mixture of 30 to 99 mole percent of unsaturated ester and 70 to 1 mole percent of olefin could be used.
  • copolymers that are formed are random copolymers consisting primarily of an ethylene polymer backbone along which are distributed side chains of hydrocarbon or oxy-substituted hydrocarbon.
  • the alcohols used in preparing the esters mentioned above are isomeric mixtures of branched chain aliphatic primary alcohols prepared from olefins, such as polymers and copolymers of C3 to C4 monoolefins, reacted with carbon monoxide and hydrogen in the presence of a cobalt-containing catalyst such as cobalt carbonyl, at temperatures of about 148.9-204,4°C (300°F to 400°F), under pressures of about 69.0-206,8 bar (1,000 to 3,000 p.s.i.) to form aldehydes.
  • the resulting aldehyde product is then hydrogenated to form the alcohol, the latter being recovered by distillation from the hydrogenated product.
  • the copolymers have a low degree of side chain branching; particularly they contain less than 10 preferably less than 8 methyl terminating side chains (other than the ester groups) per 100 methyl groups as measured by nuclear magnetic resonance, particularly 500 megaherz proton NMR analysis.
  • the copolymer is used in a concentration in the range of from about 0.001 to about 2 wt.%, preferably from about 0.005 to about 0.2 percent by weight, based on the weight of the distillate fuel being treated.
  • the second additive is a wax, preferably having a carbon number distribution from about 20 to about 40.
  • the wax consist predominantly of linear alkanes although it may also contain a small amount of branched hydrocarbons. It is believed that the wax nucleates the crystallisation of the n-alkanes in the fuel and also co-crystallises with the first n-alkanes to precipitate from the fuel. The preferred n-alkane distribution of the added wax therefore depends upon the particular fuel.
  • additives may also be used to give further improvements in low temperature properties, for example a diamide or preferably a half amide, half amine salt of a dicarboxylic acid or anhydride such as phthalic anhydride, and a secondary amine, the alkyl groups preferably containing 12 to 20 carbon atoms may be added.
  • a particularly preferred compound is the half amide, half amine salt of phthalic acid and dihydrogenated tallow amine - Armeen 2HT (approx. 4 wt.% n-C14 alkyl, 30 wt.% n-C16 alkyl, 60 wt.% n-C18 alkyl, the remainder being unsaturated).
  • the amount of diamide or half amide, half amine salt which is added is usually 0.001 to 2 wt.%, preferably 0.005 to 0.2 wt.%, based on the weight of distillate fuel.
  • glycol esters such as those defined in our EP-B-0 061 895
  • esters and amines of maleic anhydide copolymers such as those defined in EP-A-0214786
  • polyolefines and chlorinated polyolefines and the amines or amides of alkyl succinic anhydrides.
  • the cold flow properties of the distillate fuel can be further improved by adding thereto a wax-naphthalene condensate.
  • a typical condensate is prepared by chlorinating a wax containing n- and branched C18 to C39 paraffins (C26 average) to obtain a chlorinated wax containing about 15 weight % chlorine.
  • the chlorowax thus obtained is polymerised with naphthalene via an alkylation reaction to give a condensate using containing alternating wax and naphthalene units.
  • the amount of condensate added is usually 0.00005 to 0.1 wt.% based on the weight of the distillate fuel.
  • the additives of the present invention may be supplied as concentrates for incorporation into the bulk fuel, such a concentrate comprising a solution containing from 30 to 70 wt.% preferably, 40 to 60 wt.% of a mixture of the copolymer of ethylene and another ethylenically unsaturated monomer and the hydrocarbon wax.
  • CFPPT cold filter plugging point test
  • 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 the last filtration commenced is recorded and reported as the cold filter plugging point.
  • the value for the untreated fuel and the fuel containing 1500 ppm of the ethylene/vinyl acetate copolymer solution as sole additive was -1°C.
  • n-alkane distributions of these waxes are as follows: The treated fuels were tested in the CFPP test with the following results: Use of each wax as sole additive had no effect on the CFPP performance.
  • This example shows the effects of the addition of wax to a base of cloud point +5°C distillate fuel obtained from a chinese crude.
  • the D-86 distillation of the distillate was:. IBP 205 10% 233 20% 245 50% 278 90% 335 FBP 355
  • N-alkanes Base Fuel Wax B Wax E Wax F Wax G C10 0.36 C11 1.02 C12 2.13 C13 2.89 C14 2.80 C15 2.92 C16 2.81 C17 2.82 C18 2.71 C19 2.53 C20 2.36 0.03 0.20 C21 2.02 0.25 0.10 0.14 0.13 C22 1.56 1.31 0.60 0.87 0.56 C23 1.19 3.75 3.00 2.83 1.74 C24 0.63 7.12 8.63 6.15 3.81 C25 0.39 8.73 13.08 9.66 7.26 C26 0.19 10.00 15.43 13.44 10.72 C27 0.08 8.85 12.16 14.47 13.91 C28 0.04 8.08 9.20 13.92 15.12 C29 0.01 6.77 6.24 11.17 11.50 C30 0.004 5.70 4.23 6.65 7.19 C31 4.34 2.67 3.13 3.12 C32 3.53 1.62 1.22 1.13 C33 2.52 1.11 0.43 0.81 C34 1.79 0.69 0.20 0.50 C35 1.09 0.
  • additive treat rates are amounts of polymer

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (9)

  1. Composition de combustible liquide comprenant une proportion dominante, en poids, d'un combustible distillé contenant 4 à 10 % en poids d'une cire à une température inférieure de 10°C au point de trouble et ne contenant pratiquement aucune paraffines plus longues que le n-triacontane, 0,001 à 2,0 % en poids, sur la base du poids du combustible distillé, d'un copolymère d'éthylène et d'au moins un second monomère insature, et 0,1 à 0,5 % en poids d'une cire hydrocarbonée.
  2. Composition suivant la revendication 1, dans laquelle le combustible distillé contient environ 8 % en poids de cire à une température inférieure de 10°C au point de trouble.
  3. Composition suivant la revendication 1 ou la revendication 2, dans laquelle la quantité de copolymère est comprise dans l'intervalle de 0,005 à 0,2 % en poids, sur la base du poids du combustible distillé.
  4. Composition suivant l'une quelconque des revendications précédentes, dans laquelle la cire hydrocarbonée possède une distribution du nombre d'atomes de carbone de 20 à 40.
  5. Composition suivant l'une quelconque des revendications précédentes, dans laquelle le combustible possède un point d'ébullition final inférieur à 370°C.
  6. Utilisation, comme agent améliorant l'écoulement à froid pour un combustible distillé contenant 4 à 10 % en poids d'une cire à une température inférieure de 10°C au point de trouble et ne contenant aucune parrafines plus longues que le n-triacontane, d'un mélange de 0,1 à 0,5 % en poids d'une cire hydrocarbonée et de 0,001 à 2,0 % en poids d'un copolymère d'éthylène et d'au moins un second monomère insaturé.
  7. Utilisation suivant la revendication 6, dans laquelle la cire contient 20 à environ 40 atomes de carbone.
  8. Utilisation suivant la revendication 6 ou 7, dans laquelle le copolymère est un copolymère d'éthylène et d'un ester insaturé.
  9. Utilisation suivant la revendication 8, dans laquelle l'ester insaturé est l'acétate de vinyle.
EP87306670A 1986-07-29 1987-07-28 Compositions de combustibles liquides Expired - Lifetime EP0255345B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB868618397A GB8618397D0 (en) 1986-07-29 1986-07-29 Liquid fuel compositions
GB8618397 1986-07-29

Publications (2)

Publication Number Publication Date
EP0255345A1 EP0255345A1 (fr) 1988-02-03
EP0255345B1 true EP0255345B1 (fr) 1992-11-25

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EP87306670A Expired - Lifetime EP0255345B1 (fr) 1986-07-29 1987-07-28 Compositions de combustibles liquides

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EP (1) EP0255345B1 (fr)
JP (1) JP2541993B2 (fr)
KR (1) KR950014389B1 (fr)
CN (1) CN1020631C (fr)
DE (1) DE3782773T2 (fr)
ES (1) ES2052569T3 (fr)
GB (1) GB8618397D0 (fr)
IN (1) IN168378B (fr)

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GB9301752D0 (en) * 1993-01-29 1993-03-17 Exxon Chemical Patents Inc Oil and fuel oil compositions
GB9725582D0 (en) * 1997-12-03 1998-02-04 Exxon Chemical Patents Inc Fuel oil additives and compositions
GB9725579D0 (en) 1997-12-03 1998-02-04 Exxon Chemical Patents Inc Additives and oil compositions
GB9725581D0 (en) * 1997-12-03 1998-02-04 Exxon Chemical Patents Inc Additives and oil compositions
GB9725578D0 (en) 1997-12-03 1998-02-04 Exxon Chemical Patents Inc Oil additives and compositions
US6136049A (en) * 1998-05-15 2000-10-24 Tonen Corporation Diesel fuel oil composition
GB9827366D0 (en) * 1998-12-11 1999-02-03 Exxon Chemical Patents Inc Macromolecular materials
US9051527B2 (en) * 2005-02-11 2015-06-09 Infineum International Limited Fuel oil compositions
EP1690919B1 (fr) * 2005-02-11 2016-03-02 Infineum International Limited Compositions d'huile combustible
EP2078743A1 (fr) 2008-01-10 2009-07-15 Shell Internationale Researchmaatschappij B.V. Composition de carburant

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3620696A (en) * 1968-09-17 1971-11-16 Exxon Research Engineering Co Fuel oil with improved flow properties
US3640691A (en) * 1968-09-17 1972-02-08 Exxon Research Engineering Co Enhancing low-temperature flow properties of fuel oil
GB1264638A (fr) * 1968-09-17 1972-02-23
US3733184A (en) * 1971-02-09 1973-05-15 Exxon Co Composition for improving air-fuel ratio distribution in internal combustion engines
AR208270A1 (es) * 1972-05-08 1976-12-20 Texaco Development Corp Un poli(acrilato de n-alquilo)interpolimerico
US4153423A (en) * 1975-03-28 1979-05-08 Exxon Research & Engineering Co. Polymer combinations useful in distillate hydrocarbon oils to improve cold flow properties
DE2837341C2 (de) * 1978-08-26 1983-02-17 Akzo Gmbh, 5600 Wuppertal Verfahren zur Herstellung von organischen Mono- und Polyisocyanaten durch thermische Spaltung der Hydrochloride trisubstituierter Harnstoffe
US4464182A (en) * 1981-03-31 1984-08-07 Exxon Research & Engineering Co. Glycol ester flow improver additive for distillate fuels
JPS57207696A (en) * 1981-06-17 1982-12-20 Nippon Sekiyu Seisei Kk Diesel gas oil composition
JPS5839472A (ja) * 1981-09-03 1983-03-08 Mitsubishi Electric Corp プリンタ装置
JPS5880386A (ja) * 1981-11-06 1983-05-14 Nippon Cooper Kk 燃料油添加剤
JPS597757A (ja) * 1982-07-05 1984-01-14 Diesel Kiki Co Ltd 内燃スタ−リング機関
JPS602355A (ja) * 1983-06-21 1985-01-08 第一工業製薬株式会社 金属塗装物
JPS6017320A (ja) * 1983-07-08 1985-01-29 Tsuneo Hirai 粉粒体分配供給方法
JPS6035396A (ja) * 1984-06-15 1985-02-23 Nec Corp 半導体メモリ装置の駆動方法
GB8609293D0 (en) * 1986-03-18 1986-05-21 Exxon Chemical Patents Inc Liquid fuel compositions

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Publication number Publication date
CN87106411A (zh) 1988-04-13
JPS63108096A (ja) 1988-05-12
DE3782773T2 (de) 1993-04-01
DE3782773D1 (de) 1993-01-07
GB8618397D0 (en) 1986-09-03
ES2052569T3 (es) 1994-07-16
IN168378B (fr) 1991-03-23
KR880001795A (ko) 1988-04-26
EP0255345A1 (fr) 1988-02-03
CN1020631C (zh) 1993-05-12
KR950014389B1 (ko) 1995-11-27
JP2541993B2 (ja) 1996-10-09

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