EP0343981B2 - Utilisation d'un additif dans une composition de fuel-oil comme agent améliorant l'écoulement - Google Patents

Utilisation d'un additif dans une composition de fuel-oil comme agent améliorant l'écoulement Download PDF

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EP0343981B2
EP0343981B2 EP89305290A EP89305290A EP0343981B2 EP 0343981 B2 EP0343981 B2 EP 0343981B2 EP 89305290 A EP89305290 A EP 89305290A EP 89305290 A EP89305290 A EP 89305290A EP 0343981 B2 EP0343981 B2 EP 0343981B2
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copolymer
polymer
amine
alkyl
salt
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EP0343981A1 (fr
EP0343981B1 (fr
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Robert Dryden Tack
Iain More
Kenneth Lewtas
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • 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
    • 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
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • 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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • 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
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • 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
    • C10L1/1985—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 polyethers, e.g. di- polygylcols and derivatives; ethers - esters

Definitions

  • Wax separation in crude oils, middle distillate fuels, heavy and residual fuels and lubricating oils limits their flow at low temperatures.
  • the usual method of overcoming these problems is to add wax crystal modifying compounds that cause the wax crystals to be smaller (nucleators) and/or to be smaller and to grow into more compact shapes (growth inhibitors).
  • the wax crystals may be modified so as to improve filterability and reduce the pour point and the tendency of the wax crystals to agglomerate may be reduced by the addition of certain amino or quaternary ammonium salts.
  • JP Patent Publication No. 56-54038 describes fuel oils containing copolymers of olefins and maleic anhydride derivatised to amide or amide/amine salt groups, in combination with certain other additives.
  • JP Patent Application No. 61-211397 describes fuel oils containing an esteramide or esteramidoamine salt of a specific ⁇ -olefin/maleic anhydride copolymer.
  • EP-A-0 283 293 describes flow improver polymers containing more than one amide group derived from a secondary amine.
  • a fuel oil composition as a flow improver, alone or in combination with another flow improver, of an additive comprising a polymer or copolymer containing more than one amino group in the form of a salt of a primary or tertiary amine or a quatemary ammonium salt, said copolymer being derived from an intermediate polymer or copolymer containing acid or anhydride groups and selected from one or more of the following:
  • the liquid hydrocarbon fuel oils can be distillate fuel oils, such as the middle distillate fuel oils, e.g. a diesel fuel, aviation fuel, kerosene, fuel oil, jet fuel, heating oil, etc.
  • suitable distillate fuels are those boiling in the range of 120°C to 500°C (ASTM D86). preferably those boiling in the range 150°C to 400°C.
  • a representative heating oil specification calls for a 10 percent distillation point no higher than about 226°C, a 50 percent point no higher than about 272°C and a 90 percent point of at least 282°C and no higher than about 338°C to 343°C, although some specifications set the 90 percent point as high as 357°C.
  • Heating oils are preferably made of a blend of virgin distillate, e.g. gas oil, naphtha, etc. and cracked distillates, e.g. catalytic cycle stock.
  • the polymer containing more than one amino group can be prepared by reacting a polymer having a plurality of carboxylic acid or anhydride groups with a primary or tertiary amine.
  • the polymers can be reacted with a tetra-hydrocarbyl ammonium halide.
  • they may be prepared by reaction of a tertiary amine with a hydrocarbyl halide and so the polymer from which the desired polymer is derived should have halide groups and be reacted respectively with a tertiary amine.
  • said polymer, or copolymer has at least one hydrogen- and carbon-containing group where the total number of carbon atoms in said group(s) is at least 10 carbon atoms. Preferably there are 12 to 18 carbon atoms in at least one of said groups. Any such group which is preferably a straight chain or branched alkyl groups, can be present either attached directly or through a carboxylate group to the backbone of the polymer or attached to the nitrogen atom of the amine salt or quaternary ammonium salt group.
  • the polymers may also contain such groups attached both to the nitrogen atom and to the backbone or to the carboxylate group.
  • the alkyl groups of the mono- and di-alkyl fumarate, of the alkyl acrylate or of the alkyl methacrylate from which the polymers are derived can contain at least 10 carbon atoms.
  • Particularly suitable monomers are therefore di dodecyl fumarate, di tetra decyl fumarate, di octadecyl fumarate and the corresponding mono alkyl fumarates and mixtures thereof.
  • dodecyl, tetradecyl, hexadecyl and octadecyl acrylates and methacrylates are particularly suitable.
  • type III polymers one could use for example di-decyl, di-dodecyl, di-tetradecyl maleates.
  • the long chain group into the polymer by using a long chain p- or t-amine or tetrahydrocarbyl ammonium halide or mixtures thereof in forming the salt.
  • the amines can be represented by the formulae R 1 NH 2 and R 1 R 2 R 3 N and the tetrahydrocarbyl ammonium halide by the formula R 1 R 2 R 3 R 4 NX wherein R 1 , R 2 , R 3 , and R 4 are hydrocarbyl groups, preferably alkyl groups and wherein at least one of R 1 , R 2 , R 3 and R 4 preferably contains at least 10 carbon atoms, for instance 12 to 18 carbon atoms, for example dodecyl, tetradecyl, hexadecyl and octadecyl and wherein X is halogen, preferably chlorine.
  • Suitable polyamines can be represented by the formulae H 2 N[RHN] x H where R is a divalent hydrocarbyl group, preferably alkylene or hydrocarbyl substituted alkylene and x is an integer.
  • Suitable primary amines are hexyl amine, octyl amine, and those containing at least 10 carbon atoms, for instance decyl amine, tetradecyl amine, octadecyl amine, eicosylamine, the mixed amine RNH 2 (Armeen C) where R is 0.5 wt % C 6 alkyl, 8 wt % C 8 alkyl, 7 wt % C 10 alkyl, 50 wt % C 12 alkyl, 18 wt % C 14 alkyl, 8 wt % G 16 alkyl, 1.5 wt % C 18 alkyl and 7.0 wt % C 18 /C 19 unsaturated.
  • tertiary amines examples include tri hexyl amine, tri octyl amine and those containing alkyl groups with at least 10 carbon atoms, for instance, hexyl di-decyl amine, tri decyl amine and tri hexadecyl amine.
  • quaternary ammonium halides are tri-octyl-methyl ammonium chloride, and those containing alkyl groups with at least 10 carbon atoms, for instance tri-dodcyl-methyl ammonium chloride, tri-tetradecyl, dodecyl ammonium chloride and hexadecyl, dimethyl, phenyl amine.
  • the polymer salts of this invention usually have a number average molecular weight of 1,000 to 500,000, for example 10,000 to 100,000.
  • amino group-containing polymers for use in the present invention are:
  • additives known for improving the cold flow properties of distillate fuels generally are the polyoxyalkylene esters, ethers, ester/ethers, amide/esters and mixtures thereof, particularly those containing at least one, preferably at least two C 10 to C 30 linear saturated alkyl groups of a polyoxyalkylene glycol of molecular weight 100 to 5,000 preferably 200 to 5,000, the alkyl group in said polyoxyalkylene glycol containing from 1 to 4 carbon atoms.
  • EP-A-0,061,895 describe some of these additives.
  • esters, ethers or ester/ethers may be structurally depicted by the formula: R 5 -O-(A)-O-R 6 where R 5 and R 6 are the same or different and may be:
  • Suitable glycols generally are the substantially linear polyethylene glycols (PEG) and polypropylene glycols (PPG) having a molecular weight of about 100 to 5,000, preferably about 200 to 2,000.
  • Esters are preferred and fatty acids containing from 10-30 carbon atoms are useful for reacting with the glycols to form the ester additives and it is preferred to use a C 18 -C 24 fatty acid, especially behenic acids.
  • the esters may also be prepared by esterifying polyethoxylated fatty acids or polyethoxylated alcohols.
  • a particularly preferred additive of this type is polyethylene glycol dibehenate, the glycol portion having a molecular weight of about 600 and is often abbreviated as PEG 600 dibehenate. Similar polyethylene glycol dibehenates where the glycol portion has molecular weights of about 200 and 400 are often abbreviated as PEG 200 and PEG 400 respectively.
  • ethylene unsaturated ester copolymer flow improvers are ethylene unsaturated ester copolymer flow improvers.
  • the unsaturated monomers which may be copolymerised with ethylene include unsaturated mono and diesters of the general formula: wherein R 8 is hydrogen or methyl, R 7 is a -OOCR 10 group wherein R 10 is hydrogen or a C 1 to C 28 , more usually C 1 to C 17 . and preferably a C 1 to C 8 , straight or branched chain alkyl group; or R 7 is a -COOR 10 group wherein R 10 is as previously defined but is not hydrogen and R 9 is hydrogen or -COOR 10 as previously defined.
  • the monomer where R 7 and R 9 are hydrogen and R 8 is -OOCR 10 , includes vinyl alcohol esters of C 1 to C 29 , more usually C 1 to C 18 , monocarboxylic acid, and preferably C 2 to C 29 , more usually C 2 to C 18 , monocarboxylic acid, and preferably C 2 to C 5 monocarboxylicacid.
  • vinyl esters which may be copolmerised with ethylene include vinyl acetate, vinyl propionate and vinyl butyrate or isobutyrate, vinyl acetate being preferred. It is preferred that the copolymers contain from 20 to 40 wt % of the vinyl ester, more preferably from 25 to 35 wt % vinyl ester.
  • copolymers may also be mixtures of two copolymers such as those described in US-A-3,961,916. It is preferred that these copolymers have a number average molecular weight as measured by vapor phase osmometry of 1,000 to 6,000, preferably 1,000 to 3,000.
  • polar compounds either ionic or non-ionic, which have the capability in fuels of acting as wax crystal growth inhibitors.
  • Polar nitrogen containing compounds have been found to be especially effective when used in combination with the glycol esters, ethers or ester/ethers.
  • These polar compounds are generally amine salts and/or amides formed by reaction of at least one molar proportion of hydrocarbyl substituted amines with a molar proportion of hydrocarbyl acid having 1 to 4 carboxylic acid groups or their anhydrides; ester/amides may also be used containing 30 to 300, preferably 50 to 150 total carbon atoms.
  • These nitrogen compounds are described in US-A-4,211,534.
  • Suitable amines are usually long chain C 12 -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 and therefore normally containing about 30 to 300 total carbon atoms.
  • the nitrogen compound preferably contains at least one straight chain C 8 -C 40 , preferably C 14 to C 24 alkyl segment.
  • Suitable amines include primary, secondary, tertiary and quaternary, but preferably are secondary. Tertiary and quaternary amines can only form amine salts. Examples of amines include tetradecyl amine, cocoamine, hydrogenated tallow amine and the like. Examples of secondary amines include dioctadecyl amine, methyl-behenyl amine and the like. Amine mixtures are also suitable and many amines derived from natural materials are mixtures.
  • the preferred amine is a secondary hydrogenated tallow amine of the formula HNR 1 R 2 wherein R 1 and R 2 are alkyl groups derived from hydrogenated tallow fat composed of approximately 4% C 14 , 31% C 16 , 59% C 18 .
  • carboxylic acids for preparing these nitrogen compounds (and their anhydrides) include cyclohexane, 1,2 dicarboxylic acid, cyclopentane 1,2 dicarboxylic acid, naphthalene dicarboxylic acid and the like. Generally, these acids will have about 5-13 carbon atoms in the cyclic moiety.
  • Preferred acids are benzene dicarboxylic acid such as phthalic acid, tere-phthalic acid, and iso-phthalic acid. Phthalic acid or its anhydride is 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 di-hydrogenated tallow amine. Another preferred compound is the diamide formed by dehydrating this amide-amine salt.
  • the relative proportions of additives used in the mixtures are preferably from 0.05 to 20 parts by weight, more preferably from 0.1 to 5 parts by weight of the amine salt - or quaternary ammonium salt - containing polymer to 1 part of the other additives, such as the polyoxyalkylene esters, ether, ester/ether or amide ether.
  • the amount of amine salt - or quaternary ammonium salt - containing polymer added to the liquid hydrocarbon fuel is preferably 0.0001 to 5.0 wt. %, for example, 0.001 to 0.5 wt %, especially 0.01 to 0.05 wt %, (active matter) based on the weight of hydrocarbon fuel.
  • the polymer may conveniently be dissolved in a suitable solvent to form a concentrate of from 20 to 90, e.g., 30 to 80 weight % of the polymer in the solvent.
  • suitable solvents include kerosene, aromatic naphthas, mineral lubricating oils, etc.
  • polymers BB and DD show superior results to those shown by polymer AA which does not possess an amino group.
  • the cold filter properties of the blend were determined by the Cold Filter Plugging Point Test (CFPPT). This test is carried out by the procedure described in detail in "Journal of the Institute of Petroleum", Vol. 52, No. 510, June 1966, pp. 173-185. In brief, a 40 ml. sample of the oil to be tested is cooled by a bath maintained at about -34°C. Periodically (at each one degree of Centigrade drop in temperature starting from 2°C above the cloud point) the cooled oil is tested for its ability to flow through a fine screen in a time period. This cold property is tested with a device consisting of a pipette to whose lower end is attached an inverted funnel positioned below the surface of the oil to be tested.
  • CFPPT Cold Filter Plugging Point Test
  • the various polymers blended in each case with PEG 600 dibehenate in a weight ratio of 4 parts of polymer per part of PEG 600 dibehenate were as follows: Polymer-Salt Details C The mono-trioctyl amine salt of di-tetradecyl fumarate-vinyl acetate - 10 mole % maleic anhydride copolymer. F The mono-trioctyl amine salt of di-tetradecyl fumarate-vinyl acetate - 5 mole % maleic anhydride copolymer. G The di-trioctyl amine salt of di-tetradecyl fumarate-vinyl acetate - 5 mole % maleic anhydride copolymer.
  • the cold flow properties of the described fuels containing the additives are determined by the PCT as follows. 300 ml of fuel are cooled linearly at 1°C/hour to the test temperature and the temperature then held constant. After 2 hours at the test temperature, approximately 20 ml of the surface layer is removed by suction to prevent the test being influenced by the abnormally large wax crystals which tend to form on the oil/air interface during cooling. Wax which has settled in the bottle is dispersed by gentle stirring, then a CFPPT filter assembly is inserted.
  • the tap is opened to apply a vacuum of 500 mm of mercury, and closed when 200 ml of fuel have passed through the filter into the graduated receiver: a PASS is recorded if the 200 ml are collected within ten seconds through a given mesh size or A fail if the flow rate is too slow indicating that the filter has become blocked.
  • the mesh number passed at the test temperature is recorded.
  • Copolymer X which is included for comparison purposes is a copolymer of vinyl acetate and ditetradecyl fumarate. The results are as follows: Polymer Salt ⁇ CFPP 1500 ppm (active ingredient) 3000 ppm (active ingredient) C 1 2 F 0 3 G 0 2.5 X 1.5 3.5
  • Example 2 the polymer salts F, G used in Example 2 were added to F4, a high boiling point distillate fuel and the CFPP (F4 alone) and the ⁇ CFPP measured in each case.
  • the ASTM D86 distillation details of F4 are as follows: IBP 172°C D20 228°C D50 276°C D90 362°C FBP 389°C
  • copolymer Y is a 3:1 weight mixture of an ethylene/vinyl acetate copolymer containing 36 weight % of vinyl acetate of molecular weight about 2000 and an ethylene/vinyl acetate copolymer containing 13 weight % vinyl acetate of molecular weight about 3000.
  • Example polymer salt C (as used in Example 2) was added to a distillate fuel F6 having the D86 distillation properties: IBP 173°C D20 222°C D50 297°C D90 356°C FBP 371°C
  • This polymer salt C was also blended in a 1:1 mole ratio with ethylene-vinyl acetate copolymer mixture (Y) (see Example 3).
  • Example 3 the following polymer salt was added to the distillate fuel oil F6 of Example 5.
  • the polymer salt was blended in a 1:1 mole ratio with the copolymer mixture Y as used in Example 3.
  • the polymer salt blended with copolymer mixture Y was added to the fuel oil at two different concentrations, i.e. 300 and 600 ppm (0.03 wt % and 0.05 wt %) active ingredient and submitted to the PCT and CFPPT.
  • the results obtained were as follows: Additive + Y (1:1) Concentration (ppm) PCT (-8°C) CFPP F 300 - 20 F 600 - 20 +2 + 2 F 300 30 40 -1 -2 F 600 80 100 -5 -8 Base fuel oil alone 20 30 +3 +3
  • This invention relates to fuel oil compositions containing a low improver.
  • Wax separation in crude oils, middle distillate fuels, heavy and residual fuels and lubricating oils limits their flow at low temperatures.
  • the usual method of overcoming these problems is to add wax crystal modifying compounds that cause the wax crystals to be smaller (nucleators) and/or to be smaller and to grow into more compact shapes (growth inhibitors).
  • Another difficulty is that small wax crystals can stick together and form larger agglomerates and these agglomerates as well as the individual crystals can block the filter screens through which the individual crystals would pass and they will settle more rapidly than do the individual, small crystals.
  • the wax crystals may be modified so as to improve filterability and reduce the pour point and the tendency of the wax crystals to agglomerate may be reduced by the addition of certain amino or quaternary ammonium salts.
  • JP Patent Publication No. 56-54038 describes fuel oils containing copolymers of olefins and maleic anhydride derivatised to amide or amide/amine salt groups, in combination with certain other additives.
  • JP Patent Application No. 61-211397 describes fuel oils containing an esteramide or esteramidoamine salt of a specific ⁇ -olefin/maleic anhydride copolymer.
  • a fuel oil composition as a flow improver, alone or in combination with another flow improver, of an additive comprising a polymer or copolymer containing more than one amino group in the form of a salt of a primary, secondary or tertiary amine or a quaternary ammonium salt, said copolymer being derived from an intermediate polymer or copolymer containing acid or anhydride groups and selected from one or more of the following:
  • the liquid hydrocarbon fuel oils can be distillate fuel oils, such as the middle distillate fuel oils, e.g. a diesel fuel, aviation fuel, kerosene, fuel oil, jet fuel, heating oil, etc.
  • suitable distillate fuels are those boiling in the range of 120°C to 500°C (ASTM D86), preferably those boiling in the range 150°C to 400°C.
  • a representative heating oil specification calls for a 10 percent distillation point no higher than about 226°C, a 50 percent point no higher than about 272°C and a 90 percent point of at least 282°C and no higher than about 338°C to 343°C, although some specifications set the 90 percent point as high as 357°C.
  • Heating oils are preferably made of a blend of virgin distillate, e.g. gas oil, naphtha, etc. and cracked distillates, e.g. catalytic cycle stock.
  • the polymer containing more than one amino group can be prepared by reacting a polymer having a plurality of carboxylic acid or anhydride groups with a primary, secondary or tertiary amine.
  • the polymers can be reacted with a tetra-hydrocarbyl ammonium halide.
  • they may be prepared by reaction of a tertiary amine with a hydrocarbyl halide and so the polymer from which the desired polymer is derived should have halide groups and be reacted respectively with a tertiary amine.
  • said polymer, or copolymer has at least one hydrogen- and carbon-containing group where the total number of carbon atoms in said group(s) is at least 10 carbon atoms. Preferably there are 12 to 18 carbon atoms in at least one of said groups. Any such group which is preferably a straight chain or branched alkyl groups, can be present either attached directly or through a carboxylate group to the backbone of the polymer or attached to the nitrogen atom of the amine salt or quaternary ammonium salt group.
  • the polymers may also contain such groups attached both to the nitrogen atom and to the backbone or to the carboxylate group.
  • the alkyl groups of the mono- and di-alkyl fumarate, of the alkyl acrylate or of the alkyl methacrylate from which the polymers are derived can contain at least 10 carbon atoms.
  • Particularly suitable monomers are therefore di dodecyl fumarate, di tetra decyl fumarate, di octadecyl fumarate and the corresponding mono alkyl fumarates and mixtures thereof.
  • dodecyl, tetradecyl, hexadecyl and octadecyl acrylates and methacrylates are particularly suitable.
  • type III polymers one could use for example di-decyl, di-dodecyl, di-tetradecyl maleates.
  • the long chain group into the polymer by using a long chain p-, s- or t-amine or tetrahydrocarbyl ammonium halide or mixtures thereof in forming the salt.
  • the amines can be represented by the formulae R 1 NH 2 , R 1 R 2 NH and R 1 R 2 R 3 N and the tetrahydrocarbyl ammonium halide by the formula R 1 R 2 R 3 R 4 NX wherein R 1 , R 2 , R 3 , and R 4 are hydrocarbyl groups, preferably alkyl groups and wherein at least one of R 1 , R 2 , R 3 and R 4 preferably contains at least 10 carbon atoms, for instance 12 to 18 carbon atoms, for example dodecyl, tetradecyl, hexadecyl and octadecyl and wherein X is halogen, preferably chlorine.
  • Suitable polyamines can be represented by the formulae H 2 N[RHN] x H and R 1 NH[RNR 1 ] x H where R 1 is a hydrocarbyl group, R is a divalent hydrocarbyl group, preferably alkylene or hydrocarbyl substituted alkylene and x is an integer.
  • Suitable primary amines are hexyl amine, octyl amine, and those containing at least 10 carbon atoms, for instance decyl amine, tetradecyl amine, octadecyl amine, eicosylamine, the mixed amine RNH2 (Armeen C) where R is 0.5 wt % C 6 alkyl, 8 wt % C 8 alkyl, 7 wt % C 10 alkyl, 50 wt % C 12 alkyl, 18 wt % C 14 alkyl, 8 wt % C 16 alkyl, 1.5 wt % C 18 alkyl and 7.0 wt % C 18 /C 19 unsaturated.
  • RNH2 Armeen C
  • R is 0.5 wt % C 6 alkyl, 8 wt % C 8 alkyl, 7 wt % C 10 alkyl, 50 wt % C 12 alkyl,
  • suitable secondary amines are di-octyl amine, and those containing alkyl groups with at least 10 carbon atoms, for instance di-decyl amine, di-docyl amine, di-coco amine (i.e. di mixed C 12 to C 14 alkyl amines), di octadecyl amine, hexadecyl, octadecyl amine, dihydrogenated tallow amine (Armeen 2HT) (approx.
  • di-decyl amine di-docyl amine
  • di-coco amine i.e. di mixed C 12 to C 14 alkyl amines
  • di octadecyl amine hexadecyl
  • octadecyl amine dihydrogenated tallow amine (Armeen 2HT) (approx.
  • n-coco-propyl di amine C 12 /C 14 alkyl-propyl di amine - Duomeen C
  • n-tallow-propyl diamine C 16 /C 18 alkyl propyl diamine - Duomeen T
  • tertiary amines examples include tri hexyl amine, tri octyl amine and those containing alkyl groups with at least 10 carbon atoms, for instance, hexyl di-decyl amine, tri decyl amine and tri hexadecyl amine.
  • quaternary ammonium halides are tri-octyl-methyl ammonium chloride, and those containing alkyl groups with at least 10 carbon atoms, for instance tri-dodcyl-methyl ammonium chloride, tri-tetradecyl, dodecyl ammonium chloride and hexadecyl, dimethyl, phenyl amine.
  • polyamines examples include N-octadecyl propane diamine; N'N' dioctadecyl propane diamine, N tetradecyl butane diamine and N,N' dihexadecyl hexane diamine.
  • the polymer salts of this invention usually have a number average molecular weight of 1,000 to 500,000, for example 10,000 to 100,000.
  • amino group-containing polymers for use in the present invention are:
  • additives known for improving the cold flow properties of distillate fuels generally are the polyoxyalkylene esters, ethers, ester/ethers, amide/esters and mixtures thereof, particularly those containing at least one, preferably at least two C 10 to C 30 linear saturated alkyl groups of a polyoxyalkylene glycol of molecular weight 100 to 5,000 preferably 200 to 5,000, the alkyl group in said polyoxyalkylene glycol containing from 1 to 4 carbon atoms.
  • EP-A-0,061,895 describe some of these additives.
  • esters, ethers or ester/ethers may be structurally depicted by the formula: R 5 -O-(A)-O-R 6 where R 5 and R 6 are the same or different and may be:
  • Suitable glycols generally are the substantially linear polyethylene glycols (PEG) and polypropylene glycols (PPG) having a molecular weight of about 100 to 5,000, preferably about 200 to 2,000.
  • Esters are preferred and fatty acids containing from 10-30 carbon atoms are useful for reacting with the glycols to form the ester additives and it is preferred to use a C 18 -C 24 fatty acid, especially behenic acids.
  • the esters may also be prepared by esterifying polyethoxylated fatty acids or polyethoxylated alcohols.
  • a particularly preferred additive of this type is polyethylene glycol dibehenate, the glycol portion having a molecular weight of about 600 and is often abbreviated as PEG 600 dibehenate. Similar polyethylene glycol dibehenates where the glycol portion has molecular weights of about 200 and 400 are often abbreviated as PEG 200 and PEG 400 respectively.
  • ethylene unsaturated ester copolymer flow improvers are ethylene unsaturated ester copolymer flow improvers.
  • the unsaturated monomers which may be copolymerised with ethylene include unsaturated mono and diesters of the general formula: wherein R 8 is hydrogen or methyl, R 7 is a -OOCR 10 group wherein R 10 is hydrogen or a C 1 to C 28 , more usually C 1 to C 17 , and preferably a C 1 to C 8 , straight or branched chain alkyl group; or R 7 is a -COOR 10 group wherein R 10 is as previously defined but is not hydrogen and R 9 is hydrogen or -COOR 10 as previously defined.
  • the monomer where R 7 and R 9 are hydrogen and R 8 is -OOCR 10 , includes vinyl alcohol esters of C 1 to C 29 , more usually C 1 to C 18 , monocarboxylic acid, and preferably C 2 to C 29 , more usually C 2 to C 18 , monocarboxylic acid, and preferably C 2 to C 5 monocarboxylicacid.
  • vinyl esters which may be copolmerised with ethylene include vinyl acetate, vinyl propionate and vinyl butyrate or isobutyrate, vinyl acetate being preferred. It is preferred that the copolymers contain from 20 to 40 wt % of the vinyl ester, more preferably from 25 to 35 wt % vinyl ester.
  • copolymers may also be mixtures of two copolymers such as those described in US-A-3,961,916. It is preferred that these copolymers have a number average molecular weight as measured by vapor phase osmometry of 1,000 to 6,000, preferably 1,000 to 3,000.
  • polar compounds either ionic or non-ionic, which have the capability in fuels of acting as wax crystal growth inhibitors.
  • Polar nitrogen containing compounds have been found to be especially effective when used in combination with the glycol esters, ethers or ester/ethers.
  • These polar compounds are generally amine salts and/or amides formed by reaction of at least one molar proportion of hydrocarbyl substituted amines with a molar proportion of hydrocarbyl acid having 1 to 4 carboxylic acid groups or their anhydrides; ester/amides may also be used containing 30 to 300, preferably 50 to 150 total carbon atoms.
  • These nitrogen compounds are described in US-A-4,211,534.
  • Suitable amines are usually long chain C 12 -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 and therefore normally containing about 30 to 300 total carbon atoms.
  • the nitrogen compound preferably contains at least one straight chain C 8 -C 40 , preferably C 14 to C 24 alkyl segment.
  • Suitable amines include primary, secondary, tertiary and quaternary, but preferably are secondary. Tertiary and quaternary amines can only form amine salts. Examples of amines include tetradecyl amine, cocoamine, hydrogenated tallow amine and the like. Examples of secondary amines include dioctadecyl amine, methyl-behenyl amine and the like. Amine mixtures are also suitable and many amines derived from natural materials are mixtures.
  • the preferred amine is a secondary hydrogenated tallow amine of the formula HNR 1 R 2 wherein R 1 and R 2 are alkyl groups derived from hydrogenated tallow fat composed of approximately 4% C 14 , 31% C 16 , 59% C 18 .
  • carboxylic acids for preparing these nitrogen compounds (and their anhydrides) include cyclohexane, 1,2 dicarboxylic acid, cyclopentane 1,2 dicarboxylic acid, naphthalene dicarboxylic acid and the like. Generally, these acids will have about 5-13 carbon atoms in the cyclic moiety.
  • Preferred acids are benzene dicarboxylic acid such as phthalic acid, tere-phthalic acid, and iso-phthalic acid. Phthalic acid or its anhydride is 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 di-hydrogenated tallow amine. Another preferred compound is the diamide formed by dehydrating this amide-amine salt.
  • the relative proportions of additives used in the mixtures are preferably from 0.05 to 20 parts by weight, more preferably from 0.1 to 5 parts by weight of the amine salt - or quaternary ammonium salt - containing polymer to 1 part of the other additives, such as the polyoxyalkylene esters, ether, ester/ether or amide ether.
  • the amount of amine salt - or quaternary ammonium salt - containing polymer added to the liquid hydrocarbon fuel is preferably 0.0001 to 5.0 wt. %, for example, 0.001 to 0.5 wt %, especially 0.01 to 0.05 wt %, (active matter) based on the weight of hydrocarbon fuel.
  • the polymer may conveniently be dissolved in a suitable solvent to form a concentrate of from 20 to 90, e.g., 30 to 80 weight % of the polymer in the solvent.
  • suitable solvents include kerosene, aromatic naphthas, mineral lubricating oils, etc.
  • polymers BB, CC and DD show superior results to those shown by polymer AA which does not possess an amino group.
  • the cold filter properties of the blend were determined by the Cold Filter Plugging Point Test (CFPPT). This test is carried out by the procedure described in detail in "Journal of the Institute of Petroleum", Vol. 52, No. 510, June 1966, pp. 173-185. In brief, a 40 ml. sample of the oil to be tested is cooled by a bath maintained at about -34°C. Periodically (at each one degree of Centigrade drop in temperature starting from 2°C above the cloud point) the cooled oil is tested for its ability to flow through a fine screen in a time period. This cold property is tested with a device consisting of a pipette to whose lower end is attached an inverted funnel positioned below the surface of the oil to be tested.
  • CFPPT Cold Filter Plugging Point Test
  • the various polymers blended in each case with PEG 600 dibehenate in a weight ratio of 4 parts of polymer per part of PEG 600 dibehenate were as follows: Polymer-Salt Details A Half amide, half amine salt of di tetradecyl fumarate - vinyl acetate - 10 mole % maleic anhydride copolymer, the amine being R 2 NH where R is as given previously for Armeen C. B Half amide, half amine salt of di-tetra decyl fumarate-vinyl acetate - 10 mole % maleic anhydride, the amine being n-tallow propyl diamine.
  • F The mono-trioctyl amine salt of di-tetradecyl fumarate-vinyl acetate - 5 mole % maleic anhydride copolymer.
  • G The di-trioctyl amine salt of di-tetradecyl fumarate-vinyl acetate - 5 mole % maleic anhydride copolymer.
  • the cold flow properties of the described fuels containing the additives are determined by the PCT as follows. 300 ml of fuel are cooled linearly at 1°C/hour to the test temperature and the temperature then held constant. After 2 hours at the test temperature, approximately 20 ml of the surface layer is removed by suction to prevent the test being influenced by the abnormally large wax crystals which tend to form on the oil/air interface during cooling. Wax which has settled in the bottle is dispersed by gentle stirring, then a CFPPT filter assembly is inserted.
  • the mesh number passed at the test temperature is recorded.
  • Copolymer X which is included for comparison purposes is a copolymer of vinyl acetate and ditetradecyl fumarate. The results are as follows: Polymer Salt ⁇ CFPP 1500 ppm (active ingredient) 3000 ppm (active ingredient) B 1.5 2.5 C 1 2 D -2 5.5 E 0.5 3 F 0 3 G 0 2.5 H 0.5 3.5 I 0.5 3 X 1.5 3.5
  • the PCT (+2°C) was also carried out on F3 blends containing polymers D, E, F, G, H, and I, all blended with PEG 600 dibehenate in a weight ratio of 4:1 respectively.
  • the results obtained were as follows: Polymer Salt PCT Mesh Passed at 2°C 1500 ppm a.i. 3000 ppm a.i. D 60 150 E 30 80 F 40 80 G 30 80 H 100 200 I 30 60 X 80 150 No polymer (base fuel oil alone) ⁇ 20
  • Example 2 the polymer salts D, E, F, G, H and I used in Example 2 were added to F4, a high boiling point distillate fuel and the CFPP (F4 alone) and the ⁇ CFPP measured in each case.
  • the ASTM D86 distillation details of F4 are as follows: IBP 172°C D20 228°C D50 276°C D90 362°C FBP 389°C
  • Copolymer Y is a 3:1 weight mixture of an ethylene/vinyl acetate copolymer containing 36 weight % of vinyl acetate of molecular weight about 2000 and an ethylene/vinyl acetate copolymer containing 13 weight % vinyl acetate of molecular weight about 3000.
  • Example polymer salt C (as used in Example 2) and another polymer salt J was added to a distillate fuel F6 having the D86 distillation properties: IBP 173°C D20 222°C D50 297°C D90 356°C FBP 371°C
  • Polymer salt J is the half amide, half amine salt of the copolymer of di-tetradecyl fumarate-vinyl acetate - 10 mole % maleic anhydride, the amine being R 2 NH where R is C 16 /C 18 alkyl.
  • Example polymer salts A and B (as used in Example 2) and J (as used in Example 5) were added to the distillate fuel oil F6 of Example 5.
  • the following polymer salts were also added to this fuel oil.
  • Each polymer salt was blended in a 1:1 mole ratio with the copolymer mixture Y as used in Example 3.
  • Each polymer salt blended with copolymer mixture Y was added to the fuel oil at two different concentrations, i.e. 300 and 600 ppm (0.03 wt % and 0.05 wt %) active ingredient and submitted to the PCT and CFPPT.

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  • General Chemical & Material Sciences (AREA)
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Claims (13)

  1. Utilisation dans une composition de fuel-oil comme agent améliorant l'écoulement, seul ou en association avec un autre agent améliorant l'écoulement, d'un additif comprenant un polymère ou copolymère contenant plus d'un groupe amino sous forme d'un sel d'une amine primaire, secondaire ou tertiaire ou d'un sel d'ammonium quaternaire, ledit copolymère étant dérivé d'un polymère ou copolymère intermédiaire contenant des groupes acide ou anhydride et consistant en un ou plusieurs des suivants :
    I. un polymère d'un ou plusieurs esters insaturés comprenant également un groupe acide libre, ou provenant d'un copolymère de monomères ester insaturé dont au moins un possède un groupe acide libre,
    II. un copolymère d'un ester d'acide carboxylique insaturé avec un anhydride carboxylique insaturé,
    III. un polymère ou copolymère obtenu par hydrolyse partielle d'un polymère ou copolymère contenant des groupes ester de manière à obtenir des groupes acide ou anhydride carboxylique,
    IV. un polymère ou copolymère obtenu par réaction d'un polymère tel que défini dans le paragraphe III précité avec un anhydride carboxylique,
    et réaction avec un composé à fonction amino choisi entre des alkylamines primaires, secondaires ou tertiaires et des halogénures de tétraalkylammonium,
       ledit polymère ou copolymère possédant au moins un groupe contenant de l'hydrogène et du carbone, le nombre total d'atomes de carbone dans ledit ou lesdits groupes étant au moins égal à 10.
  2. Utilisation suivant la revendication 1, dans laquelle le polymère ou copolymère intermédiaire comprend un copolymère d'un fumarate, maléate, citraconate ou itaconate de dialkyle avec l'anhydride maléique.
  3. Utilisation suivant la revendication 1, dans laquelle le polymère ou copolymère intermédiaire comprend un copolymère d'un ester vinylique avec l'anhydride maléique.
  4. Utilisation suivant la revendication 1, dans laquelle le polymère ou copolymère intermédiaire comprend un copolymère d'un fumarate, maléate, citraconate ou itaconate de dialkyle avec l'anhydride maléique et l'acétate de vinyle.
  5. Utilisation suivant la revendication 1, dans laquelle le polymère ou copolymère intermédiaire comprend un polymère partiellement hydrolysé d'un fumarate, maléate, citraconate ou itaconate d'alkyle ou un de ses copolymères avec une oléfine en C10 à C30.
  6. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle au moins un des groupes contenant de l'hydrogène et du carbone possède 12 à 18 atomes de carbone.
  7. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle, dans le polymère ou copolymère intermédiaire, le ou chaque groupe contenant de l'hydrogène et du carbone est fixé directement par un groupe carboxylate au squelette du polymère.
  8. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle, dans le polymère ou copolymère intermédiaire, le ou chaque groupe contenant de l'hydrogène et du carbone est fixé à l'atome d'azote du sel d'amine ou du sel d'ammonium quaternaire.
  9. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le composé à fonction amino comprend une alkylamine primaire, secondaire ou tertiaire contenant au moins un groupe alkyle ayant au moins 10 atomes de carbone.
  10. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le composé à fonction amino comprend une amine secondaire ou tertiaire choisie entre la trioctylamine, la di-amine de suif hydrogéné, une (alkyle en C12 à C14)-propyl-diamine mixte, et une n-(radical dérivé du suif)-propyl-diamine.
  11. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle la quantité de copolymère contenant un sel d'amine va de 0,0001 à 5,0 % en poids (matière active) sur la base du poids du combustible.
  12. Utilisation suivant l'une quelconque des revendications précédentes, qui comprend un autre agent améliorant l'écoulement choisi entre : un ester, éther, ester/éther ou amide/éther de polyoxyalkylène ; un agent améliorant l'écoulement consistant en un copolymère d'éthylène et d'un ester insaturé ; un composé azoté polaire ; et leurs mélanges.
  13. Utilisation suivant la revendication 12, dans laquelle l'autre agent améliorant l'écoulement est un copolymère éthylène - acétate de vinyle.
EP89305290A 1988-05-25 1989-05-25 Utilisation d'un additif dans une composition de fuel-oil comme agent améliorant l'écoulement Expired - Lifetime EP0343981B2 (fr)

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GB8812380 1988-05-25
GB888812380A GB8812380D0 (en) 1988-05-25 1988-05-25 Fuel oil compositions

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EP0343981B1 EP0343981B1 (fr) 1994-12-14
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DE4025586A1 (de) * 1990-08-11 1992-02-13 Basf Ag Kaeltestabile erdoelmitteldestillate, enthaltend polymere als paraffindispergatoren
JP2875076B2 (ja) * 1990-11-29 1999-03-24 三井化学株式会社 フレキシブル配線基板
US5232963A (en) * 1992-07-09 1993-08-03 Nalco Chemical Company Dispersing gums in hydrocarbon streams with β-olefin/maleic anhydride copolymer
US5214224A (en) * 1992-07-09 1993-05-25 Comer David G Dispersing asphaltenes in hydrocarbon refinery streams with α-olefin/maleic anhydride copolymer
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
FR2802940B1 (fr) * 1999-12-28 2003-11-07 Elf Antar France Composition d'additifs multifonctionnels d'operabilite a froid des distillats moyens
JP2003014874A (ja) * 2001-07-05 2003-01-15 Daikin Ind Ltd 目覚まし装置
US9222046B2 (en) 2013-04-26 2015-12-29 Afton Chemical Corporation Alkoxylated quaternary ammonium salts and diesel fuels containing the salts

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EP0343981A1 (fr) 1989-11-29
GB8812380D0 (en) 1988-06-29
DE68919907D1 (de) 1995-01-26
CN1038298A (zh) 1989-12-27
KR900018339A (ko) 1990-12-21
DE68919907T3 (de) 1998-10-08
CN1024680C (zh) 1994-05-25
KR960013611B1 (ko) 1996-10-09
JPH0224394A (ja) 1990-01-26
EP0343981B1 (fr) 1994-12-14
JP2723972B2 (ja) 1998-03-09
DE68919907T2 (de) 1995-05-04

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