EP1541663B1 - Huiles combustibles comprenant des distillats moyens et des huiles d'origine végétale ou animale et ayant des propriétés à froid améliorées - Google Patents

Huiles combustibles comprenant des distillats moyens et des huiles d'origine végétale ou animale et ayant des propriétés à froid améliorées Download PDF

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EP1541663B1
EP1541663B1 EP04028307.9A EP04028307A EP1541663B1 EP 1541663 B1 EP1541663 B1 EP 1541663B1 EP 04028307 A EP04028307 A EP 04028307A EP 1541663 B1 EP1541663 B1 EP 1541663B1
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fuel oil
alkyl
esters
oil composition
mol
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EP1541663A1 (fr
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Matthias Dr. Krull
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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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
    • 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
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds 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 an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • 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
    • C10L1/146—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
    • C10L1/18—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
    • C10L1/197—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
    • C10L1/22—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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • 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
    • C10L1/22—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

Definitions

  • the present invention relates to mineral fuel oils containing ingredients of plant or animal origin with improved cold properties and the use of an additive as a cold flow improver for such fuel oils.
  • biofuels include, in particular, natural oils and fats of plant or animal origin. These are typically triglycerides of fatty acids with 10 to 24 C atoms, which have a calorific value comparable to conventional fuels, but at the same time are considered less harmful to the environment.
  • Biofuels ie fuels derived from animal or plant material, are obtained from renewable sources and thus produce only as much CO 2 as was previously converted into biomass. It has been reported that combustion produces less carbon dioxide than equivalent amounts of petroleum distillate fuel, eg, diesel fuel, and that very little sulfur dioxide is produced. In addition, they are biodegradable.
  • Oils obtained from animal or vegetable material are mainly metabolites comprising triglycerides of monocarboxylic acids, eg of acids having 10 to 25 carbon atoms, and the formula in which R is an aliphatic radical of 10 to 25 carbon atoms, which may be saturated or unsaturated.
  • oils include glycerides of a variety of acids, the number and variety of which varies with the source of the oil, and may additionally contain phosphoglycerides.
  • Such oils can be obtained by methods known in the art.
  • rapeseed-oil methyl ester RME
  • RME has a Cold Filter Plugging Point (CFPP) of -14 ° C
  • soybean oil methyl ester a CFPP of -5 ° C
  • animal fat a CFPP of + 9 ° C.
  • EP-B-0 665 873 discloses a fuel oil composition
  • a fuel oil composition comprising a biofuel, a petroleum-based fuel oil and an additive which comprises (a) an oil-soluble ethylene copolymer or (b) a comb polymer or (c) a polar nitrogen compound or (d) a compound in which at least one substantially linear alkyl group having from 10 to 30 carbon atoms is bonded to a non-polymeric organic radical to provide at least one linear chain of atoms which includes the carbon atoms of the alkyl groups and one or more non-terminal oxygen atoms, or (e) one or more of the components ( a), (b), (c) and (d).
  • EP-B-0 153 176 discloses the use of polymers based on unsaturated C 4 -C 8 dicarboxylic acid di-alkyl esters having average alkyl chain lengths of 12 to 14 as cold flow improvers for certain petroleum distillate fuel oils.
  • Suitable comonomers are unsaturated esters, in particular vinyl acetate, but also ⁇ -olefins.
  • WO 94/10267 teaches a fuel oil composition comprising a biofuel, a petroleum-based fuel oil and an additive which comprises (a) an oil-soluble ethylene copolymer or (b) a comb polymer or (c) a polar nitrogen compound or (d) a compound in which at least one substantially linear alkyl group having from 10 to 30 carbon atoms is bonded to a non-polymeric organic radical to provide at least one linear chain of atoms which includes the carbon atoms of the alkyl groups and one or more non-terminal oxygen atoms, or (e) one or more of the components ( a), (b), (c) and (d).
  • an additive which comprises (a) an oil-soluble ethylene copolymer or (b) a comb polymer or (c) a polar nitrogen compound or (d) a compound in which at least one substantially linear alkyl group having from 10 to 30 carbon atoms is bonded to a non-polymeric organic radical to provide at least one linear chain of
  • EP-B-0 746 598 discloses comb polymers as a cold additive in fuel oils having a cloud point of at most -10 ° C.
  • fuel oils of middle distillates and oils of vegetable and / or animal origin which comprise an ethylene copolymer and certain comb polymers containing additive, show excellent cold properties.
  • Another object of the invention is the use of 0.001 to 5 wt .-% of the additive defined above, containing the components A) and B), for improving the cold flow properties of fuel oil compositions F) containing fuel oils mineral (F1) and more than 2 to 35% by volume of animal and / or vegetable (F2) origin containing more than 4% by weight of esters of saturated fatty acids.
  • Another object of the invention is a process for the preparation of fuel oil compositions F) containing fuel oils mineral (F1) and more than 2 to 35 vol .-%. animal and / or vegetable (F2) origin, containing more than 4% by weight of esters of saturated fatty acids, with improved refrigerating properties, by mixing the mixture of mineral (F1) and more than 2 to 35% by volume animal oils and / or vegetable (F2) origin the additive defined above in an amount of 0.001 to 5 wt .-%, containing the components A) and B), added.
  • Preferred oils of mineral origin are middle distillates.
  • the mixing ratio between the fuel oils of animal and / or vegetable origin (which are also referred to below as biofuel oils) and middle distillates can be between 1:99 and 99: 1.
  • Particular preference is given to mixtures which contain from 2 to 50% by volume, in particular from 5 to 40% by volume and especially from 10 to 30% by volume, of biofuel oils.
  • R assumes values between 11.5 and 13.5, in particular 12.0 to 13.0.
  • Suitable ethylene copolymers A) are those which contain from 8 to 21 mol% of one or more vinyl and / or (meth) acrylic esters and from 79 to 92% by weight of ethylene. Particularly preferred are ethylene copolymers with 10 to 18 mol% and especially 12 to 16 mol% of at least one vinyl ester. Suitable vinyl esters are derived from fatty acids with linear or branched alkyl groups having 1 to 30 carbon atoms.
  • Examples which may be mentioned are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, Vinylheptanoat, vinyl octanoate, vinyl laurate and vinyl stearate and branched fatty acid based esters of vinyl alcohol such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, iso-Nonanklarevinylester, Neononanklavinylester, vinyl neodecanoate and Neoundecanklavinylester.
  • esters of acrylic and methacrylic acid having 1 to 20 C atoms in the alkyl radical such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and isobutyl (meth) acrylate, hexyl , Octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl (meth) acrylate and mixtures of two, three, four or more of these comonomers.
  • Particularly preferred terpolymers of 2-ethylhexanoic acid vinyl ester, vinyl neononanoate or vinyl neodecanoate contain, in addition to ethylene, preferably 3.5 to 20 mol%, in particular 8 to 15 mol% vinyl acetate and 0.1 to 12 mol%, in particular 0.2 to 5 mol% of the respective long-chain vinyl ester, wherein the total comonomer content is between 8 and 21 mol%, preferably between 12 and 18 mol%.
  • copolymers contain, in addition to ethylene and from 8 to 18 mol% of vinyl esters, from 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
  • olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
  • the copolymers A preferably have molecular weights which correspond to melt viscosities at 140 ° C. of from 20 to 10,000 mPas, in particular from 30 to 5,000 mPas and especially from 50 to 1,000 mPas.
  • the determined by 1 H NMR spectroscopy degrees of branching are preferably between 1 and 9 CH 3/100 CH 2 groups, especially between 2 and 6 CH 3/100 CH 2 groups, such as 2.5 to 5 CH 3/100 CH 2 groups not derived from the comonomers.
  • the copolymers (A) can be prepared by the usual copolymerization methods such as suspension polymerization, solvent polymerization, gas phase polymerization or high-pressure bulk polymerization.
  • the high-pressure mass polymerization is preferably carried out at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 100 to 300 ° C, preferably 150 to 220 ° C.
  • the polymerization takes place in a multi-zone reactor, wherein the temperature difference between the peroxide dosages along the tubular reactor is kept as low as possible, i. ⁇ 50 ° C, preferably ⁇ 30 ° C, in particular ⁇ 15 ° C.
  • the temperature maxima in the individual reaction zones preferably differ by less than 30 ° C., more preferably by less than 20 ° C. and especially by less than 10 ° C.
  • the reaction of the monomers is initiated by free radical initiators (free radical initiators).
  • This class of substance includes e.g. Oxygen, hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permalate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl ) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on
  • the high-pressure mass polymerization is carried out batchwise or continuously in known high-pressure reactors, for example autoclaves or tubular reactors, tube reactors have proven particularly useful.
  • Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene may be present in the reaction mixture. Preferred is the substantially solvent-free operation.
  • Preferred moderators are, for example, hydrogen, saturated and unsaturated hydrocarbons such as propane or propene, aldehydes such as propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone and alcohols such as butanol.
  • the comonomers as well as the moderators can be metered into the reactor both together with ethylene and separately via side streams. In this case, the monomer streams can be composed differently ( EP-A-0 271 738 and EP-A-0 922 716 ).
  • the polymers underlying the mixtures differ in at least one characteristic.
  • they may contain different comonomers, have different comonomer contents, molecular weights and / or degrees of branching.
  • the mixing ratio of the various ethylene copolymers is preferably between 20: 1 and 1:20, preferably 10: 1 to 1:10, in particular 5: 1 to 1: 5.
  • the copolymers B are derived from alkyl acrylates, alkyl methacrylates, alkyl acrylamides, alkyl methacrylamides, alkyl vinyl esters, alkyl vinyl ethers, alkyl allyl ethers and alkyl diketenes having 8 to 16 carbon atoms in the alkyl radical. These comonomers are referred to below as comonomers B1).
  • the copolymers constituting ingredient B are those containing comonomers derived from esters, amides and / or imides of ethylenically unsaturated monocarboxylic acids having from 3 to 8 carbon atoms with alcohols or amines, respectively, wherein Alcohols or amines carry alkyl radicals having 8 to 16 carbon atoms.
  • the copolymers B) may also contain comonomers B2) which comprise i) esters, amides and / or imides of ethylenically unsaturated dicarboxylic acids having 4 to 8 C atoms and alcohols or amines having 8 to 16 C atoms in the alkyl radicals and / or or ii) C 10 to C 20 olefins.
  • comonomers B2 comprise i) esters, amides and / or imides of ethylenically unsaturated dicarboxylic acids having 4 to 8 C atoms and alcohols or amines having 8 to 16 C atoms in the alkyl radicals and / or or ii) C 10 to C 20 olefins.
  • the alkyl radicals of the comonomers B1 and B2 are preferably linear, but may also contain minor amounts of branched isomers of up to 30 mol%, preferably up to 20 mol% and in particular 2 to 5 mol%.
  • the proportion of the comonomers B1) and optionally B2) in the polymer is preferably more than 50 mol%, in particular more than 70 mol% and especially at least 80 mol%, for example 90 to 95 mol%.
  • the proportion of the monomers B2), if present, is preferably less than 80 mol%, in particular less than 50 mol% and especially less than 20 mol%, for example from 2 to 10 mol% of the total amount of the monomers B1 ) and B2).
  • the polymers B) consist only of the monomers B1) and optionally B2), which then add up to 100 mol%.
  • Preferred monomers of the copolymers B) are esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid with octanol, nonanol, decanol, undecanol, dodecanol, n-tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol and mixtures thereof.
  • Further preferred monomers are amides and optionally imides of these acids with octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine and mixtures thereof.
  • the copolymers making up Component B contain comonomers which are esters and / or ethers of ethylenically unsaturated alcohols of 2 to 10 carbon atoms, and carboxylic acids or alcohols bearing alkyl groups of 8 to 16 carbon atoms.
  • Such preferred monomers of the copolymers B) are, for example, esters of vinyl alcohol with octanoic acid, 2-ethylhexanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid and mixtures thereof.
  • Further preferred monomers of the copolymers B) are, for example, ethers of allyl and in particular vinyl alcohol with octanol, nonanol, decanol, undecanol, dodecanol, n-tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol and mixtures thereof.
  • comonomers B2 are also olefins having 10-20 carbon atoms, preferably with 12-18 C atoms and in particular with 10-16 C atoms suitable. These are preferably linear ⁇ - olefins with terminal double bond. In a further preferred embodiment, it is branched olefins such as in particular oligomers of isobutylene and propylene having 10 to 20 carbon atoms.
  • side chain length of olefins is meant here the alkyl radical leaving the polymer backbone, ie the chain length of the monomeric olefin minus the two olefinically bonded C atoms.
  • side chain length of olefins is meant here the alkyl radical leaving the polymer backbone, ie the chain length of the monomeric olefin minus the two olefinically bonded C atoms.
  • alkyl (meth) acrylates alkyl (meth) acrylates, alkyl vinyl esters, alkyl vinyl ethers having 1 to 5 carbon atoms in the alkyl radical and ethylenically unsaturated free carboxylic acids
  • acrylic acid methacrylic acid, maleic acid, fumaric acid, itaconic acid and functional groups
  • -OH, -SH, -N -CN-bearing monomers can also be present in minor amounts of up to 20 mol%, preferably ⁇ 10 mol%, especially ⁇ 5 mol% in the copolymers B.
  • the polymers according to the invention can be prepared by direct polymerization from the monomers mentioned in known polymerization processes such as bulk, solution, emulsion, suspension or precipitation polymerization.
  • Acid- or hydroxyl-bearing base polymer can be prepared with corresponding fatty acids, fatty alcohols or fatty amines having 8 to 16 carbon atoms in the alkyl radical.
  • the esterifications, etherifications, amidations and / or imidations are carried out by known condensation methods.
  • the derivatization may be complete or partial.
  • Partially esterified or amidated acid-based polymers (solvent-free) preferably have acid numbers of 60-140 mg KOH / g and in particular 80-120 mg KOH / g.
  • Copolymers with acid numbers of less than 80, especially less than 60 mg KOH / g are considered to be fully derivatized.
  • Partially esterified or etherified hydroxyl-bearing polymers have OH numbers of 40 to 200 mg KOH / g, preferably 60 to 150 mg KOH / g; Copolymers having hydroxyl numbers less than 60 and especially less than 40 mg KOH / g are considered fully derivatized. Particularly preferred are partially derivatized polymers.
  • suitable acid-bearing polymers are homo- and copolymers of ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid or their reactive equivalents such as lower esters or anhydrides such as Methyl methacrylate and maleic anhydride with each other as well as with other monomers copolymerizable with these acids.
  • carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid or their reactive equivalents such as lower esters or anhydrides such as Methyl methacrylate and maleic anhydride with each other as well as with other monomers copolymerizable with these acids.
  • Suitable examples are poly (acrylic acid), poly (methacrylic acid), poly (maleic acid), poly (maleic anhydride), poly (acrylic acid-co-maleic acid).
  • Suitable fatty alcohols and fatty amines are particularly linear, but they can also minor amounts, eg. B. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to 10 wt .-% branched alkyl radicals.
  • the branches are preferably in the 1- or 2-position. Shorter as well as longer-chain fatty alcohols or fatty amines can be used, but their proportion is preferably below 20 mol% and especially below 10 mol%, such as between 1 and 5 mol% based on the total amount of amines used.
  • Particularly preferred fatty alcohols are octanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol and hexadecanol.
  • Suitable amines are primary and secondary amines having one or two C 8 -C 16 alkyl radicals. They can carry one, two or three amino groups which are linked via alkylene radicals having two or three carbon atoms. Preference is given to monoamines.
  • primary amines are octylamine, 2-ethylhexylamine, decylamine, undecylamine, dodecylamine, n-tridecylamine, iso-tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine and mixtures thereof.
  • Preferred secondary amines are dioctylamine, dinonylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, and amines having different alkyl chain lengths such as N-octyl-N-decylamine, N-decyl-N-dodecylamine, N-decyl-N-tetradecylamine, N-decyl N-hexadecylamine, N-dodecyl-N-tetradecylamine, N-dodecyl-N-hexadecylamine, N-tetradecyl-N-hexadecylamine.
  • Secondary amines which, in addition to a C 8 -C 16 -alkyl radical, bear shorter side chains having 1 to 5 C atoms, for example methyl or ethyl groups, are suitable according to the invention.
  • the alkyl chain length n is taken into account as the mean value of the alkyl chain lengths of C 8 to C 16 for the calculation of the Q factor.
  • Shorter and longer alkyl radicals, if present, are not included in the calculation because they do not contribute to the effectiveness of the additives. Therefore, the proportion of shorter and longer alkyl chains is preferably less than 20 mol%, preferably less than 10 mol%, based on the total amount of amine used.
  • Particularly preferred are amides derived from primary monoamines and imides.
  • Polymers which are particularly suitable for derivatization with fatty acids and / or fatty alcohols to esters and / or ethers are homopolymers and copolymers of monomers carrying hydroxyl groups, such as vinyl alcohol, allyl alcohol or also hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
  • Suitable fatty acids have 8 to 16 carbon atoms in the alkyl radical.
  • the alkyl radical is essentially linear, but may also be minor amounts, e.g. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to 10 wt .-% of branched isomers.
  • Nonadecanklare and mixtures thereof are nonanoic, decanoic, undecanoic, dodecanoic, tridecanoic, tetradecanoic, pentadecanoic, hexadecanoic, heptadecanoic and octadecanoic and Nonadecanklare and mixtures thereof.
  • the effectiveness of the additives according to the invention can be further adapted to special fatty acid ester compositions.
  • the molecular weights of the copolymers B of the invention are between 1,000 and 100,000, in particular between 2,000 and 50,000 and in particular between 2,500 and 25,000 g / mol, measured by gel permeation chromatography (GPC) against poly (styrene).
  • Copolymers of the invention must be oil-soluble in practice-relevant dosing quantities, ie they must dissolve in the oil to be additized at 50 ° C. without residue.
  • mixtures of the copolymers B according to the invention are used, with the proviso that the mean value of the R values of the mixture components in turn has values of from 11.0 to 14.0, preferably from 11.5 to 13.5 and in particular values of 12 , 0 to 13.0.
  • the mixing ratio of the additives A and B according to the invention is (in parts by weight) 10: 1 to 1:10, in particular 5: 1 to 1: 2.
  • the additives of the invention are added to oils in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 1 wt .-% and especially 0.01 to 0.5 wt .-%.
  • solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene, naphtha, diesel, fuel oil, isoparaffins or commercial solvent mixtures such as Solvent naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® Isopar and ® Shellsol D types can be used.
  • solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fraction
  • the fuel oil F2 which is often referred to as “biodiesel”, “biofuel” or “biofuel”, to fatty acid alkyl esters of fatty acids having 12 to 24 carbon atoms and alcohols having 1 to 4 carbon atoms ,
  • a major part of the fatty acids contains one, two or three double bonds.
  • oils F2 derived from animal or vegetable material which can be used in the present invention are rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, beef tallow, Bone oil, fish oils and used cooking oils.
  • oils derived from wheat, jute, sesame, shea nut, arachis oil and linseed oil can be derived from these oils by methods known in the art.
  • Rapeseed oil which is a mixture of glycerol partially esterified fatty acids, is preferred because it is available in large quantities and is readily available by squeezing rapeseed. Furthermore, the also widespread oils of sunflower and soybeans and their mixtures with rapeseed oil are preferred.
  • biofuels F2 are lower alkyl esters of fatty acids.
  • examples of commercially available mixtures of the ethyl, propyl, butyl and especially methyl esters of fatty acids having 14 to 22 carbon atoms for example lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, elaeostearic acid, Linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid, which preferably have an iodine value of 50 to 150, in particular 90 to 125.
  • Mixtures with particularly advantageous properties are those which contain mainly, ie at least 50 wt .-%, methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 double bonds.
  • the preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and erucic acids.
  • a biofuel is an oil obtained from plant or animal matter or both, or a derivative thereof, which can be used as a fuel and especially as a diesel or fuel oil.
  • vegetable oil derivatives are preferred, with particularly preferred biofuels being alkyl ester derivatives of rapeseed oil, cottonseed oil, soybean oil, sunflower oil, olive oil or palm oil, with methyl rapeseed oil, methyl sunflower oil and soybean oil methyl ester being most preferred.
  • particularly preferred biofuel or as a component in the biofuel are also old fat esters such as, for example, used fat methyl ester.
  • middle distillates are suitable, which are obtained by distillation of crude oil and boiling in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil.
  • the 0.05 wt .-% sulfur and less, more preferably less than 350 ppm sulfur, in particular less than 200 ppm sulfur and in special cases contain less than 50 ppm sulfur, such as less than 10 ppm sulfur.
  • middle distillates which have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds.
  • middle distillates which have 95% distillation points below 370.degree. C., in particular 350.degree. C. and in special cases below 330.degree.
  • Synthetic fuels such as those obtainable by the Fischer-Tropsch process, are also suitable as middle distillates.
  • the additive may be added to the oil to be added according to methods known in the art.
  • additive component or co-additive component such components may be incorporated into the oil together or separately in any combination and order.
  • the CFPP value of mixtures of biodiesel and mineral oils can be improved much more efficiently than with the known additives of the prior art.
  • the additives according to the invention are particularly advantageous in oil mixtures whose mineral oil component F1) has a boiling range between the 20 and 90% distillation point of less than 120 ° C, in particular less than 110 ° C and especially less than 100 ° C.
  • they are particularly advantageous in oil blends whose mineral oil component F1) has a cloud point of below -4 ° C, especially from -6 ° C to -20 ° C such as from -7 ° C to -9 ° C, as they be used for use especially in winter.
  • the additives according to the invention are particularly advantageous in oil mixtures containing more than 2% by volume of biofuel F 2, preferably more than 5% by volume of biofuel F 2 and especially more than 10% by vol. Of biofuel F 2, for example 15 to 35% by vol. % Biofuel F2 included.
  • the additives according to the invention are furthermore particularly advantageous in problematic oils whose biofuel component F2 contains a high proportion of esters of saturated fatty acids of more than 4%, in particular more than 5% and especially from 7 to 25%, for example from 8 to 20% it is the case for example in sunflower and soybean oils.
  • Such biofuels preferably have a cloud point above -5 ° C and especially above -3 ° C.
  • Oil mixtures F in which the additives according to the invention show particularly advantageous action, preferably have cloud points above -9 ° C and especially above -6 ° C.
  • Oil mixtures F in which the additives according to the invention show particularly advantageous action, preferably have cloud points above -9 ° C and especially above -6 ° C.
  • the additives according to the invention can also be used together with one or more oil-soluble co-additives, which in themselves improve the cold flow properties of crude oils, lubricating oils or fuel oils.
  • oil-soluble co-additives are polar compounds which differ from the polymers B according to the invention and which effect a paraffin dispersion (paraffin dispersants), alkylphenol condensates, esters and ethers of polyoxyalkylene compounds, olefin copolymers and oil-soluble amphiphiles.
  • the additives according to the invention can be used to further reduce the sedimentation in the cold precipitated paraffins and fatty acid esters in admixture with paraffin dispersants.
  • Paraffin dispersants reduce the size of the paraffin and fatty acid ester crystals and cause the paraffin particles to not settle but remain colloidally dispersed with significantly reduced sedimentation effort.
  • Suitable paraffin dispersants are both low molecular weight and polymeric, oil-soluble compounds having ionic or polar groups such as amine salts and / or amides have proven.
  • paraffin dispersants contain reaction products of fatty amines with alkyl radicals having 18 to 24 C atoms, in particular with secondary fatty amines such as Ditalgfettamin, distearylamine and dibehenylamine with carboxylic acids and derivatives thereof.
  • Paraffin dispersants which have been obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides have proven particularly suitable (cf. US 4 211 534 ).
  • amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as paraffin dispersants (cf. EP 0 398 101 ).
  • paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be reacted (see. EP 0 154 177 ) and the reaction products of alkenyl spiro-bis-lactones with amines (cf.
  • EP-0 413 279 B1 and after EP-A-0 606 055 A2 Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
  • Alkylphenol-aldehyde resins are described, for example, in Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p. 3351 et seq. described.
  • the alkyl radicals of the o- or p-alkylphenol may be the same or different in the case of the alkylphenol-aldehyde resins which can be used with the additives according to the invention and have 1-50, preferably 1-20, in particular 4-12 carbon atoms; it is preferably n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl , n- and iso-dodecyl and octadecyl.
  • the aliphatic aldehyde in the alkylphenol-aldehyde resin preferably has 1 to 4 carbon atoms.
  • Particularly preferred aldehydes are formaldehyde, acetaldehyde and butyraldehyde, especially formaldehyde.
  • the molecular weight of the alkylphenol-aldehyde resins is 400-10,000, preferably 400-5,000, g / mol. The prerequisite here is that the resins are oil-soluble.
  • these alkylphenol-formaldehyde resins are those which are oligomers or polymers having a repeating structural unit of the formula wherein R 5 is C 1 -C 50 alkyl or alkenyl and n is a number from 2 to 100.
  • R 5 is preferably C 4 -C 20 -alkyl or -alkenyl and in particular C 6 -C 16 -alkyl or alkenyl.
  • n is a number from 4 to 50 and especially from 5 to 25.
  • Suitable flow improvers are polyoxyalkylene compounds such as esters, ethers and ethers / esters, which carry at least one alkyl radical having 12 to 30 carbon atoms.
  • the alkyl groups are derived from an acid, the remainder is derived from a polyhydric alcohol; If the alkyl radicals come from a fatty alcohol, the remainder of the compound derives from a polyacid.
  • Suitable polyols are polyethylene glycols, polypropylene glycols, polybutylene glycols and their copolymers having a molecular weight of about 100 to about 5000, preferably 200 to 2000.
  • alkoxylates of polyols such as glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, as well as from them Condensation accessible oligomers having 2 to 10 monomer units, such as Polyglycerol.
  • Preferred alkoxylates are those having from 1 to 100, in particular from 5 to 50, mol of ethylene oxide, propylene oxide and / or butylene oxide per mole of polyol. Esters are especially preferred.
  • Fatty acids containing 12 to 26 carbon atoms are preferred for reaction with the polyols to form the ester additives, preferably using C 18 to C 24 fatty acids, especially stearic and behenic acid.
  • the esters can also be prepared by esterification of polyoxyalkylated alcohols. Preference is given to completely esterified polyoxyalkylated polyols having molecular weights of 150 to 2,000, preferably 200 to 1,500. Particularly suitable are PEG-600 dibehenate and glycerol-ethylene glycol tribehenate.
  • Suitable olefin polymers as part of the additive according to the invention can be derived directly from monoethylenically unsaturated monomers or prepared indirectly by hydrogenation of polymers derived from polyunsaturated monomers such as isoprene or butadiene.
  • Preferred copolymers contain, in addition to ethylene structural units derived from ⁇ -olefins having 3 to 24 carbon atoms and having molecular weights of up to 120,000.
  • Preferred ⁇ -olefins are propylene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene.
  • the comonomer content of olefins is preferably between 15 and 50 mol%, more preferably between 20 and 35 mole% and especially between 30 and 45 mole%. These copolymers may also contain minor amounts, eg, up to 10 mol% of other comonomers such as non-terminal olefins or non-conjugated olefins. Preferred are ethylene-propylene copolymers.
  • the olefin copolymers can be prepared by known methods, for example by Ziegler or metallocene catalysts.
  • olefin copolymers are block copolymers containing blocks of olefinically unsaturated aromatic monomers A and blocks of hydrogenated polyolefins B.
  • Particularly suitable are block copolymers of the structure (AB) n A and (AB) m , where n is a number between 1 and 10 and m is a number between 2 and 10.
  • the mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants, comb polymers, alkylphenol condensates, polyoxyalkylene derivatives or olefin copolymers is in each case from 1:10 to 20: 1, preferably from 1: 1 to 10: 1, for example from 1: 1 to 4: 1.
  • the additives can be used alone or together with other additives, e.g. with other pour point depressants or dewaxing aids, with antioxidants, cetane improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, conductivity improvers, sludge inhibitors, odorants and / or cloud point depressants.
  • other pour point depressants or dewaxing aids with antioxidants, cetane improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, conductivity improvers, sludge inhibitors, odorants and / or cloud point depressants.
  • the ethylene copolymers used are commercial products having the characteristics given in Table 4. The products were used as 65% settings in kerosene.
  • Table 4 Characterization of the ethylene copolymers (A) used example Comonomer (s) V140 CH 3/100 CH 2 A1 13.6 mole% vinyl acetate 130 mPas 3.7 A2 13.7 mole percent vinyl acetate and 1.4 mole percent vinyl neodecanoate 105 mPas 5.3 A3 i) 14.0 mol% vinyl acetate and 1.6 mol% vinyl neodecanoate and 97 mPas 4.7 ii) 12.9 mol% of vinyl acetate in the ratio i): ii) of 6: 1 145 mPas 5.4
  • Ethylene copolymer comb polymer co-additive CFPP 100 ppm 150 ppm 200 ppm 300 ppm 14 80% A3 20% B4 150 ppm C6 -18 -20 -22 -24 15 80% A3 20% B6 150 ppm C6 -20 -21 -24 -25 16 80% A3 20% B2 150 ppm C6 -20 -21 -23 -26 17 80% A3 20% B1 150 ppm C6 -21 -22 -25 -27 19 85% A1 15% B5 150 ppm C6 -20 -22 -24 -27 20 80% A1 20% B3 150 ppm C7 -19 -21 -23 -25 21 (Cf.) 80% A3 20% B8 150 ppm C6 -17 -18 -19 -21 22 (See) 80% A1 20% B9 150 ppm C6 -11 -16 -19 -19 23 (Cf.) 80% A1 20% B10 150 ppm C7 -15 -16 -18 -22 24 (

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Claims (16)

  1. Composition d'huile combustible (F), contenant (F1) une huile combustible d'origine minérale, et F2) plus de 2 à 35 % en volume d'une huile combustible d'origine végétale et/ou animale, qui contient plus de 4 % en poids d'esters d'acides gras saturés et, en tant qu'additif pour le froid en une quantité de 0,001 à 5 % en poids, en un rapport en poids A) :B) = 10:1 à 1:10, les constituants
    A) au moins un copolymère d'éthylène et 8 à 21 % en moles d'au moins un ester acrylique ou vinylique contenant un radical alkyle en C1-C18, et
    B) au moins un polymère en peigne contenant des unités structurales comprenant des radicaux alkyle en C8-C16, les unités structurales étant choisies parmi les (méth) acrylates d'alkyle en C8-C16, les esters vinyliques d'alkyle en C8-C16, les éthers vinyliques d'alkyle en C8-C16 et les (méth) acrylamides d'alkyle en C8-C16, les éthers allyliques d'alkyle en C8-C16 et les (alkyle en C8-C16) dicétènes,
    la somme R R = m 1 ⋅ ∑ i w 1 ⁢ i ⋅ n 1 ⁢ i + m 2 ⋅ ∑ j w 2 ⁢ j ⋅ n 2 ⁢ j + ....... + m g ⋅ ∑ p w gp ⋅ n gp
    Figure imgb0009
    de la moyenne molaire des distributions de longueurs de chaînes C dans les radicaux alkyle des monomères B) étant de 11,0 à 14,0,
    avec
    m1, m2, ... mg représentant les fractions molaires des monomères B) susmentionnés dans le polymère, la somme des fractions molaires m1 à mg = 1,
    w1i, w1j, w2i, w2j... wgp représentant les proportions en poids des longueurs de chaînes individuelles i, j, ... p des radicaux alkyle des différents monomères B) 1 à g, et
    n1i, n1j, n2i, n2j... ngp représentant les longueurs de chaînes des radicaux alkyle i, j, ... p des monomères B) 1 à g.
  2. Composition d'huile combustible selon la revendication 1, dans laquelle R vaut de 11,5 à 13,5.
  3. Composition d'huile combustible selon la revendication 1 et/ou 2, dans laquelle, dans le constituant A, outre l'éthylène, 3,5 à 20 % en moles d'acétate de vinyle et 0,1 à 12 % en moles d'ester vinylique de l'acide néononanoïque, d'ester vinylique de l'acide néodécanoïque et d'ester vinylique de l'acide 2-éthylhexanoïque sont contenus, la teneur totale en comonomères étant comprise entre 8 et 21 % en moles.
  4. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 3, dans laquelle, dans le constituant A, outre l'éthylène et 8 à 18 % en moles d'esters vinyliques, 0,5 à 10 % en moles d'oléfines choisies parmi le propène, le butène, l'isobutylène, l'hexène, le 4-méthylpentène, l'octène, le diisobutylène ou le norbornène sont contenues.
  5. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 4, dans laquelle les copolymères qui constituent le constituant A présentent des viscosités à l'état fondu à 140 °C comprise entre 20 et 10 000 mPa·s.
  6. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 5, dans laquelle les copolymères qui composent le constituant A présentent des degrés de ramifications déterminés par spectroscopie RMN 1H compris entre 1 et 9 groupes CH3/100 groupes CH2, qui ne proviennent pas des comonomères.
  7. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 6, dans laquelle les copolymères qui composent le constituant B contiennent des comonomères qui dérivent d'esters ou d'amides d'acides monocarboxyliques éthyléniquement insaturés de 3 à 8 atomes de carbone avec d'alcools ou d'amines de carbone avec des alcools ou des amines, les alcools ou les amines portant des radicaux alkyle de 8 à 16 atomes de carbone.
  8. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 7, dans laquelle les copolymères B) contiennent jusqu'à 50 % en moles de comonomères B2), qui sont i) des esters, des amides et/ou des imides d'acides dicarboxyliques éthyléniquement insaturés de 4 à 8 atomes C et d'alcools ou d'amines de 8 à 16 atomes C dans les radicaux alkyle, et/ou ii) des oléfines en C10 à C20.
  9. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 8, dans laquelle les esters et/ou les amides du constituant B dérivent d'amines et/ou d'alcools à radicaux alkyle linéaires.
  10. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 9, dans laquelle les copolymères B) sont des esters de l'acide acrylique, l'acide méthacrylique, l'acide maléique, l'acide fumarique et l'acide itaconique avec l'octanol, le nonanol, le décanol, l'undécanol, le dodécanol, le n-tridécanol, l'iso-tridécanol, le tétradécanol, le pentadécanol, l'hexadécanol et leurs mélanges, et éventuellement des imides de ces acides avec l'octylamine, la nonylamine, la décylamine, l'undécylamine, la dodécylamine, la tridécylamine, la tétradécylamine, la pentadécylamine, l'hexadécylamine et leurs mélanges.
  11. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 10, dans laquelle les copolymères qui composent le constituant B contiennent des comonomères B2) qui dérivent d'α-oléfines de 10 à 20 atomes C.
  12. Composition d'huile combustible selon l'une des revendications 1 à 11, contenant des dispersants paraffiniques polaires contenant de l'azote.
  13. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 12, qui contient un ou plusieurs esters d'un acide monocarboxylique de 14 à 24 atomes C et d'un alcool de 1 à 4 atomes C.
  14. Composition d'huile combustible selon la revendication 13, dans laquelle l'alcool de 1 à 4 atomes C est le méthanol ou l'éthanol.
  15. Utilisation de 0,001 à 5 % en poids d'un additif tel que défini dans une ou plusieurs des revendications 1 à 12 pour l'amélioration des propriétés d'écoulement à froid de mélanges d'huiles combustibles minérales F1 avec plus de 2 à 35 % en volume d'huiles combustibles d'origine animale ou végétale F2, qui contiennent plus de 4 % en poids d'esters d'acides gras saturés.
  16. Procédé de fabrication de compositions d'huiles combustibles F), contenant des huiles combustibles d'origine minérale (F1) et animale et/ou végétale (F2), qui contiennent plus de 4 % en poids d'esters d'acides gras saturés, la composition d'huile combustible F) contenant, en plus de l'huile combustible d'origine minérale F1), plus de 2 à 35 % en volume d'une huile combustible d'origine végétale et/ou animale F2), à propriétés à froid améliorées, selon lequel 0,001 à 5 % en poids d'un additif tel que défini dans une ou plusieurs des revendications 1 à 13 est ajouté au mélange d'huiles combustibles d'origine minérale F1) et animale et/ou végétale F2).
EP04028307.9A 2003-12-11 2004-11-30 Huiles combustibles comprenant des distillats moyens et des huiles d'origine végétale ou animale et ayant des propriétés à froid améliorées Active EP1541663B1 (fr)

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HUE028480T2 (en) 2016-12-28
DE10357878B4 (de) 2008-05-29
KR20050058217A (ko) 2005-06-16
CA2490031C (fr) 2013-07-09
US7473284B2 (en) 2009-01-06
JP2005200637A (ja) 2005-07-28
DE10357878C5 (de) 2013-07-25
CA2490031A1 (fr) 2005-06-11
DE10357878A1 (de) 2005-07-28
US20050126070A1 (en) 2005-06-16
KR101136333B1 (ko) 2012-04-23
PL1541663T3 (pl) 2016-07-29
JP5025081B2 (ja) 2012-09-12

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