EP1857529B2 - Agent d'amélioration de l'écoulement à froid pour huiles combustibles d'origine végétale ou animale - Google Patents

Agent d'amélioration de l'écoulement à froid pour huiles combustibles d'origine végétale ou animale Download PDF

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Publication number
EP1857529B2
EP1857529B2 EP07008847.1A EP07008847A EP1857529B2 EP 1857529 B2 EP1857529 B2 EP 1857529B2 EP 07008847 A EP07008847 A EP 07008847A EP 1857529 B2 EP1857529 B2 EP 1857529B2
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Prior art keywords
monomer
fuel oil
chain lengths
alkyl
alkyl radicals
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German (de)
English (en)
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EP1857529B1 (fr
EP1857529A1 (fr
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Bettina Siggelkow
Ulrike Neuhaus
Markus Kupetz
Waltraud Nagel
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Clariant International Ltd
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Clariant International Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—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
    • C10L1/19—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
    • C10L1/197—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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties

Definitions

  • the present invention relates to the use of an additive as a cold flow improver for vegetable or animal fuel oils and correspondingly fueled fuel oils.
  • renewable raw materials include, in particular, natural oils and fats of plant or animal origin. These are usually triglycerides of fatty acids with 10 to 24 carbon atoms, which have a comparable calorific value to conventional fuels, but at the same time are considered to be 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 and generally of the formula in which R is an aliphatic radical of 10 to 25 carbon atoms, which may be saturated or unsaturated.
  • oils contain 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.
  • EP-A-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 10 to 30 carbon atoms is bonded to a non-polymeric organic group to provide at least one linear chain of atoms including the carbon atoms of the alkyl groups and one or more non-terminal oxygen atoms, or (e) one or more of Components (a), (b), (c) and (d).
  • EP-A-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.
  • EP-A-1 491 614 discloses oils of vegetable or animal origin and blends thereof with petroleum distillate fuel oils which, to improve their low temperature properties, contain an ethylene / vinyl ester copolymer containing at least 17 mole percent vinyl ester and a degree of branching of 5 or more alkyl branches per 100 methylene groups.
  • fatty acid esters which are derived, for example, from rapeseed, waste-oil, sunflower and / or soybean oil and which contain at least 7% by weight of palmitic and stearic acid methyl esters.
  • CFPP values of -10 ° C and -20 ° C and below are to be set and the set CFPP value remains constant even after prolonged storage of the oil in the region of its cloud point or below.
  • these additives should help to prevent the sedimentation of these oils, so that even after storage for several days of the fatty acid esters, they remain homogeneous and flowable and their CFPP does not change.
  • the fuel oil comprises a mixture of fatty acid esters of C 1 to C 4 alcohols, and wherein the fatty acid esters methyl stearate and methyl palmitate are contained in a proportion of more than 7 wt .-%.
  • Another object of the invention is the use of the additive defined above to improve the cold flow properties of animal fuel oils or of vegetable origin.
  • Another object of the invention is a method for improving the cold flow properties of fuel oils of animal or vegetable origin by adding to fuel oils of animal or vegetable origin, the additive defined above.
  • Q assumes values of 24 to 26.
  • Chain length of olefins is understood here as the chain length of the monomeric olefin minus the two olefinically bonded C atoms.
  • the chain length is equal to the total chain length of the olefin minus the two olefinically bonded carbon atoms.
  • the chain length is the length of the alkyl radicals which, introduced into the polymer by the olefin, depart from the polymer backbone.
  • Preferred ethylene copolymers A) are those which contain from 13 to 17 mol% of one or more vinyl and / or (meth) acrylic esters and from 83 to 87% by weight of ethylene. Particularly preferred are ethylene copolymers with 15 to 17 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. Preferred ethylene copolymers have a melt viscosity V 140 of preferably 10 to 80, in particular 20 to 60 mPas.
  • vinyl esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, 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-nonanoic acid vinyl ester, vinyl neononanoate, vinyl neodecanoate and Neoundecanklaklad.
  • 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. Also suitable are mixtures of two, three, four or more of these comonomers.
  • copolymers contain, in addition to ethylene and 13 to 17 mol% of vinyl esters, 0.5 to 10 mol% of olefins having 3 to 10 carbon atoms, such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
  • olefins having 3 to 10 carbon atoms, such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
  • the copolymers A preferably have weight-average molecular weights M w, measured by gel permeation chromatography (GPC) against polystyrene standards in THF of from 1000 to 10 000, in particular from 1500 to 5000 g / mol.
  • Their means of 1 H NMR spectroscopy (400 MHz with CDCl 3 as solvent) degrees of branching determined are preferably smaller than 6, especially less than 5 CH 3/100 CH 2 groups.
  • the methyl groups are derived from the short and long chain branches, and not from copolymerized 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 from 50 to 400 MPa, preferably from 100 to 300 MPa, and at temperatures of from 100 to 300 ° C., preferably from 150 to 250 ° 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).
  • free radical initiators for example, 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 monomer mixture.
  • 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.
  • the mixture of the monomers, the initiator and, if used, the moderator a tubular reactor via the reactor inlet and via one or more side branches supplied.
  • 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 ).
  • Suitable copolymers or terpolymers include, for example: ethylene-vinyl acetate copolymers with 10 to 40% by weight of vinyl acetate and 60 to 90% by weight of ethylene; from DE-A-34 43 475 known ethylene-vinyl acetate-hexene terpolymers; in the EP-A-0 203 554 described ethylene-vinyl acetate-diisobutylene terpolymers; from EP-A-0 254 284 known mixture of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene / vinyl acetate copolymer; in the EP-A-0 405 270 disclosed blends of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer; in the EP-A-0 463 518 described ethylene / vinyl acetate / iso-butyl vinyl
  • 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 preferred 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 the amides and imides of ethylenically unsaturated dicarboxylic acids.
  • Preferred dicarboxylic acids are maleic acid, fumaric acid and itaconic acid.
  • Monoolefins B1 having from 10 to 20, in particular from 12 to 18, carbon atoms are particularly suitable as comonomers. These are preferably linear and the double bond is preferably terminal, as for example in dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene and octadecene.
  • the molar ratio of dicarboxylic acid amide / imide to olefin or olefins in the polymer is preferably in the range 1: 1.5 to 1.5: 1, in particular it is equimolar.
  • copolymer B which are copolymerizable with ethylenically unsaturated dicarboxylic acid amides / imides and the said olefins, such as Olefins having 2 to 50 carbon atoms, allyl polyglycol ethers, C 1 -C 30 -alkyl (meth) acrylates, vinylaromatics or C 1 -C 20 -alkyl vinyl ethers.
  • the preparation of the copolymers B) according to the invention is preferably carried out at temperatures between 50 and 220 ° C, in particular 100 to 190 ° C.
  • the preferred method of preparation is solvent-free bulk polymerization, but it is also possible to carry out the polymerization in the presence of aprotic solvents such as benzene, toluene, xylene or higher-boiling aromatic, aliphatic or isoaliphatic solvents or solvent mixtures such as kerosene or solvent naphtha.
  • the polymerization is particularly preferably in less moderating, aliphatic or isoaliphatic solvents.
  • the proportion of solvent in the polymerization mixture is generally between 10 and 90% by weight, preferably between 35 and 60% by weight.
  • the reaction temperature can be set particularly easily by the boiling point of the solvent or by working under reduced or elevated pressure.
  • the average molecular weight Mw of the copolymers B according to the invention is generally between 1,200 and 200,000 g / mol, in particular between 2,000 and 100,000 g / mol, measured by gel permeation chromatography (GPC) against polystyrene standards in THF.
  • 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.
  • the reaction of the monomers is initiated by free radical initiators (free radical initiators).
  • This class of substances includes, for example, oxygen, hydroperoxides and peroxides such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permalonate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, Di (t-butyl) peroxide, and azo compounds such as 2,2'-azobis (2methylpropanonitrile) or 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 Mono
  • the copolymers can be prepared either by reaction of maleic, fumaric and / or itaconic acid or their anhydrides with the corresponding amine and subsequent copolymerization or by copolymerization of olefin or olefins with at least one unsaturated dicarboxylic acid or its derivative such as itacon and / or Maleic anhydride and subsequent reaction with amines are produced.
  • a copolymerization with anhydrides is preferably carried out and the resulting copolymer is converted after production into an amide and / or an imide.
  • reaction with amines takes place in both cases, for example by reaction with 0.8 to 2.5 moles of amine per mole of anhydride, preferably with 1.0 to 2.0 moles of amine per mole of anhydride at 50 to 300 ° C.
  • 0.8 to 2.5 moles of amine per mole of anhydride preferably with 1.0 to 2.0 moles of amine per mole of anhydride at 50 to 300 ° C.
  • about 1 mol of amine per mol of anhydride formed at reaction temperatures of about 50 to 100 ° C preferably hemiamides, which additionally carry a carboxyl group per amide group.
  • reaction temperatures of about 100 to 250 ° C arise from primary amines with elimination of water preferably imides.
  • amine preferably 2 moles of amine per mole of anhydride formed at about 50 to 200 ° C amide ammonium salts and at higher temperatures, for example, 100 - 300 ° C, preferably 120 - 250 ° C diamides.
  • the water of reaction can be distilled off by means of an inert gas stream or discharged in the presence of an organic solvent by means of azeotropic distillation. Preference is given to 20-80, in particular 30-70, especially 35-55 wt .-% of at least one organic solvent used.
  • half-amides here are considered (50% in solvent) copolymers having acid numbers of 30 - 70 mg KOH / g, preferably from 40 - 60 mg KOH / g.
  • Corresponding copolymers with acid numbers of less than 40, especially less than 30 mg KOH / g are considered diamides or imides. Particularly preferred are hemi-amides and diamides.
  • 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. In particular, they carry linear alkyl radicals, but they can also minor amounts, e.g. B. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to 10 wt .-% (in 1- or 2-position) contain branched amines. Shorter as well as longer-chain amines can be used, but their proportion is preferably less than 20 mol% and especially less than 10 mol%, for example between 1 and 5 mol%, based on the total amount of amines used.
  • 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 average value of the alkyl chain lengths of C 8 to C 16 is taken into account for the calculation of the parameter Q as alkyl chain length n. Shorter and longer alkyl radicals, if present, are not included in the calculation because they do not contribute to the effectiveness of the additives.
  • Particularly preferred copolymers B contain hemiamides and diamides of primary monoamines as monomer 2.
  • the effectiveness can be further adapted to specific fatty acid ester compositions.
  • the additives may also contain polymers and copolymers based on C 10 -C 24 -alkyl acrylates or methacrylates (component C).
  • These poly (alkyl acrylates) and methacrylates have molecular weights Mw of 800 to 1,000,000 g / mol, and are preferably derived from caprylic, capric, undecyl, lauryl, myristyl, cetyl, palmitoleyl, stearyl alcohol or mixtures thereof, such as, for example, coconut palm - tallow fat or behenyl alcohol.
  • mixtures of different copolymers B are used, the average (weight average) of the parameters Q of the mixture components assuming values of 23 to 27 and preferably values of 24 to 26.
  • the mixing ratio of the additive components A and B is (in parts by weight) especially 5: 1 to 1: 5.
  • the proportion of component C in the formulations of A, B and C may be up to 40% by weight; it is preferably less than 20% by weight, in particular between 1 and 10% by weight, based on the total weight of A, B and C.
  • the additives are added to oils in amounts of 0.001 to 5 wt%, preferably 0.005 to 1 wt%, and especially 0.01 to 0.6 wt%. They may be dissolved as such or dissolved or dispersed in solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such.
  • toluene xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene, naphtha, diesel, fuel oil, isoparaffins or commercial solvent mixtures such as solvent naphtha, ® Hydrolsol A 200 N, ® Shellsol A 150 ND, ® Caromax 20 LN, ® Shellsol AB , ® Solvesso 150, ® Solvesso 150 ND, ® Solvesso 200, ® Exxsol, ® Isopar and ® Shellsol D types.
  • they are dissolved in fuel oil of animal or vegetable origin based on fatty acid alkyl esters.
  • the additives contain 1 - 80%, especially 10 - 70%, in particular 25 - 60% solvent.
  • the fuel oil which is often referred to as “biodiesel” or “biofuel”
  • biodiesel is fatty acid alkyl esters of fatty acids having 12 to 24 carbon atoms and alcohols having 1 to 4 carbon atoms.
  • 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 derived from animal or vegetable material and in which the additive may be used 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 edible 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 used fat, palm oil, sunflower and soybeans and their mixtures with rapeseed oil are preferred.
  • Particularly suitable as biofuels are lower alkyl esters of fatty acids.
  • lower alkyl esters of fatty acids are, for example, commercially available mixtures of ethyl, propyl, butyl and especially methyl esters of fatty acids having 14 to 22 carbon atoms, for example of lauric, myristic, palmitic, palmitolic, stearic, oleic, elaidic, petroselic, ricinoleic, elaeostearic, linoleic, linolenic , Eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid, which preferably have an iodine value of from 50 to 150, in particular from 90 to 125.
  • Mixtures with particularly advantageous properties are those which are mainly d. H. at least 50 wt .-%, contain 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, palm oil methyl ester and soybean oil methyl ester being most preferred. Due to the high demand for biofuels, more and more manufacturers of fatty acid methyl esters are switching to other raw material sources with higher availability.
  • oil which is used as Altfettölmethylester as biodiesel alone or in admixture with other fatty acid methyl esters, such as. Rapsölklaremethylester, sunflower oil, methyl oleate and soybean oil is used.
  • RapsölTexremethylester sunflower oil, methyl oleate and soybean oil is used.
  • mixtures of rapeseed oil methyl ester with Soyaölmethylester or rapeseed oil methyl ester with a mixture of Soyaölmethylester and palm oil methyl ester are particularly noteworthy.
  • the additive may be added to the oil to be treated according to methods known in the art. If more than one additive component or co-additive component is to be used, such components may be incorporated into the oil together or separately in any combination.
  • the CFPP value of biodiesel can be adjusted to values of -10 ° C and below -20 ° C and sometimes to values below -25 ° C, as required for marketing for use, especially in winter , At the same time, the pour point of biodiesel is lowered by the addition of additives.
  • the additives are particularly advantageous in problematic oils containing a high proportion of esters of the saturated fatty acids palmitic acid and stearic acid of more than 7% by weight, as for example in fatty acid methyl esters from Altfettöl, sunflower and soy are included.
  • the additives thus also to adjust mixtures of Rapsölklaremethylester and / or Altfettölmethylester and / or sunflower and / or soybean oil fatty acid methyl ester to CFPP values of -10 ° C and -20 ° C and below. It is thus possible with the additives also, Altfettölmethylester or sunflower or soybean oil fatty acid methyl ester to CFPP values of -10 ° C and -20 ° C and below set.
  • the oils thus added have a good resistance to cold chill, ie the CFPP value remains constant even when stored under winter conditions and does not tend to sediment at constant low temperatures (eg -10 ° C. or -22 ° C.).
  • the additives 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 cause a paraffin dispersion (paraffin dispersants) and oil-soluble amphiphiles.
  • the additives can be used in admixture with paraffin dispersants.
  • Paraffin dispersants reduce the size of the paraffin crystals and cause the paraffin particles to not settle but remain colloidally dispersed with significantly reduced sedimentation effort.
  • paraffin dispersants both low molecular weight and polymeric, oil-soluble compounds having ionic or polar groups such.
  • amine salts and / or amides proven.
  • Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines having 20 to 44 carbon atoms, in particular dicocoamine, ditallow fatty amine, 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 be reacted with primary monoalkylamines and / or aliphatic alcohols (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.
  • the mixing ratio (in parts by weight) of the additives with paraffin dispersants is 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • oils treated with the additive can also be added to petroleum-derived middle distillates.
  • the resulting mixtures of biofuel and middle distillate can in turn be mixed with cold additives such as flow improvers or wax dispersants, and Performance Packages.
  • the middle distillate is in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil.
  • such middle distillates are used which contain 0.05% by weight of sulfur and less, more preferably less than 350 ppm of sulfur, in particular less than 200 ppm of sulfur and in special cases less than 50 ppm of sulfur.
  • These are generally those 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 additives can be used alone or together with other additives with other pour point depressants or dewaxing aids, with antioxidants, cetane number 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 number improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, conductivity improvers, sludge inhibitors, odorants and / or cloud point depressants.
  • V 140 The viscosity (V 140 ) was measured with a Haake Reostress 600 viscometer.
  • the total amount of additive is shown in the table header.
  • Table 6 CFPP Testing in Test Oil E1 Ex. comb polymer ethylene copolymer polyacrylate 2000 ppm 3000 ppm 4000 ppm 1 B1 A2 - -18 -22 -20 2 (V) B1 A1 - -12 -16 -10 3 B1 A2 C3 -18 -21 -21 Ex.

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Claims (11)

  1. Composition d'huile combustible, contenant une huile combustible d'origine végétale ou animale et un additif pour huile combustible, contenant dans un rapport pondéral A:B = 10:1 à 1:10
    A) un copolymère d'éthylène et de 13-17% en mole d'au moins un ester d'acryle ou de vinyle présentant un radical C1-C18-alkyle et une viscosité de la masse fondue V140 de 5 à 80 mPa.s et
    B) un polymère en peigne contenant des unités structurales
    B1) au moins une oléfine comme monomère 1 qui porte sur la double liaison oléfinique au moins un radical C8-C18-alkyle, et
    B2) au moins un acide dicarboxylique éthyléniquement insaturé comme monomère 2, qui porte au moins un radical C8-C16-alkyle lié via un groupe amide et/ou imide,
    dans lequel le paramètre Q Q = ∑ i w 1 ⁢ i ∗ n 1 ⁢ i + ∑ j w 2 ⁢ j ∗ n 2 ⁢ j
    Figure imgb0008
     où
    w1 représente la proportion molaire des différentes longueurs de chaîne n1 dans les radicaux alkyle du monomère 1,
    w2 représente la proportion molaire des différentes longueurs de chaîne n2 dans les radicaux alkyle des groupes amide et/ou imide du monomère 2,
    n1 représente les différentes longueurs de chaîne dans les radicaux alkyle du monomère 1,
    n2 représente les différentes longueurs de chaîne dans les radicaux alkyle des groupes amide et/ou imide du monomère 2,
    i représente la variable indépendante contrôlée pour les longueurs de chaîne dans les radicaux alkyle du monomère 1, et
    j représente la variable indépendante contrôlée pour les longueurs de chaîne dans les radicaux alkyle des groupes amide et/ou imide du monomère 2,
    présente des valeurs de 23 à 27, dans laquelle l'huile combustible comprend un mélange d'esters d'acide gras d'alcools en C1-C4 et dans laquelle les esters d'acide gras, ester méthylique de l'acide stéarique et ester méthylique de l'acide palmitique, sont contenus en une proportion de plus de 7% en poids.
  2. Composition d'huile combustible selon la revendication 1, Q présentant des valeurs de 24 à 26.
  3. Composition d'huile combustible selon la revendication 1 et/ou 2, le constituant A) comprenant 15 à 17% en mole d'au moins un ester de vinyle.
  4. Composition d'huile combustible selon l'une ou plusieurs des revendications 1 à 3, le constituant A) comprenant 0,5 à 10% en mole d'oléfines comprenant 3 à 10 atomes de carbone.
  5. Composition d'huile combustible selon l'une ou plusieurs des revendications 1 à 4, le degré de ramification du constituant A) étant inférieur à 6 CH3/100 groupes CH2, déterminé au moyen de la spectroscopie 1H-RMN.
  6. Composition d'huile combustible selon l'une ou plusieurs des revendications 1 à 5, les oléfines qui forment le constituant B1) étant des α-oléfines.
  7. Composition d'huile combustible selon l'une ou plusieurs des revendications 1 à 6, le rapport molaire des comonomères B1) aux comonomères B2) dans le copolymère B) se situant entre 1,5:1 et 1:1,5.
  8. Composition d'huile combustible selon l'une ou plusieurs des revendications 1 à 7, le copolymère B contenant, outre les comonomères B1) et B2), encore jusqu'à 20% en mole d'autres comonomères, différents de B1) et de B2), choisis parmi les oléfines comprenant 2 à 50 atomes de carbone, les allylpolyglycoléthers, les (méth)acrylates de C1-C30-alkyle, les aromatiques de vinyle ou les C1-C20-alkylvinyléthers, ainsi que les polyisobutènes présentant des poids moléculaires de jusqu'à 5000 g/mole.
  9. Composition d'huile combustible selon l'une ou plusieurs des revendications 1 à 8, le constituant A) présentant un poids moléculaire de 1000 à 10 000 g/mole.
  10. Composition d'huile combustible selon l'une ou plusieurs des revendications 1 à 9, le constituant B) présentant un poids moléculaire de 1200 à 200 000 g/mole.
  11. Utilisation d'un additif pour huile combustible, contenant dans un rapport pondéral A:B = 10:1 à 1:10
    A) un copolymère d'éthylène et de 13 à 17% en mole d'au moins un ester d'acryle ou de vinyle présentant un radical C1-C18-alkyle et une viscosité de la masse fondue V140 de 5 à 80 mPa.s et
    B) un polymère en peigne contenant des unités structurales
    B1) au moins une oléfine comme monomère 1 qui porte sur la double liaison oléfinique au moins un radical C8-C18-alkyle, et
    B2) au moins un acide dicarboxylique éthyléniquement insaturé comme monomère 2, qui porte au moins un radical C8-C16-alkyle lié via un groupe amide et/ou imide,
    dans laquelle le paramètre Q Q = ∑ i w 1 ⁢ i ⋅ n 1 ⁢ i + ∑ j w 2 ⁢ j ⋅ n 2 ⁢ j
    Figure imgb0009
     où
    w1 représente la proportion molaire des différentes longueurs de chaîne n1 dans les radicaux alkyle du monomère 1,
    w2 représente la proportion molaire des différentes longueurs de chaîne n2 dans les radicaux alkyle des groupes amide et/ou imide du monomère 2,
    n1 représente les différentes longueurs de chaîne dans les radicaux alkyle du monomère 1,
    n2 représente les différentes longueurs de chaîne dans les radicaux alkyle des groupes amide et/ou imide du monomère 2,
    i représente la variable indépendante contrôlée pour les longueurs de chaîne dans les radicaux alkyle du monomère 1, et
    j représente la variable indépendante contrôlée pour les longueurs de chaîne dans les radicaux alkyle des groupes amide et/ou imide du monomère 2,
    présente des valeurs de 23 à 27 pour améliorer la tenue au froid d'huiles combustibles d'origine végétale ou animale, dans laquelle l'huile combustible comprend un mélange d'esters d'acide gras d'alcools en C1-C4 et dans laquelle les esters d'acide gras, ester méthylique de l'acide stéarique et ester méthylique de l'acide palmitique, sont contenus en une proportion d'au moins 7% en poids.
EP07008847.1A 2006-05-16 2007-05-02 Agent d'amélioration de l'écoulement à froid pour huiles combustibles d'origine végétale ou animale Active EP1857529B2 (fr)

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JP5271593B2 (ja) * 2008-04-25 2013-08-21 株式会社Ａｄｅｋａ バイオディーゼル燃料用低温流動性向上剤
JP5810576B2 (ja) * 2010-04-22 2015-11-11 日油株式会社 バイオディーゼル燃料油用流動性向上剤
US10557096B2 (en) 2014-11-27 2020-02-11 Basf Se Copolymer and use thereof for reducing crystallization of paraffin crystals in fuels
EP4095217B1 (fr) 2016-05-24 2024-05-08 Basf Se Copolymère et son utilisation pour réduire la cristallisation des cristaux de paraffine dans les carburants
WO2018054892A1 (fr) 2016-09-21 2018-03-29 Basf Se Terpolymères d'anhydride de l'acide maléique, d'acrylates et d'alpha-oléfines, en particulier destinés à être utilisés comme agent d'amélioration de l'écoulement de pétrole
EP3913035A1 (fr) 2020-05-20 2021-11-24 Basf Se Nouvelles compositions de réduction de cristallisation de cristaux de paraffine dans des carburants
WO2024037904A1 (fr) 2022-08-16 2024-02-22 Basf Se Composition pour réduire la cristallisation de cristaux de paraffine dans des combustibles

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EP1857529A1 (fr) 2007-11-21
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US20070266620A1 (en) 2007-11-22
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