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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
• 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, comprising the components A) and B), for improving the cold flow properties of fuel oil compositions F), as defined in claim 15.
• Another object of the invention is a process for the preparation of fuel oil compositions containing an oil mixture F) with a cloud point of -9 ° C from fuel oils of mineral (F1) and animal and / or vegetable (F2) origin, with improved cold properties, by the additive defined above is added to the mixture of fuel oils of mineral (F1) and animal and / or vegetable (F2) origin in an amount of 0.001 to 5% by weight, comprising constituents A) and B).
• Preferred oils of mineral origin are middle distillates.
• the mixing ratio between the fuel oil animal and / or of the plant origin (which in hereinafter also referred to as biofuel oils) and middle distillates is preferably between 88 to 65 vol .-% middle distillate and 12 to 35 vol .-% biofuel oil. These mixtures give the additives of the invention superior cold properties.
• Q assumes values of 23.0-26.0 and, for example, 23, 24, 24.5, 25 or 26.
• 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.
• 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 vinyl 2-ethylhexanoate, 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 20 to 10,000 mPas, in particular 30 to 5,000 mPas and especially 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 from 50 to 400 MPa, preferably from 100 to 300 MPa, and at temperatures of from 100 to 300 ° C., preferably from 150 to 220 ° C.
• the polymerization is carried out in a multizone reactor, wherein the temperature difference between the peroxide doses 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 substances includes, 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 permaloate, 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 mono
• 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 preferably derived from copolymers of ethylenically unsaturated dicarboxylic acids and derivatives thereof, such as lower esters and anhydrides. Preference is given to maleic acid, fumaric acid, itaconic acid and especially maleic anhydride. Monoolefins having 10 to 20, in particular 12 to 18, carbon atoms are particularly suitable as comonomers. These are preferably linear and the double bond is preferably terminal such as in dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene and octadecene. The ratio of maleic anhydride to olefin or olefins in the polymer is preferably in the range 1: 1.5 to 1.5: 1, especially it is equimolar.
• 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, especially 130 to 170 ° C.
• the preferred method of preparation is the solvent-free bulk polymerization, but it is also possible, 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 perform.
• 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 wt .-%, preferably between 35 and 60 wt .-%.
• 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 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 substance includes e.g. Oxygen, hydroperoxides and peroxides such as e.g. 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-butyl cumyl peroxide, di (t-butyl) peroxide, and azo compounds such as eg 2,2'-azobis (2-methylpropanonitrile) 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 w
• the copolymers can be prepared either by esterification of maleic, fumaric and / or itaconic acid with the corresponding alcohols and subsequent copolymerization or by copolymerization of olefin or olefins with itaconic and / or maleic anhydride and subsequent esterification.
• a copolymerization with anhydrides is carried out and esterified the resulting copolymer after preparation.
• This esterification takes place in both cases, for example by reaction with 0.8 to 2.5 moles of alcohol per mole of anhydride, preferably with 1.0 to 2.0 moles of alcohol per mole of anhydride at 50 to 300 ° C.
• esterification temperatures of about 70 to 120 ° C are preferred.
• larger amounts of alcohol preferably 2 moles of alcohol per mole of anhydride formed at 100 - 300 ° C, preferably 120 - 250 ° C diester.
• 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.
• half esters copolymers having acid numbers of 30-70 mg KOH / g, preferably 40-60 mg KOH / g, are considered here. Copolymers with acid numbers of less than 40, especially less than 30 mg KOH / g are considered as diesters. Particularly preferred are half esters.
• Suitable alcohols are especially linear, but may also contain minor amounts, e.g. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to 10 wt .-% (in 1- or 2-position) branched alcohols. Shorter as well as longer-chain alcohols can be used, but their proportion is preferably below 20 mol% and especially below 10 mol%, for example between 1 and 5 mol%, based on the total amount of the alcohols used. When calculating the Q-factor, these shorter and longer-chain alcohols, if present, are not taken into account because they do not contribute to the effectiveness of the additives.
• Particularly preferred alcohols are octanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol and hexadecanol.
• the effectiveness can be further adapted to specific fatty acid ester compositions.
• mixtures of the copolymers B according to the invention are used, with the proviso that the mean value of the Q values of the mixture components again assumes values of 22.0 to 27.0 and especially values of 23.0 to 26.0.
• the mixing ratio of the additives A and B according to the invention is (in parts by weight) 20: 1 to 1:20, preferably 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 .-%. They may be dissolved as such or dissolved or dispersed in solvents, e.g. aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as e.g.
• the additives according to the invention preferably contain 1 to 80%, especially 10 to 70%, in particular 25 to 60%, of solvent.
• 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.
• fatty acids 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, i. 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 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.
• middle distillates are used which contain 0.05% by weight of sulfur and less, more preferably less than 350 ppm of sulfur, especially less than 200 ppm of sulfur and in special cases less than 50 ppm of sulfur such as less than 10 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 additive may be added to the oil to be added 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 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 -8 ° C to -20 ° C, as they be used for use especially in winter.
• the additives according to the invention are particularly advantageous in oil mixtures which contain more than 11% by volume of biofuel F 2, preferably more than 12% by volume of biofuel F 2 and especially more than 15% by volume 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%, as for example in sunflower and soybean oils Case is.
• Such biofuels preferably have a cloud point above -5 ° C and especially above -3 ° C.
• Oil blends F in which the additives according to the invention show particularly advantageous action, 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 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.
• 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, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. 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 acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
• Alkylphenol-aldehyde resins are, for example, in Rompp 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 the thereof 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 mol% and especially between 30 and 45 mol%. 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, for example 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 additives for lowering the cloud point.
• 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 additives for lowering the cloud point.
• the CFPP value is determined according to EN 116 and the determination of the cloud point according to ISO 3015. Both properties are determined in ° C. Table 1: Characterization of the biofuel oils (F2) used Oil no. CP CFPP E 1 Rapsölklaremethylester -2.3 -14 ° C E 2 80% rapeseed oil methyl ester + 20% sunflower oil methyl ester -1.6 -10 ° C E 3 90% rapeseed oil methyl ester + 10% soybean oil methyl ester -2.0 -8 ° C C chain distribution of the fatty acid methyl esters used for the preparation of the test oils (main constituents,% by volume according to GC): C 16 C 16 ' C 18 C 18 ' C 18 " C 18 '" C 20 C 20 ' C 22 ⁇ saturated RME 4.5 0.5 1.7 61.6 18.4 8.7 0.7 1.5 0.4 7.3 SBME 6.0 0.1 3.8 28.7 58.7 0.1 0.3 0.3 0.7 10.8 SojaME 10.4 0.1 4.1 2
• 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 ii) 12.9 mol% of vinyl acetate in the ratio i): ii) of 6: 1 97 mPas 145 mPas 4.7 5.4
• the polymerization of maleic anhydride (MSA) with ⁇ -olefins is carried out in a higher boiling aromatic hydrocarbon mixture at 160 ° C in the presence of a mixture of equal parts tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate as a radical chain initiator.
• Table 5 shows, by way of example, various copolymers and the molar proportions of the monomers used for their preparation, as well as the chain length and molar amount (based on MSA) of the alcohol used for the derivatization and the factor Q calculated therefrom.
• the esterifications are carried out in the presence of solvent naphtha (40 to 50 wt .-%) at 90 to 100 ° C for half ester and at 160 to 180 ° C with azeotropic culling of water of reaction to the diester.
• the degree of esterification is inversely proportional to the acid number.
• the further flow improvers used C are commercial products with the characteristics given in Table 6. The products were used as 50% settings in solvent naphtha. Table 6: Characterization of the further flow improvers used C3 Reaction product of a copolymer of C 14 / C 16 olefin and maleic anhydride with 2 equivalents of secondary tallow fatty amine per maleic anhydride unit C4 Reaction product of phthalic anhydride with 2 equivalents of di (hydrogenated tallow fatty amine) to the amide ammonium salt C5
• Nonylphenol resin prepared by condensing a mixture of dodecylphenol with formaldehyde, Mw 2000 g / mol C6 Mixture of 2 parts C3 and 1 part C5 C7 Mixture of equal parts C4 and C5
• CFPP value (according to EN 116, in ° C) of various biofuels according to the above table after addition of 1200 ppm, 1500 ppm and 2000 ppm additive mixture was determined. Percentages refer to parts by weight in the respective mixtures.
• Tables 5 to 7 show that comb polymers with the factor Q according to the invention achieve excellent CFPP reductions even at low dosing rates and offer additional potential at higher dosing rates.
• Ethylene copolymer comb polymer co-additive CFPP 100 ppm 150 ppm 200 ppm 300 ppm 15 80% A3 20% B1 150 ppm C6 -20 -20 -21 -24 16 80% A3 20% B2 150 ppm C6 -20 -22 -25 -24 17 80% A3 20% B3 150 ppm C6 -20 -20 -24 -25 18 80% A3 20% B4 150 ppm C6 -20 -21 -23 -26 19 75% A3 25% B5 150 ppm C6 -19 -20 -26 20 85% A1 15% B6 150 ppm C6 -20 -22 -24 -27 21 80% A1 20% B9 150 ppm C7 -20 -22 -25 -27 22 (V) 80% A3 20% B10 150 ppm C6 -19 -20 -19 -20 23 (V) 80% A3 20% B11 150 ppm C6 -9 -14 -18 -19 24 (V) 80% A1 20% B10
• Ethylene copolymer comb polymer CFPP 100 ppm 200 ppm 250 ppm 300 ppm 26 80% A3 20% B1 -17 -20 -25 -26 27 80% A3 20% B2 -21 -24 -23 -26 28 80% A3 20% B3 -21 -23 -25 -27 29 80% A3 20% B4 -20 -23 -26 -29 30 80% A3 20% B5 -16 -20 -26 -26 31 75% A1 25% B6 -20 -23 -26 -29 32 75% A1 25% B9 -21 -24 -25 -28 33 (V) 80% A3 20% B10 -17 -19 -22 -23 34 (V) 80% A3 20% B11 -10 -16 -17 -21 35 (V) 80% A1 20% B12 -15 -17 -19 -21 36 (V) 100% A1 - -11 -20 -22 -22 -22 -22 -22

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