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
  • C10L1/18—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
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/165—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • 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
• • 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
  • C10L1/18—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

Definitions

• the present invention relates to an additive, to its use as a cold flow improver for vegetable or animal fuel oils and to correspondingly additized fuel oils.
• renewable raw materials include in particular natural oils and fats of vegetable or animal origin. These are generally triglycerides of fatty acids having from 10 to 24 carbon atoms and a calorific value comparable to conventional fuels, but are at the same time regarded as being less harmful to the environment.
• Biofuels i.e. fuels derived from animal or vegetable material, are obtained from renewable sources and, when they are combusted, therefore generate only as much CO 2 as had previously been converted to biomass. It has been reported that less carbon dioxide is formed in the course of combustion than by the equivalent amount of crude oil distillate fuel, for example diesel fuel, and that very little sulfur dioxide is formed. In addition, they are biodegradable.
• Oils obtained from animal or vegetable material are mainly metabolism products which include triglycerides of monocarboxylic acids, and generally correspond to the formula
• R is an aliphatic radical which has from 10 to 25 carbon atoms and may be saturated or unsaturated.
• oils contain glycerides from a series of acids whose number and type vary with the source of the oil, and they may additionally contain phosphoglycerides.
• Such oils can be obtained by processes known from the prior art.
• EP-A-0 665 873 discloses a fuel oil composition which includes a biofuel, a fuel oil based on crude 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 nonpolymeric organic radical, in order to provide at least one linear chain of atoms which includes the carbon atoms of the alkyl groups and one or more nonterminal oxygen atoms, or (e) one or more of components (a), (b), (c) and (d).
• EP-A-0 629 231 discloses a composition which comprises a relatively large proportion of oil which consists substantially of alkyl esters of fatty acids which are derived from vegetable or animal oils or both, mixed with a small proportion of mineral oil cold flow improvers, which comprises one or more of the following:
• EP-A-0 543 356 discloses a process for preparing compositions having improved low temperature performance for use as fuels or lubricants, starting from the esters of naturally occurring long-chain fatty acids with monohydric C 1 -C 6 -alcohols (FAE), which comprises
• DE-A-40 40 317 discloses mixtures of fatty acid lower alkyl esters having improved cold stability comprising
• EP-A-0 153 176 discloses the use of polymers based on unsaturated dialkyl C 4 -C 8 -dicarboxylates having an average alkyl chain length of from 12 to 14 as cold flow improvers for certain crude oil distillate fuel oils. Mentioned as suitable comonomers are unsaturated esters, in particular vinyl acetate, but also ⁇ -olefins.
• EP-A-0 153 177 discloses an additive concentrate which comprises a combination of
• EP-A-1 491 614 discloses oils of vegetable or animal origin and their blends with crude oil distillate fuel oils, which comprise an ethylene-vinyl ester copolymer which contains at least 17 mol % of vinyl ester and has a degree of branching of 5 or more alkyl branches per 100 methylene groups to improve their low temperature properties.
• fatty acid esters especially those which comprise a total of more than 7% by weight of palmitic acid methyl ester and stearic acid methyl ester, to a CFPP of ⁇ 10° C. which is required for use as winter diesel in Southern Central Europe and of ⁇ 20° C. in Northern Central Europe, and of ⁇ 22° C. and lower for specific applications.
• An additional problem with the existing additives is a lack of cold transition stability of the additized oils, i.e. the set CFPP value of the oils rises gradually when the oil is stored for a prolonged period at varying temperatures in the region of its cloud point or lower.
• oils having a high content of palmitic acid methyl ester and stearic acid methyl ester exhibit a strong tendency to sedimentation in the course of storage at low temperatures. It is known from practice that sedimentation of the additized fatty acid esters which occurs in laboratory experiments under cold conditions, in spite of the CFPP being attained, can lead to filter blockages in the engine and the fuel is thus not suitable for use in transport.
• these additives should contribute to preventing the sedimentation tendency of these oils, such that, even after storage of the fatty acid esters for several days, they remain homogeneous and free-flowing and their CFPP does not change either.
• the invention provides an additive comprising
• the invention further provides a fuel oil composition comprising a fuel oil of animal or vegetable origin and the above-defined additive.
• the invention further provides for the use of the above-defined additive for improving the cold flow properties of fuel oils of animal or vegetable origin.
• the invention further provides a process for improving the cold flow properties of fuel oils of animal or vegetable origin by adding the above-defined additive to fuel oils of animal or vegetable origin.
• Q assumes values of from 24 to 26.
• Chain length of olefins is understood here to mean the chain length of the monomeric olefin minus the two olefinically bonded carbon 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.
• Suitable ethylene copolymers A) are preferably those which contain from 13 to 17 mol % of one or more vinyl esters and/or (meth)acrylic esters and from 83 to 87% by weight of ethylene. Particular preference is given to ethylene copolymers having from 15 to 17 mol % of at least one vinyl ester. Suitable vinyl esters derive from fatty acids having linear or branched alkyl groups having from 1 to 30 carbon atoms. Preferred ethylene copolymers have a melt viscosity V 140 of at least 5 mPas, preferably from 10 to 80 mPas, in particular from 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 esters of vinyl alcohol based on branched fatty acids, such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl isononanoate, vinyl neononanoate, vinyl neodecanoate and vinyl neoundecanoate.
• esters of acrylic acid and methacrylic acid having from 1 to 20 carbon atoms in the alkyl radical such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n- and isobutyl(meth)acrylate, hexyl(meth)acrylate, octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, tetradecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate.
• mixtures of two, three, four or even more of these comonomers are also suitable.
• copolymers contain, in addition to ethylene and from 13 to 17 mol % of vinyl esters, also from 0.5 to 10 mol % of olefins having from 3 to 10 carbon atoms, for example propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and/or norbornene.
• olefins having from 3 to 10 carbon atoms
• the copolymers A preferably have weight-average molecular weights Mw, measured by means of gel permeation chromatography (GPC) against polystyrene standards in THF of from 1000 to 10 000 g/mol, in particular from 1500 to 5000 g/mol.
• Their degrees of branching determined by means of 1 H NMR spectroscopy are preferably less than 6 CH 3 /100 CH 2 groups, in particular less than 5 CH 3 /100 CH 2 groups.
• the methyl groups stem from the short-chain and long-chain branches, and not from copolymerized comonomers.
• the copolymers (A) can be prepared by customary copolymerization processes, for example suspension polymerization, solution polymerization, gas phase polymerization or high pressure bulk polymerization. Preference is given to carrying out the high pressure bulk polymerization at pressures of from 50 to 400 MPa, preferably from 100 to 300 MPa, and temperatures from 100 to 300° C., preferably from 150 to 250° C.
• the polymerization is effected in a multizone reactor in which the temperature difference between the peroxide feeds along the tubular reactor is kept to a minimum, i.e. ⁇ 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-forming initiators (free radical chain initiators).
• This substance class includes, for example, oxygen, hydroperoxides, peroxides and azo compounds, such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis(2-ethylhexyl)peroxodicarbonate, t-butyl perpivalate, t-butyl permaleate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di(t-butyl)peroxide, 2,2′-azobis(2-methyl-propanonitrile), 2,2′-azobis(2-methylbutyronitrile).
• the initiators are used individually or as a mixture of two or more substances in amounts of from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, based on the monomer mixture.
• the high-pressure bulk polymerization is carried out in known high-pressure reactors, for example autoclaves or tubular reactors, batchwise or continuously; tubular reactors have been found to be particularly useful.
• Solvents such as aliphatic and/or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene may be present in the reaction mixture. Preference is given to the substantially solvent-free procedure.
• the mixture of the monomers, the initiator and, if used, the moderator is fed to a tubular reactor via the reactor entrance and also via one or more side branches.
• Preferred moderators are, for example, hydrogen, saturated and unsaturated hydrocarbons, for example propane or propene, aldehydes, for example propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and alcohols, for example butanol.
• the comonomers and also the moderators may be metered into the reactor either together with ethylene or else separately via sidestreams.
• the monomer streams may have different compositions (EP-A-0 271 738 and EP-A-0 922 716).
• Suitable co- or terpolymers include:
• ethylene-vinyl acetate copolymers having 10-40% by weight of vinyl acetate and 60-90% by weight of ethylene;
• ethylene/vinyl acetate/vinyl neononanoate or vinyl neodecanoate terpolymers which, apart from ethylene, contain 10-35% by weight of vinyl acetate and 1-25% by weight of the particular neo compound, known from EP-A-0 493 769;
• the polymers on which the mixtures are based more preferably differ in at least one characteristic.
• they may contain different comonomers, different comonomer contents, molecular weights and/or degrees of branching.
• the mixing ratio of the different ethylene copolymers is preferably between 20:1 and 1:20, preferably from 10:1 to 1:10, in particular from 5:1 to 1:5.
• the copolymers B are preferably derived from dicarboxylic acids B2 and their derivatives such as esters and anhydrides. Preference is given to maleic acid, fumaric acid, itaconic acid and especially maleic anhydride.
• Particularly suitable comonomers are monoolefins B1 having from 10 to 20, in particular having from 12-18, carbon atoms. 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 acids/derivitives to olefin or olefins in the polymer is preferably in the range from 1:1.5 to 1.5:1, and is especially equimolar. It is possible for copolymers B also to contain minor amounts of up to 20 mol %, preferably ⁇ 10 mol %, especially ⁇ 5 mol %, of further comonomers apart from B1 and B2 which are copolymerizable with dicarboxylic acids/derivatives and the olefins mentioned.
• comonomers are, for example olefins having from 2 to 50 carbon atoms, allyl polyglycol ethers, C 1 -C 30 -alkyl(meth)acrylates, vinylaromatics or C 1 -C 20 -alkyl vinyl ethers. Equally, minor amounts of poly(isobutylenes) having molecular weights of up to 5000 g/mol are used with preferance, preference being given to highly reactive variants having a high proportion of terminal vinylidene groups. These further comonomers are not taken into account in the calculation of the factor Q which is critical for the effectiveness.
• R 1 is hydrogen or methyl
• R 2 is hydrogen or C 1 -C 4 -alkyl
• n is a number from 1 to 100
• R 3 is C 1 -C 24 -alkyl, C 5 -C 20 -cycloalkyl, C 6 -C 18 -aryl or —C(O)—R 4 ,
• R 4 is C 1 -C 40 -alkyl, C 5 -C 10 -cycloalkyl or C 6 -C 18 -aryl.
• the inventive copolymers B) are prepared preferably at temperatures between 50 and 220° C., in particular from 100 to 190° C.
• the preferred preparation process is solvent-free bulk polymerization, but it is also possible to carry out the polymerization in the presence of aprotic solvent such as benzene, toluene, xylene or of higher-boiling aromatic, aliphatic or isoaliphatic solvents or solvent mixtures such as kerosene or Solvent Naphtha.
• aprotic solvent such as benzene, toluene, xylene or of higher-boiling aromatic, aliphatic or isoaliphatic solvents or solvent mixtures such as kerosene or Solvent Naphtha.
• Particular preference is given to polymerizing in a small amount of 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%
• the average molecular mass Mw of the inventive copolymers B is generally between 1200 and 200 000 g/mol, in particular between 2000 and 100 000 g/mol, measured by means of gel permeation chromatography (GPC) against polystyrene standards in THF.
• Inventive copolymers B have to be oil-soluble in doses relevant in practice, i.e. they have to dissolve without residue at 50° C. in the oil to be additized.
• the reaction of the monomers is initiated by free radical-forming initiators (free-radical chain starters).
• This substance class includes, for example, oxygen, hydroperoxides and peroxides, for example cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis(2-ethylhexyl) peroxodicarbonate, t-butyl perpivalate, t-butyl permaleate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di(t-butyl)peroxide, and also azo compounds, for example 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 from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, based on the
• the copolymers may be prepared either by reacting maleic acid, fumaric acid and/or itaconic acid or their anhydrides with the corresponding alcohol and subsequently copolymerizing, or by copolymerizing olefin or olefins with at least one unsaturated dicarboxylic acid or derivative thereof, for example itaconic anhydride and/or maleic anhydride and subsequently reacting with alcohols. Preference is given to carrying out a copolymerization with anhydrides and converting the resulting copolymer to an ester and/or a diester after the preparation.
• this esterification is effected, for example, by reacting with from 0.8 to 2.5 mol of alcohol per mole of anhydride, preferably with from 1.0 to 2.0 mol of alcohol per mole of anhydride, at from 50 to 300° C.
• monoesters are formed.
• esterification temperatures of from approx. 70 to 120° C. are preferred.
• diesters are formed at 100-300° C., preferably 120-250° C.
• the water of reaction may be distilled off by means of an inert gas stream or removed by means of azeotropic distillation in the presence of an organic solvent.
• copolymers having acid numbers of 30-70 mg KOH/g, preferably of 40-60 mg KOH/g are regarded as monoesters.
• Copolymers having acid numbers of less than 40 mg, especially less than 30 mg KOH/g are regarded as diesters. Particular preference is given to monoesters.
• Suitable alcohols are, in particular, linear, but may also contain minor amounts, for example up to 30% by weight, preferably up to 20% by weight and especially up to 10% by weight of branched alcohols (in the 1- or 2-position). Particular preference is given to octanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol and hexadecanol.
• Particularly preferred copolymers B contain monoesters of primary alcohols as monomer B2.
• the additives, as well as constituents A and B may also comprise polymers and copolymers based on C 10 -C 24 -alkyl acrylates or methacrylates (constituent C).
• These poly(alkyl acrylates) and methacrylates have molecular weights Mw of from 800 to 1 000 000 g/mol, and derive preferably from caprylic alcohol, capric alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol or mixtures thereof, for example coconut alcohol, palm alcohol, tallow fat alcohol or behenyl alcohol.
• mixtures of different copolymers B are used, the mean (weight average) of the parameter Q of the mixture components assuming values of from 23 to 27 and preferably values of from 24 to 26.
• the mixing ratio of the inventive additive constituents A and B is (in parts by weight) from 20:1 to 1:20, preferably from 10:1 to 1:10, in particular from 5:1 to 1:5.
• the proportion of component C in the formulations composed 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 inventive additives are added to oils in amounts of from 0.001 to 5% by weight, preferably from 0.005 to 1 % by weight and especially from 0.01 to 0.6% by weight. They may be used as such or else dissolved or dispersed in solvents, for example aliphatic and/or aromatic hydrocarbons or hydrocarbon mixtures, for example toluene, xylene, ethylbenzene, decane, pentadecane, petroleum fractions, kerosene, naphtha, diesel, heating oil, isoparaffins or commercial solvent mixtures such as Solvent Naphtha, ®Hydrosol A 200 N, ®Shellsol A 150 ND, ®Caromax 20 LN, ®Shellsol AB, ®Solvesso 150, ®Solvesso 150 ND, ®Solvesso 200, ®Exxsol, ®lsopar and ®Shellsol D types. They are preferably dissolved in fuel oil of animal or vegetable origin
• the fuel oil which is frequently also referred to as biodiesel or biofuel, comprises fatty acid alkyl esters composed of fatty acids having from 12 to 24 carbon atoms and alcohols having from 1 to 4 carbon atoms. Typically, a relatively large portion of the fatty acids contains one, two or three double bonds.
• oils which are derived from animal or vegetable material and in which the inventive additive can be used are rapeseed oil, coriander oil, soya oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, maize oil, almond oil, palm kernel oil, coconut oil, mustardseed oil, bovine tallow, bone oil, fish oils and used cooking oils. Further examples include oils which are derived from wheat, jute, sesame, shea tree nut, arachis oil and linseed oil.
• the fatty acid alkyl esters also referred to as biodiesel can be derived from these oils by processes disclosed by the prior art.
• rapeseed oil which is a mixture of fatty acids partially esterified with glycerol, since it is obtainable in large amounts and is obtainable in a simple manner by extractive pressing of rapeseeds.
• Particularly suitable biofuels are lower alkyl esters of fatty acids. These include, for example, commercially available mixtures of the ethyl, propyl, butyl and in particular methyl esters of fatty acids having from 14 to 22 carbon atoms, for example of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, ricinolic acid, elaeostearic acid, linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid, each of which preferably has an iodine number of from 50 to 150, in particular from 90 to 125.
• Mixtures having particularly advantageous properties are those which comprise mainly, i.e. comprise at least 50% by weight of, methyl esters of fatty acids having from 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 acid, linoleic acid, linolenic acid and erucic acid.
• a biofuel is therefore an oil which is obtained from vegetable or animal material or both or a derivative thereof which can be used as a fuel and in particular as a diesel or heating oil.
• vegetable oil derivatives particularly preferred biofuels being alkyl ester derivatives of rapeseed oil, cottonseed oil, soya oil, sunflower oil, olive oil or palm oil, and very particular preference is given to rapeseed oil methyl ester, sunflower oil methyl ester, palm oil methyl ester and soya oil methyl ester.
• the additive can be introduced to the oil to be additized by processes known in the prior art. When more than one additive component or coadditive component is to be used, such components can be introduced into the oil together or separately in any combination.
• the inventive additives allow the CFPP value of biodiesel to be adjusted to values of ⁇ 10° C. and below ⁇ 20° C. and in some cases to values of below ⁇ 25° C., as required for marketing for use especially in winter. Equally, the pour point of biodiesel is lowered by the addition of the inventive additives.
• the inventive additives are particularly advantageous in problematic oils which have a high proportion of esters of the saturated fatty acids palmitic acid and stearic acid of more than 7% by weight, as present, for example, in fatty acid methyl esters obtained from used oil, sunflowers and soybean.
• oils thus additized have a good cold transition stability, i.e. the CFPP value remains constant even in the case of storage under winter conditions, and do not tend to sediment at constant low temperatures (e.g. ⁇ 10° C. or ⁇ 22° C.).
• inventive additives may also be used together with one or more oil-soluble coadditives which, even alone, improve the cold flow properties of crude oils, lubricant oils or fuel oils.
• oil-soluble coadditives are polar compounds which bring about paraffin dispersancy (paraffin dispersants) and oil-soluble amphiphiles.
• the inventive additives may be used in a mixture with paraffin dispersants.
• Paraffin dispersants reduce the size of the paraffin crystals and have the effect that the paraffin particles do not settle out but rather remain dispersed in colloidal form with significantly reduced sedimentation tendency.
• Useful paraffin dispersants have been found to be both low molecular weight and polymeric oil-soluble compounds having ionic or polar groups, for example amine salts and/or amides.
• Particular preferred paraffin dispersants comprise reaction products of secondary fatty amines having from 20 to 44 carbon atoms, in particular dicoconut amine, ditallow fat amine, distearylamine and dibehenylamine with carboxylic acids and their derivatives.
• paraffin dispersants have been found to be those which are obtained by reacting aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides (cf. U.S. Pat. No. 4,211,534).
• Equally suitable as paraffin dispersants are amides and ammonium salts of aminoalkylenepolycarboxylic acids, such as nitrilotriacetic acid or ethylenediaminetetraacetic acid, with secondary amines (cf. EP 0 398 101).
• paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds which may optionally be reacted with primary monoalkylamines and/or aliphatic alcohols (cf. EP 0 154 177), and the reaction products of alkenyl-spiro-bislactones with amines (cf. EP 0 413 279 B1), and, according to 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 inventive additives with paraffin dispersants is from 1:10 to 20:1, preferably from 1:1 to 10:1.
• the oils treated with the inventive additive may also be added to middle distillates obtained from crude oil.
• the mixtures of biofuel and middle distillate thus obtained can in turn be admixed with cold additives such as flow improvers or wax dispersants, and also performance packages.
• Middle distillate refers in particular to those mineral oils which are obtained by distilling crude oil and boil within the range from 120 to 450° C., for example kerosene, jet fuel, diesel and heating oil. Preference is given to using those middle distillates 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. They are generally those middle distillates which have been subjected to refining under hydrogenating conditions, and which therefore contain only small proportions of polyaromatic and polar compounds. They are preferably those middle distillates which have 95% distillation points below 370° C., in particular 350° C. and in special cases below 330° C. Suitable middle distillates are also synthetic fuels, as made available, for example, by the Fischer-Tropsch process.
• the additives may be used alone or else 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 vinyl ester content was measured by means of pyrolysis and subsequent titration.
• V 140 The viscosity (V 140 ) was measured with a Haake Reostress 600 viscometer.
• the degree of branching (CH 3 /100CH 2 ) was measured on a 1 H NMR unit at 400 MHz in CDCl 3 , and calculated by means of integration of the individual signals.
• the total amount of additive is evident from the top row of the table.

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• 2006
  • 2006-05-16 DE DE102006022718A patent/DE102006022718B4/de not_active Expired - Fee Related
• 2007
  • 2007-05-02 EP EP07008845A patent/EP1857530A1/de not_active Withdrawn
  • 2007-05-15 JP JP2007128724A patent/JP2007308702A/ja active Pending
  • 2007-05-15 CA CA002588559A patent/CA2588559A1/en not_active Abandoned
  • 2007-05-16 KR KR1020070047810A patent/KR20070111386A/ko not_active Application Discontinuation
  • 2007-05-16 US US11/803,874 patent/US20070270319A1/en not_active Abandoned

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