EP3177699B1 - Additifs pauvres en soufre pour diésel marin - Google Patents

Additifs pauvres en soufre pour diésel marin Download PDF

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Publication number
EP3177699B1
EP3177699B1 EP15739226.7A EP15739226A EP3177699B1 EP 3177699 B1 EP3177699 B1 EP 3177699B1 EP 15739226 A EP15739226 A EP 15739226A EP 3177699 B1 EP3177699 B1 EP 3177699B1
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mol
alkyl
fuel oil
oil composition
weight
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EP3177699A1 (fr
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Michael Feustel
Matthias Krull
Michael MÖRSCHER
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Clariant International Ltd
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Clariant International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • C10L10/16—Pour-point depressants
    • 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
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic 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 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G 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
    • C10L1/192—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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
    • 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
    • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
    • C10L2250/04—Additive or component is a polymer
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

  • the present invention relates to low sulfur marine diesel with improved cold properties and storage stability.
  • Heavy oils are usually used to propel ships, especially ocean-going vessels. Such fuels are also referred to as marine diesel oil (marine fuel oil), marine residual oil (residual fuel oil) or bunker oil (bunker fuel, bunker C). These very inexpensive fuels are based on residues from mineral oil distillation, to which more or less large quantities of less viscous distillates (“cutter stocks") are added in order to adjust various physicochemical parameters such as density, viscosity, flash point and / or the sulfur content.
  • the residual oils used to produce such marine fuels mainly contain relatively heavy molecules: long-chain alkanes and alkenes, higher molecular weight cycloalkanes and highly condensed aromatic hydrocarbons (asphaltenes) as well as metal compounds such as nickel, vanadium, sodium and calcium.
  • metal compounds such as nickel, vanadium, sodium and calcium.
  • nitrogen and sulfur compounds There are also various nitrogen and sulfur compounds.
  • the sulfur content of such residual oils is often up to 6% by weight, so that an addition of lower-sulfur components is also required to set the specified upper limit of 3.5% in bunker oil C.
  • higher-quality marine fuels which are based predominantly or entirely on mineral oil distillates, usually contain up to 3.5% by weight and sometimes up to 4.5% by weight of sulfur.
  • the nitrogen content of residual oils is often 0.5% by weight or more.
  • the above-mentioned contaminants lead to various undesirable effects during combustion, such as, for example, apparatus corrosion, ash and fine dust formation, and toxic emissions.
  • the high sulfur content of the heavy oil leads to high sulfur dioxide emissions; Compounds containing nitrogen lead to NO x emissions.
  • ships e.g. oil tankers, other transport ships, cruise ships
  • pour point depressants are additives that modify the crystal structure of the paraffins that precipitate at low temperatures and shift the solidification of the oil to lower temperatures.
  • comb polymers which are derived from ethylenically unsaturated monomers with longer (for example C 8 -C 30 ), preferably linear, alkyl radicals. These are mainly found in crude oils, heating oils containing residues and higher-boiling, paraffin-rich mineral oil distillates also used in combination with ethylene copolymers to improve the cold flow properties. The pour point and, in the case of mineral oil distillates, the cold filterability (CFPP value, determinable according to EN 116) of the oil are reduced.
  • C 8 -C 30 ethylenically unsaturated monomers with longer (for example C 8 -C 30 ), preferably linear, alkyl radicals.
  • US 3726653 discloses the joint use of ethylene copolymers with oil-soluble polymers which carry aliphatic alkyl chains with at least 14 C atoms as pour point depressants for crude and residual oils. Exemplified as a comb polymer is poly (eicosyl acrylate).
  • DE-A-2022588 discloses flow improvers for use in residual fuels, heating oils and crude oils which contain a polymer having a multiplicity of essentially linear paraffinic side chains each having at least 18 C atoms and an ethylene copolymer with at least one further ethylenically unsaturated compound. These additives are particularly suitable for the treatment of heating oils containing residues and for the treatment of flash distillates (distillate heating oils).
  • CA 2106185 discloses a method for lowering the viscosity of residual oils, in which a mixture of an ethylene-vinyl acetate copolymer and a dialkyl fumarate-vinyl acetate copolymer is added to the residual oil.
  • EP-A-1022293 discloses terpolymers of esters of ethylenically unsaturated dicarboxylic acids, ⁇ -olefins and ethylenically unsaturated polyolefins with 50 to 350 C atoms and their use together to improve the cold flow properties of crude oils, distillate oils or fuel oils and lubricating oils. These can also be used together with paraffin dispersants.
  • EP1881053 describes additive mixtures containing A) at least one terpolymer of ethylene, propene and at least one ethylenically unsaturated ester which i) contains 6.0 to 12.0 mol% of structural units derived from at least one ethylenically unsaturated ester with a C1 to C3 alkyl radical , ii) contains 0.5 to 4.0 methyl groups derived from propene per 100 aliphatic C atoms, iii) has less than 8.0 chain ends-derived methyl groups per 100 CH2 groups and B) 0.5 to 20 parts by weight, based on A) at least one further component, effective as a cold additive for mineral oils, selected from B1) copolymers of ethylene and ethylenically unsaturated compounds whose content of ethylenically unsaturated compounds is at least 2 mol% higher than the content of the terpolymer defined under A) ethylenically unsaturated esters, B2) comb polymers
  • US2012246999 describes the use of a composition as a marine and / or bunker fuel, the fuel composition comprising: 30% by volume to 100% by volume of an uncracked, hydrogen-treated gas oil product with a sulfur content of at most 5000 ppm by weight, a pour point of at least 7 ° C and a kinematic viscosity of at least 12 cSt at 50 ° C; and up to 70% by volume of other components selected from viscosity modifiers, pour point depressants, lubricity modifiers, antioxidants and combinations thereof, the fuel composition having the following properties: maximum 5000 wppm sulfur content; at most 25% by volume, based on all components of the fuel composition, residue components selected from residues of the crude oil vacuum fractionation, deasphalted vacuum residue, slurry oil and combinations thereof; less than 50% by volume based on all of the components of the fuel composition, residual components, components that have undergone a cracking step, or both; and a kinematic viscosity at 50 ° C from
  • residues from a cracking plant operated with heavy gas oil such as the vacuum gas oil originating from a vacuum distillation, such as a hydrocracker, an FCC plant or an isocracker
  • a vacuum distillation such as a hydrocracker, an FCC plant or an isocracker
  • Such oils are often referred to in the refinery as "unconverted oil” (UCO).
  • UCO unconverted oil
  • cutter stocks such as diesel, kerosene or vacuum gas oil.
  • Such a dilution is often necessary to improve the response to cold additives.
  • low-sulfur marine diesel is usually filtered before it is fed into the combustion chamber. While impurities are usually separated from the classic, much more viscous residual oils using separators such as cyclones, this is done from low-sulfur marine diesel using felt or paper filters with a pore size of often less than 100 ⁇ m and sometimes less than 10 ⁇ m. If low-sulfur marine diesel is used at temperatures below the cloud point, this can lead to the fuel filter becoming blocked by the paraffins that are then excreted and thus to engine failure.
  • low-sulfur marine diesel should be clear and bright; According to ISO 8217, the self-pour point is now limited to a maximum of +6 ° C and in winter to a maximum of -6 ° C in some cases. According to ISO 8217, its viscosity is limited to a maximum of 11 mm 2 / s at 40 ° C and, in special qualities, to 1.4 to 5.5 mm 2 / s at 40 ° C. On the other hand, the heavy components used in its manufacture and especially the residues from refinery processes contain large amounts of long-chain paraffins.
  • Nitrogen-containing compounds in particular amide ammonium salts of polycarboxylic acids and fatty amines, are usually used for the dispersion of paraffins in middle distillates. These do not show a satisfactory effectiveness in low-sulfur marine diesel or require very high dosing rates.
  • the object of the invention was therefore to provide low-sulfur marine diesel engines which have the lowest possible pour point, determined according to ISO 3016. At the same time, they should show little or ideally no sedimentation of paraffins when stored below the cloud point. Their filterability below the cloud point should be as uniform as possible over the entire volume; compared to the filterability above the cloud Points should not be affected or only slightly affected.
  • the additives to be used for this purpose should be free of sulfur and nitrogen compounds in order not to increase the oil's content of environmentally harmful components.
  • both the pour point of low-sulfur marine diesel can be lowered and at the same time the sedimentation of the paraffins precipitating in the cold can be reduced or suppressed. This ensures the manageability and filterability of the fuels so additized and the safe operation of the machine even after the fuel has been stored for a long time at temperatures below its cloud points.
  • Another object of the invention is the use of at least one comb polymer (B) for dispersing those precipitating from a low-sulfur marine diesel containing at least one ethylene copolymer (A) with a sulfur content of less than 1% by weight when stored below the cloud point paraffins.
  • the invention further relates to a process for dispersing paraffins which precipitate out of a low-sulfur marine diesel with a sulfur content of 1% by weight or less when stored below the cloud point, the low-sulfur marine diesel containing an ethylene copolymer (A), by adding a comb polymer (B).
  • compositions of ethylene copolymer (A) and comb polymer (B) are also referred to here as an additive.
  • Particularly suitable ethylene copolymers (A) are those which contain 8.0 to 17 mol% of one or more vinyl and / or (meth) acrylic esters and 92.0 to 83 mol% ethylene.
  • Ethylene copolymers (A) which contain 10.0 to 16.0 mol% of one or more vinyl and / or (meth) acrylic esters and 84.0 to 90.0 mol% ethylene are particularly preferred.
  • Ethylene copolymers with 10.5 to 15.5 mol% of at least one vinyl and / or (meth) acrylic ester and 84.5 to 89.5 mol% ethylene and especially 10.5 to 15.0 mol are particularly preferred -% of at least one vinyl and / or (meth) acrylic ester and 85.0 to 89.5 mol% of ethylene.
  • They can also contain minor amounts of other comonomers such as olefins, the molar content of which is subtracted from the molar ethylene content.
  • Vinyl esters suitable as comonomers are derived from fatty acids with linear or branched alkyl groups with 1 to 30 C atoms and in particular with 1 to 18 C atoms. 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 pivalic acid, vinyl 2-ethylhexanoate, vinyl iso-nonanoic acid, vinyl neononanoate, vinyl neodecanoate and neoundecanoic acid vinyl ester.
  • Suitable ethylene copolymers (A) are both those which are composed of ethylene and a vinyl ester and those which, in addition to ethylene, contain two or more, for example three, four or five, different vinyl esters. Also suitable as ethylene copolymers (A) are those which, in addition to ethylene, contain one, two or more vinyl esters and one, two or more (meth) acrylic esters (all ethylene copolymers containing two or more comonomers are also referred to here as terpolymers). In addition, suitable ethylene copolymers (A) may contain minor structural amounts of structural elements derived from initiators and / or moderators.
  • Preferred ethylene copolymers (A) are copolymers of ethylene and vinyl acetate.
  • Preferred terpolymers (A) are built up from ethylene, vinyl acetate and vinyl neononanoate or from ethylene, vinyl acetate and vinyl neodecanoate or from ethylene, vinyl acetate and vinyl neoundecanoate or from ethylene, vinyl acetate and vinyl 2-ethylhexanoate.
  • Particularly preferred terpolymers of vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate and vinyl 2-ethylhexanoate contain, in addition to ethylene, 7.7 to 15.9 mol%, in particular 9.5 to 15.4 mol% and especially 10.0 to 15, 0 mol% such as 10.5 to 15.0 mol% of vinyl acetate and 0.1 to 6 mol%, in particular 0.2 to 5 mol% and especially 0.3 to 5 mol% of the respective long-chain vinyl ester , the total comonomer content between 8.0 and 16.0 mol%, in particular between 10.0 and 15.5 mol% and especially between 10.5 and 15.0 mol% such as between 10.5 and 14, 5 mol%.
  • (Meth) acrylic esters suitable as comonomers are esters of acrylic and methacrylic acid and preferably those having 1 to 20 carbon atoms in the alkyl radical, such as methyl (meth) acrylate, ethyl (meth) acrylate, n- and isopropyl (meth) acrylate, n- and iso-butyl (meth) acrylate, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl (meth) acrylate.
  • terpolymers of ethylene, a vinyl ester and a (meth) acrylic ester such as, for example, terpolymers of ethylene, vinyl acetate and methyl acrylate, of ethylene, vinyl acetate and isobutyl acrylate or of ethylene, vinyl acetate and 2-ethylhexyl acrylate are used.
  • particularly preferred terpolymers contain 7.7 to 16.9 mol%, in particular 9.5 to 15.9 mol% and especially 10.0 to 15.4 mol%, such as 10.5 to 14.9 mol% % Vinyl acetate and 0.1 to 6 mol%, in particular 0.2 to 5 mol% and especially 0.3 to 5 mol% of the respective (meth) acrylic ester, the total comonomer content being between 8.0 and 17, 0 mol%, in particular between 10.0 and 16.0 mol% and especially between 10.5 and 15.5 mol%, for example between 10.5 and 15.0 mol%.
  • further preferred copolymers (A) contain 8.0 to 17 mol%, particularly preferably 10 to 16.0 mol% and especially 10.5 to 15.5 such as 10.5 to 15.0 mol% one or more vinyl and / or (meth) acrylic esters still 0.1 to 5 mol% and preferably 0.2 to 4 mol% of one or more olefins having 3 to 8 carbon atoms, such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene, the molar content of which is subtracted from the molar ethylene content.
  • the preferred olefin is propene.
  • Particularly preferred terpolymers made from ethylene, one or more vinyl and / or (meth) acrylic esters and propene have 0.5 to 4.0 methyl groups derived from propene per 100 aliphatic carbon atoms.
  • the number of methyl groups (propene-CH 3 ) derived from propene per 100 aliphatic carbon atoms is determined by means of 13 C-NMR spectroscopy.
  • Terpolymers made of ethylene, vinyl ester and propene show a characteristic signal of methyl groups bound to the polymer backbone between about 19.3 and 19.9 ppm, which have a positive sign in the DEPT experiment.
  • the Integral of this signal of the propene-derived methyl side groups of the polymer backbone is related to that of all other aliphatic carbon atoms of the polymer backbone between about 6 and 44 ppm. Signals derived from the alkyl radicals of the unsaturated esters and superimposed with the signals from the polymer backbone are subtracted from the total integral of the aliphatic carbon atoms on the basis of the signal of the methine group adjacent to the carbonyl group of the unsaturated ester. Such measurements can be carried out, for example, using NMR spectrometers at a measuring frequency of 125 MHz at 30 ° C. in solvents such as CDCl 3 or C 2 D 2 Cl 4 .
  • Terpolymers of ethylene, vinyl acetate and propene, of ethylene, vinyl neononanoate and propene, of ethylene, vinyl neodecanoate and propene and of ethylene, vinyl 2-ethylhexanoate and propene are particularly preferred.
  • the copolymers (A) preferably have average molecular weights Mn between 1,000 and 7,000 g / mol and especially between 1,200 and 5,000 g / mol.
  • the weight average molecular weight is preferably between 2,000 and 20,000 g / mol, particularly preferably between 3,000 and 15,000 g / mol and especially between 3,500 and 12,000 g / mol, each determined by means of gel permeation chromatography (GPC) in THF against poly (styrene) standards.
  • GPC gel permeation chromatography
  • the molecular weight of the copolymers (A) can also be characterized by their melt viscosity; the melt viscosity of preferred copolymers (A) measured at 140 ° C.
  • solvent-free is between 20 and 5,000 mPas, in particular between 30 and 2,000 mPas and especially between 50 and 1,500 mPas.
  • the determined by 1 H NMR spectroscopy degrees of branching of the copolymers (A) are preferably between 2 and 7 CH 3/100 CH 2 groups, in particular between 2.5 and 6 CH 3/100 CH 2 groups such as 2,7 to 5 CH 3/100 CH 2 groups, which do not stem from the comonomers.
  • the copolymers (A) can be prepared by known copolymerization processes such as, for example, suspension polymerization, solvent polymerization or high-pressure bulk polymerization.
  • the copolymers (A) are preferred by means of high-pressure bulk polymerization at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 100 to 300 ° C, preferably 150 to 220 ° C.
  • the polymerization takes place in a multi-zone reactor, the temperature difference between the peroxide meterings along the tube reactor being kept as low as possible, ie ⁇ 50 ° C., preferably ⁇ 30 ° C., in particular ⁇ 15 ° C.
  • the temperature maxima in the individual reaction zones preferably differ by less than 30 ° C., particularly preferably by less than 20 ° C. and especially by less than 10 ° C.
  • radical initiators Radical chain initiators
  • This class of substances include e.g. B. 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 permaleinate, t-butyl perbenzoate, dicumyl peroxide, dicumyl peroxide (t-butyl) peroxide, 2,2'-azo-bis (2-methylpropanonitrile), 2,2'-azo-bis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the monomer mixture.
  • the high pressure bulk polymerization is in known high pressure reactors, e.g. B. autoclaves or tubular reactors, carried out batchwise or continuously, tubular reactors have proven particularly useful.
  • Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene can be contained in the reaction mixture.
  • the essentially solvent-free mode of operation is preferred.
  • the mixture of the monomers, the initiator and, if used, the moderator is fed to a tubular reactor via the reactor inlet and via one or more side branches.
  • 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 and their mixtures.
  • the copolymers (A) may contain structural elements derived from the respective moderators at the chain ends.
  • the comonomers and the moderators can be metered into the reactor either together with ethylene or separately via side streams.
  • the monomer streams can have different compositions ( EP-A-0271 738 and EP-A-0 922 716 ).
  • mixtures of the same or different copolymers (A) are used, the copolymers on which the mixtures are based differ in at least one characteristic.
  • they can contain different comonomers, have different comonomer contents, molecular weights and / or different degrees of branching.
  • Mixtures of copolymers (A) whose comonomer content differs by at least 2 mol% have proven particularly useful.
  • the mixing ratio of the various ethylene copolymers (A) is preferably between 20: 1 and 1:20, preferably 10: 1 to 1:10, in particular 5: 1 to 1: 5, for example between 20: 1 and 1:10, between 20: 1 and 1: 5, between 1:20 and 10: 1 or between 1:20 and 5: 1.
  • Preferred comb polymers (B) contain at least 40 mol%, preferably 50 to 100 mol%, particularly preferably 60 to 95 mol% and especially 65 to 90 mol% of repetitive structural units (B1), the C 10 -C 28 -alkyl radicals wear.
  • the proportion of comb polymers (B) in repetitive structural units (B1) can be between 50 and 100 mol%, between 60 and 100 mol%, between 65 and 100 mol%, between 40 and 90 mol%, between 50 and 90 mol%, between 60 and 90 mol%, between 65 and 90 mol%, between 40 and 95 mol%, between 50 and 95 mol%, between 60 and 95 mol% and also between 65 and 95 mol% are.
  • the comb polymers (B) consist of repetitive structural units (B1).
  • These repetitive structural units (B1) are preferably derived from C 10 -C 28 alkyl esters of unsaturated mono- and dicarboxylic acids, C 10 -C 28 alkyl vinyl esters, C 10 -C 28 alkyl vinyl ethers, C 10 -C 28 alkyl allyl ethers and / or linear C 12 -C 30 alpha olefins.
  • Especially repetitive structural units (B1) which contain C 12 -C 28 -alkyl radicals and in particular those which carry C 14 -C 28 -alkyl radicals and differ from the correspondingly preferred alkyl esters of unsaturated mono- and dicarboxylic acids, alkyl vinyl esters, alkyl vinyl ethers, alkyl allyl ethers and / or are preferred derive linear ⁇ -olefins.
  • At least 20 mol% of the alkyl radicals bonded to the repetitive structural units (B1) have 12 to 16 carbon atoms and at least 5 mol% of alkyl radicals with 18 or more carbon atoms. It is particularly preferred that at least 20 mol% of the alkyl radicals bonded to the repetitive structural units (B1) have 14 and / or 16 carbon atoms. Furthermore, particularly preferably, at least 5 mol% of the alkyl radicals having 20 or more carbon atoms bonded to the repetitive structural units (B1) have
  • the content of C 12 -C 16 alkyl radicals in the alkyl radicals bound to the repetitive structural units (B1) is particularly preferably between 25 and 95 mol%, in particular between 30 and 92 mol% and especially between 50 and 90 mol% and particularly especially between 60 and 90 mol%, for example between 20 and 95 mol%, between 30 and 95 mol%, between 50 and 95 mol%, between 60 and 95 mol%, between 20 and 92 mol%, between 25 and 92 mol%, between 50 and 92 mol%, between 60 and 92 mol%, between 20 and 90 mol%, between 25 and 90 mol%, between 30 and 90 mol% or even between 60 and 90 mol%.
  • the content of C 14 -C 16 alkyl radicals in the alkyl radicals bound to the repetitive structural units (B1) is between 25 and 95 mol%, in particular between 30 and 92 mol% and especially between 50 and 90 mol% and especially especially between 60 to 90 mol%, such as between 20 and 95 mol%, between 30 and 95 mol%, between 50 and 95 mol%, between 60 and 95 mol%, between 20 and 92 mol% %, between 25 and 92 mol%, between 50 and 92 mol%, between 60 and 92 mol%, between 20 and 90 mol%, between 25 and 90 mol%, between 30 and 90 mol% or also between 60 and 90 mol%.
  • the content of alkyl radicals with 18 or more carbon atoms in the alkyl radicals bound to the repetitive structural units (B1) is particularly preferably between 5 and 75 mol%, in particular between 8 and 70 mol% and especially between 10 and 50 mol% and particularly specifically between 10 and 40 mol%, for example between 5 and 80 mol%, between 5 and 70 mol%, between 5 and 50 mol%, between 5 and 40 mol%, between 8 and 80 mol% , between 8 and 75 mol%, between 8 and 50 mol%, between 8 and 40 mol%, between 10 and 80 mol%, between 10 and 75 mol%, between 10 and 70 mol% or else between 10 and 40 mol%.
  • the content of alkyl radicals having 20 or more carbon atoms in the alkyl radicals bound to the repetitive structural units (B1) is between 5 and 75 mol%, in particular between 8 and 70 mol% and especially between 10 and 50 mol% and especially between 10 and 40 mol% such as between 5 and 80 mol%, between 5 and 70 mol%, between 5 and 50 mol%, between 5 and 40 mol%, between 8 and 80 mol%, between 8 and 75 mol%, between 8 and 50 mol%, between 8 and 40 mol%, between 10 and 80 mol%, between 10 and 75 mol%, between 10 and 70 mol -% or between 10 and 40 mol%.
  • the proportions of the alkyl radicals bound to the repetitive structural units (B1) with 12 to 16 carbon atoms add up to 100% with the proportions of the alkyl radicals bound to the repetitive structural units (B1) with 100%.
  • the proportions of the alkyl radicals bound to the repetitive structural units (B1) with 14 and / or 16 C atoms and the proportions of the alkyl radicals bound to the repetitive structural units (B1) with 18 or more C atoms add up to 100 %.
  • the proportions of the alkyl radicals bound to the repetitive structural units (B1) having 12 to 16 carbon atoms add up to 100% of the proportions of the alkyl radicals bound to the repetitive structural units (B1).
  • the proportions of the alkyl radicals bonded to the repetitive structural units (B1) having 14 and / or 16 carbon atoms add up to the proportions of the to the repetitive structural units (B1) 100% bound alkyl radicals with 20 or more carbon atoms.
  • S takes values between 15.1 and 19.5, in particular between 15.3 and 18.9 and especially between 15.5 and 18.5, for example between 15.0 and 19.5, between 15 , 0 and 18.9, between 15.0 and 18.5, between 15.1 and 18.0, between 15.1 and 18.9, between 15.1 and 18.5, between 15.3 and 19, 5, between 15.3 and 18.5, between 15.5 and 20.0, between 15.5 and 19.5 or between 15.5 and 18.9.
  • p stands for 1
  • monomers bearing two alkyl radicals such as for example diesters of ethylenically unsaturated dicarboxylic acids such as maleic acid or fumaric acid, p is 2.
  • Additives from (A) and (B), the alkyl chain distribution of which are both the above-mentioned proportions of C 12 - to C 16 - and preferably of C 14 - and / or C 16 -alkyl radicals and the above-mentioned proportions of alkyl radicals with 18, are particularly effective and contains more C atoms and preferably with 20 and more C atoms and whose molar mean of the C chain length distributions in the alkyl radicals of the repetitive structural units (B1) falls within the range of the sum S defined above.
  • the alkyl radicals of the structural units B1 are preferably linear, but can also contain minor amounts of branched isomers of up to 30 mol%, preferably up to 20 mol% and in particular 2 to 5 mol%.
  • the distribution of the alkyl chain lengths of the repetitive units (B1) preferred in accordance with the invention is realized in a polymer.
  • the distribution of the alkyl chain lengths according to the invention is achieved by mixing two or more polymers, for example three, four or more polymers.
  • mixing a polymer (B ') with a higher proportion of C 14 / C 16 side chains with a polymer (B ") with a higher proportion of side chains with more than 18 C atoms leads to additives which are suitable according to the invention, provided that the side chain distribution and / or the sum S is in the preferred range.
  • the comb polymer (B) contains up to 60 mol%, preferably 1 to 50 mol%, in particular 10 to 40 mol% and especially 20 to 40 mol% such as 1 to 60 mol%, 1 up to 40 mol%, 10 to 60 mol%, 10 to 50 mol%, 20 to 60 mol% or also 20 to 50 mol% of further repetitive structural units (B2).
  • Preferred further repetitive structural units of (B2) are derived from unsaturated mono- and dicarboxylic acids and their C 1 - to C 9 -alkyl, C 1 -C 9 -Alkylvinylestern, C 1 -C 9 -alkyl vinyl ethers, C 1 -C 9 -Alkylallylethern, linear C 3 -C 8 ⁇ -olefins and / or branched C 4 -C 50 olefins from.
  • the repetitive structural units (B2) can also carry heteroatoms such as oxygen, nitrogen and / or sulfur.
  • Suitable further comonomers from which repetitive structural units (B2) are derived are vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hexene, styrene, and branched olefins such as, in particular, oligomers of isobutylene and propylene with 10 to 20 carbonyls. atoms.
  • the polymers B) particularly preferably consist only of the repetitive structural units B1) and optionally B2), which then add up to 100 mol%.
  • Preferred monomers from which the repetitive structural units (B1) of the copolymers (B) are derived are esters of unsaturated carboxylic acids with 3 to 8 carbon atoms and especially with 3 to 6 carbon atoms, such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid Alcohols which carry alkyl residues with 10 to 28 carbon atoms.
  • Preferred alcohols are linear, but they can also be minor amounts, e.g. B. up to 20 wt .-%, preferably up to 10 wt .-% and especially up to 5 wt .-% of branched alkyl radicals. If present, the branches are preferably in the 1- or 2-position.
  • Examples of preferred alcohols are decanol, undecanol, dodecanol, n-tridecanol, iso-tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol and mixtures thereof.
  • Dicarboxylic acids can be used as partial esters; however, their diesters are preferably used.
  • Diesters are understood to mean those compounds in which at least 70 mol%, in particular 70 to 98 mol% and especially 80 to 95 mol% such as, for example, 70 to 100 mol%, 70 to 95 mol%, 80 to 100 mol% or also 80 to 98 mol% of the carboxyl groups are esterified.
  • Further preferred monomers from which the repetitive structural units (B1) of the copolymers (B) are derived are esters and / or ethers from ethylenically unsaturated alcohols with 2 to 10 and in particular with 2 to 4 Carbon atoms and carboxylic acids or alcohols which carry alkyl radicals with 10 to 28 carbon atoms.
  • Examples of such monomers are esters of vinyl alcohol with decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid, icosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid and mixtures thereof, octacosanoic acid.
  • Such monomers are ethers of allyl and in particular vinyl alcohol with decanol, undecanol, dodecanol, n-tridecanol, iso-tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol and mixtures thereof.
  • olefins with 12 to 30 C atoms, preferably with 12 to 24 C atoms and in particular with 14 to 18 C atoms and mixtures thereof. These are preferably linear ⁇ -olefins with a terminal double bond. Side chain length of olefins is understood here to mean the alkyl radical leaving the polymer backbone, that is to say the chain length of the monomeric olefin minus the two olefinically bonded carbon atoms.
  • Suitable olefins are, for example, dodecene, tetradecene, hexadecen, octadecen, eicosen, docosen, tetracosen, hexacosen, octacosen and mixtures thereof.
  • alkyl (meth) acrylates alkyl (meth) acrylates, alkyl vinyl esters, alkyl vinyl ethers with 1 to 5 carbon atoms in the alkyl radical and ethylenically unsaturated free carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and functional groups such as -OH, -SH, -N -, -CN-bearing monomers and other compounds copolymerizable with the monomers mentioned, such as allyl polyglycol ethers, vinyl aromatics and higher molecular weight olefins such as poly (isobutylene) can be used in minor amounts of up to 20 mol%, preferably up to 10 mol% and especially up to 5 mol% may also be present in the copolymers (B).
  • alkyl (meth) acrylates alkyl vinyl esters
  • the polymers according to the invention can be prepared by direct polymerization from the monomers mentioned in known polymerization processes such as bulk, solution, emulsion, suspension or precipitation polymerization.
  • a z. B. acid or hydroxyl-bearing base polymer with the fatty alcohols described for the preparation of the corresponding esters from unsaturated carboxylic acids or unsaturated alcohols or fatty acids each having 10 to 28 carbon atoms in the alkyl radical.
  • the esterifications and / or etherifications are carried out according to known condensation processes.
  • the derivatization can be complete or partial.
  • Partially esterified, acid-based polymers (solvent-free) preferably have acid numbers of 60-140 mg KOH / g and in particular 80-120 mg KOH / g.
  • Copolymers with acid numbers of less than 60 mg KOH / g, in particular less than 30 mg KOH / g and especially less than 15 mg KOH / g are considered to be completely derivatized.
  • Partially esterified or etherified hydroxyl-bearing polymers have OH numbers of 40 to 200 mg KOH / g, preferably 60 to 150 mg KOH / g; Copolymers with hydroxyl numbers of less than 40 mg KOH / g, in particular less than 25 mg KOH / g and in particular less than 20 mg KOH / g are considered to be completely derivatized.
  • Fully derivatized polymers are particularly preferred.
  • Polymers bearing acid groups suitable for derivatization with fatty alcohols are homo- and copolymers of ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid or their reactive equivalents such as lower esters or anhydrides such as methyl methacrylate and maleic anhydride with one another and with one another further monomers copolymerizable with these acids.
  • Suitable examples are poly (acrylic acid), Poly (methacrylic acid), poly (maleic acid), poly (maleic anhydride), poly (acrylic acid-co-maleic acid) and poly (acrylic acid-co-maleic anhydride).
  • Polymers bearing hydroxyl groups that are particularly suitable for derivatization with fatty acids and / or fatty alcohols to form esters and / or ethers are monomers bearing hydroxyl groups, such as vinyl alcohol, allyl alcohol or else hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
  • the number average molecular weights of the copolymers B according to the invention are between 1,000 and 100,000, in particular between 2,000 and 50,000 and in particular between 2,500 and 25,000 g / mol, measured by means of gel permeation chromatography (GPC) against poly (styrene) standards.
  • Copolymers B according to the invention must be oil-soluble in practice-relevant metered amounts, that is to say they must dissolve without residue in the oil to be added at 50 ° C.
  • mixtures of the copolymers (B) according to the invention are used, with the proviso that the mean value of the S values of the mixture components in turn has values from 15.0 to 20.0, preferably between 15.1 and 19.5, in particular between 15.3 and 18.9 and especially between 15.5 and 18.5 such as between 15.0 and 19.5, between 15.0 and 18.9, between 15.0 and 18.5, between 15.1 and 18.0, between 15.1 and 18.9, between 15.1 and 18.5, between 15.3 and 19.5, between 15.3 and 18.5, between 15.5 and 20.0, between 15.5 and 19.5 or between 15.5 and 18.9.
  • 15.0 to 20.0 preferably between 15.1 and 19.5, in particular between 15.3 and 18.9 and especially between 15.5 and 18.5 such as between 15.0 and 19.5, between 15.0 and 18.9, between 15.0 and 18.5, between 15.1 and 18.0, between 15.1 and 18.9, between 15.1 and 18.5, between 15.3 and 19.5, between 15.3 and 18.5, between 15.5 and 20.0, between 15.5 and 19.5 or between 15.5 and 18.9.
  • Components (A) and (B) can be added separately to the oils to be added. They are preferably added as a mixture.
  • the mixing ratio of 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: 3, for example between 20: 1 and 1:10, between 20: 1 and 1: 3, between 10: 1 and 1:20, between 10: 1 and 1: 3, between 10: 1 and 1:20, between 10: 1 and 1: 3, between 5: 1 and 1 : 20 or between 5: 1 and 1:10.
  • Ethylene copolymers (A) alone usually only have an unsatisfactory effect on the cold properties, such as the pour point of low-sulfur marine diesel. However, their presence leads to a pronounced sedimentation of the paraffins precipitating below the cloud point.
  • Comb polymers (B) alone usually have little or no effectiveness in lowering the pour point and / or paraffin-dispersing activity in low-sulfur marine diesel.
  • the combination of comb polymers (B) with ethylene copolymers (A) achieves a synergistic lowering of the pour point and a dispersion of the paraffins, so that the additive oil remains pumpable even after prolonged storage below the cloud point and does not lead to filter clogging.
  • the low-sulfur marine diesel according to the invention preferably contain the additives from (A) and (B) in amounts of 0.001 to 2% by weight, preferably 0.005 to 1% by weight and especially 0.01 to 0.5% by weight. They can be dissolved or dispersed as such or as a concentrate in solvents such as.
  • the additives according to the invention preferably contain 1 to 90% by weight, especially 10 to 75% by weight and in particular 25 to 60% by weight of solvent as a concentrate.
  • Low-sulfur marine diesel is understood to mean marine fuels which contain a maximum of 1.5% by weight of sulfur, preferably a maximum of 1.0% by weight of sulfur and in particular a maximum of 0.5% by weight of sulfur, for example a maximum of 0.1% by weight of sulfur contain.
  • They preferably have a viscosity of less than 200 mm 2 / s, particularly preferably below 100 mm 2 / s, particularly preferably between 1.0 and 20 mm 2 / s, particularly preferably between 1.0 and 15 mm 2 / s, in particular between 1.2 and 15 mm 2 / s and especially between 1.4 and 10 mm 2 / s such as between 1.0 and 200 mm 2 / s, between 1.2 and 200 mm 2 / s, between 1.4 and 200 mm 2 / s, between 1.0 and 100 mm 2 / s, between 1.2 and 100 mm 2 / s, between 1.4 and 100 mm 2 / s, between 1.0 and 20 mm 2 / s , between 1.0 and 10 mm 2 / s, between 1.2 and 20 mm 2 / s, between 1.2 and 10, between 1.4 and 20 or also between 1.4 and 15 mm 2 / s, each determined according to ISO 3104 at 40 ° C.
  • the pour point of particularly suitable low-sulfur marine diesel is untreated, i. H. before adding the pour point lowering additives at at least 6 ° C, preferably between 6 and 36 ° C, particularly preferably between 6 and 33 ° C, especially between 9 and 33 ° C such as between 12 and 30 ° C.
  • the beginning of the paraffin excretion is preferably above 0 ° C, particularly preferably above +5 ° C and in particular above +10 ° C.
  • the start of the paraffin deposition can be determined optically by measuring the cloud point (according to ISO 3015) or calorimetrically by measuring the heat flow during cooling (using differential scanning calorimetry, DSC).
  • Low-sulfur marine diesel suitable according to the invention can be produced from mineral oil fractions such as kerosene, light gas oil, heavy gas oil, light and possibly heavy cycle oil, or vacuum gas oil.
  • mineral oil fractions such as kerosene, light gas oil, heavy gas oil, light and possibly heavy cycle oil, or vacuum gas oil.
  • the additives containing (A) and (B) and (B) and the processes using them for the treatment of low-sulfur marine diesel, which contains a residue from the further processing of a possibly previously desulfurized mineral oil distillate, have proven successful. Suitable residues occur in FCC plants in the production of olefins from heavy gas oil.
  • Residues that are preferably used for the production of marine diesel suitable according to the invention have a boiling end above 450 ° C., particularly preferably above 480 ° C., in particular above 500 ° C. and especially above 510 ° C. (can be determined in accordance with ASTM D-2887). Further preferred residues have a 50% distillation point of above 400 ° C, particularly preferably above 420 ° C, in particular above 435 ° C and specifically above 450 ° C (also determinable according to ASTM D-2887).
  • Preferred residues usually contain more than 3% by weight and preferably 3 to 40% by weight, particularly preferably 4 to 30% by weight, in particular 5 to 25% by weight and especially 6 to 20% by weight, for example 3 to 30 wt%, 3 to 25 wt%, 3 to 20 wt%, 4 to 40 wt%, 4 to 25 wt%, 4 to 20 wt%, 5 to 40% by weight, 5 to 30% by weight, 5 to 20% by weight, 6 to 40% by weight, 6 to 30% by weight or else 6 to 25% by weight of paraffins with C -Chain lengths of more than 24 carbon atoms.
  • GC Gas chromatography
  • high-temperature GC have proven their worth for determining the C chain distribution and the content of n-paraffins in the low-sulfur residue.
  • the latter method can be used to analyze paraffins with 80 and more carbon atoms.
  • the paraffin contents given above relate to paraffins with 25 to 80 carbon atoms.
  • the sulfur content of the residues preferred for the production of marine diesel suitable according to the invention is preferably below 0.5% by weight, preferably between 1 and 3,000 ppm by weight, particularly preferably between 5 and 2,000 ppm by weight, in particular between 10 and 1,500% by weight.
  • the viscosity measured at 40 ° C. for the production of preferred residues suitable marine diesel according to the invention is usually between 10 and 1,000 mm 2 / s, in particular between 15 and 500 mm 2 / s and especially between 20 and 100 mm 2 / s, for example between 10 and 500 mm 2 / s, between 10 and 100 mm 2 / s, between 15 and 1,000 mm 2 / s, between 20 and 500 mm 2 / s or also between 20 and 500 mm 2 / s.
  • the pour point for the production of marine diesel of preferred residues suitable according to the invention is usually 9 ° C or higher, often 12 to 60 ° C and especially 15 to 51 ° C, for example 9 to 60 ° C, 15 to 60 ° C, at 9 to 51 ° C or also at 15 to 51 ° C. They preferably contain no or only small amounts of asphaltenes, for example less than 2% by weight and in particular less than 1% by weight.
  • the proportion of process residues in the low-sulfur marine diesel is preferably 5 to 90% by weight, particularly preferably 10 to 80% by weight, in particular 15 to 75% by weight and especially 20 to 70% by weight, for example 5 to 80% by weight %, 5 to 75% by weight, 5 to 70% by weight, 10 to 90% by weight, 10 to 75% by weight, 10 to 70% by weight, 35 to 90% by weight , 15 to 90% by weight, 15 to 80% by weight, 15 to 70% by weight, 20 to 90% by weight, 20 to 80% by weight or else 20 to 75% by weight.
  • Low-sulfur marine diesel suitable according to the invention preferably contain less than 10% by weight of a residue from crude oil distillation, particularly preferably 0.1 to 3% by weight and in particular they are free of residues from crude oil distillation. Accordingly, the total content of metals according to the invention which is particularly suitable for low-sulfur marine diesel (determined, for example, according to ICP) is below 500 ppm (m / m), preferably below 200 ppm (m / m) and in particular below 100 ppm (m / m), for example below 50 ppm (m / m).
  • such residues are preferably mixed with lighter components (“cutter stocks”) such as kerosene, light gas oil, heavy gas oil, light and possibly heavy cycle oil or vacuum gas oil.
  • carbon stocks such as kerosene, light gas oil, heavy gas oil, light and possibly heavy cycle oil or vacuum gas oil.
  • the percentages of low-sulfur marine diesel in process residues and lighter components add up to 100%.
  • the low-sulfur marine diesel is preferably 10 to 20,000 ppm by weight, particularly preferably 50 to 10,000 ppm by weight and in particular 100 to 5,000 ppm by weight such as 10 to 10,000 ppm by weight, 10 to 5,000 ppm by weight . ppm or 100 to 10,000 ppm by weight of the mixture of A) and B) added.
  • low-sulfur marine diesel treated according to the invention contain 10 to 20,000 ppm by weight, particularly preferably 50 to 10,000 ppm by weight and in particular 100 to 5,000 ppm, such as 10 to 10,000 ppm by weight, 10 to 5,000 ppm by weight or else 100 to 10,000 ppm by weight of the mixture of A) and B).
  • the additives as well as the low-sulfur marine diesel containing them can also contain further additives such as, for example, further paraffin inhibitors, corrosion inhibitors, antioxidants, defoamers, combustion improvers and / or lubrication improvers.
  • Preferred further paraffin inhibitors are ethylene copolymers, which differ from (A) differ in at least one property such as comonomer content, molecular weight and / or degree of branching, polyoxyalkylene compounds, alkylphenol resins and / or nitrogen-containing paraffin dispersants (WASA).
  • WASA paraffin dispersants
  • the marine diesel listed in Table 2 was mixed from the components characterized in Table 1.
  • the content of n-paraffins with 25 to 80 C atoms is determined by gas chromatography (GC) or high-temperature GC, the sulfur content by means of wavelength-dispersive X-ray fluorescence analysis according to ISO 14596.
  • Ethylene copolymers produced by means of high-pressure bulk polymerization and having the properties listed in Table 3 are used as ethylene copolymers A).
  • the comonomer content is determined by means of 1 H-NMR spectroscopy, and the viscosity is determined on the solvent-free polymer at 140 ° C. as a measure of the molecular weight.
  • Molecular weights are determined using GPC in THF against poly (styrene) standards.
  • the polymers are used as 65% by weight concentrates or in the case of A2 as 35% concentrate in higher-boiling organic solvents.
  • the essentially alternating copolymers B1 to B3 and B8 to B10 from 50 mol% maleic anhydride (MA) and 50 mol% linear ⁇ -olefin are prepared in a free-radically initiated solution polymerization in organic solvent and then with 2 mol of the ones given in Table 4 Alcohol mixture esterified.
  • the polyalkyl acrylates B4, B5 and B11 and copolymer B6 were prepared in a free-radical solution polymerization.
  • the olefin copolymer B7 was produced in an anionic polymerization.
  • the composition of the alcohols and olefins relates to the mol% of the components in the respective mixture.
  • the comb polymers are used as 50% concentrates in higher-boiling aromatic solvents.
  • Table 4A Comb polymers used (B)
  • B1 Poly (MSA-co-C 18 - ⁇ -olefin), esterified with 2 mol of an alcohol mixture of chain length distribution 80% C 14 -OH, 1% C 18 -OH, 13% C 20 -OH and 6% C 22 -OH per mole of anhydride group.
  • the upper and lower 50% by volume are visually assessed for the presence of turbidity.
  • the quantification of the amount of sediment relates to the total test volume.
  • the upper 50% by volume are then carefully suctioned off from above and the upper and lower phase are determined according to ASTM D97 [pour point (after)] and cloud point according to ISO 3015.
  • a cloudy or at least cloudy upper phase and slight differences between the pour point and / or cloud point in the upper and lower phase show good dispersion.
  • a small amount of sediment indicates weak dispersion and a compact, paraffin-rich sediment.
  • the dispersion was only assessed qualitatively here as very good (++) if the upper phase was homogeneously cloudy, good (+) if the upper phase was cloudy and the lower phase without separated sediment or as bad (-) when the upper phase was clear and a sediment was visible.
  • Table 8 Filterability of test oil 1 at 19 ° C (after storage at 19 ° C) example Additive (dosing rate) dispersion filtration A [ppm] B [ppm] t [sec.] Vol [ml] 55 A1 (500) B1 (125) + 150 100 56 A1 (625) B1 (150) ++ 120 100 57 A1 (625) B2 (150) ++ 130 100 58 A1 (500) B3 (125) + 180 100 59 A1 (625) B3 (150) ++ 150 100 60 A1 (625) B4 (150) ++ 200 100 61 A1 (625) B5 (150) ++ 130 100 62 A3 (625) B1 (150) ++ 200 100 63 A4 (625) B1 (150) ++ 220 100 64 A6 (625) B1 (150) + 240 100 65 (see) A1 (625) B8 (150) - 300 50 66 (see) A1 (625) B9 (150) - 300 28 67 (see
  • bunker oil used was a density (at 20 ° C) of 0.995 g / cm 3 , a viscosity (at 40 ° C) of 28 0 cSt, a pour point of 33 ° C and a wax appearance temperature (corresponds to the cloud Point that cannot be determined in oils containing residues) of 47 ° C.
  • Table 12 Improvement of flowability, dispersion and filterability of a bunker oil with 2.9% sulfur at 30 ° C (after storage at 30 ° C) example Additive (dosing rate) Pour point [° C] dispersion filtration A1 [ppm] B1 [ppm] WAT (top) WAT (below) t [sec.] Vol [ml] 93 (See) 500 125 30 47 ° C 47 ° C 300 ⁇ 10 94 (See) 1000 250 27 47 ° C 47 ° C 300 ⁇ 10 95 (See) 0 0 33 47 ° C 47 ° C 300 ⁇ 10
  • Comparative experiments 93 to 95 show that the phenomenon of paraffin sedimentation observed in low-sulfur marine diesel does not occur in conventional, sulfur-rich bunker oil and that filtration through fine filters is not possible.

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Claims (30)

  1. Composition d'huile combustible, contenant un diesel marin pauvre en soufre, ayant une teneur en soufre inférieure à 1 % en poids et
    (A) au moins un copolymère d'éthylène, qui contient en plus de l'éthylène 8,0 à 17 % en moles d'un ou de plusieurs esters vinyliques et/ou (méth)acryliques, et
    (B) au moins un polymère en peigne (B) qui comprend des unités structurales B1, qui dérivent d'esters alkyliques en C10-C28 d'acides mono- et dicarboxyliques insaturés, d'esters alkylvinyliques en C10-C28, d'éthers alkylvinyliques en C10-C28, d'éthers alkylallyliques en C10-C28 et/ou d'α-oléfines en C12-C30 linéaires, au moins 20 % en moles des radicaux alkyle reliés aux unités structurales de répétition (B1) comprenant 12 à 16 atomes C, et au moins 5 % en moles des radicaux alkyle comprenant 18 ou davantage d'atomes C, le diesel marin pauvre en soufre non traité présentant un point d'écoulement (pour point) de +6 °C ou plus.
  2. Composition d'huile combustible selon la revendication 1, dans laquelle le diesel marin pauvre en soufre présente une viscosité d'au plus 200 mm2/s à 40 °C.
  3. Composition d'huile combustible selon la revendication 1 et/ou 2, dans laquelle le diesel marin pauvre en soufre présente une viscosité d'au plus 11 mm2/s à 40 °C.
  4. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 3, dans laquelle le diesel marin pauvre en soufre contient un résidu issu de la transformation d'un distillat d'huile minérale.
  5. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 4, dans laquelle le diesel marin pauvre en soufre présente une teneur en soufre de 0,1 % en poids ou moins.
  6. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 5, dans laquelle le résidu issu de la transformation d'un distillat d'huile minérale utilisé pour la fabrication du diesel marin pauvre en soufre contient au moins 3 % en poids de paraffines contenant plus de 24 atomes C.
  7. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 6, dans laquelle le résidu issu de la transformation d'un distillat d'huile minérale utilisé pour la fabrication du diesel marin pauvre en soufre présente un point d'écoulement de 9 °C ou plus.
  8. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 7, dans laquelle le copolymère d'éthylène (A) contient en plus de l'éthylène et de 8,0 à 17 % en moles d'un ou de plusieurs esters vinyliques et/ou (méth)acryliques également 0,1 à 5 % en moles d'une ou de plusieurs oléfines contenant 3 à 8 atomes de carbone.
  9. Composition d'huile combustible selon la revendication 8, dans laquelle l'oléfine est le propène.
  10. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 9, dans laquelle le copolymère d'éthylène (A) contient un ou plusieurs esters de vinyle, qui sont dérivés d'acides carboxyliques contenant 3 à 12 atomes de carbone.
  11. Composition d'huile combustible selon la revendication 10, dans laquelle l'ester de vinyle est l'acétate de vinyle.
  12. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 11, dans laquelle le poids moléculaire moyen en nombre Mn du copolymère d'éthylène (A) est compris entre 1 000 et 7 000 g/mol.
  13. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 12, dans laquelle au moins 40 % en moles d'unités structurales de répétition (B1) qui portent des radicaux alkyle en C10-C28 sont contenues dans le polymère en peigne (B).
  14. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 13, dans laquelle la somme S : S = m 1 ⋅ p 1 ⋅ ∑ i w 1 ⁢ i ⋅ n 1 ⁢ i + m 2 ⋅ p 2 ⋅ ∑ j w 2 ⁢ j ⋅ n 2 ⁢ j + ....... + m g ⋅ p g ∑ p w gp ⋅ n gp m 1 ⋅ p 1 + m 2 ⋅ p 2 + … … + m g ⋅ p g
    Figure imgb0004
    des moyennes molaires des distributions de longueurs de chaînes C dans les radicaux alkyle des unités structurales (B1) est de 15,0 à 20,0,
    m1, m2..., mg étant les fractions molaires des monomères susmentionnés dans le polymère (B), avec la somme des fractions molaires m1 à mg = 1,
    p1, p2..., pg étant le nombre de radicaux alkyle par unité monomère, et représente un nombre entier de 1, 2 ou 3,
    w1i, w1j..., W2i, W2j..., Wgp étant les proportions en poids des longueurs de chaînes individuelles i, j..., p des radicaux alkyle des différents monomères (B) 1 à g dans le polymère, et
    n1i, n1j..., n2i, n2j..., ngp étant les longueurs de chaînes des radicaux alkyle i, j..., p des monomères dans le polymère (B) 1 à g.
  15. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 14, dans laquelle les distributions de longueurs de chaînes C dans les radicaux alkyle des unités structurales (B1) sont réalisées dans un polymère.
  16. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 15, dans laquelle les distributions de longueurs de chaînes C dans les radicaux alkyle des unités structurales (B1) sont réalisées par mélange de deux ou davantage de polymères.
  17. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 16, dans laquelle le polymère en peigne (B) contient 1 à 60 % en moles d'unités structurales de répétition (B2), qui sont différentes des unités structurales (B1).
  18. Composition d'huile combustible selon la revendication 17, dans laquelle les unités structurales de répétition (B2) dérivent d'acides mono- et dicarboxyliques insaturés ou leurs esters alkyliques en C1 à C9, d'esters alkylvinyliques en C1-C9, d'éthers alkylvinyliques en C1-C9, d'éthers alkylallyliques en C1-C9, d'α-oléfines en C3-C8 linéaires et/ou d'oléfines en C4-C50 ramifiées.
  19. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 18, dans laquelle le poids moléculaire moyen en nombre des polymères en peigne (B) est compris entre 1 000 et 100 000 g/mol.
  20. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 19, dans laquelle les polymères en peigne (B) sont choisis parmi :
    a) les homo- et copolymères d'esters alkylvinyliques en C10-C28, les éthers alkylvinyliques en C10-C28 et les esters alkyliques en C10-C28 d'acides monocarboxyliques insaturés,
    b) les copolymères estérifiés avec des alcools en C10-C28 d'acides dicarboxyliques insaturés ou leurs anhydrides avec des α-oléfines en C12-C30, les acrylates d'alkyle en C10-C28, les méthacrylates d'alkyle en C10-C28, les esters alkylvinyliques en C10-C28 et/ou les éthers alkylvinyliques en C10-C28,
    c) les copolymères de fumarate d'alkyle en C10-C28-ester alkylvinylique en C1-C5, et
    d) les polymères d'α-oléfines en C12-C30.
  21. Composition d'huile combustible selon une ou plusieurs des revendications 17 à 20, dans laquelle la somme des monomères B1 et B2 dans le polymère en peigne (B) est de 100 % en moles.
  22. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 21, qui contient au total 0,001 à 2 % en poids des composants additifs (A) et (B).
  23. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 22, dans laquelle la composition d'huile combustible contient 0,05 à 20 parties en poids du polymère en peigne B) par partie en poids du copolymère d'éthylène A).
  24. Composition d'huile combustible selon une ou plusieurs des revendications 1 à 23, qui contient, par rapport à la quantité totale de A) et B), moins de 10 % en poids d'un composé azoté, efficace en tant que dispersant de paraffines dans les distillats moyens.
  25. Utilisation d'un additif contenant les constituants (A) et (B), tel que décrit dans une ou plusieurs des revendications 1 ou 8 à 23, pour la dispersion des paraffines précipitées à partir d'un diesel marin pauvre en soufre ayant une teneur en soufre de moins de 1 % en poids, qui présente sous forme non traitée un point d'écoulement (pour point) de +6 °C ou plus, lors d'un stockage en dessous du point de trouble.
  26. Utilisation selon la revendication 25, dans laquelle au total entre 10 et 20 000 ppm en poids des composants additifs (A) et (B) sont ajoutés au diesel marin pauvre en soufre.
  27. Utilisation d'un polymère en peigne (B) pour la dispersion des paraffines précipitées en dessous du point de trouble à partir d'un diesel marin pauvre en soufre contenant au moins un copolymère d'éthylène (A), le copolymère d'éthylène (A) contenant en plus de l'éthylène 8,0 à 17 % en moles d'un ou de plusieurs esters vinyliques et/ou (méth)acryliques, et
    le polymère en peigne (B) comprenant des unités structurales B1, qui dérivent d'esters alkyliques en C10-C28 d'acides mono- et dicarboxyliques insaturés, d'esters alkylvinyliques en C10-C28, d'éthers alkylvinyliques en C10-C28, d'éthers alkylallyliques en C10-C28 et/ou d'α-oléfines en C12-C30 linéaires, au moins 20 % en moles des radicaux alkyle reliés aux unités structurales de répétition (B1) comprenant 12 à 16 atomes C, et au moins 5 % en moles des radicaux alkyle comprenant 18 ou davantage d'atomes C, et
    le diesel marin pauvre en soufre non traité présentant un point d'écoulement (pour point) de +6 °C ou plus.
  28. Composition d'huile combustible selon l'une quelconque des revendications 1 à 24, dans laquelle le diesel marin pauvre en soufre contient au plus 5 % en poids d'un résidu issu de l'usinage d'un gazole lourd désulfuré.
  29. Procédé de dispersion de paraffines, qui précipitent lors d'un stockage à des températures inférieures au point de trouble à partir d'un diesel marin pauvre en soufre ayant une teneur en soufre de 1 % en poids ou moins, selon lequel un copolymère d'éthylène (A) et un polymère en peigne (B), tels que décrits dans une ou plusieurs des revendications 7 à 23, sont ajoutés au diesel marin pauvre en soufre, le disel marin pauvre en soufre non traité présentant un point d'écoulement (pour point) de +6 °C ou plus.
  30. Procédé de dispersion de paraffines, qui précipitent à partir d'un diesel marin pauvre en soufre ayant une teneur en soufre de 1 % en poids ou moins lors d'un stockage en dessous du point de trouble, le diesel marin pauvre en soufre contenant un copolymère d'éthylène (A), selon lequel un polymère en peigne (B), tel que décrit dans une ou plusieurs des revendications 13 à 21, est ajouté, le disel marin pauvre en soufre non traité présentant un point d'écoulement (pour point) de +6 °C ou plus, et le copolymère d'éthylène (A) contenant en plus de l'éthylène 8,0 à 17 % en moles d'un ou de plusieurs esters vinyliques et/ou (méth)acryliques.
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