EP1526167B1 - Agent d'amélioration de l'écoulement à froid pour huiles combustibles d'origine végétale ou animale - Google Patents

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

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Publication number
EP1526167B1
EP1526167B1 EP20040024234 EP04024234A EP1526167B1 EP 1526167 B1 EP1526167 B1 EP 1526167B1 EP 20040024234 EP20040024234 EP 20040024234 EP 04024234 A EP04024234 A EP 04024234A EP 1526167 B1 EP1526167 B1 EP 1526167B1
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Prior art keywords
additive
monomer
mol
constituent
vinyl
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English (en)
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EP1526167A3 (fr
EP1526167A2 (fr
EP1526167B2 (fr
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Matthias Dr. Krull
Bettina Dr. Siggelkow
Martina Hess
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides

Definitions

  • the present invention relates to an additive, its use as a cold flow improver for vegetable or animal fuel oils and correspondingly fueled fuel oils.
  • renewable raw materials include, in particular, natural oils and fats of plant or animal origin. These are typically triglycerides of fatty acids with 10 to 24 C atoms, which have a calorific value comparable to conventional fuels, but at the same time are considered less harmful to the environment.
  • Biofuels ie fuels derived from animal or plant material, are obtained from renewable sources and thus produce only as much CO 2 as was previously converted into biomass. It has been reported that combustion produces less carbon dioxide than equivalent amount of petroleum distillate fuel, eg, diesel fuel, and that very little sulfur dioxide is produced. In addition, they are biodegradable.
  • Oils obtained from animal or vegetable material are mainly metabolites comprising triglycerides of monocarboxylic acids, eg acids having 10 to 25 carbon atoms, and the formula in which R is an aliphatic radical of 10 to 25 carbon atoms, which may be saturated or unsaturated.
  • oils include glycerides of a variety of acids, the number and variety of which varies with the source of the oil, and may additionally contain phosphoglycerides.
  • Such oils can be obtained by methods known in the art.
  • EP-B-0 665 873 discloses a fuel oil composition
  • a fuel oil composition comprising a biofuel, a petroleum-based fuel oil and an additive which comprises (a) an oil-soluble ethylene copolymer or (b) a comb polymer or (c) a polar oil Or (d) a compound in which at least one substantially linear alkyl group having from 10 to 30 carbon atoms is bonded to a non-polymeric organic group to provide at least one linear chain of atoms containing the carbon atoms of the alkyl groups and one or more or (e) comprises one or more of components (a), (b), (c) and (d).
  • EP-B-0 153 176 discloses the use of polymers based on unsaturated C 4 -C 8 dicarboxylic acid di-alkyl esters having average alkyl chain lengths of 12 to 14 as cold flow improvers for certain petroleum distillate fuel oils.
  • Suitable comonomers are unsaturated esters, in particular vinyl acetate, but also ⁇ -olefins.
  • US-2003/0163951 teaches multifunctional cold additives containing copolymers of dicarboxylic acid derivatives and olefins, whereupon nitrogen-containing compounds or esters are grafted on.
  • US 5391632 teaches terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers according to claim 1 of US 5391632 , and a method for producing the same according to claim 5 of US 5391632 ,
  • terpolymer according to claim 1 a mixture of at least one terpolymer according to claim 1 and at least one ethylene-vinyl ester copolymer.
  • the terpolymers of the invention, as well as their mixtures, are used as paraffin inhibitors in crude oils and petroleum products.
  • US 4985048 teaches polymer blends of a copolymer (A 1 ) of 10-60 wt .-% vinyl acetate and 40-90 wt .-% of ethylene or a Copoylmer (A 2 ) of 15-50 wt .-% vinyl acetate, 0.5-20 wt % C 6 -C 24 ⁇ -olefin and 30-70% by weight of ethylene and a copolymer (B) of 10-90% by weight of C 6 -C 24 ⁇ -olefin and 10-90% by weight.
  • a 1 a copolymer of 10-60 wt .-% vinyl acetate and 40-90 wt .-% of ethylene or a Copoylmer (A 2 ) of 15-50 wt .-% vinyl acetate, 0.5-20 wt % C 6 -C 24 ⁇ -olefin and 30-70% by weight of ethylene and a copolymer (B) of 10-9
  • WO 95/22300 discloses comb polymers in which the alkyl radicals have on average less than 12 carbon atoms. These additives are particularly suitable for oils with cloud points of less than -10 ° C, where the oils may also be native hydrocarbon oils (page 21, line 16 ff.). However, native oils have cloud points from about -2 ° C upwards.
  • Another object of the invention is a fuel oil composition containing a fuel oil of animal or vegetable origin and 0.001 to 5 wt .-% of the additive defined above.
  • Another object of the invention is the use of 0.001 to 5 wt .-% of the additive defined above to improve the cold flow properties of fuel oils of animal or vegetable origin.
  • Another object of the invention is a method for improving the cold flow properties of fuel oils of animal or vegetable origin, by adding to fuel oils of animal or vegetable origin the above-defined additive in an amount of 0.001 to 5 wt .-%.
  • Q has values from 24 to 26.
  • side chain length of olefins is meant here the alkyl radical leaving the polymer backbone, ie the chain length of the monomeric olefin minus the two olefinically bonded C atoms.
  • side chain length of olefins is meant here the alkyl radical leaving the polymer backbone, ie the chain length of the monomeric olefin minus the two olefinically bonded C atoms.
  • Suitable ethylene copolymers A) are those which contain from 8 to 21 mol% of one or more vinyl and / or (meth) acrylic esters and from 79 to 92% by weight of ethylene. Particularly preferred are ethylene copolymers with 10 to 18 mol% and especially 12 to 16 mol% of at least one vinyl ester.
  • Suitable vinyl esters are derived from fatty acids having linear or branched alkyl groups having 1 to 18 C atoms and preferably 1 to 12 C atoms.
  • vinyl acetate vinyl propionate, vinyl butyrate, vinyl hexanoate, Vinylheptanoat, vinyl octanoate, vinyl laurate and vinyl stearate and branched fatty acid based esters of vinyl alcohol such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, iso-Nonanklarevinylester, Neononanklarevinylester, vinyl neodecanoate and Neoundecanklavinylester.
  • vinyl acetate vinyl propionate, vinyl butyrate, vinyl hexanoate, Vinylheptanoat, vinyl octanoate, vinyl laurate and vinyl stearate and branched fatty acid based esters of vinyl alcohol such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, iso-Nonanklarevinylester, Neononanklawrevinylester, vinyl neodecan
  • esters of acrylic and methacrylic acid having 1 to 20 C atoms in the alkyl radical such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and isobutyl (meth) acrylate, hexyl , Octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl (meth) acrylate and mixtures of two, three, four or more of these comonomers.
  • Particularly preferred terpolymers of 2-ethylhexanoic acid vinyl ester, vinyl neononanoate or vinyl neodecanoate contain, in addition to ethylene, preferably 3.5 to 20 mol%, in particular 8 to 15 mol% vinyl acetate and 0.1 to 12 mol%, in particular 0.2 to 5 mol% of at least one long-chain
  • ethylene and 8 to 18 mol% of vinyl esters contain 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
  • the copolymers A preferably have molecular weights which correspond to melt viscosities at 140 ° C. of from 20 to 10,000 mPas, in particular from 30 to 5,000 mPas and especially from 50 to 1,000 mPas.
  • the determined by 1 H NMR spectroscopy degrees of branching are preferably between 1 and 9 CH 3/100 CH 2 groups, especially between 2 and 6 CH 3/100 CH 2 groups, such as 2.5 to 5 CH 3/100 CH 2 groups not derived from the comonomers.
  • the copolymers (A) can be prepared by the usual copolymerization methods such as suspension polymerization, solvent polymerization, gas phase polymerization or high-pressure bulk polymerization.
  • the high-pressure mass polymerization is preferably carried out at pressures of from 50 to 400 MPa, preferably from 100 to 300 MPa, and at temperatures of from 100 to 300 ° C., preferably from 150 to 220 ° C.
  • the polymerization is carried out in a multizone reactor, wherein the temperature difference between the peroxide doses along the tubular reactor is kept as low as possible, i. ⁇ 50 ° C, preferably ⁇ 30 ° C, in particular ⁇ 15 ° C.
  • the temperature maxima in the individual reaction zones preferably differ by less than 30 ° C., more preferably by less than 20 ° C. and especially by less than 10 ° C.
  • the reaction of the monomers is initiated by free radical initiators (free radical initiators).
  • This class of substances includes, for example, oxygen, hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permalate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide , Di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the monomer
  • the high-pressure mass polymerization is carried out batchwise or continuously in known high-pressure reactors , for example autoclaves or tubular reactors, tube reactors have proven particularly useful.
  • Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene may be present in the reaction mixture. Preferred is the substantially solvent-free operation.
  • Preferred moderators are, for example, hydrogen, saturated and unsaturated hydrocarbons such as propane or propene, aldehydes such as propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and alcohols such as butanol.
  • the comonomers as well as the moderators can be metered into the reactor both together with ethylene and separately via side streams. In this case, the monomer streams can be composed differently ( EP-A-0 271 738 and EP-A-0 922 716 ).
  • Suitable copolymers or terpolymers include, for example: ethylene-vinyl acetate copolymers with 10 to 40% by weight of vinyl acetate and 60 to 90% by weight of ethylene; from DE-A-34 43 475 known ethylene-vinyl acetate-hexene terpolymers; in the EP-B-0 203 554 described ethylene-vinyl acetate-diisobutylene terpolymers; from EP-B-0 254 284 known mixture of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene / vinyl acetate copolymer; in the EP-B-0 405 270 disclosed blends of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer; in the EP-B-0 463 518 described ethylene / vinyl acetate / iso-butyl vinyl
  • the polymers underlying the mixtures differ in at least one characteristic.
  • they may contain different comonomers, have different comonomer contents, molecular weights and / or degrees of branching.
  • the mixing ratio of the various ethylene copolymers is preferably between 20: 1 and 1:20, preferably 10: 1 to 1:10, in particular 5: 1 to 1: 5.
  • the copolymers B are preferably derived from ethylenically unsaturated dicarboxylic acids and their derivatives, such as esters and anhydrides. Preference is given to maleic acid, fumaric acid, itaconic acid and their esters with lower alcohols having 1 to 6 C atoms and their anhydrides, such as, for example, maleic anhydride. Monoolefins having from 10 to 20, in particular from 12 to 18, carbon atoms are particularly suitable as comonomers. These are preferably linear and the double bond is Dicarboxylic acids and their derivatives such as esters and anhydrides.
  • Monoolefins having from 10 to 20, in particular from 12 to 18, carbon atoms are particularly suitable as comonomers. These are preferably linear and the double bond is preferably terminal such as in dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene and octadecene.
  • the ratio of dicarboxylic acid or dicarboxylic acid derivative to olefin or olefins in the polymer is in the range 1: 1.5 to 1.5: 1, in particular it is equimolar.
  • copolymer B which are copolymerizable with ethylenically unsaturated dicarboxylic acids and the olefins mentioned, such as, for example, and longer-chain olefins, allyl polyglycol ethers, C 1 -C 30 -alkyl (meth) acrylates, vinylaromatics or C 1 -C 20 -alkyl vinyl ethers.
  • poly (isobutylenes) having molecular weights of up to 5,000 g / mol are used, with highly reactive variants having a high content of terminal vinylidene groups being preferred.
  • poly (isobutylenes) having molecular weights of up to 5,000 g / mol are used, with highly reactive variants having a high content of terminal vinylidene groups being preferred.
  • the preferred method of preparation is solvent-free bulk polymerization, but it is also possible to carry out the polymerization in the presence of aprotic solvents such as benzene, toluene, xylene or higher-boiling aromatic, aliphatic or isoaliphatic solvents or solvent mixtures such as kerosene or solvent naphtha.
  • aprotic solvents such as benzene, toluene, xylene or higher-boiling aromatic, aliphatic or isoaliphatic solvents or solvent mixtures such as kerosene or solvent naphtha.
  • the polymerization is particularly preferably in less moderating, aliphatic or isoaliphatic solvents.
  • the proportion of solvent in the polymerization mixture is generally between 10 and 90 wt .-%, preferably between 35 and 60 wt .-%.
  • the reaction temperature can be set particularly easily by the boiling point of the solvent or by working under reduced or elevated pressure.
  • the average molecular weight of the copolymers B according to the invention is generally between 1,200 and 200,000 g / mol, in particular between 2,000 and 100,000 g / mol, measured by gel permeation chromatography (GPC) against polystyrene standards in THF.
  • Copolymers of the invention must be oil-soluble in practice-relevant dosing quantities, ie they must dissolve in the oil to be additized at 50 ° C. without residue.
  • the reaction of the monomers is initiated by free radical initiators (free radical initiators).
  • This class of substance includes e.g. Oxygen, hydroperoxides and peroxides such as e.g. Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permalate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, and azo compounds such as eg 2,2'-azobis (2-methylpropanonitrile) or 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 w
  • the copolymers can be prepared either by reaction of maleic, fumaric and / or itaconic acid or their derivatives with the corresponding amine and subsequent copolymerization or by copolymerization of olefin or olefins with at least one unsaturated dicarboxylic acid or its derivative such as For example, itaconic and / or maleic anhydride and subsequent reaction with amines are produced.
  • a copolymerization with anhydrides is preferably carried out and the resulting copolymer is converted after production into an amide and / or an imide.
  • reaction with amines takes place in both cases, for example by reaction with 0.8 to 2.5 moles of amine per mole of anhydride, preferably with 1.0 to 2.0 moles of amine per mole of anhydride at 50 to 300 ° C.
  • 0.8 to 2.5 moles of amine per mole of anhydride preferably with 1.0 to 2.0 moles of amine per mole of anhydride at 50 to 300 ° C.
  • about 1 mol of amine per mol of anhydride formed at reaction temperatures of about 50 to 100 ° C preferably hemiamides, which additionally carry a carboxyl group per amide group.
  • reaction temperatures of about 100 to 250 ° C arise from primary amines with elimination of water preferably imides.
  • amine preferably 2 moles of amine per mole of anhydride formed at about 50 to 200 ° C amide ammonium salts and at higher temperatures, for example, 100 - 300 ° C, preferably 120 - 250 ° C diamides.
  • the water of reaction can be distilled off by means of an inert gas stream or discharged in the presence of an organic solvent by means of azeotropic distillation. Preference is given to 20-80, in particular 30-70, especially 35-55 wt .-% of at least one organic solvent used.
  • half-amides here are considered (50% in solvent) copolymers having acid numbers of 30 - 70 mg KOH / g, preferably from 40 - 60 mg KOH / g.
  • Corresponding copolymers with acid numbers of less than 40, especially less than 30 mg KOH / g are considered diamides or imides. Particularly preferred are hemiamides and imides.
  • Suitable amines are primary and secondary amines having one or two C 8 -C 16 alkyl radicals. They can carry one, two or three amino groups which are linked via alkylene radicals having two or three carbon atoms. Preference is given to monoamines. In particular, they carry linear alkyl radicals, but they can also minor amounts, eg. B. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to 10 wt .-% (in 1- or 2-position) contain branched amines. Shorter as well as longer-chain amines can be used, but their proportion is preferably less than 20 mol% and especially less than 10 mol%, for example between 1 and 5 mol%, based on the total amount of amines used.
  • primary amines are octylamine, 2-ethylhexylamine, decylamine, undecylamine, dodecylamine, n-tridecylamine, iso-tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine and mixtures thereof.
  • Preferred secondary amines are dioctylamine, dinonylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, and amines having different alkyl chain lengths such as N-octyl-N-decylamine, N-decyl-N-dodecylamine, N-decyl-N-tetradecylamine, N-decyl N-hexadecylamine, N-dodecyl-N-tetradecylamine, N-dodecyl-N-hexadecylamine, N-tetradecyl-N-hexadecylamine.
  • Secondary amines which, in addition to a C 8 -C 16 -alkyl radical, bear shorter side chains having 1 to 5 C atoms, for example methyl or ethyl groups, are suitable according to the invention.
  • the alkyl chain length n is taken into account as the mean value of the alkyl chain lengths of C 8 to C 16 for the calculation of the Q factor. Shorter and longer alkyl radicals, if present, are not included in the calculation because they do not contribute to the effectiveness of the additives.
  • Particularly preferred copolymers B are hemiamides and imides of primary monoamines.
  • the effectiveness can be further adapted to specific fatty acid ester compositions.
  • the additives may also contain polymers and copolymers based on C 10 -C 24 -alkyl acrylates or methacrylates (component C).
  • These poly (alkyl acrylates) and methacrylates have molecular weights of 800 to 1,000,000 g / mol, and are preferably derived from caprylic, capric, undecyl, lauryl, myristyl, cetyl, palmitoleyl, stearyl alcohol or the like Mixtures such as coconut, palm, tallow or behenyl from.
  • mixtures of the invention Copolymers B are used, with the proviso that the mean value of the Q values of the mixture components again assumes values of 23 to 27 and preferably values of 24 to 26.
  • the mixing ratio of the additives A and B according to the invention is (in parts by weight) 20: 1 to 1:20, preferably 10: 1 to 1:10, in particular 5: 1 to 1: 2.
  • the proportion of component C in the formulations of A, B and C may be up to 40% by weight; it is preferably less than 20% by weight, in particular between 1 and 10% by weight.
  • the additives of the invention are added to oils in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 1 wt .-% and especially 0.01 to 0.5 wt .-%. They may be dissolved as such or dissolved or dispersed in solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such.
  • toluene xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene, naphtha, diesel, fuel oil, isoparaffins or commercial solvent mixtures such as solvent naphtha, ®Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol- ® Isopar- and ® Shellsol D types are used.
  • solvent naphtha ®Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol- ® Isopar- and ® Shellsol D types
  • they are dissolved in fuel oil of animal or vegetable origin based on fatty acid alkyl esters.
  • the additives according to the invention preferably contain 1 to 80%, especially 10 to 70%, in particular 25 to 60%, of solvent.
  • the fuel oil which is often referred to as a “biodiesel” or “biofuel,” is fatty acid alkyl esters of fatty acids having 12 to 24 carbon atoms and alcohols having 1 to 4 carbon atoms Part of the fatty acids one, two or three double bonds.
  • oils derived from animal or vegetable material and in which the additive according to the invention can be used are rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, Beef tallow, bone oil, fish oils and used edible oils.
  • oils derived from wheat, jute, sesame, shea nut, arachis oil and linseed oil can be derived from these oils by methods known in the art.
  • Rapeseed oil which is a mixture of glycerol partially esterified fatty acids, is preferred because it is available in large quantities and is readily available by squeezing rapeseed. Furthermore, the also widespread oils of sunflower and soybeans and their mixtures with rapeseed oil are preferred.
  • Particularly suitable as biofuels are lower alkyl esters of fatty acids.
  • lower alkyl esters of fatty acids are, for example, commercially available mixtures of ethyl, propyl, butyl and especially methyl esters of fatty acids having 14 to 22 carbon atoms, for example of lauric, myristic, palmitic, palmitolic, stearic, oleic, elaidic, petroselinic, ricinoleic, elaeostearic, linoleic, linolenic , Eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid, which preferably have an iodine value of 50 to 150, in particular 90 to 125.
  • Mixtures with particularly advantageous properties are those which are mainly d. H. at least 50 wt .-%, contain methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 double bonds.
  • the preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and erucic acids.
  • a biofuel is an oil obtained from plant or animal matter or both, or a derivative thereof, which can be used as a fuel and especially as a diesel or fuel oil.
  • Vegetable oil derivatives are preferred, with particularly preferred biofuels being alkyl ester derivatives of rapeseed oil, cottonseed oil, soybean oil, sunflower oil, olive oil or palm oil, methyl rapeseed oil, methyl sunflower oil and soybean oil methyl ester being most preferred.
  • particularly preferred biofuel or as a component in the biofuel are also old fat esters such as, for example, used fat methyl ester.
  • the additive may be added to the oil to be treated according to methods known in the art. If more than one additive component or co-additive component is to be used, such components may be incorporated into the oil together or separately in any combination.
  • the CFPP value of biodiesel can be adjusted to values below -20 ° C. and in some cases to values below -25 ° C., as required for marketing in particular for use in winter.
  • the pour point of biodiesel is reduced by the addition of the additives according to the invention.
  • the additives according to the invention are particularly advantageous in problematic oils which have a high content of esters of saturated fatty acids of more than 4%, in particular more than 5% and especially 7 to 25%, for example 8 to 20%, as is the case, for example, in oils Sunflowers and soy are included.
  • Such oils are characterized by cloud points above -5 ° C and especially above -3 ° C.
  • the additives according to the invention also to adjust mixtures of Rapsölklaremethylester and sunflower and / or soybean oil fatty acid methyl ester to CFPP values of -20 ° C and below.
  • the oils thus added have a good resistance to cold chilling, ie the CFPP value remains constant even when stored under winter conditions.
  • the additives according to the invention can also be used together with one or more oil-soluble co-additives, which in themselves improve the cold flow properties of crude oils, lubricating oils or fuel oils.
  • oil-soluble co-additives are polar compounds which cause paraffin dispersion (Paraffin dispersants) and oil-soluble amphiphiles, with the proviso that they differ from the comb polymers B.
  • paraffin dispersants reduce the size of the paraffin crystals and cause the paraffin particles to not settle but remain colloidally dispersed with significantly reduced sedimentation effort.
  • Suitable paraffin dispersants are both low molecular weight and polymeric, oil-soluble compounds having ionic or polar groups such as amine salts and / or amides have proven.
  • Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines having 20 to 44 carbon atoms, in particular dicocoamine, ditallow fatty amine, distearylamine and dibehenylamine with carboxylic acids and derivatives thereof.
  • Paraffin dispersants which have been obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides have proven particularly suitable (cf. US 4 211 534 ).
  • amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as paraffin dispersants (cf. EP 0 398 101 ).
  • paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP 0 154 177 ) and the reaction products of alkenyl spiro-bis-lactones with amines (cf. EP 0 413 279 B1 ) and after EP-A-0 606 055 A2 Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
  • the mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants is 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • the additives may be used alone or together with other additives, for example with other pour point depressants or dewaxing aids, with antioxidants, cetane number improvers, dehazers, demulsifiers, detergents, Dispersants, defoamers, dyes, corrosion inhibitors, conductivity improvers, sludge inhibitors, odorants, and / or cloud point depressants.
  • other pour point depressants or dewaxing aids with antioxidants, cetane number improvers, dehazers, demulsifiers, detergents, Dispersants, defoamers, dyes, corrosion inhibitors, conductivity improvers, sludge inhibitors, odorants, and / or cloud point depressants.
  • the CFPP value is determined in accordance with EN 116 and the determination of the cloud point in accordance with ISO 3015.
  • the ethylene copolymers used are commercial products having the characteristics given in Table 2. The products were used as 65% and 50% (A3) settings in kerosene, respectively.
  • Table 3 Characterization of the ethylene copolymers used example Comonomer (s) V140 CH 3/100 CH 2 A1 13.6 mole% vinyl acetate 130 mPas 3.7 A2 13.7 mole percent vinyl acetate and 1.4 mole percent vinyl neodecanoate 105 mPas 5.3 A3 9.4 mol% vinyl acetate 220 mPas 6.2 A4 Mixture of EVA copolymer with 16 mol% vinyl acetate and EVA with 95 mPas 3.2 5 mol% vinyl acetate in the ratio 13: 1 350 mPas 5.7
  • the polymerization of maleic anhydride (MSA) with ⁇ -olefins is carried out in a higher boiling aromatic hydrocarbon mixture at 160 ° C in the presence of a mixture of equal parts tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate as a radical chain initiator.
  • Table 3 shows, by way of example, various copolymers and the molar proportions of the monomers used for their preparation, as well as the chain length (R) and molar amount (based on MSA) of the amine used for the derivatization and the factor Q calculated therefrom.
  • the amines used are, unless stated otherwise, monoalkylamines.
  • the reactions with amines are carried out in the presence of solvent naphtha (50 wt .-%) at 50 to 100 ° C to the half-amide or amide ammonium salt and at 160 to 200 ° C with azeotropic removal of water of reaction to the imide or diamid.
  • solvent naphtha 50 wt .-%
  • the degree of amidation is inversely proportional to the acid number.
  • CFPP value (according to EN 116, in ° C) of various biofuels according to the above table after addition of 1200 ppm, 1500 ppm and 2000 ppm additive mixture was determined. Percentages refer to parts by weight in the respective mixtures.
  • Tables 5 to 7 show that comb polymers with the factor Q according to the invention achieve excellent CFPP reductions even at low dosing rates and offer additional potential at higher dosing rates.
  • Table 6 CFPP testing in test oil E1 Ex.
  • the CFPP value according to DIN EN 116 is compared before and after a standardized cold-change treatment.
  • test oil E1 500 ml of biodiesel (test oil E1) are treated with the appropriate cold additive, placed in a cylinder and stored in a programmable cold chamber for one week. During this time, a program is run through which repeatedly cools to -13 ° C and then warms up again to -3 ° C. 6 cycles are consecutively run through (Table 8).
  • Cooling program for determining the resistance to cold chill section begin The End duration description A ⁇ B + 5 ° C -3 ° C 8 h Pre-cooling to cycle start temperature B ⁇ C -3 ° C -3 ° C 2 h stationary temperature, start of cycle C ⁇ D -3 ° C -13 ° C 14 h Temperature reduction, incipient crystal formation D ⁇ E -13 ° C - 13 ° C 2 h Stationary temperature, crystal growth E ⁇ F -13 ° C -3 ° C 6 h Temperature increase, melting of the crystals F ⁇ B Another 6 cycles B ⁇ F are carried out.
  • the additiviere oil sample is reheated to room temperature without shaking. From each of the upper, middle and lower sections of the cylinder a sample of 50 ml is drawn for CFPP measurements.
  • Table 10 Resistance to cold-resistance of the additized oil: additive CFPP CFPP after storage example comb polymer ethylene copolymer metering before storage below ⁇ CFPP (below) center ⁇ CFPP (middle) above ⁇ CFPP (above) 39 20% B2 80% A2 1500 ppm -24 ° C -23 ° C 1K -24 ° C 0K -25 ° C -1K 40 19% B2 5% C1 76% A2 1500 ppm -24 ° C -22 ° C 2K -23 ° C 1K -24 ° C 0K 41 20% B14 80% A4 1500 ppm -23 ° C -22 ° C 1K -21 ° C 2K -22 ° C 1K 42 25% B13 75% A4 1500 ppm

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Claims (18)

  1. Additif, contenant les constituants A) et B) en un rapport en poids de 10:1 à 1:10
    A) un copolymère d'éthylène et de 8 à 21 % en moles d'au moins un ester acrylique ou vinylique comprenant un radical alkyle en C1-C18 et
    B) un polymère en peigne, contenant des unités structurales de
    B1) au moins une oléfine en tant que monomère 1, qui porte au moins un radical alkyle en C8-C18 sur la double liaison oléfinique et
    B2) au moins un acide dicarboxylique éthyléniquement insaturé en tant que monomère 2, qui porte au moins un radical alkyle en C8-C16 relié par un groupe amide et/ou imide, la somme Q Q = ∑ i w 1 ⁢ i ⋅ n 1 ⁢ i + ∑ j w 2 ⁢ j ⋅ n 2 ⁢ j
    Figure imgb0008
    des moyennes molaires des distributions de longueurs de chaînes C dans les radicaux alkyle du monomère 1 d'un côté et les radicaux alkyle des groupes amide et/ou imide du monomère 2 d'un autre côté étant de 23 à 27, en un rapport molaire B1) :B2) de 1:1,5 à 1,5:1,
    w1 étant la proportion molaire des longueurs de chaînes individuelles dans les radicaux alkyle du monomère 1,
    w2 étant la proportion molaire des longueurs de
    chaînes individuelles dans les radicaux alkyle des groupes amide et/ou imide du monomère 2,
    n1 étant les longueurs de chaînes individuelles dans les radicaux alkyle du monomère 1,
    n2 étant les longueurs de chaînes individuelles dans les radicaux alkyle des groupes amide et/ou imide du monomère 2,
    i étant la variable de contrôle pour les longueurs de chaînes individuelles dans les radicaux alkyl du monomère 1 et
    j étant la variable de contrôle pour les longueurs de chaînes individuelles dans les radicaux alkyle des groupes amide et/ou imide du monomère 2.
  2. Additif selon la revendication 1, dans lequel Q vaut de 24 à 26.
  3. Additif selon la revendication 1 et/ou 2, dans lequel, outre l'éthylène, le constituant A contient 3,5 à 20 % en moles d'acétate de vinyle et 0,1 à 12 % en moles d'ester vinylique de l'acide 2-éthylhexanoïque, d'ester vinylique de l'acide néononanoïque et/ou d'ester vinylique de l'acide néodécanoïque, la teneur totale en comonomères étant comprise entre 8 et 21 % en moles.
  4. Additif selon une ou plusieurs des revendications 1 à 3, dans lequel, outre l'éthylène et 8 à 18 % en moles d'esters vinyliques, le constituant A contient encore 0,5 à 10 % en moles d'oléfines, choisies parmi le propène, le butène, l'isobutylène, l'hexène, le 4-méthylpentène, l'octène, le diisobutylène ou le norbornène.
  5. Additif selon une ou plusieurs des revendications 1 à 4, dans lequel les copolymères qui composent le constituant A présentent des viscosités à l'état fondu comprises entre 20 et 10 000 mPas.
  6. Additif selon une ou plusieurs des revendications 1 à 5, dans lequel les copolymères qui composent le constituant A présentent des degrés de ramification compris entre 1 et 9 groupes CH3/100 groupes CH2, qui ne proviennent pas des comonomères.
  7. Additif selon une ou plusieurs des revendications 1 à 6, dans lequel les copolymères qui composent le constituant B contiennent des comonomères qui dérivent d'amides et/ou d'imides de l'acide maléique, de l'acide fumarique et/ou de l'acide itaconique.
  8. Additif selon une ou plusieurs des revendications 1 à 7, dans lequel les amides et/ou les imides du constituant B dérivent d'amines primaires.
  9. Additif selon une ou plusieurs des revendications 1 à 8, dans lequel les amides et/ou les imides du constituant B dérivent d'amines à radicaux alkyle linéaires.
  10. Additif selon une ou plusieurs des revendications 1 à 9, dans lequel les amides et/ou les imides du constituant B dérivent de monoamines.
  11. Additif selon une ou plusieurs des revendications 1 à 10, dans lequel les copolymères qui composent le constituant B contiennent des comonomères qui dérivent d'α-oléfines.
  12. Additif selon une ou plusieurs des revendications 1 à 11, dans lequel, outre les constituants A et B, un polymère ou copolymère qui comprend des unités acrylate ou méthacrylate d'alkyle en C10-C24, d'un poids moléculaire de 800 à 1 000 000 g/mol, est contenu en tant que constituant C en une quantité de jusqu'à 40 % en poids, par rapport au poids total de A, B et C.
  13. Additif selon l'une quelconque des revendications 1 à 12, contenant des dispersants paraffiniques azotés polaires.
  14. Composition d'huile combustible, contenant une huile combustible d'origine animale ou végétale et 0,001 à 5 % en poids d'un additif selon une ou plusieurs des revendications 1 à 13.
  15. Composition d'huile combustible selon la revendication 14, caractérisée en ce que l'huile combustible d'origine animale ou végétale contient un ou plusieurs esters d'un acide monocarboxylique de 14 à 24 atomes C et d'un alcool de 1 à 4 atomes C.
  16. Composition d'huile combustible selon la revendication 15, caractérisée en ce que l'alcool est le méthanol ou l'éthanol.
  17. Composition d'huile combustible selon une ou plusieurs des revendications 14 à 16, caractérisée en ce que l'huile combustible d'origine animale ou végétale contient plus de 5 % en poids d'esters d'acides gras saturés.
  18. Utilisation d'un additif selon une ou plusieurs des revendications 1 à 13 en une quantité de 0,001 à 5 % en poids pour l'amélioration des propriétés d'écoulement à froid d'huiles combustibles d'origine animale ou végétale.
EP04024234.9A 2003-10-25 2004-10-12 Agent d'amélioration de l'écoulement à froid pour huiles combustibles d'origine végétale ou animale Expired - Lifetime EP1526167B2 (fr)

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CA2486035C (fr) 2012-03-13
PL1526167T5 (pl) 2019-09-30
KR101139274B1 (ko) 2012-04-26
JP2005126720A (ja) 2005-05-19
PL1526167T3 (pl) 2015-10-30
EP1526167A3 (fr) 2005-05-11
JP4859361B2 (ja) 2012-01-25
EP1526167A2 (fr) 2005-04-27
HUE025057T2 (en) 2016-01-28
US20050113266A1 (en) 2005-05-26
DE10349851B4 (de) 2008-06-19
US7500996B2 (en) 2009-03-10
KR20050039682A (ko) 2005-04-29
EP1526167B2 (fr) 2019-01-30
CA2486035A1 (fr) 2005-04-25

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