EP1419224B1 - Huiles combustibles, contenant des additifs améliorant le pouvoir lubrifiant et presentant une tendance reduite d'émulsionnement - Google Patents

Huiles combustibles, contenant des additifs améliorant le pouvoir lubrifiant et presentant une tendance reduite d'émulsionnement Download PDF

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EP1419224B1
EP1419224B1 EP02762334A EP02762334A EP1419224B1 EP 1419224 B1 EP1419224 B1 EP 1419224B1 EP 02762334 A EP02762334 A EP 02762334A EP 02762334 A EP02762334 A EP 02762334A EP 1419224 B1 EP1419224 B1 EP 1419224B1
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Prior art keywords
fuel oil
weight
contain
additives
ester
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EP1419224A2 (fr
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Matthias Krull
Markus Kupetz
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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 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
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols

Definitions

  • the present invention relates to additives of esters between polyols and fatty acid mixtures, as well as their use for improving the lubricity of highly desulfurized fuel oils with reduced emulsification tendency.
  • Mineral oils and mineral oil distillates used as fuel oils generally contain 0.5% by weight and more sulfur which causes the formation of sulfur dioxide upon combustion. In order to reduce the resulting environmental impact, the sulfur content of fuel oils is lowered further and further.
  • the standard EN 590 relating to diesel fuels currently prescribes a maximum sulfur content of 350 ppm in Germany. In Scandinavia fuel oils of less than 50 ppm and in exceptional cases less than 10 ppm of sulfur are used. These fuel oils are usually prepared by hydrogenating the fractions obtained from the petroleum by distillation. In the desulfurization but other substances are removed, which give the fuel oils a natural lubricating effect. These substances include polyaromatic and polar compounds.
  • EP-A-0 680 506 discloses that esters of fatty acids impart improved lubricity to highly desulfurized fuel oils.
  • esters of fatty acids impart improved lubricity to highly desulfurized fuel oils.
  • glycerol monooleate and diisodecyl adipate are mentioned.
  • EP-A-0 739 970 discloses the suitability of fatty acid mixtures for improving the lubricity of low sulfur fuel oils. Compositions of different degrees of esterification and different degrees of saturation of the fatty acids are disclosed.
  • EP-A-0 839 174 discloses in its lubricity improved fuel oils which are low in sulfur and comprise a mixture of polyol esters with unsaturated fatty acids.
  • DE-A-196 14 722 discloses lubricant and fuel additives, which consist essentially of fatty acid monoesters or mono- and diester mixtures of unsaturated fatty acids having 16 to 22 carbon atoms with at least two different polyols, have a more favorable low-temperature behavior than corresponding monoesters or mono- and diesters of uniform polyols.
  • the polyol is preferably a mixture of glycerol and another polyol from the group trimethylolpropane, pentaerythritol and dipentaerythritol in a molar ratio of 1: 1 to 3: 1.
  • the fatty acid esters of the prior art based on commercial fatty acid mixtures show a pronounced tendency to emulsify in the fuel oils that are additized with them. This means that when such a fuel oil comes in contact with water, emulsification of the water in the fuel oil takes place.
  • These emulsions which can be found in particular at the oil / water interface, can not be separated or can be separated only with great effort. Since these emulsions can not be used as such as fuel oils, they reduce the value of the products. This problem is particularly pronounced when esters based on natural fatty acid mixtures are used.
  • the object of the present invention was therefore to find lubricant-improving additives for desulfurized fuel oils, which have a reduced emulsifier tendency compared with the prior art.
  • esters of fatty acid mixtures which show a certain combination of hydroxyl number and iodine number, do not have the emulsifying ability of the esters of the prior art, and have an excellent lubricating effect in desulfurized fuel oils.
  • the reduced tendency for emulsification is brought about by two effects.
  • the polarity range of the additives which is determined by the OH number, causes a reduced affinity of the amphiphilic active substances for water.
  • the formation of micellar surface-active structures is disturbed by the number of double bonds in the alkyl radicals determined by iodine number.
  • the invention therefore relates to fuel oils with a maximum of 0.035 wt .-% sulfur content, containing at least one ester of a dihydric or polyhydric alcohol and a mixture of unsaturated and optionally saturated fatty acids whose carbon chain lengths are between 8 and 30 carbon atoms, said esters a OH number of between 110 and 195 mg KOH / g ester and an iodine value of more than 100 gl / 100 g ester, in amounts of 0.001 to 0.5 wt .-% based on the fuel oil.
  • Another object of the invention is the use of the additives of the invention in amounts of 0.001 to 0.5 wt .-% based on the fuel oil, to improve the lubricity of fuel oils with at most 0.035 wt .-% sulfur content.
  • Preferred fatty acids which are part of the fatty acid mixture are those having 10 to 26 C atoms, in particular 12 to 22 C atoms.
  • the alkyl radicals of the fatty acids consist essentially of carbon and hydrogen. However, you can choose other substituents such as hydroxy, halogen, amino or
  • the fatty acids contained in the fatty acid mixture preferably contain at least one double bond. They may contain multiple double bonds, for example 2 or 3 double bonds, and be of natural or synthetic origin. In the case of polyunsaturated carboxylic acids, their double bonds may be isolated or else conjugated. In preferred fatty acid mixtures contain at least 50 wt .-%, in particular at least 75 wt .-%, especially at least 90 wt .-% of the fatty acids one or more double bonds.
  • the iodine numbers of the fatty acids on which the esters according to the invention are based are preferably between 105 and 190, in particular 110 to 180 and especially 120 to 180 g l / 100 g of ester.
  • Suitable fatty acid mixtures contain at least two unsaturated fatty acids having 10 to 26 carbon atoms.
  • Suitable unsaturated fatty acids are, for example, oleic acid, erucic acid, palmitoleic, myristoleic, linoleic, linolenic, elaeosterolic, arachidonic acid, and / or ricinoleic acid.
  • the fatty acid mixtures may contain minor amounts, i. up to 10 wt .-%, preferably less than 5%, especially less than 2% of saturated fatty acids such as lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearic, isostearic, arachin and Contain behenic acid.
  • saturated fatty acids such as lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearic, isostearic, arachin and Contain behenic acid.
  • dicarboxylic acids such as dimer fatty acids and alkyl- and alkenylsuccinic acids with C 8 -C 50 -alk (en) yl radicals, preferably with C 8 -C 40 -, in particular with C 12 -C 22 -alkyl radicals.
  • the alkyl radicals can be linear or branched (oligomerized alkenes, PIB). Preferred are proportions of up to 10 wt .-%, in particular less than 5 wt .-%.
  • the fatty acids may further contain 1-40, especially 1-25 wt .-%, in particular 1-5 wt .-% resin acids.
  • Suitable alcohols preferably contain 2 to 6, in particular 3 to 4 carbon atoms, and 2 to 5, in particular 3 to 4 hydroxyl groups, but at most one hydroxyl group per carbon atom.
  • Particularly suitable alcohols are ethylene glycol, diethylene glycol, propylene glycol, glycerol and pentaerythritol.
  • esters can be prepared from alcohols and fatty acids in a known manner by esterification. Alternatively, the partial saponification of naturally occurring fats and oils is possible.
  • Esters of the invention are those which can be prepared from a dihydric or polyhydric alcohol and a mixture of fatty acids. Both mixtures of, for example, monoesters of an alcohol with various fatty acids, of monoesters of different alcohols with different fatty acids, and of mixtures of mono-, di- and / or triesters, or optionally higher esters, of one or more alcohols with different fatty acids are included , According to the invention, the esters are if they can be prepared from a fatty acid mixture.
  • the iodine numbers of the esters according to the invention are preferably between 100 and 180, in particular 110 to 150 g l / 100 g ester.
  • the iodine numbers result from the iodine value of the basic fatty acid mixture and the alcohol used for the esterification in a stoichiometric manner.
  • the OH number of the esters in the additive according to the invention is between 110 and 195, in particular between 130 and 190 mg KOH / g of ester.
  • these are mixtures of different esters, eg. As mixtures of mono-, di- and triglycerides, mixtures, such as those resulting from the esterification of polyols.
  • the additives according to the invention are added to oils in amounts of 0.001 to 0.5% by weight, preferably 0.005 to 0.3% by weight and especially 0.01 to 0.1% by weight. They can be used as such or dissolved in solvents, such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene or commercial solvent mixtures such as Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol-, ® Isopar- and ® Shellsol D types are used.
  • solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene or commercial solvent mixtures such as Solvent Na
  • the additives according to the invention preferably contain 1 to 80%, especially 10 to 70%, in particular 25 to 60%, of solvent.
  • the additives which can be used without problems even at low temperatures of, for example, -30 ° C. and lower, improve the lubricity of the additized oils while at the same time reducing emulsification.
  • 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 and / or lubricity of crude oils, lubricating oils or fuel oils.
  • oil-soluble co-additives are vinyl acetate-containing copolymers or terpolymers of ethylene, paraffin dispersants, comb polymers, alkylphenol-aldehyde resins and oil-soluble amphiphiles.
  • the additives according to the invention are used in admixture with ethylene / vinyl acetate / vinyl neononanoate terpolymers or ethylene / vinyl acetate / vinyl neodecanoate terpolymers to simultaneously improve the flowability and lubricity of mineral oils or mineral oil distillates.
  • the terpolymers of vinyl neononanoate or vinyl neodecanoate contain, in addition to ethylene, 10 to 35% by weight of vinyl acetate and 1 to 25% by weight of the respective neo compound.
  • copolymers contain, in addition to ethylene and from 10 to 35% by weight of vinyl esters, from 0.5 to 20% by weight of olefin, such as diisobutylene, 4-methylpentene or norbornene.
  • olefin such as diisobutylene, 4-methylpentene or norbornene.
  • the mixing ratio of the additives according to the invention with the above described ethylene / vinyl acetate copolymers or the terpolymers of ethylene, vinyl acetate and the vinyl esters of neononan or neodecanoic acid is (in parts by weight) 20: 1 to 1:20, preferably 10: 1 to 1:10.
  • the reaction products according to the invention can also be used together with paraffin dispersants.
  • Paraffin dispersants reduce the size of the paraffin crystals and cause the paraffin particles to not settle but remain colloidally dispersed with significantly reduced sedimentation effort. Furthermore, they increase the lubricity of the additives of the invention.
  • Suitable paraffin dispersants are oil-soluble polar compounds having ionic or polar groups, eg amine salts and / or amides, which are prepared 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 are obtained (see. US 4 211 534 ).
  • Other paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, which may optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf.
  • the additives according to the invention can be used in mixture with alkylphenol-formaldehyde resins.
  • the additives according to the invention are used together with comb polymers.
  • This term refers to polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone.
  • they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms.
  • at least 20%, preferably at least 30% of the monomers have side chains (cf. Comblike Polymers-Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff ).
  • Suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1 ), Copolymers of a C 6 -C 24 ⁇ - olefin and a NC 6 -C 22 -alkylmaleimide (cf. EP 0 320 766 ), further esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ - olefins and esterified copolymers of styrene and maleic anhydride.
  • fumarate / vinyl acetate copolymers cf. EP 0 153 176 A1
  • Copolymers of a C 6 -C 24 ⁇ - olefin and a NC 6 -C 22 -alkylmaleimide cf. EP 0 320 766
  • further esterified olefin / maleic anhydride copolymers polymers and
  • the mixing ratio (in parts by weight) of the inventive additives with resins or comb polymers is 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • the additives of the invention are particularly well suited for use in middle distillates.
  • middle distillates are in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil.
  • the oils may also contain or consist of alcohols such as methanol and / or ethanol.
  • the additives of the invention are used in such middle distillates containing less than 350 ppm of sulfur, especially less than 200 ppm of sulfur and in special cases less than 50 ppm of sulfur.
  • These are generally those middle distillates that have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds that give them a natural lubricating effect.
  • the additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 370.degree. C., in particular 350.degree. C. and in special cases below 330.degree. They can also be used as components in lubricating oils.
  • the mixtures can be used alone or together with other additives can be used, for example, with pour point depressants or dewaxing aids, with corrosion inhibitors, antioxidants, sludge inhibitors, dehazers, conductivity improvers, lubricity additives, and additives for lowering the cloud point. Furthermore, they are successfully used together with additive packages containing, among others, known ashless dispersing additives, detergents, defoamers and corrosion inhibitors. Between the additives according to the invention and the other additives mentioned, the synergisms with regard to cold flow properties described in the prior art are used WO-95/03377 and Lubricity according to WO 96/18708 such as WO 96/23855 achieved.
  • Iodine numbers are determined by Kaufmann. For this purpose, a sample of known composition is admixed with a defined, excess amount of a methanolic bromine solution, with an amount of bromine equivalent to the content of double bonds in the sample being added to the double bonds. The excess of bromine is back titrated with sodium thiosulfate.
  • esters according to the prior art (comparative values) ester OH number [mg KOH / g] Iodine number [g J / 100 g] Glycerol monooleate (pure) 315 71 Glycerol dioleate (pure) 90 82 EP 0 839 174 , Eg A 181 78 EP 0 839 174 , Eg B 315 71 EP 0 839 174 , Eg C 317 143 EP 0 739 970 , Eg A 181 77 EP 0 739 970 , Eg G 284 120 EP 0 739 970 , Eg H 141 44 EP 0 739 970 , I 155 72 EP 0 739 970 , Eg J 111 74 EP 0 739 970 , Eg K 185 78 EP 0 739 970 , Eg L 122 81 EP 0 739 970 , Eg M 192 77 EP 0 739 970 , E
  • the testing of the emulsification of additives is carried out according to ASTM D 1094-85.
  • 80 ml of a diesel fuel are mixed in a 100 ml cylinder with 250 ppm of the additive to be tested and tempered for 15 minutes at 60 ° C and shaken. After cooling to room temperature, 2 ml of buffer solution are added and shaken for 2 minutes. After 5 minutes, the sample is assessed visually according to the following criteria: Table 3: Emulsification of the additives Evaluation of the separation layer Evaluation of the phase separation 1 Clear and clean 1 Complete absence of all emulsions and / or precipitates in both phases or on top of the oil phase. 1 b small, clear bubbles that are estimated to cover no more than 50% of the release layer.
  • the lubricating effect of the additives was carried out using an HFRR instrument from PCS Instruments on additized oils at 60 ° C.
  • the High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 2, p. 217, 1986 , The results are given as coefficient of friction and Wear Scar (WS 1.4). A low coefficient of friction and a low Wear Scar show a good lubricating effect.
  • test oil used was a Scandinavian winter diesel with the following characteristics: boiling range: 185 - 320 ° C Density: 0.820 g / cm 3 Cloud Point: - 29 ° C sulfur content: 3 ppm

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'objet de l'invention est un additif destiné à améliorer l'action lubrifiante d'huiles combustibles présentant une teneur en soufre maximale de 0,035 % en poids. Cet additif contient au moins un ester d'un alcool bivalent ou polyvalent et d'un mélange d'acides gras insaturés et éventuellement saturés dont la chaîne carbonée présente une longueur comprise entre 8 et 30 atomes de carbone, lesdits esters présentant un indice OH inférieur à 200 mg KOH/g d'ester et un indice d'iode supérieur à 100 g I/100 g d'ester. L'invention concerne également des huiles combustibles présentant une teneur en soufre maximale de 0,035 % en poids contenant ce type d'additifs. Ces additifs présentent une tendance réduite à l'émulsion comparé aux additifs connus.

Claims (15)

  1. Huiles combustibles présentant une teneur en soufre maximale de 0,035% en poids, contenant au moins un ester d'un alcool divalent ou polyvalent et d'un mélange d'acides gras insaturés et le cas échéant saturés, dont les longueurs de chaînes carbonées sont situées entre 8 et 30 atomes de carbone, les esters mentionnés présentant un indice d'OH entre 110 et 195 mg de KOH/g d'ester et un indice d'iode supérieur à 100 g d'l/100 g d'ester, en des quantités de 0,001 à 0,5% en poids par rapport à l'huile combustible.
  2. Huiles combustibles selon la revendication 1, l'indice d'iode étant situé entre 100 et 180 g d'l/100 g d'ester.
  3. Huiles combustibles selon la revendication 1 et/ou 2, les acides gras faisant partie du mélange d'acides gras contenant 10 à 26 atomes de carbone.
  4. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 3, les mélanges d'acides gras contenant jusqu'à 10% en poids d'acides gras saturés.
  5. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 4, les alcools contenant 2 à 6 en poids atomes de carbone.
  6. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 5, les alcools contenant 2 à 5 groupes hydroxyle, mais au maximum un groupe hydroxyle par atome de carbone.
  7. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 6, un constituant des acides gras étant des acides dicarboxyliques.
  8. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 7, une résine d'alkylphénol-formaldéhyde, dans un rapport additif:résine de 1:10 à 20:1 en poids étant contenue.
  9. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 7, contenant en outre
    des copolymères qui contiennent 10 à 40% en poids d'acétate de vinyle et 60 à 90% en poids d'éthylène.
    des terpolymères d'éthylène/acétate de vinyle/ester vinylique de l'acide néononanoïque ou des terpolymères d'éthylène/acétate de vinyle/ester vinylique de l'acide néodécanoïque, qui contiennent outre de l'éthylène, 10 à 35% en poids d'acétate de vinyle et 1 à 25% en poids de chaque composé néo, ou
    des copolymères, qui contiennent outre l'éthylène et 10 à 35% en poids d'esters de vinyle, encore 0,5 à 20% en poids d'oléfine,
    dans un rapport de mélange additif aux copolymères ou, selon le cas, terpolymères décrits ci-dessus (en parties en poids) de 20:1 à 1:20.
  10. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 7, contenant en outre des composés azotés polaires solubles dans l'huile contenant des groupes ioniques ou polaires, qui sont obtenus par réaction d'amines aliphatiques ou aromatiques avec des acides aliphatiques ou aromatiques monocarboxyliques, dicarboxyliques, tricarboxyliques ou tétracarboxyliques ou leurs anhydrides.
  11. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 7, contenant en outre des polymères en peigne de formule
    Figure imgb0004
     où
    A signifie R', COOR', OCOR', R"-COOR' ou OR' ;
    D signifie H, CH3, A ou R ;
    E signifie H ou A ;
    G signifie H, R", R"-COOR', un radical aryle ou un radical hétérocyclique ;
    M signifie H, COOR", OCOR", OR" ou COOH ;
    N signifie H, R", COOR", OCOR, COOH ou un radical aryle ;
    R' signifie une chaîne hydrocarbonée comprenant 8-150 atomes de carbone ;
    R" signifie une chaîne hydrocarbonée comprenant 1 à 10 atomes de carbone ;
    m vaut un nombre entre 0,4 et 1,0 ; et
    n vaut un nombre entre 0 et 0,6.
    dans un rapport de mélange (en parties en poids) des additifs avec les polymères en peigne de 1:10 à 20:1.
  12. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 7, contenant en outre des copolymères de l'anhydride de l'acide maléique et de composés α,ß-insaturés, qui peuvent le cas échéant être transformés avec des monoalkylamines primaires et/ou des alcools aliphatiques.
  13. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 7, contenant en outre des produits de transformation d'alcénylspirobislactones avec des amines.
  14. Huiles combustibles selon l'une ou plusieurs des revendications 1 à 7, contenant en outre des produits de transformation de terpolymères à base d'anhydrides d'acides dicarboxyliques α,ß-insaturés, de composés α,ß-insaturés et de polyoxyalkylène-éthers d'alcools insaturés inférieurs.
  15. Utilisation d'un additif selon l'une ou plusieurs des revendications 1 à 7, en des quantités de 0,001 à 0,5% en poids par rapport à l'huile combustible, pour améliorer l'effet lubrifiant d'huiles combustibles contenant au plus 0,035% en poids de teneur en soufre.
EP02762334A 2001-07-27 2002-07-09 Huiles combustibles, contenant des additifs améliorant le pouvoir lubrifiant et presentant une tendance reduite d'émulsionnement Expired - Lifetime EP1419224B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10136828A DE10136828B4 (de) 2001-07-27 2001-07-27 Schmierverbessernde Additive mit verminderter Emulgierneigung für hochentschwefelte Brennstofföle
DE10136828 2001-07-27
PCT/EP2002/007616 WO2003012015A2 (fr) 2001-07-27 2002-07-09 Additifs ameliorant l'action lubrifiante d'huiles combustibles hautement desulfurees et presentant une tendance reduite a l'emulsion

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EP1419224A2 EP1419224A2 (fr) 2004-05-19
EP1419224B1 true EP1419224B1 (fr) 2012-06-27

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DE (1) DE10136828B4 (fr)
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US20150113864A1 (en) 2013-10-24 2015-04-30 Basf Se Use of a complex ester to reduce fuel consumption
US20150113859A1 (en) 2013-10-24 2015-04-30 Basf Se Use of polyalkylene glycol to reduce fuel consumption
CN109996857A (zh) 2016-12-20 2019-07-09 巴斯夫欧洲公司 复合酯和一元羧酸的混合物减小摩擦的用途
GB202408873D0 (en) * 2024-06-20 2024-08-07 Innospec Ltd Compositions and methods and uses relating thereto
GB202408872D0 (en) * 2024-06-20 2024-08-07 Innospec Ltd Improvements relating to fuel compositions

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WO2003012015A2 (fr) 2003-02-13
ES2385646T3 (es) 2012-07-27
DE10136828A1 (de) 2003-02-13
US20060254128A1 (en) 2006-11-16
EP1419224A2 (fr) 2004-05-19
CA2455679A1 (fr) 2003-02-13
JP4822665B2 (ja) 2011-11-24
DE10136828B4 (de) 2005-12-15
US7431745B2 (en) 2008-10-07
WO2003012015A3 (fr) 2003-12-11
CA2455679C (fr) 2010-04-27
JP2004536216A (ja) 2004-12-02

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