EP3529338B1 - Mischung von additiven für brennstoff - Google Patents

Mischung von additiven für brennstoff Download PDF

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Publication number
EP3529338B1
EP3529338B1 EP17794021.0A EP17794021A EP3529338B1 EP 3529338 B1 EP3529338 B1 EP 3529338B1 EP 17794021 A EP17794021 A EP 17794021A EP 3529338 B1 EP3529338 B1 EP 3529338B1
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ppm
fuel
compound
esters
composition
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French (fr)
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EP3529338A1 (de
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Bernard Dequenne
Thomas Dubois
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TotalEnergies Onetech SAS
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TotalEnergies Onetech SAS
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Priority claimed from FR1660208A external-priority patent/FR3057877B1/fr
Priority claimed from RU2016141391A external-priority patent/RU2719587C2/ru
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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
    • C10L1/143—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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • 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
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
    • 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
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • 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
    • 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 a combination of fuel additives capable of preventing the crystallization of water, in particular the formation of ice flakes, at low temperatures. It also relates to a method for preventing the formation of ice crystals in a fuel at low temperature.
  • Engine fuels especially diesel (including biodiesel) naturally incorporate up to 300ppm of water.
  • this water can crystallize and form flakes (“flakes”) in suspension, more or less large. These flakes can affect fuel quality and, in particular, can lead to filter clogging problems.
  • Liquid internal combustion engine fuels contain components that can degrade during engine operation.
  • the problem of deposits in the internal parts of combustion engines is well known to engine manufacturers. So-called detergent additives used in fuels are used to keep the engine clean by limiting deposits (“Keep-clean” effect) or by reducing the deposits already present in the internal parts of the combustion engine (“clean-clean” effect). up” in English).
  • the presence of deposits can alter combustion performance, in particular increase pollutant emissions and particle emissions.
  • Other consequences of the excessive presence of deposits have been reported in the literature, such as increased fuel consumption and drivability (or engine running) problems. Preventing and reducing deposits in these new engines is essential for optimum operation of today's engines.
  • the technical problem solved by the invention consists in proposing a composition of additives for fuel making it possible to prevent or prevent the formation of flakes while maintaining the properties of the fuel, in particular, when the fuel is additived with a detergent additive intended to guarantee the cleanliness of the engine.
  • anti-icing additives in English “deicing agent”
  • DIEGME diethylene glycol methyl ether
  • ethylene glycol methyl ether or EGME for “ethylene glycol methyl ether” in English
  • additives are added to fuels used in aviation to prevent the formation of ice crystals which could affect the proper functioning of the components of the fuel system of an aircraft at low temperature (filters, pumps and valves).
  • UK 2,071,140 discloses the use of methanol, 2-methoxyethanol and/or compounds of the glycol ether type as antifreeze additives for fuel of internal combustion engines, and in particular for diesel engines.
  • US 4,661,120 discloses additive diesel fuels with improved low temperature properties.
  • the additive fuels comprise (a) an agent acting on the formation of wax crystals, (b) a dispersing/stabilizing agent for deposits, (c) a hydrocarbon solvent and (d) an aqueous solvent comprising a compound having -CH units 2 CH 2 O-.
  • the objective of the invention has therefore been to find additives which make it possible to prevent the freezing of water in the form of crystals in a fuel, in particular in a diesel fuel, these additives being compatible with the use of additives detergents to keep the engine clean.
  • compositions of additives whose cost is lower than that of DIEGME and EGME while having performances of a comparable level.
  • the invention is based on the combination of a polyalkylene glycol compound (T1) chosen from: polyalkylene glycols, C1-C12 alkyl and polyalkylene glycol ethers, and mixtures thereof, and at least one compound (T2) chosen from esters of polyols and monocarboxylic aliphatic hydrocarbons, C 1 to C 36 , preferably C 4 to C 30 , saturated or unsaturated, linear or branched, cyclic or acyclic, said esters possibly being taken alone or as a mixture.
  • T1 polyalkylene glycol compound
  • T2 chosen from: polyalkylene glycols, C1-C12 alkyl and polyalkylene glycol ethers, and mixtures thereof
  • T2 chosen from esters of polyols and monocarboxylic aliphatic hydrocarbons, C 1 to C 36 , preferably C 4 to C 30 , saturated or unsaturated, linear or branched, cyclic or acyclic, said esters possibly
  • This combination of additives makes it possible, surprisingly, to prevent the formation of ice flakes in a fuel at a temperature less than or equal to -15°C, or even less than or equal to -25°C, or even less than or equal to at -30°C.
  • This property is observed with reduced amounts of polyalkylene glycol compound, and therefore with a reduced raw material cost compared to a polyalkylene glycol alone, while maintaining high performance in terms of resistance to the formation of ice crystals.
  • the fuel comprises at least 50% by mass of a diesel fuel, preferably at least 70% by mass, more preferably at least 90% by mass, relative to the total mass of fuel, even more preferably the fuel consists of diesel fuel.
  • the fuel comprises at least 50 ppm of water, preferably at least 100 ppm, even more preferably at least 150 ppm.
  • the compound (T1) is chosen from polyethylene glycols, C 1 -C 12 alkyl and polyethylene glycol ethers and mixtures thereof.
  • compound (T1) is chosen from C 1 -C 6 alkyl ethers and polyethylene glycol comprising two to six ethylene glycol units, preferably diethylene glycol methyl ether.
  • the alkyl carboxylic and alkenyl carboxylic acids are chosen from the group consisting of stearic, isostearic, linolenic, oleic, linoleic, behenic, arachidonic, ricinoleic, palmitic, myristic, lauric, capric acids, taken alone or in a mixture.
  • the polyol is chosen from oxygenated C 4 -C 20 hydrocarbon molecules comprising at least two, preferably at least three hydroxyl functions.
  • the polyol is chosen from the group consisting of erythritol, xylitol, arabitol, ribitol, sorbitol, maltitol, isomaltitol, lactitol, volemitol, mannitol, pentaerythritol, 2-hydroxymethyl-1,3-propanediol, 1,1,1-tri(hydroxymethyl)ethane, trimethylolpropane, sorbitan, isosorbide, and carbohydrates such as sucrose, fructose, maltose, and glucose.
  • the compound (T2) is chosen from sorbitan esters and isosorbide esters, preferably from mono-, di- and tri-esters of sorbitan and mono-, and di-esters of isosorbide, taken alone or in a mixture.
  • the compound (T2) is chosen from mixtures of partial esters of sorbitan, preferably mixtures of mono, di and tri-oleate of sorbitan.
  • the compound (T2) is chosen from monoester(s) and diester(s) of polyglycerols having from 2 to 10 glycerol units per molecule, preferably from 2 to 5 glycerol units per molecule, and their mixtures.
  • the detergent additive is chosen from succinimides, polyetheramines and quaternary ammonium salts.
  • the detergent additive is chosen from polyisobutylene succinimides and polyisobutylenes functionalized with a quaternary ammonium group.
  • the mass ratio (T1): (T2) is from 10: 1 to 1: 1.
  • the fuel comprises at least 50 ppm of water, even more preferentially at least 100 ppm of water, even better, at least 150 ppm of water.
  • the expression "between X and Y" includes the terminals, unless explicitly stated otherwise. This expression therefore means that the target interval includes the values X, Y and all values from X to Y.
  • fineness means more or less large aggregates visible to the eye formed from water. It is understood that the use of the term “flake” in the description in no way refers to flakes formed from compounds other than water, for example paraffins.
  • additive is understood to mean a chemical substance, often liquid or in powder form, which is generally introduced before or during the shaping of the material, to provide or improve one or more specific property(ies).
  • the incorporation by mass is low, generally less than 1% by mass at most, unlike a filler or a base. They can be used to achieve a positive effect in the production phase, storage, processing, during and after the product use phase.
  • the polyalkylene glycol compound (T1) is chosen from polyalkylene glycols and polyalkylene glycols functionalized at the end of the chain with an alkyl ether.
  • polyalkylene glycols mention may be made of polyethylene glycol and polypropylene glycol.
  • the invention relates to polyethylene glycol and derivatives of polyethylene glycol functionalized at the end of the chain with an alkyl ether.
  • the functionalization at the end of the chain with an alkyl ether is chosen from a C 1 -C 12 , preferably C 1 -C 6 , even more advantageously C 1 -C 3 alkyl ether.
  • the alkyl group at the end of the chain can be linear or branched.
  • the polyalkylene glycol compound (T1) is chosen from ethylene glycol oligomers comprising from 2 to 20 ethylene glycol units and their derivatives functionalized at the chain end with an alkyl ether. Even more advantageously, it is chosen from ethylene glycol oligomers comprising from 2 to 10 ethylene glycol units and their derivatives functionalized at the chain end with an alkyl ether. Even better, it is chosen from ethylene glycol oligomers comprising from 2 to 6 ethylene glycol units and their derivatives functionalized at the chain end with an alkyl ether. Advantageously, it is chosen from ethylene glycol oligomers comprising from 2 to 4 ethylene glycol units and their derivatives functionalized at the chain end with an alkyl ether.
  • ethylene glycol oligomers comprising from 2 to 4 ethylene glycol units and their derivatives functionalized at the end of the chain with a C 1 -C 12 alkyl ether, preferably C 1 -C 6 , even more advantageously C 1 -C 3 .
  • the polyalkylene glycol compound (T1) is diethylene glycol methyl ether.
  • the amount of additive (T1) in the fuel composition is 5 to 1000 ppm, preferably 50 to 500 ppm, even more preferably 100 to 300 ppm.
  • Non-ionic emulsifiers T2
  • composition according to the invention further comprises a compound (T2) chosen from esters of polyols and C 1 to C 36 monocarboxylic aliphatic hydrocarbons, preferably C 4 -C 30 , more preferably C 12 -C 24 , more preferably C 16 -C 20 , said esters possibly being taken alone or as a mixture.
  • T2 a compound chosen from esters of polyols and C 1 to C 36 monocarboxylic aliphatic hydrocarbons, preferably C 4 -C 30 , more preferably C 12 -C 24 , more preferably C 16 -C 20 , said esters possibly being taken alone or as a mixture.
  • C 1 to C 36 monocarboxylic aliphatic hydrocarbon is meant an alkyl or alkenyl chain, linear or branched, cyclic or acyclic, optionally comprising more than one unsaturation and comprising a carboxylic acid function —COOH.
  • the compound (T2) is chosen from partial esters of polyols and of aliphatic monocarboxylic hydrocarbons.
  • polyol partial ester is meant that part of the alcohol functions of the polyol is free, non-esterified.
  • a partial ester of a polyol can be obtained by reacting a quantity of monocarboxylic acid less than the quantity necessary to esterify all of the alcohol functions of the polyol.
  • a partial ester of a polyol can be obtained by stopping the esterification reaction before having esterified all of the alcohol functions of the polyol.
  • the nonionic emulsifiers are chosen from partial esters of C 4 -C 20 polyols and of C 4 to C 30 monocarboxylic aliphatic hydrocarbons, preferably C 12 -C 24 , more preferably C 16 - C 20 , saturated or unsaturated, linear or branched, cyclic or acyclic, said partial esters possibly being taken alone or as a mixture.
  • Compound (T2) preferably comprises x ester units, y hydroxyl units and z ether units, x, y and z being integers such that x varies from 1 to 10, y varies from 1 to 10, and z varies from 0 to 6.
  • x varies from 1 to 10
  • y varies from 3 to 10
  • z varies from 0 to 6.
  • x varies from 1 to 4
  • y varies from 1 to 7
  • z varies from 1 to 3.
  • x varies from 2 to 4.
  • polyol esters in particular polyol partial esters
  • they can for example be prepared by esterification of fatty acid(s) and of linear and/or branched polyols optionally comprising (hetero)cycles of 5 to 6 atoms supporting hydroxyl functions.
  • this type of synthesis leads to a mixture of mono-, di-, tri- and possibly tetra-esters as well as small quantities of fatty acid(s) and polyols which have not reacted.
  • the compound (T2) is obtained by esterification reaction of one or more C 1 to C 36 acid(s), preferably of one or more C 4 -C acids 30 , even more preferably one or more C 12 -C 24 fatty acid(s), more preferably C 16 -C 20 fatty acid(s), optionally comprising one or more ethylenic bonds, and with at least one C 4 - polyol C 20 , linear or branched, cyclic or acyclic optionally comprising one or more heterocycles of 5 to 6 atoms, preferably one or more heterocycles of 4 to 5 carbon atoms and one oxygen atom, substituted by hydroxyl groups.
  • compound (T2) is a partial ester of one or more C 1 to C 36 acid(s), preferably of one or more C 4 -C 30 acids, even more preferably of one or more C 12 -C 24 , more preferably C 16 -C 20 , fatty acid(s), optionally comprising one or more ethylenic bonds, and at least one C 4 -C 20 polyol, linear or branched , cyclic or acyclic optionally comprising one or more heterocycles of 5 to 6 atoms, preferably one or several heterocycles of 4 to 5 carbon atoms and an oxygen atom, substituted by hydroxyl groups.
  • the fatty acids are advantageously chosen from the group consisting of stearic, isostearic, linolenic, oleic, linoleic, behenic, arachidonic, ricinoleic, palmitic, myristic, lauric, capric acids, taken alone or as a mixture.
  • the fatty acids can come from the transesterification or the saponification of vegetable oils and/or animal fats.
  • Preferred vegetable oils and/or animal fats will be chosen according to their oleic acid concentration. Reference may be made, for example, to Table 6.21 in Chapter 6 of the book Carburants & Moteurs by J.C. Guibet and E. Faure, 2007 edition, in which the compositions of several vegetable oils and animal fats are indicated.
  • the fatty acids can also come from fatty acids derived from tall oil (Tall Oil Fatty Acids) which comprise a major quantity of fatty acids, typically greater than or equal to 90% by mass as well as resin acids and unsaponifiables in minor amount, i.e. in amounts generally less than 10%.
  • Tall Oil Fatty Acids fatty acids derived from tall oil (Tall Oil Fatty Acids) which comprise a major quantity of fatty acids, typically greater than or equal to 90% by mass as well as resin acids and unsaponifiables in minor amount, i.e. in amounts generally less than 10%.
  • the polyol is preferably chosen from linear or branched C 4 -C 20 polyols comprising at least three hydroxyl functions and polyols comprising at least one cycle of 5 or 6 atoms, preferably a heterocycle of 4 to 5 atoms of carbon and an oxygen atom, optionally substituted by hydroxyl groups, taken alone or as a mixture.
  • the polyol is chosen from oxygenated C 4 -C 20 hydrocarbon molecules comprising one or two heterocycles of 4 to 5 carbon atoms and one oxygen atom, and several hydroxyl groups.
  • the polyol is chosen from oxygenated C 4 -C 20 hydrocarbon molecules comprising at least one cycle of 5 or 6 atoms, preferably a heterocycle of 4 to 5 carbon atoms and one oxygen atom, optionally substituted with hydroxyl groups, taken alone or as a mixture.
  • the polyol is chosen from oxygenated hydrocarbon molecules comprising at least two heterocycles of 4 or 5 carbon atoms and one oxygen atom, connected by the formation of an acetal bond between a hydroxyl function of each ring, said heterocycles being optionally substituted by hydroxyl groups.
  • the polyol is, in particular, chosen from the group consisting of erythritol, xylitol, arabitol, ribitol, sorbitol, maltitol, isomaltitol, lactitol, volemitol, mannitol, pentaerythritol, 2-hydroxymethyl-1,3-propanediol, 1,1,1-tri(hydroxymethyl)ethane, trimethylolpropane, sorbitan, isosorbide and carbohydrates like sucrose, fructose, maltose, glucose, preferably sorbitan and isosorbide.
  • the compound (T2) is chosen from sorbitan esters.
  • the compound (T2) is chosen from partial sorbitan esters, preferably di-, mono- and tri-esters of sorbitan, taken alone or as a mixture.
  • Sorbitan esters can be represented by formula (I) below
  • R1, R2, R3, R4 represent, independently, a hydrogen atom or a C 1 -C 36 alkylcarboxylic or alkenylcarboxylic group, preferably C 4 -C 30 , advantageously C 12 -C 24 , more preferentially in C 16 -C 20 , at least one of R1, R2, R3 and R4 being distinct from H.
  • the compound (T2) is chosen from esters of monocarboxylic acids and of isosorbides.
  • the compound (T2) is chosen from partial esters of monocarboxylic acids and of isosorbides, preferably monoesters of isosorbide and their mixtures with di-esters of isosorbide.
  • Esters of monocarboxylic acids and isosorbides can be represented by the formula (II) below in which R1 and R2 represent, independently, a hydrogen atom or a C 1 -C 36 alkylcarboxylic or alkenylcarboxylic group, preferably C 4 -C 30 , advantageously C 12 -C 24 , more preferably C 16 - C 20 , at least one of R1 and R2 being distinct from H.
  • the compound (T2) is chosen from partial sorbitan esters comprising more than 40% by mass of triesters of sorbitan, preferably more than 50% by mass.
  • the compound (T2) is chosen from partial sorbitan esters comprising more than 20% by mass of sorbitan monoesters and/or more than 20% by mass of sorbitan diesters, preferably more than 20% by mass of monoesters of sorbitan and/or more than 30% by weight of sorbitan diesters, more preferably more than 25% by weight of sorbitan monoesters and/or more than 35% by weight of sorbitan diesters.
  • the compound (T2) is chosen from monoester(s) and/or diester(s) of polyglycerols derived from fatty acid(s), advantageously from compounds comprising two to 10 glycerol units, even more advantageously from two to five glycerol units.
  • polyglycerol ester examples include polyglycerol polyricinoleate (composed of polyglycerol esters and fatty acids condensed from castor oil), or polyglycerol esters of dimerized fatty acids from Soya oil.
  • the compound (T2) is chosen from monoester(s) and/or diester(s) of polyglycerols derived from fatty acid(s) having more than 50% by number of fatty chains comprising between 12 and 24 carbon atoms.
  • polyglycerols have been described in the document WO2013/120985 .
  • the compound (T2) is preferably chosen from monoester(s) and/or diester(s) of diglycerol and/or of triglycerol.
  • the amount of additive (T2) in the fuel composition is 5 to 500 ppm, preferably 25 to 200 ppm, even more preferably 50 to 100 ppm.
  • the liquid fuel is derived from one or more sources selected from the group consisting of mineral, animal, vegetable and synthetic sources. Petroleum will preferably be chosen as the mineral source.
  • the liquid fuel is preferably chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, alone or as a mixture.
  • hydrocarbon fuel is meant a fuel consisting of one or more compounds consisting solely of carbon and hydrogen.
  • non-essentially hydrocarbon fuel means a fuel consisting of one or more compounds consisting not essentially of carbon and of hydrogen, that is to say which also contain other atoms, in particular oxygen atoms.
  • Hydrocarbon fuels include in particular middle distillates with a boiling temperature ranging from 100 to 500° C. or lighter distillates having a boiling temperature in the gasoline range. These distillates can for example be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates resulting from catalytic cracking and/or hydrocracking of vacuum distillates, distillates resulting from ARDS-type conversion processes (atmospheric residue desulphurization) and/or visbreaking, distillates resulting from the recovery of Fischer Tropsch cuts. Hydrocarbon fuels are typically gasoline and diesel fuel (also called diesel fuel).
  • Gasolines include, in particular, any commercially available spark ignition engine fuel compositions. Mention may be made, by way of representative example, of the gasolines complying with standard NF EN 228. The gasolines generally have sufficiently high octane numbers to avoid the knocking phenomenon. Typically, gasoline-type fuels marketed in Europe, complying with standard NF EN 228 have a motor octane number (MON in English "Motor Octane Number") greater than 85 and a research octane number (RON in English " Research Octane Number”) of a minimum of 95. Gasoline-type fuels generally have a RON ranging from 90 to 100 and a MON ranging from 80 to 90, the RON and MON being measured according to standard ASTM D 2699- 86 or D 2700-86.
  • Diesel fuels include, in particular, any commercially available diesel internal combustion engine fuel compositions. Mention may be made, by way of representative example, of diesel fuels complying with standard NF EN 590.
  • Non-essentially hydrocarbon-based fuels include in particular oxygenated fuels, for example distillates resulting from the BTL (in English “biomass to liquid”) conversion of plant and/or animal biomass, taken alone or in combination; biofuels, for example oils and/or esters of vegetable and/or animal oils; biodiesels of animal and/or vegetable origin and bioethanols.
  • oxygenated fuels for example distillates resulting from the BTL (in English “biomass to liquid”) conversion of plant and/or animal biomass, taken alone or in combination
  • biofuels for example oils and/or esters of vegetable and/or animal oils
  • biodiesels of animal and/or vegetable origin and bioethanols for example oils and/or esters of vegetable and/or animal oils
  • the mixtures of hydrocarbon-based fuel and of non-essentially hydrocarbon-based fuel are typically gas oils of type B x or gasolines of type E x .
  • Type B x diesel fuel for diesel internal combustion engines means diesel fuel which contains x% (v/v) of vegetable or animal oil esters (including waste cooking oils) transformed by a chemical process called transesterification, obtained by reacting this oil with an alcohol in order to obtain fatty acid esters (FAE). With methanol and ethanol, we obtain, respectively, fatty acid methyl esters (FAME) and fatty acid ethyl esters (FEAG). The letter “B” followed by a number indicates the percentage of EAG contained in the diesel fuel. Thus, a B99 contains 99% of EAG and 1% of middle distillates of fossil origin (mineral source), the B20, 20% of EAG and 80% of middle distillates of origin fossil etc....
  • type B 0 gas oils which do not contain oxygenated compounds
  • type Bx gas oils which contain x% (v/v) of vegetable oil esters or fatty acids, most often methyl esters (EMHV or FAME).
  • EAG methyl esters
  • FAME methyl esters
  • Type E x gasoline for spark ignition engines means a gasoline fuel which contains x% (v/v) of oxygenates, generally ethanol, bioethanol and/or ethyl-tertio-butyl-ether (ETBE).
  • x% (v/v) of oxygenates generally ethanol, bioethanol and/or ethyl-tertio-butyl-ether (ETBE).
  • the sulfur content of the liquid fuel is preferably less than or equal to 5000 ppm, preferably less than or equal to 500 ppm, and more preferably less than or equal to 50 ppm, or even less than or equal to 10 ppm and advantageously sulfur-free .
  • the fuel is chosen from the fuels as described above with the exception of fuels comprising or consisting of kerosene typically having an initial distillation point (IP) of between 150° C. and 180° C., and an end point (FP) of distillation between 225°C and 250°C. More preferably, fuels for aviation are excluded from the invention.
  • IP initial distillation point
  • FP end point
  • the fuel comprises at least 50% by mass of a gas oil, preferably at least 70% by mass, more preferentially at least 90% by mass relative to the total mass of fuel. Even more preferably, the fuel consists of diesel fuel.
  • the invention applies more particularly to gas oils.
  • gas oils that do not include FAME or EEAG.
  • the invention relates more particularly to fuels containing water, in particular fuels having a water content of at least 50 ppm, preferably at least 100 ppm, it is particularly noteworthy for the treatment of fuels having a water content at least 150 ppm.
  • the invention relates more specifically to gas oils containing water, in particular gas oils having a water content of at least 50 ppm, preferably at least 100 ppm, it is particularly noteworthy for the treatment of gas oils having a water content of at least 150 ppm.
  • the water content is evaluated during the formulation of the fuel with the composition of additives according to the invention. It is known that the mass water content can increase during storage and transport of fuel. Thus, a fuel with less than 50 ppm in water at the start can present problems with the appearance of flakes depending on its transport or storage conditions.
  • detergent additive for liquid fuel is understood to mean an additive which is incorporated in a small quantity into the liquid fuel and produces an effect on the cleanliness of said engine compared with said liquid fuel not specially containing additives.
  • Detergent additives for fuels intended for vehicles fitted with an internal combustion engine are well known and widely described in the literature. Mention may in particular be made of: the group consisting of succinimides, polyetheramines and quaternary ammonium salts; for example those described in the documents US4,171,959 (salts of quaternary ammonium and of succinimides) and WO2006135881 (quaternary ammonium salts).
  • the detergent additive is chosen from N-substituted alkenylsuccinimides.
  • N-substituted alkenyl succinimides usually have a long chain and have a variety of chemical structures, and in particular they can be chosen from a mono-succinimide or a di-succinimide.
  • the long chain alkenyl group has a number average molecular weight of 350 to 10,000, preferably 400 to 7000, even more preferably 500 to 5000, and most preferably 500 to 4000.
  • the long chain alkenyl group is a polyisobutylene group, which has a number average molecular weight of 200 to 4000 and preferably 800 to 3000, more preferably 1000 to 2000.
  • the detergent additive is chosen from quaternary ammonium salts as described in WO2006135881 and in in WO2015124575 , in particular the quaternary ammonium salts of polyisobutylene.
  • the detergent additive is preferably incorporated in a small quantity into the liquid fuel described above, the quantity of detergent being sufficient to produce a detergent effect as described above and thus improve engine cleanliness.
  • the fuel composition comprises from 1 to 1000 ppm, preferably from 5 to 400 ppm, of at least one detergent.
  • the fuel composition may also comprise one or more other additives, different from the compounds (T1) and (T2) according to the invention, and chosen for example from anti-corrosion agents, dispersants, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion and soot promoters), cloud point improvers , the pour point, the TLF (“Filtrability limit temperature”), the anti-sedimentation agents, the anti-wear agents and/or the agents modifying the conductivity.
  • additives different from the compounds (T1) and (T2) according to the invention, and chosen for example from anti-corrosion agents, dispersants, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion and soot promoters), cloud point improvers , the pour point, the TLF (“Filtrability limit temperature”), the anti
  • additives are generally added in an amount ranging from 100 to 1000 ppm each.
  • the mass ratio (T1): (T2) is from 10: 1 to 1: 10, more preferably from 10: 1 to 1: 1.
  • the mixture of compounds (T1) and (T2) is used in the form of a concentrate of additives, optionally in combination with at least one other additive for internal combustion engine fuel different from (T1 ) and (T2).
  • the additive concentrate may typically include one or more other additives selected from detergent or other additives which have been described above.
  • the alkyl carboxylic or alkenyl carboxylic acid(s) are chosen from those C 4 to C 36 , even more preferably C 12 -C 24 and advantageously C 16 -C 20 .
  • the detergent additive is chosen from chosen from succinimides, polyetheramines and quaternary ammonium salts, advantageously from those comprising a quaternary ammonium function.
  • the mass ratio (T1): (T2) is from 10: 1 to 1: 1.
  • composition of additives is advantageously used in the fuel composition in a content ranging from 5 to 5000 ppm, advantageously from 10 to 1000 ppm, even better from 20 to 500 ppm.
  • the invention also relates to a process for formulating a fuel intended for a vehicle fitted with an internal combustion engine, comprising the additivation of a fuel with at least one additive (T1) chosen from: polyalkylene glycols and C 1 -C 12 alkyl and polyalkylene glycol ethers, and at least one compound (T2) chosen from esters of polyols and C 1 to C 36 monocarboxylic aliphatic hydrocarbons, preferably C 4 to C 30 , saturated or unsaturated, linear or branched, cyclic or acyclic, said esters possibly being taken alone or as a mixture.
  • additive chosen from: polyalkylene glycols and C 1 -C 12 alkyl and polyalkylene glycol ethers
  • T2 compound chosen from esters of polyols and C 1 to C 36 monocarboxylic aliphatic hydrocarbons, preferably C 4 to C 30 , saturated or unsaturated, linear or branched, cyclic or acyclic, said est
  • the process comprises the additivation of 5 to 1000 ppm, preferably of 50 to 500 ppm, even more preferably of 100 to 300 ppm of additive (T1), and of 5 to 500 ppm, preferably of 25 to 200 ppm, even more preferably from 50 to 100 ppm of additive (T2).
  • the process for formulating a fuel further comprises additivation with at least one detergent additive.
  • This process makes it possible to avoid the formation of ice in the fuels, by particularly in gas oils, at a temperature less than or equal to -15°C, and preferably at a temperature less than or equal to -25°C.
  • This method relates more particularly to fuels comprising at least 50 ppm of water, even more preferably at least 100 ppm of water, even better still, at least 150 ppm of water.
  • the invention also relates to the use of at least one additive (T1) and at least one additive (T2) as described above, to prevent the formation of ice in fuels, in particular in gas oils, at a temperature less than or equal to - 15°C, and preferably at a temperature less than or equal to -25°C
  • the determination of the amount of detergent to be added to the fuel composition to reach the specification will typically be made by comparison with the fuel composition but without the detergent, the given specification relating to the detergent being able for example to be a target value of loss of power according to the DW10 method or a flow restriction value according to the XLTD9 method mentioned above.
  • the amount of detergent may also vary depending on the nature and origin of the fuel, in particular depending on the level of compounds with n-alkyl, iso-alkyl or n-alkenyl substituents. Thus, the nature and origin of the fuel can also be a factor to be taken into account.
  • the process for maintaining cleanliness and/or cleaning can also comprise an additional step of verifying the target reached and/or adjusting the rate of additivation with the detergent additive(s).
  • the fuel composition is left at ⁇ 15° C. for 12 hours then at ⁇ 25° C. for an additional 12 hours. Then, the quantity of crystals and their size are evaluated at each temperature level after slight manual shaking of the flask (the use of a stirring bar at the bottom of the flask may be useful). The ratings are explained in Table 2 below. Table 2: criteria for evaluating ice crystals by visual test Note Meaning Quantity of crystals 1 only one 2 Rare 3 a lot crystal size To Little b AVERAGE vs Big
  • the tests are carried out on a Peugeot XUD9 type engine (1.9L displacement) according to the CEC F23-01 standardized test.
  • the fuel used is the CEC DF79 reference fuel.
  • the test consists of measuring the loss of injector flow after 10 hours of engine operation with the fuel to be tested.
  • a commercial detergent additive composition A1 and a detergent additive composition A2 were used, the characteristics of which are reported in Table 3. below. The contents are given in mass % of commercial product relative to the total weight of the composition. Table 3: Formulation of detergent additive compositions Trade name A1 A2 detergent additive TOTAL GDPSI ( ⁇ ) 64.6 100 Solvent Solvarex 10 ® 35.4 - (*) active ingredient at 50% by weight in a solvent
  • Detergent additive composition A1 was used to formulate fuel compositions C1 to C3 detailed in Table 4 below, from Diesel fuel GO, composition C0 is the control. The contents are given in ppm by mass. Examples C1 and C2 are comparative, example C3 is according to the invention. Table 4: formulation of fuels with C0, C1, C2 and C3 additives Fuel composition C0 C1 C2 C3 Fuel Water content 150 150 150 150 Detergent additive composition A1 - 302 302 302 Anti-icing agent Nycosol 13 ® - - - 200 WASH - - 200 - Non-ionic emulsifier Radiasurf 7348 ® - - 65 65
  • Detergent additive composition A2 was used to formulate fuel compositions C1′ to C4′ detailed in Table 5 below, from Diesel fuel GO, composition C0′ is the control. The contents are given in ppm by mass. Examples C1', C2' and C4' are comparative, example C3' is according to the invention. Table 5: formulation of fuels with C0', C1', C2', C3' and C4' additives Fuel composition C0' C1' C2' C3' C4' Fuel Water content 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Detergent additive composition A2 - 60 60 60 60 60 60 60 60 60 Anti-icing agent Nycosol 13 ® - - - 25 85 Non-ionic emulsifier Radiasurf 7348 ® - - 85 60 0
  • composition C1 which comprises only the detergent additive, forms ice crystals when it is exposed to cold.
  • the presence of the detergent additive promotes the formation of ice crystals compared to virgin C0 diesel.
  • composition C2 is not effective at -25°C.
  • composition C3 according to the invention overcomes the problem of the formation of ice crystals at -15°C and -25°C.
  • Table 7 results of the visual tests on the compositions C0' to C4' Test at -15°C for 12 hours Test at -25°C for 12 hours C0' 1a/1b 2a/1b C1' 2a/1b 2a/2b C2' 1a/1b 2a/1b/1c C3' 1a/1b 2a/1b C4' 1a/1b 2a/3b/1c
  • composition C1' which comprises only the detergent additive, forms ice crystals when it is exposed to cold.
  • the presence of the detergent additive promotes the formation of ice crystals compared to virgin C0′ diesel fuel.
  • compositions C2' and C4' are not effective at -25°C.
  • composition C3' according to the invention overcomes the problem of formation of ice crystals at -15°C and -25°C.
  • compositions C0", C1" and C3" listed in Table 8 below were tested according to the protocol described above (1-B-).
  • Table 8 formulation of fuels with C0", C1" and C3" additives
  • Fuel composition C0" C1" C3" Fuel basis
  • Table 9 Flow Loss Results Fuel composition C0" C1" C3" Loss of injector flow (%) at 0.1mm needle lift 75.4%* 42.8% 42.9% * average of 2 trials: 75.7% and 75.0%.
  • the fuel compositions C1" and C3" make it possible to improve the properties of the fuel by reducing the fouling of the injectors.
  • composition C3′′ according to the invention makes it possible to keep the engine clean while minimizing the formation of ice crystals at low temperature in the diesel fuel containing water.
  • composition of additives and the fuel compositions according to the invention are particularly effective insofar as they solve the problem of the appearance of ice crystals at low temperature while avoiding the degradation of the other properties of the fuel such as, for example, the anti-corrosion properties or engine cleanliness.

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Claims (15)

  1. Kraftstoffzusammensetzung, die zumindest Folgendes umfasst:
    - einen Kraftstoff aus einer oder mehreren Quellen, die ausgewählt sind aus der Gruppe bestehend aus mineralischen, tierischen, pflanzlichen und synthetischen Quellen,
    - 5 bis 1000 ppm einer Verbindung (T1), die aus: Polyalkylenglycolen, C1-C12-Alkylethern und Polyalkylenglycol und Mischungen davon ausgewählt ist,
    - 5 bis 500 ppm einer Verbindung (T2), die aus Estern von Polyolen und gesättigten oder ungesättigten, linearen oder verzweigten, cyclischen oder acyclischen aliphatischen C1- bis C36-, vorzugsweise C4- bis C30-Monocarboxylkohlenwasserstoffen ausgewählt ist, wobei die Ester allein oder als Mischung verwendet werden können,
    - 1 bis 1000 ppm mindestens eines Detergensadditivs,
    wobei das Gewichtsverhältnis (T1):(T2) von 10:1 bis 1:10 beträgt.
  2. Kraftstoffzusammensetzung nach Anspruch 1, wobei der Kraftstoff mindestens 50 Gew.-%, vorzugsweise mindestens 70 Gew.-%, besonders bevorzugt mindestens 90 Gew.-% eines Dieselkraftstoffs, bezogen auf das Gesamtgewicht des Kraftstoffs, umfasst, wobei der Kraftstoff noch mehr bevorzugt aus Dieselkraftstoff besteht.
  3. Kraftstoffzusammensetzung nach einem der vorhergehenden Ansprüche, wobei der Kraftstoff mindestens 50 ppm, vorzugsweise mindestens 100 ppm, noch mehr bevorzugt mindestens 150 ppm Wasser umfasst.
  4. Kraftstoffzusammensetzung nach einem der vorhergehenden Ansprüche, wobei Verbindung (T1) aus Polyethylenglycolen, C1-C12-Alkylethern und Polyethylenglycol und Mischungen davon, vorzugsweise C1-C6-Alkylethern und einem zwei bis sechs Ethylenglycol-Einheiten umfassenden Polyethylenglycol, noch mehr bevorzugt Diethylenglycolmethylether, ausgewählt ist.
  5. Kraftstoffzusammensetzung nach Anspruch 1, wobei Verbindung (T2) durch eine Veresterung von Folgendem erhalten wird:
    - einer oder mehreren C1- bis C36-, vorzugsweise C4- bis C30-Alkylcarbonsäuren oder Alkenylcarbonsäuren, die gegebenenfalls eine oder mehrere ethylenische Bindungen umfassen; und
    - einem linearen oder verzweigten, cyclischen oder acyclischen C4-C20-Polyol, das gegebenenfalls ein oder mehrere Heterocyclen mit 5 bis 6 Atomen, vorzugsweise ein oder zwei Heterocyclen mit 4 bis 5 Kohlenstoffatomen und einem Sauerstoffatom, umfasst.
  6. Kraftstoffzusammensetzung nach Anspruch 5, wobei die Alkylcarbonsäuren und Alkenylcarbonsäuren aus der Gruppe bestehend aus Stearinsäure, Isostearinsäure, Linolensäure, Ölsäure, Linolsäure, Behensäure, Arachidonsäure, Rizinolsäure, Palmitinsäure, Myristinsäure, Laurinsäure, Caprinsäure, allein oder als Mischung, ausgewählt sind und das Polyol aus der Gruppe bestehend aus Erythrit, Xylit, Arabit, Ribit, Sorbit, Maltit, Isomalt, Lactit, Volemit, Mannit, Pentaerythrit, 2-Hydroxymethyl-1,3-propandiol, 1,1,1-Tri(hydroxymethyl)ethan, Trimethylolpropan, Sorbitan, Isosorbid und Kohlenhydraten wie Saccharose, Fructose, Maltose und Glucose ausgewählt ist.
  7. Kraftstoffzusammensetzung nach Anspruch 6, wobei Verbindung (T2) aus Sorbitanestern und Isosorbidestern, vorzugsweise aus Sorbitanmono-, -di- und - triestern und Isosorbidmono- und -diestern, allein oder als Mischung, oder aus Mischungen von Sorbitanpartialestern, vorzugsweise Mischungen von Sorbitanmono-, -di- und -trioleat, ausgewählt ist.
  8. Kraftstoffzusammensetzung nach einem der Ansprüche 1 bis 4, wobei Verbindung (T2) aus Polyglycerinmonoester(n) und -diester(n) mit 2 bis 10 Glycerineinheiten pro Molekül, vorzugsweise 2 bis 5 Glycerineinheiten pro Molekül, und Mischungen davon ausgewählt ist.
  9. Kraftstoffzusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Detergensadditiv aus Succinimiden, Polyetheraminen und quaternären Ammoniumsalzen, noch mehr bevorzugt aus Polyisobutylen-Succinimiden und durch eine quaternäre Ammoniumgruppe funktionalisierten Polyisobutylenen, ausgewählt ist.
  10. Kraftstoffzusammensetzung nach einem der vorhergehenden Ansprüche, die Folgendes umfasst:
    • 50 bis 500 ppm, noch mehr bevorzugt 100 bis 300 ppm Additiv (T1),
    • 25 bis 200 ppm, noch mehr bevorzugt 50 bis 100 ppm Additiv (T2).
  11. Kraftstoffzusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Gewichtsverhältnis (T1):(T2) von 10:1 bis 1:1 beträgt.
  12. Kraftstoffadditivzusammensetzung, die für ein mit einem Verbrennungsmotor ausgestattetes Fahrzeug vorgesehen ist, wobei diese Zusammensetzung zur Formulierung einer Kraftstoffzusammensetzung nach einem der Ansprüche 1 bis 11 verwendbar ist, und die zumindest Folgendes umfasst:
    - eine Verbindung (T1), die aus C1-C6-Alkylethern und einem zwei bis sechs Ethylenglycol-Einheiten umfassenden Polyethylenglycol, vorzugsweise Diethylenglycolmethylether, ausgewählt ist,
    - eine Verbindung (T2), die aus Estern einer oder mehrerer C1- bis C36-, vorzugsweise C4- bis C36-Alkylcarbonsäuren oder Alkenylcarbonsäuren und einem aus Sorbitan und Isosorbid ausgewählten Polyol, allein oder als Mischung, ausgewählt ist, und gegebenenfalls
    - ein Detergensadditiv, vorzugsweise ein Detergensadditiv, das eine quaternäre Ammoniumfunktion umfasst,
    wobei das Gewichtsverhältnis (T1):(T2) von 10:1 bis 1:10 beträgt.
  13. Additivzusammensetzung nach Anspruch 12, die zumindest Folgendes umfasst:
    - eine Verbindung (T1), bei der es sich um Diethylenglycolmethylether handelt,
    - eine Verbindung (T2), die aus Sorbitanpartialestern, allein oder als Mischung, ausgewählt ist, und gegebenenfalls
    - ein Detergensadditiv, vorzugsweise ein Detergensadditiv, das eine quaternäre Ammoniumfunktion umfasst.
  14. Verwendung einer Additivzusammensetzung in einem Kraftstoff, der für ein mit einem Verbrennungsmotor ausgestattetes Fahrzeug vorgesehen ist, um der Bildung von Eiskristallen oder -flocken im Kraftstoff vorzubeugen, sie zu vermeiden oder zu verzögern, wobei die Additivzusammensetzung Folgendes umfasst:
    - mindestens ein Additiv (T1), das aus: Polyalkylenglycolen, C1-C12-Alkylethern und Polyalkylenglycol ausgewählt ist, und
    - mindestens eine Verbindung (T2), die aus Estern von Polyolen und gesättigten oder ungesättigten, linearen oder verzweigten, cyclischen oder acyclischen aliphatischen C1- bis C36-, vorzugsweise C4- bis C30-Monocarboxylkohlenwasserstoffen ausgewählt ist, wobei die Ester allein oder als Mischung verwendet werden können,
    - ein Detergensadditiv,
    wobei die Menge an Additiv (T1) im Kraftstoff 5 bis 1000 ppm beträgt, die Menge an Additiv (T2) im Kraftstoff 5 bis 500 ppm beträgt und die Menge an Detergensadditiv im Kraftstoff 1 bis 1000 ppm beträgt und wobei das Gewichtsverhältnis (T1):(T2) von 10:1 bis 1:10 beträgt.
  15. Verwendung nach Anspruch 14, wobei der Kraftstoff mindestens 50 ppm, noch mehr bevorzugt mindestens 100 ppm Wasser, besser noch mindestens 150 ppm Wasser umfasst.
EP17794021.0A 2016-10-21 2017-10-20 Mischung von additiven für brennstoff Active EP3529338B1 (de)

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FR1660208A FR3057877B1 (fr) 2016-10-21 2016-10-21 Combinaison d’additifs pour carburant
RU2016141391A RU2719587C2 (ru) 2016-10-21 2016-10-21 Комбинация присадок для топлива
PCT/FR2017/052882 WO2018073544A1 (fr) 2016-10-21 2017-10-20 Combinaison d'additifs pour carburant

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Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2952969A (en) 1955-05-26 1960-09-20 Exxon Research Engineering Co Aviation turbo fuel
US3048479A (en) 1959-08-03 1962-08-07 Exxon Research Engineering Co Ethylene-vinyl ester pour depressant for middle distillates
NL124842C (de) 1959-08-24
US3230058A (en) * 1961-11-20 1966-01-18 Phillips Petroleum Co Additive for hydrocarbon fuels
US3627838A (en) 1964-12-11 1971-12-14 Exxon Research Engineering Co Process for manufacturing potent pour depressants
US3401118A (en) 1967-09-15 1968-09-10 Chevron Res Preparation of mixed alkenyl succinimides
US3578422A (en) * 1969-03-03 1971-05-11 Lubrizol Corp Emulsion resistant fuel compositions
US3790359A (en) 1969-03-17 1974-02-05 Exxon Research Engineering Co Middle distillate fuel having increased low temperature flowability
US3717446A (en) 1970-12-31 1973-02-20 Union Oil Co Gasoline anti-icing additives (a)
US3961961A (en) 1972-11-20 1976-06-08 Minnesota Mining And Manufacturing Company Positive or negative developable photosensitive composition
US4171959A (en) 1977-12-14 1979-10-23 Texaco Inc. Fuel composition containing quaternary ammonium salts of succinimides
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
GB2071140A (en) 1980-01-23 1981-09-16 Mccabe P H Antifreeze for fuels
FR2528051B1 (fr) 1982-06-08 1986-05-02 Inst Francais Du Petrole Additifs azotes utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs
FR2528423B1 (fr) 1982-06-10 1987-07-24 Inst Francais Du Petrole Additifs azotes utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs
FR2535723A1 (fr) 1982-11-09 1984-05-11 Inst Francais Du Petrole Additifs azotes utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs
FR2567536B1 (fr) 1984-07-10 1986-12-26 Inst Francais Du Petrole Compositions d'additifs destinees notamment a ameliorer les proprietes de filtrabilite a froid des distillats moyens de petrole
US4661120A (en) 1985-07-12 1987-04-28 Nalco Chemical Company Diesel fuel additive
IN184481B (de) 1986-09-24 2000-08-26 Exxon Chemical Patents Inc
FR2607139B1 (fr) 1986-11-21 1989-08-18 Inst Francais Du Petrole Polymeres a fonctions azotees derives de polyesters insatures et leur utilisation comme additifs d'abaissement du point d'ecoulement des distillats moyens d'hydrocarbures
FR2613371B1 (fr) 1987-04-01 1989-07-07 Inst Francais Du Petrole Copolymeres azotes, leur preparation et leur utilisation comme additifs pour ameliorer les proprietes d'ecoulement des distillats moyens d'hydrocarbures
GB9104138D0 (en) 1991-02-27 1991-04-17 Exxon Chemical Patents Inc Polymeric additives
GB9516446D0 (en) * 1995-08-09 1995-10-11 Bp Chem Int Ltd Icing inhibitors
US7182797B2 (en) * 2004-11-08 2007-02-27 Kenneth Mekonen Fuel compositions
KR101314378B1 (ko) 2005-06-16 2013-10-15 더루우브리졸코오포레이션 연료용 4차 암모늄염 청정제
GB201007756D0 (en) 2010-05-10 2010-06-23 Innospec Ltd Composition, method and use
US9523057B2 (en) * 2011-02-22 2016-12-20 Afton Chemical Corporation Fuel additives to maintain optimum injector performance
FR2987052B1 (fr) 2012-02-17 2014-09-12 Total Raffinage Marketing Additifs ameliorant la resistance a l'usure et au lacquering de carburants de type gazole ou biogazole
FR2994695B1 (fr) 2012-08-22 2015-10-16 Total Raffinage Marketing Additifs ameliorant la resistance a l'usure et au lacquering de carburants de type gazole ou biogazole
GB201313423D0 (en) * 2013-07-26 2013-09-11 Innospec Ltd Compositions and methods
FR3017875B1 (fr) 2014-02-24 2016-03-11 Total Marketing Services Composition d'additifs et carburant de performance comprenant une telle composition

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WO2018073544A1 (fr) 2018-04-26
EP3529338A1 (de) 2019-08-28
FI3529338T3 (fi) 2023-10-09
DK3529338T3 (da) 2023-09-25
PL3529338T3 (pl) 2023-12-27
CA3040612A1 (fr) 2018-04-26
US10767126B2 (en) 2020-09-08
US20190330549A1 (en) 2019-10-31
LT3529338T (lt) 2023-08-25

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