EP4065672B1 - Utilisation de diols comme additifs de détergence - Google Patents

Utilisation de diols comme additifs de détergence Download PDF

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EP4065672B1
EP4065672B1 EP20811631.9A EP20811631A EP4065672B1 EP 4065672 B1 EP4065672 B1 EP 4065672B1 EP 20811631 A EP20811631 A EP 20811631A EP 4065672 B1 EP4065672 B1 EP 4065672B1
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fuel
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EP4065672A1 (fr
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Hélène Rodeschini
Géraldine DELORME
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TotalEnergies Onetech SAS
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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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1826—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms poly-hydroxy
    • 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
    • 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
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • 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
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • 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
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • 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
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline 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 the use of particular compounds from the diol family as detergency additives in fuel compositions.
  • the present invention also relates to a process or a method for improving the cleanliness and/or cleaning of at least one internal part of an internal combustion engine using these particular compounds.
  • Liquid fuels for internal combustion engines 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. It has been shown that the formation of these deposits has consequences on engine performance and in particular has a negative impact on consumption and particle emissions. Advances in fuel additive technology have made it possible to address this problem.
  • So-called detergent additives used in fuels have already been proposed to maintain the cleanliness of the engine by limiting deposits (“keep-clean” effect) or by reducing the deposits already present in the internal parts of the combustion engine (“keep-clean” effect). clean-up” in English).
  • keep-clean a detergent additive for gasoline fuel containing a quaternary ammonium function.
  • WO2006135881 describes a detergent additive containing a quaternary ammonium salt used to reduce or clean deposits particularly on intake valves.
  • engine technology is continually evolving and fuel requirements must evolve to accommodate these technological advances in combustion engines.
  • the new direct injection systems Petrol or Diesel expose the injectors to more severe pressure and temperature conditions, which encourages the formation of deposits.
  • these new injection systems have more complex geometries to optimize spraying, in particular, more numerous holes having smaller diameters but which, on the other hand, induce greater sensitivity to deposits.
  • the presence of deposits can alter combustion performance, and in particular increase polluting emissions and particle emissions. Other consequences of excessive deposits have been reported in the literature, such as increased fuel consumption and drivability problems.
  • US7250065 describes a method for improving the cleaning of the intake system of internal combustion engines, using a fuel composition comprising a specific propoxylated additive and at least one detergency additive.
  • WO2017/203003 refers to the use of 2-ethylhexyl nitrate and one or more detergent agents in a diesel fuel composition to reduce deposits in the internal injectors of a compression ignition combustion engine.
  • WO2018/073544 relates to a method of controlling the formation of deposits on the valves of a spark-ignited direct injection internal combustion engine, which method comprises feeding the engine with a fuel composition which includes a Mannich-based detergent and a polyisobutylene amine additive.
  • the addition of the compounds according to the invention in a fuel composition has the effect of increasing the detergent properties of said composition. They make it possible to maintain the cleanliness of the engine, in particular by limiting or avoiding the formation of deposits (“keep-clean” effect in English) or by reducing the deposits already present in the internal parts of the combustion engine (“clean-clean” effect). up” in English).
  • the subject of the present invention is thus the use, to improve the detergency properties of a liquid fuel composition comprising one or more detergency additives, of an additive consisting of one or more hydrocarbon compound(s). comprising from 2 to 10 carbon atoms and two hydroxyl functions.
  • the invention also relates to a process or method for improving the cleanliness and/or cleaning of at least one internal part of an internal combustion engine powered by a liquid fuel comprising one or more detergency additives, consisting of adding to said fuel composition an additive consisting of at least one hydrocarbon compound comprising from 2 to 10 carbon atoms and two hydroxyl functions.
  • the compound according to the invention is incorporated into the fuel composition at a minimum content of 5 ppm by weight, and at a content which may go up to 500 ppm by weight.
  • the liquid fuel composition is chosen from hydrocarbon fuels, non-essentially hydrocarbon fuels, and mixtures thereof.
  • the hydrocarbon fuel is chosen from gasoline and diesel fuel, also called diesel fuel.
  • the compound according to the invention is used in the liquid fuel to maintain cleanliness and/or clean at least one of the internal parts of said internal combustion engine.
  • said compound is used in liquid fuel to limit or avoid the formation of deposits in at least one of the internal parts of said engine and/or reduce the deposits existing in at least one of the internal parts of said engine.
  • the deposits are located in at least one of the internal parts chosen from the engine intake system, the combustion chamber and the fuel injection system.
  • the compound according to the invention is used to avoid and/or reduce the formation of deposits linked to the coking phenomenon (or “coking”) and/or soap and/or varnish type deposits.
  • the compound according to the invention also makes it possible to reduce the fuel consumption of the internal combustion engine.
  • the internal combustion engine is a spark ignition engine, also known as a gasoline engine.
  • the internal combustion engine is a compression ignition engine, also known as a diesel engine.
  • C N compound or group denotes a compound or group containing N carbon atoms in its chemical structure.
  • the invention uses as an additive a hydrocarbon compound comprising from 2 to 10 carbon atoms and two hydroxyl functions.
  • this compound has the formula C n H 2n+2 O 2 , with n an integer ranging from 2 to 10.
  • n ranges from 3 to 8, more preferably from 4 to 8; better still n designates 5 or 6, and even more preferably n designates 6.
  • said compound is hexylene glycol.
  • the compound according to the invention is used as an additive to improve the detergency performance of a fuel composition.
  • incorporation, including in very small quantities, of the compound according to the invention into the liquid fuel comprising a detergent additive other than the compound according to the invention produces an effect on the cleanliness of the engines powered by said fuel, compared to the same fuel not comprising the compound according to the invention.
  • the use of said compound in the fuel composition makes it possible, compared to liquid fuel not comprising such a compound, to limit or avoid the formation of at least one type of deposits as described below, and/ or reduce at least one type of existing deposits.
  • the use of the compounds according to the invention in a liquid fuel makes it possible to maintain the cleanliness of at least one of the internal parts of the internal combustion engine and/or to clean at least one of the internal parts of the internal combustion engine. .
  • the use of said compound as an additive in liquid fuel makes it possible to observe both effects, limitation (or prevention) and reduction of deposits (“keep-clean” and “clean-up” effects). .
  • Deposits are distinguished depending on the type of internal combustion engine and the location of the deposits in the internal parts of said engine.
  • the internal combustion engine is a spark ignition engine or gasoline engine, preferably direct injection (DISI in English “Direct Injection Spark Ignition engine”).
  • the targeted deposits are located in at least one of the internal parts of said spark-ignition engine.
  • the internal part of the spark ignition engine kept clean (keep-clean) and/or cleaned (clean-up) is, advantageously, chosen from the intake system of the engine, in particular the intake valves (IVD in English " Intake Valve Deposit"), the combustion chamber (CCD in English “Combustion Chamber Deposit” or TCD in English “Total Chamber Deposit”) and the fuel injection system, in particular the injectors of an indirect injection system (PFI in English “Port Fuel Injector”) or the injectors of a direct injection system (DISI).
  • the internal combustion engine is a compression ignition engine or Diesel engine, preferably a Diesel engine with direct injection, in particular a Diesel engine with a Common-Rail injection system (CRDI in English). Common Rail Direct Injection").
  • the targeted deposits are located in at least one of the internal parts of said Diesel engine.
  • the targeted deposits are located in the injection system of the Diesel engine, preferably located on an external part of an injector of said injection system, for example the nose of the injector and/or on an internal part of an injector of said injection system (IDID in English “Internal Diesel Injector Deposits”), for example on the surface of an injector needle.
  • the deposits may consist of deposits linked to the phenomenon of coking (“coking” in English) and/or deposits of soap and/or varnish type (“lacquering”).
  • the compound(s) according to the invention as described above can advantageously be used in fuel to reduce and/or avoid the loss of power due to the formation of deposits in the internal parts of a direct injection diesel engine. , said power loss can be determined according to the standardized engine test method CEC F-98-08.
  • Said compound(s) according to the invention can, advantageously, be used in fuel to reduce and/or avoid restriction of the flow of fuel emitted by the injector of a direct injection Diesel engine during its operation.
  • said flow restriction can be determined according to the standardized engine test method CEC F-23-1-01.
  • the use of the compounds according to the invention also makes it possible to reduce the fuel consumption of the internal combustion engine.
  • the use of the compounds according to the invention also makes it possible to reduce emissions of pollutants, in particular emissions of particles from the internal combustion engine.
  • the compounds according to the invention can be added to the liquid fuel within a refinery and/or be incorporated downstream of the refinery, possibly mixed with other additives in the form of an additive package.
  • the compound(s) according to the invention are advantageously used in the fuel composition at a total content of at least 5 ppm by weight, relative to the total weight of said composition.
  • the hydrocarbon compound(s) according to the invention are used at a total content ranging from 5 to 500 ppm by weight, preferably from 10 to 200 ppm by weight, preferably from 10 to 100 ppm by weight, more preferably 10 to 50 ppm by weight, more preferably 20 to 50 ppm by weight, and more preferably 20 to 40 ppm by weight, relative to the total weight of the fuel composition.
  • the fuel composition in which the compound(s) according to the invention are used as additives typically comprises at least one cut of liquid hydrocarbons from one or more sources chosen from the group consisting of mineral sources, animal sources, vegetable and synthetic.
  • the fuel composition is advantageously chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, and mixtures thereof.
  • Hydrocarbon fuel means 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 carbon and 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 distillates under vacuum, distillates resulting from ARDS type conversion processes (in English “atmospheric residue desulfurization”) and/or visbreaking, the distillates resulting from the valorization of Fischer Tropsch cuts. Hydrocarbon fuels are typically gasoline and diesel fuel (also called diesel fuel).
  • the fuel composition is chosen from gasoline and gas oils.
  • Gasolines include, in particular, all commercially available spark ignition engine fuel compositions. As a representative example, we can cite gasolines meeting the NF EN 228 standard. Gasolines generally have sufficiently high octane indices to avoid the knocking phenomenon. Typically, gasoline-type fuels marketed in Europe, complying with the NF EN 228 standard, 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 ASTM D 2699- 86 or D 2700-86.
  • MON motor octane number
  • RON research octane number
  • Gas oils include, in particular, all commercially available fuel compositions for Diesel engines. We can cite, as a representative example, diesel fuels meeting the NF EN 590 standard.
  • Non-primarily hydrocarbon fuels include in particular oxygenated ones, 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 plant origin and bioethanols.
  • Mixtures of hydrocarbon fuel and non-essentially hydrocarbon fuel are typically type B x diesels or type E x gasolines.
  • type B x diesel fuel for Diesel engines we mean a diesel fuel which contains x% (v/v) of esters of vegetable or animal oils (including used cooking oils) transformed by a chemical process called transesterification, obtained by reacting this oil with an alcohol to obtain fatty acid esters (FAE). With methanol and ethanol, fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAFA) are obtained, respectively.
  • FAME fatty acid methyl esters
  • FFA fatty acid ethyl esters
  • B indicates the percentage of EAG contained in the diesel.
  • a B99 contains 99% of EAG and 1% of middle distillates of fossil origin (mineral source), B20, 20% of EAG and 80% of middle distillates of fossil origin etc....
  • type B 0 gas oils which do not contain oxygenated compounds
  • type Bx gas oils which contain x% (v/v) of esters of vegetable oils or fatty acids, most often methyl esters (EMHV or FAME) , x denoting a number ranging from 0 to 100.
  • EAG methyl esters
  • FAME methyl esters
  • type E x gasoline for spark ignition engines is meant a gasoline fuel which contains x% (v/v) of oxygenates, generally ethanol, bioethanol and/or ethyl-tertio-butyl-ether (ETBE), x denoting a number ranging from 0 to 100.
  • x% (v/v) of oxygenates generally ethanol, bioethanol and/or ethyl-tertio-butyl-ether (ETBE), x denoting a number ranging from 0 to 100.
  • the sulfur content of the fuel composition is preferably less than or equal to 1000 ppm, preferably less than or equal to 500 ppm, and more preferably less than or equal to 50 ppm, or even less than 10 ppm and advantageously sulfur-free. .
  • the fuel composition according to the invention comprises one or more detergent additive(s), which can be chosen from the detergency additives for fuels usually used.
  • the latter are compounds well known to those skilled in the art.
  • the detergent additives may be in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkyl polyamines, polyetheramines, quaternary ammonium salts, triazole derivatives, and Mannich bases, and more preferably among Mannich bases, quaternary ammonium salts, and polyisobutylene mono- or poly-amines (or PIB-amines), more preferably still among quaternary ammonium salts and even better among polyisobutylenes succinimides functionalized with a quaternary ammonium group, fatty acid amides functionalized with a quaternary ammonium group and their dimers such as the di-(alkylamido-propyl-quaternary ammonium) compounds described for example in the patent application WO2020/109568 , and fatty chain alkylamidoalkyl betaines.
  • detergent additives are given in the following documents: EP0938535 , US2012/0010112 , WO2012/004300 , US4171959 And WO2006135881 .
  • block copolymers formed of at least one polar unit and one apolar unit such as for example those described in the patent application FR 1761700 in the name of the Applicant.
  • the fuel composition comprises at least one detergent additive consisting of a quaternary ammonium salt, obtained by reaction with a quaternization agent of a nitrogen compound comprising a tertiary amine function, this nitrogen compound being the product of the reaction of an acylating agent substituted by a hydrocarbon group and a compound comprising at least one tertiary amine group and at least one group chosen from primary amines, secondary amines and alcohols.
  • a detergent additive consisting of a quaternary ammonium salt, obtained by reaction with a quaternization agent of a nitrogen compound comprising a tertiary amine function, this nitrogen compound being the product of the reaction of an acylating agent substituted by a hydrocarbon group and a compound comprising at least one tertiary amine group and at least one group chosen from primary amines, secondary amines and alcohols.
  • said nitrogen compound is the reaction product of a succinic acid derivative substituted by a hydrocarbon group, preferably a polyisobutenyl-succinic anhydride, and an alcohol or a primary amine or secondary also comprising a tertiary amine group.
  • the total content of detergent additive(s) of the fuel composition ranges from 5 to 5,000 ppm by weight, preferably from 10 to 1000 ppm by weight , and better still from 20 to 250 ppm by weight, relative to the total weight of the fuel composition.
  • the ratio between the total weight content of hydrocarbon compound(s) according to the invention on the one hand and the total weight content of detergent additive(s) on the other hand ranges from 1:50 to 1: 1, preferably from 1:20 to 1:1, more preferably from 1:20 to 1:2, and better still from 1:20 to 1:3.
  • the fuel composition according to the invention may also comprise other additives, in addition to the detergent additive(s) and the hydrocarbon compound(s) according to the invention.
  • additives can for example be chosen, in a non-limiting manner, from anti-corrosion/antioxidant additives, dispersing additives, demulsifying additives, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or lubricity additives, combustion aid agents (catalytic combustion and soot promoters), cold resistance additives and in particular agents improving the cloud point, the point flow, TLF (“Filterability limit temperature”), anti-sedimentation agents, anti-wear agents, tracers, solvents/carrier oils, and conductivity modifying agents.
  • anti-corrosion/antioxidant additives dispersing additives, demulsifying additives, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or lubricity additives, combustion aid agents (catalytic combustion and soot promoters), cold resistance additives and in particular agents improving the cloud point,
  • Additional additives may be present in quantities ranging, for each, from 10 to 1000 ppm (each), preferably from 50 to 500 ppm by weight, relative to the total weight of the fuel composition.
  • the process or method for improving the cleanliness and/or cleaning of at least one internal part of an internal combustion engine powered by a liquid fuel comprising one or more detergency additives consists of adding to said fuel composition an additive consisting of at least one hydrocarbon compound as described above.
  • the internal combustion engine is a spark ignition engine, preferably direct injection (DISI).
  • DISI direct injection
  • the kept clean and/or cleaned internal part of the spark ignition engine is preferably chosen from the intake system of the engine, in particular the intake valves (IVD), the combustion chamber (CCD or TCD) and the fuel injection system, in particular the injectors of an indirect injection system (PFI) or the injectors of a direct injection system (DISI).
  • the intake system of the engine in particular the intake valves (IVD), the combustion chamber (CCD or TCD) and the fuel injection system, in particular the injectors of an indirect injection system (PFI) or the injectors of a direct injection system (DISI).
  • the internal combustion engine is a Diesel engine, preferably a Diesel engine with direct injection, in particular a Diesel engine with a Common-Rail injection system (CRDI).
  • Diesel engine preferably a Diesel engine with direct injection
  • Diesel engine with a Common-Rail injection system (CRDI) preferably a Diesel engine with direct injection, in particular a Diesel engine with a Common-Rail injection system (CRDI).
  • CCDI Common-Rail injection system
  • the internal part kept clean (keep-clean) and/or cleaned (clean-up) of the Diesel engine is, preferably, the injection system of the Diesel engine, preferably an external part of an injector of said injection system , for example the nose of the injector and/or one of the internal parts of an injector of said injection system, for example the surface of an injector needle.
  • step (a) above is preceded by a prior step of determining the content of hydrocarbon compound(s) to be incorporated into said fuel composition to achieve a given specification relating to the properties detergency of the fuel composition.
  • This preliminary step is part of current practice in the field of fuel additives and involves defining at least one characteristic representative of the detergency properties of the fuel composition as well as a target value.
  • the characteristic representative of the detergency properties of the fuel will depend on the type of internal combustion engine, for example Diesel or spark ignition, the direct or indirect injection system and the location in the engine of the deposits targeted for cleaning and/or maintaining cleanliness.
  • the characteristic representative of the detergency properties of the fuel can, for example, correspond to the loss of power due to the formation of deposits in the injectors or the restriction of the flow of fuel emitted by the injector at during operation of said engine.
  • the characteristic representative of the detergency properties can also correspond to the appearance of lacquering type deposits at the level of the injector needle (IDID).
  • the process of maintaining cleanliness (keep-clean) and/or cleaning (clean-up) may also include an additional step c) after step b), checking the target achieved and/or adjusting the additivation rate with the compound(s) according to the invention.
  • hydrocarbon compounds according to the invention have remarkable properties as efficiency boosters of detergent additives in a liquid fuel, in particular in a diesel or gasoline fuel. These compounds are particularly noteworthy because they are effective for a wide range of liquid fuels, for several types of engines and against different types of deposits that form in the internal parts of internal combustion engines.
  • Example 1 “Keep clean” type detergency tests in diesel fuel
  • Performance in terms of detergency was evaluated using the XUD9 engine test, consisting of determining the loss of flow defined as corresponding to the restriction of the flow of diesel emitted by the injector of a pre-chamber Diesel engine during its operation, according to the standardized engine test method CEC F-23-1 - 01.
  • the objective of the XUD9 test is to evaluate the ability of the additive and/or the composition of additives tested to maintain the cleanliness, known as the “keep clean” effect, of the injectors of a Peugeot XUD9 engine.
  • A/L with four cylinders and Diesel prechamber injection in particular to evaluate its ability to limit the formation of deposits on the injectors.
  • the test was carried out on a virgin type B7 diesel fuel meeting the EN590 standard, additive with a known detergency additive consisting of a quaternary ammonium salt obtained by reaction of propylene oxide with the product of the reaction of 'a polyisobutenyl-succinic anhydride whose polyisobutylene group (PIB) has a number average molecular mass (Mn) of 1000 g/mol and dimethyl-aminopropylamine, at a treatment rate of 37.5 ppm by weight (37, 5 mg/kg).
  • PIB polyisobutylene group
  • Mn number average molecular mass
  • the diesel fuel thus added is called diesel fuel G.
  • the test was carried out with diesel fuel G on the one hand, and with diesel fuel G supplemented with 20 ppm by weight of hexylene glycol on the other hand.
  • the test was carried out using as candidate fuel in phase 2 diesel fuel G on the one hand, and diesel fuel G with an additive of 20 ppm in weight of hexylene glycol on the other hand, as described in Example 1 above.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Detergent Compositions (AREA)
EP20811631.9A 2019-11-29 2020-11-27 Utilisation de diols comme additifs de détergence Active EP4065672B1 (fr)

Applications Claiming Priority (2)

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FR1913471A FR3103815B1 (fr) 2019-11-29 2019-11-29 Utilisation de diols comme additifs de détergence
PCT/EP2020/083574 WO2021105321A1 (fr) 2019-11-29 2020-11-27 Utilisation de diols comme additifs de détergence

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US20230357656A1 (en) 2023-11-09
WO2021105321A1 (fr) 2021-06-03
FR3103815B1 (fr) 2021-12-17
FR3103815A1 (fr) 2021-06-04
PL4065672T3 (pl) 2024-04-08
CN115175975B (zh) 2023-11-14
CN115175975A (zh) 2022-10-11
EP4065672A1 (fr) 2022-10-05

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