Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2227—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond urea; derivatives thereof; urethane
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L7/00—Fuels produced by solidifying fluid fuels
  • C10L7/02—Fuels produced by solidifying fluid fuels liquid fuels
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
  • C10L2200/0259—Nitrogen containing 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0415—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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/043—Kerosene, jet fuel
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
  • C10L2230/08—Inhibitors
  • C10L2230/081—Anti-oxidants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
  • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
  • C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/023—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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

• the present invention relates to a gelled composition of fuel or hydrocarbon fuel, its method of preparation and a method of supplying an internal combustion engine.
• the present invention also relates to the use of an organogelling compound as a performance additive of a fuel or liquid hydrocarbon fuel.
• organogelators are well known to those skilled in the art for structuring organic solvents and giving them the desired texture or viscosity.
• Organogellators interact with each other and with a solvent to change its physical and / or chemical characteristics.
• the compounds containing ureas and more particularly bis-ureas are good organic solvent organogelators.
• Feringa et al. in Chem. Eur.J, 1997, 3, 1238-1243 or Shikata, T. et al. in J. Phys. Chem B, 2008, vol. 12, 8459-8465 The use of certain symmetrical and asymmetrical bis-ureas as an organogelator for gelling different cosmetic or dermatological products has also been envisaged in WO2002047628 and JP2003064346.
• the object of the present invention is, therefore, to provide novel gelled fuel or hydrocarbon fuel compositions and their method of manufacture.
• the subject of the present invention relates, in particular, to a gelled composition of fuel or hydrocarbon fuel comprising at least 70% by weight of a liquid hydrocarbon fuel or fuel and at least one organogelling compound capable of forming with the fuel or liquid hydrocarbon fuel. , a rheofluidifying physical gel.
• the gelled composition has a rheofluidifying behavior under the effect of a mechanical stress of between 100 and 1000s "1 , preferably between 300 and 1000s " 1 , more preferably between 500 and 1000s "1 .
• liquid hydrocarbon fuels or fuels especially those based on distillates-type containing paraffinic waxes, such as for example diesel fuels and heating fuel oils have a significant decrease in their flow properties. It is well known that the crystallization of paraffins is a limiting factor in the use of middle distillates. Also, it is important to prepare diesel fuels adapted to the temperatures at which they will be used in motorized vehicles, that is to say to the surrounding climate.
• paraffins are crystallized at the bottom of the tank, they can be driven the fuel system and especially clog filters and prefilters arranged upstream of the injection systems (pump and injectors).
• paraffins precipitate at the bottom of the tank and can be driven and obstruct the pipes upstream of the pump and the boiler supply system (nozzle and filter). It is obvious that the presence of solids, such as paraffin crystals, prevents the normal circulation of the middle distillate.
• additives that can improve the cold resistance.
• additives There are three types of additives:
• CFI cold flow improvers
• WASA Wi-Fi anti-settling additives
• WASA Wi-Fi anti-settling additives
• acronym for Wax anti-settling additives intended to prevent the deposition of paraffin crystals at the bottom of the tanks or storage tanks, by dispersing and maintaining said crystals suspended in fuels or liquid hydrocarbon fuels.
• the subject of the present invention also relates to a composition as described above, in which the liquid hydrocarbon fuel or fuel is chosen from gas oils, bio-diesel fuels and fuels, preferably domestic fuels (called FOD, acronym of the term English “household fuel oil”).
• FOD domestic fuels
• Biodiesel is defined as Bx diesel engine fuels (compression engine) which contain x% (v / v) of vegetable or animal oil esters (including used cooking oil) converted by a chemical process. called transesterification reacting this oil with an alcohol to obtain esters of fatty acid (EAG). With methanol and ethanol, fatty acid methyl esters (EMAG) and fatty acid ethyl esters (EEAG) are obtained respectively.
• EAG fatty acid methyl esters
• EEAG fatty acid ethyl esters
• the letter "B” followed by a number indicates the percentage of EAG contained in the diesel fuel.
• a B99 contains 99% of EAG and 1% of middle distillates of fossil origin, the B20, 20% of EAG and 80% of middle distillates of fossil origin etc.
• the BO gas oils which do not contain oxygenated compounds are Bx type biodiesel fuels which contain x% (v / v) of vegetable oil esters or of fatty acids, most often esters. methyl esters (EMHV or EMAG).
• EAG methyl esters
• B100 the term fuel is designated by the term B100.
• the organogelling compound is capable of forming with the fuel or liquid hydrocarbon fuel, a rheofluidifying physical gel at a temperature greater than or equal to the cloud point temperature (PTR) of said gelled composition of fuel or hydrocarbon fuel , determined according to standard NF EN 23015.
• PTR cloud point temperature
• the temperature Tsol / gel of the gelled composition of fuel or hydrocarbon fuel, determined by rheometric measurement in dynamic oscillation is greater than or equal to the cloud point temperature (PTR) of said composition, determined according to the standard NF EN 23015.
• PTR cloud point temperature
• the organogelling compound is chosen from organogelling compounds derived from ureas and bis-ureas, alone or as a mixture.
• the organogelling compound is chosen from organogelling compounds derived from N-substituted ureas and N-substituted, symmetrical or asymmetric bis-ureas, alone or as a mixture.
• the organogelling compound is chosen from organogelling compounds derived from N-substituted bis-ureas, symmetrical or asymmetrical, preferably asymmetrical, alone or in mixture.
• the organogelator compound comprises at least one substituent on a nitrogen atom of a urea function of organogelator compound, said substituent being selected from the group consisting of monocyclic or polycyclic aromatic ring C 5 -C 1 0, heterocyclic C 5 C, preferably aromatic rings monocyclic C 5 -C 6, optionally substituted by one or more hydrocarbon chains to C 1 0 linear or branched, saturated or unsaturated, preferably C, to C 4 , said chains optionally containing one or more heteroatoms selected from N, O and S.
• the organogelling compound comprises at least one substituent carried by a nitrogen atom of a urea function of the organogelling compound, said substituent being chosen from the group consisting of linear or branched C1 to C3 hydrocarbon chains.
• the organogelling compound is represented by the following formula (1):
• R 1 and R 2 are the same or different and independently represent a group selected from the group consisting of:
• C 5 to C 10 monocyclic or polycyclic aromatic rings C 5 to C 10 heterocyclics, preferably C 5 -C 6 monocyclic aromatic rings, optionally substituted with one or more linear C 1 to C 10 hydrocarbon chains, or branched, saturated or unsaturated, preferably C 1 to C , said chains optionally containing one or more heteroatoms selected from N, O and
• the organogelling compound is represented by the following formula (2):
• Y represents a group selected from the group consisting of:
• linear or branched, saturated or unsaturated C 1 to C 24 hydrocarbon chains preferably C 3 to C 18 , even more preferably C 6 to C 12, said chains optionally containing one or more heteroatoms chosen from N, O and S, R 3 and R 4 are identical or different and independently represent a group selected from the group consisting of hydrocarbon chains Ci to C 24, linear or branched, saturated or unsaturated, preferably C 3 to C 18, even more preferably in Ce to C 12, said chains possibly containing one or a plurality of heteroatoms selected from N, O and S and / or one or more C 5 to C 10 monocyclic or polycyclic aromatic rings, preferably C 5 or C 6 monocyclic aromatic rings.
• Y represents a group selected from the group consisting of monocyclic or polycyclic aromatic ring C 5 -C 10 heterocyclic C 5 C, preferably aromatic rings monocyclic C 5 -C 6, optionally substituted by a or more linear or branched, saturated or unsaturated, preferably C 1 -C 4 , hydrocarbon-based C1-C10 hydrocarbon chains, said chains optionally containing one or more heteroatoms chosen from N, O and S.
• R 3 and R 4 are identical or different and independently represent a group selected from the group consisting of the hydrocarbon chains to C 24, linear or branched, saturated or unsaturated, cyclic or acyclic, said chains optionally containing one or more heteroatoms chosen from N, O and S in the form of one or more functions chosen from ether, ester, ketone, amine, amide, imine, thiol, thioether or thioester functions and / or one or more C5 monocyclic or polycyclic aromatic rings; at C10, preferably monocyclic aromatic C 5 or C 6 , optionally substituted by one or more linear or branched, saturated or unsaturated C 1 -C 10 hydrocarbon-based chains, preferably C 1 -C 4.
• R 3 and R 4 are identical or different and independently represent the -CH (R 6 ) COOR 7 group in which:
• R 6 and R 7 are identical or different and are independently selected from the group consisting of hydrocarbon chains -C 24 linear or branched, saturated or unsaturated, cyclic or acyclic, preferably Ci to C 8, said chains optionally containing one or more monocyclic or polycyclic aromatic rings C 5 C, preferably aromatic monocyclic C 5 or C 6, optionally substituted by one or more hydrocarbon chains to C 10, linear or branched, saturated or unsaturated, preferably C 1 -C.
• the organogelling compound is represented by the following formula (3):
• R 3 and R 4 are as described above and R 5 represents a group chosen from the group consisting of linear or branched, preferably C 1 to C 6 , C 1 to C 12 hydrocarbon-based chains, more preferably C 1 to C 6 at C 3 , even more preferentially in d.
• the organogelling compound has a molar mass less than or equal to 2000 g. mol "1 .
• the gelled composition of hydrocarbon fuel or hydrocarbon fuel comprises between 0.01% and 5% by weight of the organogelling compound, preferably between 0.05 and 1% by weight, even more preferentially between 0.1 and 0.5% by mass.
• a second subject of the present invention relates to a method for preparing a gelled composition of fuel and hydrocarbon fuel as described above, characterized in that it comprises:
• composition by solubilization at a temperature of between 20 ° C. and 80 ° C. of an organogelling compound in at least 70% by weight of a liquid hydrocarbon fuel or fuel, optionally followed by a cooling to room temperature,
• a third object of the present invention relates to the use of an organogelling compound as a performance additive of a fuel or liquid hydrocarbon fuel, said organogelling compound forming with the fuel or liquid hydrocarbon fuel, a rheofluidifying physical gel, preferably having a rheofluidifying behavior under the effect of a mechanical stress of between 100 and 1000s -1 , advantageously between 300 and 1000s -1 , more preferably between 500 and 1000s -1 .
• the hydrocarbon fuel or fuel is selected from gas oils, bio-gas oils and fuels, preferably domestic fuel oils (FOD).
• FOD domestic fuel oils
• the subject of the present invention relates to the use of the organogelling compound as an additive for improving the cold-holding properties of the liquid hydrocarbon fuel or fuel, in particular, as an anti-sedimentation additive for improving the paraffin dispersion of the fuel or liquid hydrocarbon fuel.
• the object of the present invention relates to the use of the organogelling compound, to improve the resistance to oxidation.
• the subject of the present invention relates to the use of the organogelling compound, for improving the storage stability and / or oxidation of the liquid hydrocarbon fuel or fuel.
• a fourth subject of the present invention relates to a method of feeding a internal combustion engine comprising feeding said engine with a gelled composition of fuel or hydrocarbon fuel as described above.
• FIG. 1 shows the elastic modulus G 'and the viscous module G "as a function of temperature for a gelled fuel composition C 3 according to a particular embodiment of the invention.
• FIG. 2 shows the flow curves for a gelled fuel composition C 3 according to a particular embodiment of the invention, for different temperatures (0, 10, 20, 30 and 40 ° C).
• FIG. 3 represents the creep curves at different temperatures (0, 10, 20, 30 and 40 ° C.) for a gelled fuel composition C 3 according to one particular embodiment of the invention.
• a gelled composition of fuel or hydrocarbon fuel comprises at least 70% by weight, advantageously at least 85% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, even more preferably at least 98% by weight of a liquid hydrocarbon fuel or fuel and at least one organogelling compound.
• the liquid hydrocarbon fuels or fuels comprise middle distillates having a boiling point of between 100 and 500 ° C.
• These distillates may, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates obtained from catalytic cracking and / or distillate hydrocracking under vacuum, distillates resulting from ARDS type conversion processes (by residue desulfurization atmospheric) and / or visbreaking, distillates derived from the recovery of Fischer Tropsch cuts, distillates resulting from BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination and / or esters vegetable and animal oils or mixtures thereof.
• Liquid hydrocarbon fuels or fuels may also contain distillates from more complex refining operations than those derived from the direct distillation of hydrocarbons which may for example be derived from cracking, hydrocracking and / or catalytic cracking processes and visbreaking processes.
• Liquid hydrocarbon fuels or fuels may also contain new sources of distillates, among which may be mentioned in particular:
• oils and / or esters of vegetable and / or animal oils
• These new fuel bases can be used alone or mixed with conventional oil-based distillates as a fuel base and / or base of domestic fuel oil; they generally comprise long paraffinic chains greater than or equal to 10 carbon atoms and preferably from C 1 to C 30 .
• the sulfur content of liquid hydrocarbon fuels or fuels is less than 5000 mass ppm, preferably less than 500 ppm by mass, and more preferably less than 50 ppm by weight, or even less than 10 ppm by weight and advantageous without sulfur.
• the fuel or liquid hydrocarbon fuel may be chosen from fuel oils or fuels, such as fuels gasolines, diesel fuels, bio-diesel fuels domestic (called FOD (acronym for the term “domestic fuel oil”), kerosene , fuel oils and heavy fuel oils.
• biodiesel means fuels of the Bx type for a diesel engine (compression engine) as defined above.
• the liquid hydrocarbon fuel or fuel is chosen from diesel fuels, bio-gas oils and fuels, preferably domestic fuels.
• the organogelling compound is chosen from organogelling compounds capable of forming with the fuel or liquid hydrocarbon fuel, a rheofluidifying physical gel.
• physical gel a gel obtained by reversible formation of a three-dimensional network, by self-assembly of the organogelling compounds via weak interactions of the hydrogen bonding, ⁇ - ⁇ and / or Van-der-Waals type.
• Rheofluidifier means that the gel formed must break under the application of mechanical stress, for example a shear stress, with the effect of lowering the viscosity.
• mechanical stress for example a shear stress
• the viscosity is conventionally measured according to any known method.
• the gelled composition of fuel or hydrocarbon fuel preferably has a rheofluidifying behavior under the effect of a mechanical stress of between 100 and 1000s "1 , advantageously between 300 and 1000s " 1 , more preferably between 500 and 1000s "1
• the gelled composition of fuel or hydrocarbon fuel may have a rheofluidifying behavior at flow threshold that is to say that the gelled composition of fuel or hydrocarbon fuel is stable until a certain mechanical stress is applied to it, for example a shear stress which corresponds to the flow threshold. beyond this threshold, a rheofluidifying behavior is observed.
• a critical shear threshold y c corresponding to a stress value beyond which the gelled fuel or hydrocarbon fuel composition flows with a drop in viscosity can be determined.
• This critical shear threshold value y c defines the boundary between the Newtonian or quasi-Newtonian shear thinning and the area of said composition.
• the fuel composition or hydrocarbon fuel is in viscosified form, preferably gelled.
• the viscosity of said composition decreases sharply. If at a temperature of 20 ° C, the fuel composition or hydrocarbon fuel is in the form of a gel, under a stress greater than or equal to this threshold value, there is rupture of the gel (destructuration of the three-dimensional network).
• the critical shear threshold y c is determined by rheometric measurement and graphical determination of any known method.
• the gelled composition of fuel or hydrocarbon fuel has a critical shear threshold c c determined by rheometric measurement, less than 1000s -1 at a temperature of 20 ° C and at atmospheric pressure, preferably less than 500 s -1 , more preferably less than at 100 s "1 .
• the organogelling compound will preferably be selected so as to impart a thixotropic character to the gelled composition of hydrocarbon fuel or fuel. Thus, after the disappearance of the shear stress, a physical gel will be formed again.
• the rate of recovery in viscosity of the gelled composition of fuel or hydrocarbon fuel is advantageously less than 1 hour, preferably less than 10 min, more preferably less than 1 min.
• the speed of recovery in viscosity after the disappearance of the mechanical stress is advantageously between 0.01 and 3 seconds (instantaneous).
• the organogelling compound is preferably chosen from organogelling compounds capable of forming, with the fuel or hydrocarbon fuel, a gel having a rheofluidifying behavior during the application of:
• the organogelling compound is preferably chosen from organogelators able to form with the fuel or liquid hydrocarbon fuel a thermoreversible gel with a transition temperature T SO i / g ei less than or equal to 40 ° C. preferably at 30 ° C, more preferably at 20 ° C, at a pressure of between 1.11 and 1.11 Bar.
• the organogelling compound may advantageously be chosen from organogelling compounds capable of forming, with the liquid hydrocarbon fuel or fuel, a stable thermoreversible gel at a temperature of less than or equal to 60 ° C., preferably at 30 ° C., more preferably at least 30 ° C. ° C, more preferably at 5 ° C, at a pressure between 1, 01 and 1, 1 1 bar.
• stable at a temperature means that the fuel or hydrocarbon fuel is in the form of a single gel phase. Above this temperature, the hydrocarbon fuel or fuel is in the form of a sol phase.
• the rheological properties of organogels have been extensively studied in the literature. Concerning the characteristics of the organogels, reference may be made by way of example to the articles, Low Molecular Mass Gelators of Organic Liquids, Maity, G.C. 2007, Journal of Physical Sciences, Vol. 1, pp. 156-171; Acc. Chem. Res., George M., Weiss R.G., 2006, 39, 489; Chem. Rev., Steed J.W., Piepenbrock, M-O. Lloyd G. O., Clarke N., 2010, 10, 1960.
• a gelled fuel composition according to the invention stored in a tank of a vehicle, will be in gelled form.
• said composition undergoes an approximate shear rate gradient conventionally between 650 and 1000 s -1 .
• the viscosity of the composition drops during pumping to a value compatible with the operation of the engine
• the part of the gelled composition of fuel not consumed by the engine and re-circulated is transformed again into a physical gel in the tank in the absence of shear stresses.
• Suitable organogelling compounds must be at least partially soluble in the liquid hydrocarbon fuel or hydrocarbon fuel composition and capable of self-assembly within said composition to modify the rheological properties of said composition.
• partly soluble is meant that at least 95% by weight of the organogelling compound is soluble, preferably at least 99%.
• the organogelling compound is preferably soluble at room temperature in the fuel or liquid hydrocarbon fuel composition, it being understood that the solubility can be obtained by any known method.
• the gelled composition of fuel and hydrocarbon fuel is prepared according to a process which comprises:
• compositions by solubilization at a temperature of between 20 and 100 ° C., preferably between 20 and 80 ° C., of an organogelling compound in at least 70% by weight, advantageously at least 85% by weight, preferably at less than 90% by weight, more preferably at least 95% by weight, more preferably at least 98% by weight of a liquid hydrocarbon fuel or fuel as described above, optionally followed by
• freezing temperature means the temperature below which the material no longer flows over a long period of time.
• the gelled composition of fuel and hydrocarbon fuel forms a more or less pasty gel.
• LMOG Low Molecular Weight Organic Gelators
• organogelling compounds are known to be capable of modifying the rheological behavior of organic solvents, while rendering thermoreversible gelation. They are also known to be very sensitive to shearing. By way of example, mention may be made of the article “Low Molecular Mass Gelators of Organic Liquids and the Properties of Their Gels” by Terech, P. and Weiss, R. G. 1997, Chem. Rev., Vol. 97, pp. 3133-3159.
• the gelled composition of fuel and hydrocarbon fuel comprises between 0.01% and 5% by weight of the organogelling compound, preferably between 0.05 and 1% by weight, more preferably between 0.1 and 0.5% by weight.
• the organogelling compound is chosen from organogelling compounds derived from ureas and bis-ureas, alone or as a mixture, preferably from the organogelling compounds derived from N-substituted ureas and N-substituted bis-ureas. , symmetrical or asymmetrical, alone or in mixture.
• the organogelling compound may advantageously be chosen from organogelling compounds derived from N-substituted bis-ureas, symmetrical or asymmetric, preferably asymmetrical, alone or as a mixture.
• the organogelling compound may advantageously comprise a substituent compatibilizing the organogelling compound with the liquid hydrocarbon fuel or fuel.
• This substituent may be of aromatic nature and / or aliphatic nature apolar.
• the organogelling compound comprises at least one substituent carried by a nitrogen atom of a urea function of the organogelling compound.
• the substituent is chosen from the group consisting of monocyclic or polycyclic C 5 to C 10 aromatic rings, C 5 to C 6 heterocyclic rings, preferably C 5 -C 6 monocyclic aromatic rings, optionally substituted with one or more C 1 -C hydrocarbon chains. at C 10 , linear or branched, saturated or unsaturated, preferably C 1 -C 4, said chains optionally containing one or more heteroatoms selected from N, O and S.
• the organogelling compound preferably comprises at least one substituent borne by a nitrogen atom of a urea function of the organogelling compound.
• the substituent is selected from the group consisting of linear or branched hydrocarbon chains to C 24 saturated or unsaturated, more preferably C 3 to C 10, said chains optionally containing one or more heteroatoms selected from N, O and S.
• the organogelling compound is represented by the following formula (1):
• R 1 and R 2 are the same or different and independently represent a group selected from the group consisting of:
• C 5 to C 5 monocyclic or polycyclic aromatic rings C 5 to C 6 heterocyclics, preferably C 5 -C 6 monocyclic aromatic rings, optionally substituted by one or more C 1 to C 10 hydrocarbon chains, linear or branched saturated or unsaturated, preferably C 1 to C , said chains optionally containing one or more heteroatoms selected from N, O and S.
• the organogelling compound is represented by the following formula 2):
• Y represents a group selected from the group consisting of:
• C 5 to C 5 monocyclic or polycyclic aromatic rings C 5 to C 6 heterocyclic rings, preferably C 5 -C 6 monocyclic aromatic rings, optionally substituted with one or more linear or branched C1 to C C hydrocarbon chains; saturated or unsaturated, preferably d to C, said chains optionally containing one or more heteroatoms selected from N, O and S,
• linear or branched, saturated or unsaturated preferably C 3 to C 18 , d 4 or C 4 hydrocarbon-based chains, even more preferentially C 6 to C 12, said chains optionally containing one or more heteroatoms chosen from N, O and S;
• R 3 and R 4 are identical or different and independently represent a group chosen from the group consisting of linear or branched, saturated or unsaturated, preferably C 3 to C, d 4 hydrocarbon-based chains, even more preferentially from C 3 to C 4 ; at C-12, said chains optionally containing one or more heteroatoms selected from N, O and S and / or one or more monocyclic or polycyclic C 5 to C aromatic aromatics, preferably C 5 or C 6 monocyclic aromatic aromatics.
• Y advantageously represents a group selected from the group consisting of monocyclic or polycyclic aromatic rings C 5 do, heterocyclic C 5 C, preferably aromatic rings monocyclic C 5 -C 6, optionally substituted by a or more linear or branched, saturated or unsaturated, preferably d-C, hydrocarbon-based chains, said chains optionally containing one or more heteroatoms chosen from N, O and S.
• R 3 and R 4 are identical or different and independently represent a group chosen from the group consisting of linear or branched, saturated or unsaturated, cyclic or acyclic hydrocarbon chains in d to C 24 , said chains optionally containing one or more heteroatoms chosen from N, O and S in the form of one or more functions chosen from ether, ester, ketone, amine, amide, imine, thiol, thioether or thioester functions and / or one or more C 5 monocyclic or polycyclic aromatic rings; C, or C 6 monocyclic aromatic compounds, optionally substituted with one or more linear or branched, saturated or unsaturated C 1 -C 10 hydrocarbon chains, preferably C 1 -C 4.
• R 3 and R 4 are identical or different and independently represent the group -CH (R 6) COOR 7 in which:
• R 6 and R 7 are identical or different and are independently selected from the group consisting of the hydrocarbon chains to C-2 4, linear or branched, saturated or unsaturated, cyclic or acyclic, preferably Ci-Cm, said chains containing optionally one or more C 5 to C m monocyclic or polycyclic aromatic rings, preferably C 5 or C 6 monocyclic aromatic rings, optionally substituted with one or more linear or branched, saturated or unsaturated C to C chain hydrocarbon chains, preferably d to C.
• R 6 or R 7 may, for example, be selected from the group consisting of methyl, ethyl, propyl, butyl, t-butyl, phenyl, tolyl, xylyl, benzyl, 3,7-dimethyloctyl, 2-hexyl -decyl oleyl 2-hexyl-decyl, 2-butyl-octyl, farnesyl, 1-dodecyl, 2-dodecyl, cyclododecyl-methyl, 2-ethyl-1-hexyl.
• the organogelling compound is represented by the following formula (3):
• R 3 and R 4 are as described above and R 5 represents a group chosen from the group consisting of linear or branched, preferably C 1 to C 6, and more preferably C 1 to C 12 hydrocarbon-based chains; 3, even more preferentially in d.
• N, N'-2,4-bis ((2-ethylhexyl) ureido) toluene (EHUT) corresponding to the formula (3) in which R 3 and R 4 are a 2-ethyl-hexyl substituent and R5 is a methyl substituent.
• the organogelling compound as described above may advantageously be used as a performance additive for the fuel or liquid hydrocarbon fuel described above.
• performance additive is meant an additive which improves the cold behavior, in addition to the cold operability and / or the quality of the combustion (power, consumption, deposition, etc.) and / or the stability in storage and / or the oxidation of the fuel or hydrocarbon fuel.
• the Applicant has discovered that this use is particularly advantageous when the fuel or liquid hydrocarbon fuel is selected from gas oils, bio-gas oils and fuels, preferably domestic fuel oils (FOD).
• FOD domestic fuel oils
• the gelled compositions of fuel or hydrocarbon fuel according to the invention have excellent cold resistance, particularly in combination with a so-called cold flow flow-enhancing additive (in English “cold flow improvers "or CFI), preferably a CFI additive improving the TLF, also called TLF additive.
• the gelled composition of fuel or hydrocarbon fuel further comprises at least one CFI additive improving the kept cold.
• the organogelling compound as described above may, advantageously, be used in combination with a CFI additive, to improve the cold resistance of the fuel or hydrocarbon fuel.
• the additive CFI is preferably chosen from co- and ter-polymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.
• copolymers of ethylene and of unsaturated ester such as ethylene / vinyl acetate copolymers (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate described, for example, in US3048479, US3627838, US3790359, US3961961 and EP261957.
• the gelled fuel or hydrocarbon fuel composition comprises from 100 to 1000 ppm by weight of the CFI additive described above, preferably from 100 to 500 mass ppm.
• organogelling compounds are particularly advantageous when the organogelling compound is capable of forming with the fuel or hydrocarbon fuel, a rheofluidifying physical gel at a temperature greater than or equal to the cloud point temperature (PTR) of said gel, determined according to standard NF EN 23015.
• PTR cloud point temperature
• the Tsol / gel temperature of the gelled fuel composition or hydrocarbon fuel determined by rheometric measurement in dynamic oscillation is preferably greater than or equal to the cloud point temperature (PTR) of said fuel composition or hydrocarbon fuel, determined according to the standard NF EN 23015.
• PTR cloud point temperature
• the organogelling compound as described above may advantageously be used as an additive for improving the cold properties of the liquid hydrocarbon fuel or fuel, in particular as an additive for improving the properties of cold holding of the fuel or liquid hydrocarbon fuel and / or anti-settling additive to improve the paraffin dispersion.
• the organogelling compound is advantageously chosen from organogelling compounds capable of forming, with the liquid hydrocarbon fuel or fuel, a rheofluidifying physical gel at a temperature greater than or equal to the cloud point temperature (PTR) of the gelled fuel or fuel composition.
• PTR cloud point temperature
• hydrocarbon determined according to standard NF EN 23015.
• Sol-gel transition is called the change of state of a system which passes from a single phase, the ground, to a gel phase.
• the gel / sol transition temperature is the temperature at which the gel completely loses its structure.
• the rheological properties of organogels have been extensively studied in the literature. Examples include Low Molecular Mass Gelators of Organic Liquids, Maity G. C., Journal of Physical Sciences, 2007, Vol. 11, 156-171; Acc. Chem. Res., George M., Weiss R.G., 2006, 39, 489; Chem. Rev., Steed J.W., Piepenbrock, M-O. Lloyd G.
• the temperature T g / sol of the gelled composition of fuel or hydrocarbon fuel determined by rheometric measurement in dynamic oscillation is preferably greater than the cloud point temperature (PTR) of said composition, determined according to standard NF EN 23015.
• the hydrocarbon fuel and fuel compositions may also contain one or more other additives different from the organogelling compound according to the invention, chosen from detergents, anti-corrosion agents, dispersants and demulsifiers. anti-foam agents, biocides, deodorants, pro-cetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot), cloud point improving agents, pour point, filterability limit temperature, anti-clouding agents, sedimentation, anti-wear agents and / or conductivity modifiers.
• additives different from the organogelling compound according to the invention, chosen from detergents, anti-corrosion agents, dispersants and demulsifiers. anti-foam agents, biocides, deodorants, pro-cetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot), cloud point improving agents, pour point, filterability limit temperature, anti-cloud
• procetane additives in particular (but not limited to) selected from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;
• anti-foam additives in particular (but not limited to) selected from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides from vegetable or animal oils. Examples of such additives are given in EP 861 882, EP 663 000, EP 736 590;
• detergent and / or anti-corrosion additives in particular (but not limited to) selected from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkylamines, polyetheramines and quaternary ammonium salts; examples of such additives are given in EP0938535; US2012 / 00101 12 and WO2012 / 004300.
• lubricant additive or anti-wear agent in particular (but not limited to) selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and mono- and polycyclic carboxylic acid derivatives .
• lubricant additive or anti-wear agent selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and mono- and polycyclic carboxylic acid derivatives .
• examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784.
• cloud point additives including (but not limited to) selected from the group consisting of long-chain olefin terpolymers / (meth) acrylic ester / maleimide, and fumaric acid / maleic acid ester polymers. Examples of such additives are given in FR2528051, FR2528051, FR2528423, EP1 12195, EP172758, EP271385, EP291367;
• anti-sedimentation additives and / or paraffin dispersants in particular (but not limited to) selected from the group consisting of (meth) acrylic acid / alkyl (meth) acrylate copolymers amidated by a polyamine, alkenyl succinimides polyamine, phthalamic acid derivatives and double chain fatty amine; alkyl phenol resins.
• examples of such additives are given in EP261959, EP593331, EP674689, EP327423, EP512889, EP832172; US2005 / 0223631; US5998530; W093 / 14178.
• polyfunctional cold operability additives selected from the group consisting of olefin and alkenyl nitrate polymers as described in EP573490. ;
• additives are generally added in an amount ranging from 100 to 1000 mass ppm (each).
• the organogelling compounds according to the invention may be added to the hydrocarbon compositions within the refinery, and / or incorporated downstream of the refinery, optionally mixed with other additives, in the form of an additive package.
• the gelled fuel or hydrocarbon fuel composition as described above is particularly advantageous in that it can be used directly in a method of supplying an internal combustion engine.
• the method comprises, in particular, feeding said engine with a gelled composition of fuel or hydrocarbon fuel according to any known method.
• the gelled hydrocarbon fuel composition according to the invention is remarkable in that it makes it possible to improve the cold resistance and / or the oxidation stability of the hydrocarbon fuel, without affecting the proper functioning of the fuel in the combustion engine. internal.
• the gelled hydrocarbon fuel composition according to the invention is remarkable in that it makes it possible to improve the cold resistance and / or the oxidation stability of the hydrocarbon fuel or fuel, while at the same time facilitating transport of said fuel.
• Organogel compounds according to the invention are evaluated as a performance additive in distillates of the diesel type by incorporating them into three distillates of the diesel engine type referenced GOM 1, GOM 2 and GOM 3, the characteristics of which are listed in Table 1 below. : Table 1. Fuel Characteristics
• Each composition d, C 2 and C 3 is made by solubilizing respectively 750, 1000 and 5000 mass ppm of EHUT at a temperature of 80 ° C with GOM1 gas oil, with magnetic stirring until a homogeneous solution is obtained. . . Rheological properties of the fuel compositions Ci, C 2 and C 3
• the rheological characterizations of the fuel compositions C 1 , C 2 and C 3 were carried out using an Anton Paar MCR rheometer with a Coaxial Couette type cylinder system.
• the Couette geometry used for rheometric measurements has a volume of 19 mL.
• a dynamic oscillation test is carried out on the fuel compositions Ci, C 2 and C 3 in which a small deformation set at 10% is applied to said compositions, at a frequency of 1 Hz between 0 and 60 ° C.
• the evolution of the elastic modulus G 'and of the viscous modulus G "of said composition is monitored as a function of the temperature variation. and 40 ° C, with a speed of 2 ° C / min starting with the cooling ramp followed by the heating ramp.
• the dynamic oscillation test makes it possible to determine the solid or liquid nature of a material.
• the solid-type materials gel
• the liquid-type materials solution
• G'VG 'less than 1 G' being greater than G
• the transition temperature sol / gel Tsol / gel
• the fuel composition does not form a gel.
• Gelled fuel compositions are obtained only for the C 2 and C 3 fuel compositions.
• the amount of organogelling compound must therefore be sufficient to allow the formation of a three-dimensional network responsible for the structuring of the gel fuel composition.
• the evolution of the dynamic viscosity of the gelled fuel composition C 3 as a function of the shear rate is followed, for each temperature, 0 ° C., 10 ° C., 20 ° C., 30 ° C. and 40 ° C.
• the flow curves are obtained by logarithmic variation of the shear rate from 0.01 to 1000 s -1 followed directly by the return scan (from 1000 s -1 to 0.01 s -1 ).
• the presence of the organogelling compound EHUT in the fuel composition C 3 increases the dynamic viscosity of said composition.
• the very low shear dynamic viscosity (0.01 s "1) pass through the effect of 2 mPa ⁇ s at 40 ° C for the sole GOM1 diesel, 800 mPa.s for fuel composition 3 C gelled.
• the dynamic viscosity of the gelled fuel composition C 3 decreases with temperature (reversibility of the gel).
• the viscosity is higher than at temperatures of 30 and 40 ° C corresponding to the temperatures of use.
• use temperatures are meant the temperatures encountered in the fuel system of a combustion engine. Nevertheless, in the absence of shear stresses, the dynamic viscosity of the fuel composition C 3 remains too high at the temperatures of use. This high viscosity may disturb the circulation of the fuel composition C 3 in the tank supply circuit of a motor vehicle.
• the virgin diesel GOM 1 behaves like a Newtonian fluid because its viscosity is constant regardless of the imposed shear rate.
• the gelled fuel composition C 3 has a rheofluidifying behavior. Indeed, the increase in the shear rate causes a decrease in the viscosity of the gelled fuel composition C 3 . A Newtonian plateau is observed at low shear rates, the length of which increases with temperature. The dynamic viscosity remains constant up to a critical shear threshold y c . From the critical shear threshold y c the value of the viscosity decreases rapidly. The value of the critical shear threshold y c can be determined graphically for each temperature. The results are listed in 3 below.
• the viscosity of the fuel composition C 3 increases from 6300 mPa.s to 25 mPa.s ( at 20 ° C.)
• the mechanical stresses imposed on the fuel composition C 3 destructurize the three-dimensional gel network of said composition.
• the dynamic viscosity drops to a low viscosity value, compatible with the operating conditions of a combustion engine.
• the rheofluidifying nature of the gelled fuel composition C 3 avoids any risk of disturbance of the circulation of the fuel composition C 3 in the tank feed circuit while retaining the advantages of the gel structure of said composition at temperatures storage.
• VD dynamic viscosity at 40 ° C
• a shear rate of 1000 s -1 is applied for 50 s This rate must be sufficiently high to ensure that the gelled fuel composition C 3 is destructured at a given temperature.
• dynamic viscosity at low shear rate 0.01s -1 .
• the measurements are carried out at a temperature of 0, 10, 20, 30 and 40 ° C.
• composition C, C 5 , C 6 , C 7 and C 8 is carried out by solubilizing, respectively, 150, 500, 750, 1000 and 5000 ppm by mass of EHUT at a temperature of 80 ° C. with GOM1 gas oil, additive with 300 ppm mass of a TLF additive which is an ethylene-vinyl acetate (EVA of English Ethylene-vinyl acetate) in solution at 70% by mass in an aromatic solvent (Solvesso 150) marketed under the name CP7936C, with magnetic stirring until a homogeneous solution is obtained.
• EVA ethylene-vinyl acetate
• Solvesso 150 aromatic solvent
• the anti-sedimentation properties of the fuel compositions C, C 5 , C 6 , C 7 and Ce are evaluated by the following ARAL sedimentation test: 250mL of fuel compositions C, C 5 , C 6 , C 7 and C 8 are cooled in test tubes of 250mL in a climatic chamber at -13 ° C according to the following temperature cycle: passage from + 10 ° C to -13 ° C in 4h and isothermal at -13 ° C for 16h.
• a visual quotation of the appearance of the sample and the sedimented phase volume is performed, then the 20% of the lower volume are taken, for characterization in PTR cloud point (NF EN 23015).
• the difference in PTR before and after sedimentation ie on the 20% by volume of the bottom of the test piece) is then compared, the smaller the difference, the better the antisedimentation effect.
• Table 5 The results are summarized in Table 5 below.
• the gel does not form or when the gel is formed at a temperature below the cloud point temperature (PTR) no anti-sedimentation effect is observed.
• the anti-settling effect is observed only when the Tsol / gel temperature of the fuel composition is greater than or equal to the cloud point temperature (PTR). Indeed, the first paraffin crystals are formed at -7 ° C for the fuel compositions C, C 5 , C 6 , C 7 and C 8 . If the temperature Tsol / gel is lower than -7 ° C then the first paraffin crystals sediment even before the formation of the three-dimensional network of the organogelling compound EHUT which then becomes ineffective.
• the gelling effect of the organogelling compound in the fuel composition is decisive for the anti-sedimentation performance of said fuel.
• the use of the organogelling compound as anti-settling additive is conditioned to the formation of a gel at a temperature greater than or equal to the temperature of the cloud point (PTR) of said composition.
• the content of organogelling compound required to form a gelled fuel composition at a temperature greater than or equal to the temperature of the cloud point (PTR) can be determined by any known method, in particular by routine tests accessible to those skilled in the art.
• composition C 9 , C 10 and C fuel compositions Each composition C 9 , C 12 and C n is carried out by solubilizing respectively, 750, 1000 and 5000 mass ppm of EHUT at a temperature of 80 ° C. with GOM2 gasoline of type B7 (see Table 1), additivated with 300 ppm by mass.
• GOM2 gasoline of type B7 see Table 1
• an additive of TLF which is an ethylene-vinyl acetate (EVA of English Ethylene-vinyl acetate) in solution at 70% by mass in an aromatic solvent (Solvesso 150) marketed under the name CP7936C, with magnetic stirring up to to obtain a homogeneous solution.
• EVA ethylene-vinyl acetate
• Solvesso 150 aromatic solvent
• Tsol / gel temperature of the compositions C 9 , C 0 and C n are determined according to the dynamic oscillation test used for example 1 as well as the dynamic and kinetic viscosities. The results are listed in Table 6 below.
• VD dynamic viscosity at 40 ° C
• the addition of the EHUT will make it possible to form a gel in the GOM2 (B7), in the same way as in the GOM 1; with the difference that the EHUT is more soluble in the GOM 2 than in the GOM 1.
• the formation of the gel will therefore require a minimum concentration of more important EHUT in the GOM 2 (composition Cn).
• the bis-urea ester is obtained by reacting an ammonium-ester precursor with 2-hexyldecanol.
• the amino ester precursor is prepared by esterification reaction between racphenylalanine ( ⁇ -amino phenylacetic acid) and 2-hexyldecanol.
• 200 ml of toluene is refluxed in a Dean-Stark apparatus for 18 hours at 130 ° C. After cooling, and removal of the solvent in vacuo, a yellow oil is obtained.
• An amino ester is formed in situ by adding 3.3 g of triethylamine (2.3 eq.) In nitrogen to a solution of 17.4 g of the ammonium-ester precursor (2.2 eq.) previously synthesized in 100 ml of dichloromethane.
• composition C 12, C13 and C is carried out by solubilizing respectively, 5000, 10000, and 20000 ppm by weight of ester of bis-urea of formula (4) synthesized above, at a temperature of 80 ° C with gas oil GOM2 type B7 (see Table 1), additive with 300 ppm by weight of a TLF additive which is an ethylene vinyl acetate (EVA of Ethylene-vinyl acetate) in solution at 70% by weight in an aromatic solvent (Solvesso 150) sold under the name CP7936C, with magnetic stirring until a homogeneous solution is obtained.
• EVA ethylene vinyl acetate
• Solvesso 150 aromatic solvent sold under the name CP7936C
• Tsol / gel temperature of compositions C 12 , C 13 and C 1 is determined according to the dynamic oscillation test used for example 1 as well as the dynamic and kinetic viscosities. The results are listed in Table 7 below.
• compositions C 12 , C 13 and C M are evaluated according to the same method as in example 1. The results are listed in the following table 7: Table 7
• VD dynamic viscosity at 40 ° C
• the EHUT will form a gel in the GOM2 (B7) at a lower concentration than the ester of bis-urea (C13 and C 4). Indeed, the EHUT forms a gel at 5000 mass ppm unlike the bis-urea ester (C12) at this concentration.
• the viscosity at 10 000 ppm by weight of the bis-urea ester (C13 and Ci) is 363 compared with 335 to 5000 ppm by weight for the EHUT in the GOM 2.
• the concentration of the bis-urea ester (C12) does not seem sufficient to form the three-dimensional network at a temperature above the PTR.
• the oxidation stability of the fuel compositions C15, C16 and GOM3 was evaluated according to standard NF EN 15751.
• the induction period expressed in hours is determined according to a procedure specified by standard NF EN 15751. Period refers to the flow time between the start of the measurement and the moment when the formation of the oxidation products begins to increase rapidly.
• the induction time is representative of the oxidation stability. Plus the induction period is important, the higher the fuel composition is stable to oxidation.
• Table 8 The results obtained are listed in Table 8 below:
• Fuel gelled compositions C15 and C 6 are more stable to oxidation than the GOM3 diesel.
• the effect on the oxidation stability is more marked for the gelled fuel composition Ci6, with a gain of 17 hours, namely a gain advantageously greater than 10 hours.
• the gelled structure of the fuel or fuel compositions according to the present invention makes it possible to increase the oxidation and / or storage stability of fuels, preferably FOD and middle distillates, preferably diesel fuels and bio-diesel fuels. particularly sensitive to oxidation.
• fuels preferably FOD and middle distillates, preferably diesel fuels and bio-diesel fuels.
• the use of an organogelling compound as described above in a fuel or fuel composition improves the oxidation stability of said compositions.

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