WO2015181013A1

WO2015181013A1 - Gelled composition of liquid hydrocarbon fuel and method for preparing such a composition

Info

Publication number: WO2015181013A1
Application number: PCT/EP2015/061077
Authority: WO
Inventors: Julie Prevost
Original assignee: Total Marketing Services
Priority date: 2014-05-28
Filing date: 2015-05-20
Publication date: 2015-12-03
Also published as: FR3021663B1; EP3149120A1; FR3021663A1

Abstract

The invention concerns a gelled composition of liquid hydrocarbon fuel and the method for preparing same. The gelled composition of liquid hydrocarbon fuel comprises at least 70% by mass of a liquid hydrocarbon fuel and at least one organogelator compound that forms, with the liquid hydrocarbon fuel, a shear-thinning physical gel, said organogelator compound being chosen from the amine salts and saturated fatty acids having 14 to 24 carbon atoms, substituted by at least one hydroxyl moiety. The invention also concerns the use of an organogelator compound as an additive for improving the cold resistance properties of a liquid hydrocarbon fuel.

Description

GELIFIED COMPOSITION OF FUEL OR LIQUID HYDROCARBON FUEL AND PROCESS FOR PREPARING SUCH A COMPOSITION

The present invention relates to a gelled composition of fuel or liquid 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 an additive for improving the cold-holding properties of a fuel or liquid hydrocarbon fuel.

STATE OF THE PRIOR ART

The use of organogellators is 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. In particular, it is known to those skilled in the art that the compounds containing ureas and more particularly bis-ureas are good organic solvent organogelators. We can for example quote 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.

In the patent application PCT / EP2013 / 077610, the Applicant Company discloses effective urea and bis-urea derivatives as organogelling compounds in fuel compositions or liquid hydrocarbon fuel, particularly for cold-holding applications. The Applicant has been interested in other types of organogelling molecules. OBJECT OF THE INVENTION

The object of the present invention is, therefore, to provide novel gelled compositions of fuel or liquid hydrocarbon fuel and their manufacturing process.

The object of the present invention relates, in particular, to a gelled composition of fuel or liquid hydrocarbon fuel comprising at least 70% by weight of a liquid hydrocarbon fuel or fuel and at least one organogelling compound forming with the liquid hydrocarbon fuel or fuel, a rheofluidifying physical gel, said organogelling compound being chosen from amine and saturated fatty acid salts having from 14 to 24 carbon atoms, substituted with at least one hydroxyl group. Advantageously, the gel is a rheofluidifying and thixotropic physical gel.

According to one particular embodiment, the amine and saturated fatty acid salts are obtained from amines represented by the following formula (I): R-NH ₂ , in which the R group is a hydrocarbon chain saturated with C1 to C2 ₄ , preferably C ₄ to Cis, linear or branched, said chain optionally containing one or more oxygen atoms.

According to a preferred embodiment, the group R comprises at least one of the following reasons:

· - (CH ₂ ) _n - where n is an integer greater than or equal to 2, preferably greater than or equal to 1 1,

• -CH- (CH ₃ ) ₂ ,

• -O- (CH ₃ ) _2, and

• -O- (CH ₂ ) _m -CH ₃ where m is an integer between 0 and 2, preferably equal to 1.

According to a preferred embodiment, the amine is chosen from the group consisting of butylamine, hexylamine, 2-ethylhexylamine, dodecylamine, octadecylamine, isobutylamine, 2-methylbutylamine, tert-octylamine, isoannylannine, 1,3-dimethylbutylamine, tert-amylamine, 3,3-dimethylbutylannine, 3-isopropoxypropylamine, 4-aminobutyraldehyde diethyl acetal and 2,2- (ethylenedioxy) bis (ethylamine). Advantageously, the amine is chosen from the group consisting of 2-ethylhexylamine, octadecylamine, isoamylamine, 3-isopropoxypropylamine and 3,3-dimethylbutylamine.

According to a particular embodiment, the organogelling compound is chosen from amine and saturated fatty acid salts having from 14 to 24 carbon atoms, substituted with a hydroxyl group.

According to a particular preferred embodiment, the organogelling compound is chosen from amine salts and 12-hydroxystearic acid.

According to a particular embodiment, the organogelling compound has a molar mass less than or equal to 2000 g. mol ^"1 .

According to another particular embodiment, the composition comprises between 0.001% and 5% by weight of the organogelling compound, preferably 0.001% and 1% by mass, more preferably between 0.05 and 0.8% by weight, more preferably between 0, 1 and 0.8% by weight.

Advantageously, the gelled composition has a rheofluidifying behavior under the effect of a mechanical stress of between 100 and 1000 s ^"1 , preferably between 300 and 1000 s ^{" 1} , more preferably between 500 and 1000 s ^"1 .

The Applicant has furthermore found that these novel gelled fuel or liquid hydrocarbon fuel compositions have excellent cold-holding properties.

At reduced temperature, liquid hydrocarbon fuels or fuels, in particular those based on distillates-type containing paraffin waxes, such as for example diesel fuels and fuel oils for heating 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. It is the same for domestic fuel oils (stored outside buildings (houses, buildings ...) .This suitability of the cold operability of middle distillate type fuels is important, especially when starting cold engines If the paraffins are crystallized at the bottom of the tank, they can be driven to start in the fuel system and particularly clog the filters and prefilters arranged upstream of the injection systems (pump and injectors). Paraffins precipitate at the bottom of the tank and can be entrained and clog up the pipes upstream of the pump and the boiler supply system (jet and filter) .It is obvious that the presence of solids, such as crystals paraffins, prevents the normal circulation of the middle distillate.

To overcome this problem, it is conventional to add in fuels or liquid hydrocarbon fuels, additives that can improve the cold resistance. There are three types of additives:

the so-called cold flow improvers ("cold flow improvers" or "CFI") for improving the filterability limit temperature (TLF) and the pour point (PE). These additives inhibit crystal growth by promoting the dispersion of paraffin crystals,

additives known as "cloud point depressant", which slow down the formation of paraffin crystals,

anti-settling additives called WASA (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-gas oils and fuel oils, preferably domestic fuel oils (called FOD, acronym for the term "Domestic fuel oil"). Bio-diesel fuels are Bx type fuels for diesel engines (compression engines) which contain x% (v / v) of vegetable or animal oil esters (including used cooking oils) converted by a chemical process. called transesterification reacting this oil with an alcohol to obtain fatty acid esters (EAG). With methanol and ethanol, fatty acid methyl esters (EMAG) and fatty acid ethyl esters (EEAG) are obtained respectively.

The letter "B" followed by a number indicates the percentage of EAG contained in the diesel fuel. Thus, a B99 contains 99% of EAG and 1% of middle distillates of fossil origin, the B20, 20% of EAG and 80% of middle distillates of fossil origin etc.

Thus, B0 type gasoil fuels which do not contain oxygenated compounds can be distinguished from Bx type biodiesel fuels which contain x% (v / v) of vegetable oil or fatty acid esters, most often esters. methyl esters (EMHV or EMAG). When the EAG is used alone in the engines, the term fuel is designated by the term B100.

According to a particular embodiment, the organogelling compound forms 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 liquid hydrocarbon fuel or fuel, determined according to ASTM D7689.

According to a particular preferred embodiment, the temperature Tsol / gel of the gelled composition of fuel or liquid 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 ASTM D7689. A second subject of the present invention relates to a method for preparing a gelled composition of fuel and liquid hydrocarbon fuel, characterized in that it comprises:

the formation of said composition by solubilization at a temperature of between 20 ° C. and 100 ° C. of an organogelling compound in at least 70% by mass a liquid hydrocarbon fuel or fuel, optionally followed by - cooling to room temperature,

said organogelling compound forming with the fuel or liquid hydrocarbon fuel, a rheofluidifying physical gel.

A third object of the present invention relates to the use of an organogelling compound as an additive for improving the cold-holding properties of a liquid hydrocarbon fuel or fuel, said organogelling compound forming with the fuel or liquid hydrocarbon fuel, a physical gel. rheofluidifier, preferably having a rheofluidifying behavior under the effect of a mechanical stress of between 100 and 1000 s ^-1 , advantageously between 300 and 1000 s ^-1 , more preferably between 500 and 1000 s ^-1 , said organogelling compound being chosen from amine and saturated fatty acid salts having from 14 to 24 carbon atoms, substituted by at least one hydroxyl group.

According to a preferred embodiment, the gel is a thixotropic rheofluidifying physical gel.

According to another preferred embodiment, the liquid hydrocarbon fuel or fuel is selected from gas oils, bio-gas oils and fuel oils, preferably domestic fuel oils (FOD).

According to another preferred embodiment, the liquid hydrocarbon fuel or fuel further comprises at least one cold-cooling additive (CFI) improving the cold-resistance.

According to a particular embodiment, the subject of the present invention relates to the use of the organogelling compound as an anti-sedimentation additive, for improving the paraffin dispersion of the fuel or liquid hydrocarbon fuel.

A fourth object of the present invention relates to a method of supplying an internal combustion engine comprising feeding said engine with a gelled composition of fuel or liquid hydrocarbon fuel such as previously described.

DETAILED DESCRIPTION

Other advantages and features will emerge more clearly from the following description. The particular embodiments of the invention are given by way of non-limiting examples. According to a particular embodiment, a gelled composition of fuel or liquid hydrocarbon fuel comprises at least 70%, advantageously at least 85%, preferably at least 90%, more preferably at least 95%, even more preferably at least 98% of the product. 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 (by atmospheric residue desulphurisation) and / or visbreduction type conversion processes, the distillates resulting from the recovery of Fischer Tropsch cuts, the distillates resulting from the BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination and / or esters of vegetable and animal oils or mixtures thereof.

The liquid hydrocarbon fuels or fuels may also contain distillates resulting from more complex refining operations than those resulting from the direct distillation of hydrocarbons which may for example come 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: the heaviest cuts resulting from cracking and visbreaking processes concentrated in heavy paraffins, comprising more than 18 carbon atoms,

synthetic distillates resulting from gas transformation, such as those derived from the Fischer Tropsch process,

synthetic distillates resulting from the treatment of biomass of plant and / or animal origin, such as NexBTL,

and oils and / or esters of vegetable and / or animal oils,

- or biodiesels of animal and / or vegetable origin.

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 between 14 and 30 carbon atoms. In general, the sulfur content of liquid hydrocarbon fuels or fuels is less than 5000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm and advantageously without sulfur. According to one particular development, the fuel or liquid hydrocarbon fuel may be chosen from fuel oils or fuels, such as fuels gasolines, diesel fuels, bio-diesel fuels, domestic fuel oils (called FOD which is the acronym for the term "domestic fuel oil" ), kerosene, aviation fuel oil and heavy fuel oil.

The term "biodiesel" means fuels of the Bx type for a diesel engine (compression engine) as defined above.

According to a particular preferred embodiment, the liquid hydrocarbon fuel or fuel is chosen from gas oils, bio-diesel and fuel oils, preferably domestic fuel oils.

The organogelling compound is chosen from organogelling compounds capable of forming, with the fuel or liquid hydrocarbon fuel, a physical gel shear thinning.

By physical gel is meant a gel obtained by reversible formation of a three-dimensional network, by self-assembly of the organogelling compounds via weak interactions of the hydrogen bond, ionic bond, π-π 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.

Thus, the fuel composition or liquid hydrocarbon fuel containing such an organogelling compound is viscoelastic with a viscosity which decreases when a mechanical stress applied to said composition increases. The mechanical stress is, for example, a shear stress. The viscosity is conventionally measured according to any known method.

The gelled composition of fuel or liquid hydrocarbon fuel preferably has a rheofluidifying behavior under the effect of a mechanical stress of between 100 and 1000 s ^-1 , advantageously between 300 and 1000 s ^-1 , more preferentially between 500 and 1000 s ^"1 .

The gelled composition of fuel or liquid hydrocarbon fuel may have a flow-rate rheofluidifying behavior, that is to say that the gelled composition of fuel or liquid hydrocarbon fuel is stable until it is applied to it a certain mechanical stress 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 liquid 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 domain or quasi-Newtonian shear thinning and the area of said composition. Below this threshold value, the fuel composition or liquid hydrocarbon fuel is in viscosified form, preferably gelled. For a stress greater than or equal to this threshold value, the viscosity of said composition decreases sharply. If at a temperature of 20 ° C, the fuel composition or liquid 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 liquid hydrocarbon fuel has a critical shear threshold _{c c} determined by rheometric measurement, less than 1000 s ^-1 at a temperature of 20 ° C and at atmospheric pressure, preferably less than 500 s ^-1 .

The organogelling compound will preferably be chosen so as to impart a thixotropic character to the gelled composition of liquid hydrocarbon fuel or fuel. Thus, after disappearance of the shear stress, a physical gel will form again.

The viscosity recovery rate of the gelled composition of liquid hydrocarbon fuel or fuel is advantageously less than 1 hour, preferably less than 10 min, more preferably less than 1 min. In particular, 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 liquid hydrocarbon fuel, a gel having a shear-thinning behavior during application:

a shear stress of between 100 and 1000 s ^-1 , preferably between 300 and 1000 s ^-1 , more preferably between 500 and 1000 s ^-1 , in a temperature range of less than or equal to 60 ° C, preferably less than or equal to 30 ° C, more preferably less than or equal to 15 ° C, still more preferably less than or equal to 5 ° C and,

under a pressure of between 1.11 and 1.11 bar.

According to a particular embodiment, 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 less than or equal to 30 ° C, more preferably less than or equal to 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 less than or equal to 30 ° C., more preferably less than or equal to 15 ° C, more preferably less than or equal to 5 ° C, at a pressure of between 1.11 and 1.11 bar. Stable at a temperature is understood to mean that the liquid hydrocarbon fuel or fuel is in the form of a single gel phase. Above this temperature, the liquid 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, GC 2007, Journal of Physical Sciences, Vol. 1, pp. 156-171; Acc. Chem. Res., George M., Weiss RG, 2006, 39, 489; Chem. Rev., Steed JW, Piepenbrock, MO. Lloyd GO, Clarke N., 2010, 1 10, 1960. Thus, for example, a gelled fuel composition according to the invention, stored in a tank of a vehicle, will be in gelled form. When pumping the gelled fuel composition into the feed circuit of the reservoir, said composition undergoes an approximate shear rate gradient conventionally between 650 and 1000 s ^-1 . The viscosity of the composition drops. when pumping to a value compatible with the operation of the engine. The portion of the gelled composition of fuel not consumed by the engine and recirculated is transformed again into a physical gel in the tank in the absence of shear stresses.

Suitable organogelling compounds must be at least partly 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. By 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.

In particular, the gelled composition of fuel and liquid hydrocarbon fuel is prepared according to a process which comprises:

the formation of said composition 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%, advantageously at least 85%, preferably at least 90% %, more preferably at least 95%, even more preferably at least 98% of a liquid hydrocarbon fuel or fuel as described above, optionally followed by

cooling below the freezing temperature, preferably up to room temperature. The term "freezing temperature" means the temperature below which the material no longer flows over a long period of time. The gelled composition of fuel or liquid hydrocarbon fuel may form a more or less pasty gel.

In particular, the low molecular weight organogelling compounds known by the acronym LMOG (Low Molecular Weight Organic) will be chosen. Gelators), preferably having a molar mass less than or equal to 2000 g. mol ^"1 .

These 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 or liquid hydrocarbon fuel comprises between 0.001% and 5% by weight of the organogelling compound, preferably between 0.001% and 1% by weight, even more preferably between 0.05 and 0.8% by weight, more preferably between 0 and , 1 and 0.8% by weight.

The organogelling compound is chosen from amine and saturated fatty acid salts having from 14 to 24 carbon atoms, substituted with at least one hydroxyl group. The term "amine salt and saturated fatty acid" means a salt of the product of the reaction between an amine and a saturated fatty acid according to any known method.

In order for the organogelling compound to be soluble in the liquid hydrocarbon fuel or fuel, it may advantageously comprise a substituent compatibilizing the organogelling compound with the liquid hydrocarbon fuel or fuel. This substituent may be of an aromatic nature and / or of an aliphatic apolar nature.

According to one particular embodiment, the organogelling compound is chosen from the amine and saturated fatty acid salts obtained from amines represented by the following formula (I): R-NH ₂ , in which the group R is a saturated C ₁ -C ₂ ₄ , preferably C ₄ -C 18, linear or branched hydrocarbon-based chain, said chain optionally containing one or more oxygen atoms. Advantageously, the group R comprises at least one of the following units:

• - (CH ₂ ) _n - where n is an integer greater than or equal to 2, preferably greater than or equal to 1 1,

• -CH- (CH ₃ ) ₂ ,

· -O- (CH ₃ ) _2, and

Preferably, the amine is selected from the group consisting of butylamine, hexylamine, 2-ethylhexylamine, dodecylamine, octadecylamine, isobutylamine, 2-methylbutylamine, tert-octylamine, isoamylamine, 1,3-dimethylbutylamine, tert-amylamine, 3,3-dimethylbutylamine, 3-isopropoxypropylamine, 4-aminobutyraldehyde diethyl acetal and 2,2- (ethylenedioxy) bis (ethylamine).

Advantageously, the amine is chosen from the group consisting of 2-ethylhexylamine, octadecylamine, isoamylamine, 3-isopropoxypropylamine and 3,3-dimethylbutylamine. According to a particular embodiment, the organogelling compound is chosen from amine and saturated fatty acid salts having from 14 to 24 carbon atoms, substituted with a hydroxyl group.

Advantageously, the organogelling compound is chosen from amine salts and 12-hydroxystearic acid.

According to a particular preferred embodiment, the organogelling compound has a molar mass less than or equal to 2000 g. mol ^"1. In a particular development of the invention, the organogelator compound as described above can advantageously be used as additive for improving the cold-fuel resistance properties or liquid hydrocarbon fuel as described above. The applicant has discovered that this use is particularly advantageous when the fuel or liquid hydrocarbon fuel is selected from gas oils, bio-diesel and fuel oils, preferably domestic fuel oils (FOD). Indeed, the Applicant has discovered that the gelled compositions of fuel or liquid hydrocarbon fuel according to the invention have excellent cold resistance, especially in combination with a flow improving additive known as cold flow fluidizers (in English "cold"). flow improvers "or CFI), preferably a CFI additive improving the TLF, also called TLF additive.

According to a particular preferred embodiment, the gelled composition of fuel or liquid hydrocarbon fuel further comprises at least one CFI additive improving the cold behavior. The organogelling compound as described above may, advantageously, be used in combination with a CFI additive, to improve the cold resistance of the liquid hydrocarbon fuel or 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. By way of example, mention may be made of 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 liquid hydrocarbon fuel composition comprises from 100 to 1000 ppm of the CFI additive described above, preferably from 100 to 500 ppm.

In particular, the use of such organogelling compounds is particularly advantageous when 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 gel. determined according to ASTM D7689. The temperature Tsol / gel of the gelled composition of fuel or liquid 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 liquid hydrocarbon fuel, determined according to ASTM D7689.

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 cold-holding properties of the liquid hydrocarbon fuel or fuel and / or as an anti-sedimentation 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. liquid hydrocarbon, determined according to ASTM D7689.

The so-called sol-gel transition is the change of state of a system from a single phase, the solution (sol), 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. O., Clarke N., 2010, 10, 1960.

The temperature T g / sol of the gelled fuel composition or liquid hydrocarbon fuel determined by rheometric measurement in dynamic oscillation is preferably greater than the cloud point temperature (PTR) of said composition, determined according to ASTM D7689.

In addition to the organogelling compound described above, the liquid hydrocarbon fuel or fuel compositions may also contain one or more other different additives of the organogelling compound according to the invention, chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, deodorants, pro-cetane additives, friction modifiers, lubricant additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot), cloud point improvers, pour point, filterability limit temperature, anti-slip agents, -sedimentation, the anti-wear agents and / or the agents modifying the conductivity.

Among these additives, mention may be made particularly of:

a) 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 tert-butyl peroxide;

b) 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;

c) 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.

d) lubricity additives or anti-wear agents, 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 monocarboxylic acid derivatives and

polycyclic. Examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784. e) cloud point additives, including (but not limited to) selected from the group consisting of long chain olefin / ester terpolymers

(meth) acrylic / maleimide, and fumaric / maleic acid ester polymers. Examples of such additives are given in FR2528051, FR2528051, FR2528423, EP1 12195, EP172758, EP271385, EP291367;

f) anti-sedimentation additives and / or paraffin dispersants in particular (but not limited to) selected from the group consisting of (meth) acrylic acid / polyamine amidated alkyl (meth) acrylate copolymers, polyamine alkenyl succinimides, phthalamic acid and double chain fatty amine derivatives ; alkylphenol resins. Examples of such additives are given in EP261959, EP593331, EP674689, EP327423, EP512889, EP832172; US2005 / 0223631; US5998530; WO93 / 14178.

g) polyfunctional cold operability additives selected from the group consisting of olefin and alkenyl nitrate polymers as described in EP573490.

These other additives are generally added in an amount ranging from 100 to 1000 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 composition of fuel or liquid hydrocarbon fuel 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 liquid hydrocarbon fuel according to any known method. The gelled fuel composition or liquid hydrocarbon fuel according to the invention is remarkable in that it improves the cold resistance without affecting the proper functioning of the fuel in the internal combustion engine.

Example:

The anti-sedimentation properties of organogel compounds according to the invention are evaluated by incorporating them into a distillate of the diesel fuel type referenced GOM 1, the characteristics of which are listed in Table 1 below:

Table 1: Fuel Characteristics

GOM GOM 1 (B ₇ )

Total paraffins (% by weight) 19.7

TLF (° C) NF EN 1 16 -8

PTE (° C) NF-T60-105 -15

PTR (° C) ASTM D7689 -8

MV15 (kg / m ³⁾ EN IS012185 835.6

Sulfur content (mg / kg) 10

Mono Aromatic (% mass) NF EN

4.0

12916

Di aromatics (% by mass) NF EN 12916 0

Aromatic tripping (% by mass) NF EN 12916 0

Total aromatics (% mass) NF EN

13.7

12916

Poly Aromatics (% by weight) NF EN 12916 0

Distillation ASTM D86 (° C)

0% 166

5% 186

10% 193

20% 210

30% 228

40% 246

50% 263

60% 280

70% 297

80% 316

90% 336

95% 351

100% 364

EMHV content (% vol) 7 Example: Use of 2-ethylhexylammonium 12-hydroxystearate (HSA-2EHA) as organogelling compound of a gas oil GOM 1 · Preparation of fuel compositions C 1, C 2 and C 3

Each composition C 1, C 2 and C 5 is carried out by solubilising, respectively, 750, 1000 and 5000 ppm of HSA-2EHA at a temperature of 80 ° C. with GOM1 gasoline of type B7 (see Table 1), additivated with 300 ppm by mass. a TLF additive which is an ethylene-vinyl acetate (EVA of English Ethylene-vinyl acetate) in solution at 70% by weight in an aromatic solvent (Solvesso 150) with magnetic stirring until obtaining a homogeneous solution.

• Rheological properties of the fuel compositions Ci, C2 and C3

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.

- Dynamic oscillations test

A dynamic oscillation test of the fuel compositions C 1, C 2 and C 3 in which a small strain set at 10% is applied to said compositions at a frequency of 1 Hz between 0 and 60 ° C. is carried out.

For each fuel composition, the evolution of the elastic modulus G 'and the viscous modulus G "of said composition is monitored as a function of the temperature variation according to a known method described in particular in the cited PCT / EP2013 / 077610 patent application. by way of example and / or incorporated by reference in the present application The temperature sweep is carried out between 0 and 40 ° C, with a speed of 2 ° C / min starting with the cooling ramp followed by the ramp of heater. The dynamic oscillation test makes it possible to determine the solid or liquid nature of a material. Indeed, the solid-type materials (gel), whose elastic nature is predominant, have a ratio G'VG 'less than 1 (G' being greater than G ") whereas the liquid-type materials (solution) have a ratio G'VG 'greater than 1 (G' being less than G "). When a material changes its behavior according to the temperature, one can observe the transition temperature sol / gel (Tsol / gel) when G '= G "The temperature Tsol / gel of the fuel compositions Ci, C2 and C3 corresponds to the point of intersection of curves G 'and G "during cooling. When the curves G 'and G "do not intersect and the module G" remains greater than the module G', no gel is formed.

The results are listed in Table 2 below: Table 2

* no formation of gelled fuel composition

In the temperature range explored, at a content of 1000 ppm HSA-2EHA, the fuel composition does not form a gel, whereas for a content of 5000 ppm HSA-2EHA, the fuel composition forms a gel. Gelled fuel compositions are obtained solely for the C3 fuel composition. The amount of organogelling compound must be sufficient to allow the formation of a three-dimensional network responsible for structuring the gel fuel composition. Comparison of the dynamic viscosities of the compositions Ci, C? and C3 Table 3

* VD40 = dynamic viscosity at 40 ° C - fluaqe / recouyrance test

At a temperature of 10 ° C., a shear rate of 1000 s ^-1 for 50 s is applied, this speed must be sufficiently high to ensure that the gelled fuel composition C 3 is destructured at a given temperature. dynamic viscosity recovery at a low shear rate of 0.1 sec ^-1 . The evolution of the viscosity of the composition Cs as a function of time is followed according to a known method described in particular in the patent application PCT / EP2013 / 077610 cited by way of example and / or incorporated by reference in the present application.

The viscosity recovery is almost immediate after decreasing the shear rate. The C3 fuel composition regains its initial dynamic viscosity almost instantaneously. These results make it possible to demonstrate the thixotropic character of the C3 fuel composition.

• Cold-holding properties of the fuel compositions Ci, C2 and C3

Anti-sedimentation test (ARAL)

The anti-settling properties of the fuel compositions C 1, C 2 and C 3 are evaluated by the following ARAL sedimentation test: 250 ml of fuel compositions C 1, C 2 and C 3 are cooled in 250 ml test pieces in a climatic chamber with 13 ° C according to the following temperature cycle: change from + 10 ° C to -13 ° C in 4h then isothermal at -13 ° C for 16h. At the end of the test, a visual score of the appearance of the sample and sedimented phase volume is performed, then 20% of the lower volume is taken, for characterization. PTR cloud point (ASTM D7689). 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 anti-sedimentation effect. Generally, an anti-sedimentation effect is valid when the absolute value of the PTR deviation before and after sedimentation (| Δ |) is less than 3 ° C.

The results are summarized in Table 4 below.

Table 4

* VD40 = dynamic viscosity at 40 ° C

The anti-sedimentation effect is observed only for the gelled fuel composition C3 (| Δ | <3 ° C). This C3 composition is gelled at temperatures below the Tsol / gel temperature. At a temperature below the Tsol / gel temperature (30.5 ° C.), the organogelling compound HSA-2EHA forms a three-dimensional network within said composition. Without being bound by the following theory, when a three-dimensional network is formed, the paraffin crystals are trapped in the network thus formed, which has the effect of preventing sedimentation or at least delaying the deposition of the crystals. of paraffin. Thus, at a content of 5000 ppm of HSA-2EHA, the content of organogelling compound is sufficient to form a gel and an anti-sedimentation effect is observed, with a difference of less than 3 ° C.

On the other hand, if 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 in this example. It is found that in this example, the antisedimentation effect is observed only when the Tsol / gel temperature of the fuel composition is greater than or equal to the temperature of the cloud point (PTR). If the temperature Tsol / gel of the fuel composition is lower than the cloud point (PTR), then the first paraffin crystals sediment even before the formation of the three-dimensional network of the organogelling compound HSA-2EHA which then becomes ineffective. For the fuel compositions C ₁ , C ₂ and C ₃ _, the first paraffin crystals are formed at -7 ° C, -8 ° C and -8 ° C, respectively. Only the fuel composition C3 has a Tsol / gel temperature higher than the PTR (-8 ° C.). For the composition C ₂ , the sedimented phase volume is greater than that of the composition Ci. Although there is no gel formation, the crystals remain in suspension and thus form a large volume of sedimented phase. It is therefore likely that we are at a concentration of organogelling compound close to that required to obtain a gel. Thus, 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 according to the invention as an antisedimentation additive allows 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.

Claims

Gelled composition of fuel or liquid hydrocarbon fuel comprising at least 70% by weight of a liquid hydrocarbon fuel or fuel and at least one organogelling compound forming, with the fuel or liquid hydrocarbon fuel, a rheofluidifying physical gel, said organogelling compound being chosen from the salts of amine and saturated fatty acids having from 14 to 24 carbon atoms, substituted by at least one hydroxyl group.

Composition according to Claim 1, characterized in that the gel is a rheofluidifying and thixotropic physical gel.

Composition according to one of Claims 1 and 2, characterized in that the amine and saturated fatty acid salts are obtained from amines represented by the following formula (I): R-NH ₂ , in which the group R is a saturated C 1 to C 2 ₄ , preferably C ₄ to C 18, linear or branched hydrocarbon chain, said chain optionally containing one or more oxygen atoms.

Composition according to Claim 3, characterized in that the group R comprises at least one of the following units:

• -CH- (CH ₃ ) ₂ ,

• -O- (CH ₃ ) ₂ , and

Composition according to any one of Claims 1 to 4, characterized in that the amine is chosen from the group consisting of butylamine, hexylamine, 2-ethylhexylamine, dodecylamine, octadecylamine, isobutylamine, 2- methylbutylamine, tert-octylamine, isoamylamine, 1,3-dimethylbutylamine, tert-amylamine, 3,3-dimethylbutylamine, 3-isopropoxypropylamine, 4- aminobutyraldehyde diethyl acetal and 2,2- (ethylenedioxy) bis (ethylannine).

6. Composition according to claim 5, characterized in that the amine is selected from the group consisting of 2-ethylhexylamine, octadecylamine, isoamylamine, 3-isopropoxypropylamine, 3,3-dimethylbutylamine.

7. Composition according to any one of claims 1 to 6, characterized in that the organogelling compound is selected from amine salts and saturated fatty acids having from 14 to 24 carbon atoms, substituted by a hydroxyl group.

8. Composition according to Claim 7, characterized in that the organogelling compound is chosen from amine salts and 12-hydroxystearic acid.

9. Composition according to any one of Claims 1 to 8, characterized in that the organogelling compound has a molar mass of less than or equal to 2000 g ^/ mol. 10. Composition according to any one of Claims 1 to 9, characterized in that it comprises between 0.001% and 5% by weight of the organogelling compound, preferably between 0.001% and 1% by mass, more preferably between 0.05 and 0.8% by weight, more preferably between 0.1 and 0.8% by mass.

11. Composition according to any one of claims 1 to 10, characterized in that the composition has a rheofluidifying behavior under the effect of a mechanical stress of between 100 and 1000 s ^"1 , preferably between 300 and 1000 s ^{" 1} , more preferably between 500 and 1000 s ^-1 .

12. Composition according to any one of claims 1 to 1 1, characterized in that the fuel or liquid hydrocarbon fuel is selected from gas oils, bio-diesel and fuel oils, preferably domestic fuel oils (FOD).

13. Composition according to claim 12, characterized in that the organogelling compound forms 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 fuel composition or liquid hydrocarbon fuel, determined according to ASTM D7689.

14. Composition according to one of claims 12 and 13, characterized in that the Tsol / gel temperature of the gelled composition of fuel or liquid 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 ASTM D7689.

15. Process for the preparation of a gelled composition of fuel and liquid hydrocarbon fuel according to any one of claims 1 to 14, characterized in that it comprises:

the formation of said composition by solubilization at a temperature of between 20 ° C. and 100 ° 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,

said organogelling compound forming with the fuel or liquid hydrocarbon fuel, a rheofluidifying physical gel. 16. Use of an organogelling compound as an additive to improve the cold-holding properties of a liquid hydrocarbon fuel or fuel, said organogelling compound forming with the fuel or liquid hydrocarbon fuel, a rheofluidifying physical gel, said organogelling compound being chosen from saturated fatty acid amine salts having from 14 to 24 carbon atoms, substituted with at least one hydroxyl group.

17. Use according to claim 16, characterized in that the gel is a thixotropic rheofluidifying physical gel.

18. Use according to one of claims 16 and 17, characterized in that the fuel or liquid hydrocarbon fuel is selected from gas oils, bio-gas oils and fuel oils, preferably domestic fuel oils (FOD).

19. Use according to any one of claims 16 to 18, characterized in that the fuel or liquid hydrocarbon fuel further comprises at least one cold-cooling additive (CFI) improving the cold behavior. 20. Use according to any one of claims 16 to 19, as anti-sedimentation additive to improve the paraffin dispersion of the fuel or liquid hydrocarbon fuel.

21. A method of supplying an internal combustion engine comprising supplying said engine with a gelled composition of fuel or liquid hydrocarbon fuel according to any one of claims 1 to 14.