EP1910503B1 - Use of a lubricant composition for hydrocarbon mixtures and products thus obtained - Google Patents

Description

The present invention relates to the use of a hydrocarbon mixture composition especially with a low sulfur content, intended to improve their lubricity, but also concomitantly to limit their corrosive nature with respect to the metallic parts with which they are brought into contact with each other. increase their antistatic character by increasing their conductivity. Such a composition is applicable to any hydrocarbon mixture, in whole or in part synthetic, capable of providing the energy required for the movement of land or flying vehicles, more particularly diesel fuel, kerosene or gasoline for internal combustion engines. these hydrocarbons having a low sulfur content of less than 500 ppm, less than 50 ppm and even less than 10 ppm.

Whatever hydrocarbon mixture can be used as a source of energy to move these vehicles, it is well known that it must have lubrication skills for the protection of pumps, injection systems and all moving parts. with which these mixtures can come into contact. As regulations in many countries have required limiting the upper acceptable sulfur content in fuels to less than 0.05% by weight and then less than 50 ppm and even less than 10 ppm to reduce pollutant emissions from cars, trucks or buses, particularly in urban agglomerations, the refining industry has been led to improve its processes for the treatment of the removal of sulfur compounds. Fuels have become more and more pure products and non-polluting, sulfur-free and aromatic and polar compounds often associated. However, all these compounds ensured the lubricating power of fuels. Other negative effects have appeared concomitantly with the loss of lubricity, such as the increase in static electricity problems, especially during all oil handling operations, but also storage. It has therefore become necessary to replace these compounds imparting a lubricating character to the distilled or non-distilled hydrocarbons by other compounds which are not polluting with respect to the environment but which have sufficient lubricating power to avoid the risks of wear in the engines, but also to overcome the parasitic effects of static electricity and corrosion inherent to gas oils.

The prior art is extensively supplied with solutions for improving the lubricity and / or corrosion or lubricity and / or the antistatic effect of the additives, but no document has sought to regulate as a whole the problems of lubricity while limiting the corrosion and conductivity of the hydrocarbons used in the engines while maintaining and even decreasing the added additive contents for an equal efficiency.

To improve the lubricity of a fuel, be it gasoline, kerosene or diesel, several types of additives have already been proposed. Thus, it is first of all the anti-wear additives, known for certain in the field of lubricants, of the type of fatty acid esters and dimer fatty acids, unsaturated, aliphatic amines, fatty acid esters. and diethanolamine and long-chain aliphatic monocarboxylic acids as described in US Pat. US 2,252,889 , US 4,185,594 , US 4,204,481 , US 4,208,190 , US 4,428,182 . The most of these additives, has sufficient lubricity but at concentrations far too high which is very unfavorable economically. In addition, the additives containing dimer acids can not be used at high concentrations in fuels supplied to vehicles in which the fuel may be in contact with the lubricating oil, because these acids form, by chemical reaction, sometimes deposits. insoluble in the oil, but especially incompatible with the detergent additives, usually used.

The patent US 4,609,376 the use of anti-wear additives obtained from mono- and polycarboxylic acid esters and polyhydric alcohols in fuels containing alcohols in their composition is advocated.

Another chosen route is to introduce vegetable oil esters or vegetable oils themselves into these fuels to improve their lubricity or lubricity. Among these are the esters derived from rapeseed, flax, soya, sunflower oils or the oils themselves (see patents EP 635.558 and EP 605.857 ). One of the major disadvantages of these esters is their low lubricating power at a concentration of less than 0.5% by weight in fuels.

To solve these problems, the Applicant has proposed introducing into fuels with a low sulfur content, less than 500 ppm, the compositions obtained by mixing fatty monocarboxylic acids and polyaromatic monocarboxylic acids, preferably of plant origin, under acid form, ester or amine salts ( EP 915944 , EP.1310547 and EP 1340801 ).

Currently, manufacturers are seeking to improve lubricity and conductivity or lubricity and the corrosion, by the use of a selection of mixtures that can be introduced into hydrocarbons at reasonable rates and with the same or better efficiency than the products used alone previously but sometimes at much higher concentrations.

Thus, to improve lubricity and reduce the risk of static build-up during the manufacture, handling and use of low sulfur hydrocarbons, below 500 ppm, demand WO 01/88064 claims a fuel composition comprising a liquid fuel of less than 500 ppm sulfur, 0.001 to 1 ppm of at least one monoamine or a substituted N-polyamine and 10 to 500 ppm of at least one fatty acid containing from 8 to 24 carbon atoms or its ester equivalent with an alcohol or polyhydric alcohol of not more than eight carbon atoms.

To improve lubricity, the demand WO 97/45507 proposes to introduce into the hydrocarbons, compounds derived from esterified alkenyl anhydrides, in proportions ranging from 5 to 5000 ppm. Applicants have found that by adding some of these compounds, the anti-corrosive properties of these fuels have been greatly improved.

The document US 4,448,586 discloses a liquid fuel having anti-corrosion properties comprising a major amount of monohydroxylated alkanol having 1 to 5 carbon atoms and a corrosion inhibiting amount of a mixture of an alkyl or alkenyl succinic acid or ester and of at least one polymerized unsaturated aliphatic monocarboxylic acid having from 16 to 18 carbon atoms.

The document US 4,032,303 discloses a fuel composition having a decreased tendency to deposit formation comprising a liquid fuel, a carboxylic acid ester and a liposoluble ester-type dispersant derived from a polyalcohol characterized by a hydrocarbon chain having at least 30 carbon atoms.

The document us 2004/0118033 discloses a fuel composition having improved antistatic properties and comprising a liquid fuel, a hydrocarbon monoamine or a poly (alkyleneamine) substituted with hydrocarbon compounds and at least one fatty acid comprising from 8 to 24 carbon atoms or one of its ester derivatives.

The document WO 02/02720 discloses a process for increasing the lubricity of a liquid hydrocarbon fuel having the addition of one or more component (s) derived from succinic anhydride.

Notwithstanding these improvements, it is an object of the present invention to simultaneously improve the lubricity and antistatic and anticorrosive properties of hydrocarbon mixtures with low sulfur content, while limiting their amount to equal effectiveness. It is particularly aimed at improving the characteristics of fuels, gasoline, diesel and kerosene, with low sulfur content, in the form of an emulsion in water or not, and even certain lubricants.

1. a) de 40 à 70% en poids d'au moins un composé A de formule (I) ci-après :
   
   dans laquelle R₁ est un groupement alkényle de 1 à 22 atomes de carbone et R₂ est l'hydrogène ou inversement
   et dans laquelle R₃ et R₄, identiques ou différents, sont choisis parmi les groupements OH, R₃ et R₄ ne pouvant être le groupement OH simultanément, ou dérivant d'un groupe monol ou polyol linéaire ou ramifié contenant de 1 à 20 atomes de carbone ayant une fonctionnalité de 2 à 5 inclus ;
2. b) et de 60 à 30% d'au moins un composé B correspondant à un acide gras de 16 à 24 atomes de carbone, insaturé ou non, éventuellement en mélange avec un acide carboxylique comprenant au moins un cycle ou un polycycle aromatique et/ou oléfinique, et/ou leurs dérivés esters, amides ou sel d'amine correspondant, pris seuls ou en mélange.

The present invention relates to the use of at least 50 ppm of a lubricating, anti-corrosive and antistatic hydrocarbon mixture composition comprising:

1. a) from 40 to 70% by weight of at least one compound A of formula (I) below:
   
   in which R ₁ is an alkenyl group of 1 to 22 carbon atoms and R ₂ is hydrogen or vice versa
   and in which R ₃ and R ₄ , which are identical or different, are chosen from the OH, R ₃ and R _{4 groups} which can not be the OH group simultaneously, or which are derived from a linear or branched monol or polyol group containing from 1 to 20 carbon atoms having a functionality of 2 to 5 inclusive;
2. b) and from 60 to 30% of at least one compound B corresponding to a fatty acid of 16 to 24 carbon atoms, unsaturated or unsaturated, optionally mixed with a carboxylic acid comprising at least one aromatic ring or cycle and / or olefinic, and / or their ester derivatives, amides or corresponding amine salt, taken alone or in admixture.

Notwithstanding the effects inherent to the compounds A or B, it has been observed that the combination of these compounds improves unexpectedly the lubricity of the hydrocarbon mixtures which contained them but also increased their conductivity while decreasing their corrosivity with respect to the metallic parts with which these mixtures could be brought into contact. It has further been found that this composition is compatible with all the hydrocarbon mixtures that can be used as fuel and or lubricant, necessary for the propulsion of land or flying vehicles.

In order to have optimum lubricity, anti-corrosiveness and antistatic effect efficiency in the hydrocarbon mixtures, the additive composition according to the invention will comprise from 40 to 70% by weight of at least a compound A and from 60 to 30% by weight of at least one compound B.

This efficiency can be improved if this composition further comprises at least 0.1% by weight of a compound C selected from C ₅ -C ₃₀ mono and / or polycarboxylic acid esters. The addition of such esters to the concentrations of the invention makes it possible to improve the viscosity of the additive mixture which can thus be better dispersed in the hydrocarbon mixture.

This composition will be all the more effective in terms of antistatic and lubricating efficacy that it will comprise from 30 to 60% by weight of at least one compound A, from 60 to 30% by weight of at least one compound B and from 5 to 20% by weight of at least one compound C.

To achieve this effectiveness, the compounds A, B and C will be described by definition of the radicals R ₁ and R ₂ , and R ₃ and R ₄ more precisely hereinafter.

Thus, the compounds A will be described with respect to the radicals R ₁ and R ₂ on the one hand and R ₃ and R ₄ on the other hand. Any compound with any of these characteristics will be considered as part of the compounds A of the invention.

In the compounds A of formulas (I), R ₁ is an alkenyl group of 1 to 22 carbon atoms, and R ₂ is hydrogen or vice versa.

For each of these possibilities for the radicals R ₁ and R ₂ defined above, the radicals R ₃ and R ₄ of the compound A of formula (I) may also vary.

In a first case, R ₃ and R ₄ , identical or different, are OR _s with R ₅ a group chosen from - [(CH ₂ ) _n -O] _m -H with n varying from 1 to 4 and m varying. from 1 to 5; - [CH ₂ -CHOH] _p -CH ₂ -OH, with p varying from 1 to 3; -CH ₂ -CR ₆ R ₇ -OH, with R ₆ and R ₇ which can each be hydrogen, a methyl radical or a radical -CH ₂ OH.

In a second case, R ₃ is OR ₅ with R ₅ a linear or branched alkyl group of C ₁ to C ₁₀ , optionally substituted by at least one OH group, and R ₄ is OH or vice versa.

In a third case, R ₃ and R ₄ are OR _s groups, identical or different, with R ₅ a linear or branched alkyl group of C ₁ to C ₁₀ , optionally substituted with at least one OH group.

In a fourth case, R ₃ is OH or OR _s group with R ₅ a linear or branched alkyl group of C ₁ -C _10, optionally substituted with at least an OH group, and R ₄ is OR ₅ with R ₅ a - [(CH ₂ ) _n -O] _m -H group with n varying from 1 to 4 and m varying from 1 to 5; - [CH ₂ -CHOH] _p -CH ₂ -OH, with p varying from 1 to 3; -CH ₂ -CR ₆ R ₇ -OH, with R ₆ and R ₇ which can each be hydrogen, a methyl radical or a radical -CH ₂ OH.

Preferably, the OR ₅ groups are the groups -O-CH ₂ -CH ₂ -OH or -O-CH ₂ -CHOH-CH ₂ -OH or -O-CH ₂ -C (CH ₃ ) (CH ₂ OH) -CH ₂ -OH or -O-CH ₂ -C (CH ₂ OH) (CH ₂ OH) -CH ₂ -OH.

Of course, we would not depart from the scope of the invention if mixtures of compounds A, were used.

In parallel, the compound B required for the invention will preferably be chosen as comprising at least one linear saturated or unsaturated carboxylic acid and / or their ester, amide or amine salt derivatives. Among these acids, oleic, linoleic, linolenic, palmitic, stearic and isostearic acids and their ester, amide and amine salt derivatives, alone or as a mixture, are preferred.

More specifically, compound B will comprise mainly a mixture of oleic acid and linoleic acid, and / or their derivatives esters, amides or amine salts. Preferably, compound B will comprise a mixture of linear fatty acids of plant origin, rapeseed, castor oil, sunflower, corn, copra, pine or linseed, and / or their ester, amide or salt derivatives. amines, these products being generally commercial products.

Compound B will preferably consist of a mixture of linear fatty acids derived from the distillation of pine oils and / or their derivatives esters, amides or amine salts, whatever their origins.

In another embodiment of the invention, compound B could comprise resin acids, among abietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, levopimaric acid and parastinal acid, and / or their ester, amide or amine salts.

In the latter case, the compound B consists of a mixture of fatty acids and resin acids corresponding to a heavier distillate of the vegetable oil distillation. Distillates obtained by distillation of pine oil and / or their ester, amide or amine salt derivatives are preferred.

Compound C, when added to the composition, is a vegetable oil ester of the group consisting of rapeseed, castor, sunflower, maize, coconut, pine or flax oils, the ester rapeseed methyl is preferred.

A second subject of the invention is a hydrocarbon mixture with a low sulfur content of less than 50 ppm, consisting mainly of hydrocarbons derived from the distillation of crude oil, a gasoline, a diesel fuel or a kerosene which can be used as fuel for the displacement of fuel. land or flying vehicles, this mixture comprising at least 50 ppm of the composition defined above. The composition is particularly effective for hydrocarbon mixtures with a sulfur content of less than 10 ppm.

A hydrocarbon mixture according to the invention will advantageously comprise between 50 and 350 ppm of said composition.

• une essence comprenant au moins un additif choisi dans le groupe consistant en les additifs anti-cliquetis, anti-gel, détergent, désémulsifiant, anti-oxydant, modificateurs de friction, réducteur de dépôt et leurs mélanges ;
• un carburant diesel comprenant au moins un additif choisi dans le groupe consistant en les additifs de filtrabilité, anti-mousse, détergent, désémulsifiant, procétane et leurs mélanges ;
• un fioul domestique comprenant au moins un additif choisi dans le groupe consistant en les additifs promoteurs de combustion, additifs de tenue à froid, d'écoulement, d'anti-corrosion, antioxydants, biocides, réodorants et leurs mélanges ;
• kérosène comprenant au moins un additif choisi dans le groupe consistant en les additifs anti-statique, anti-oxydant et leurs mélanges

More particularly, the invention relates to hydrocarbon mixtures, in particular comprising from 50 to 350 ppm of the composition according to the invention, which are:

• an essence comprising at least one additive selected from the group consisting of anti-knock, anti-freeze, detergent, demulsifier, anti-oxidant, friction modifier, deposition reducer additives and mixtures thereof;
• a diesel fuel comprising at least one additive selected from the group consisting of filterability, antifoam, detergent, demulsifier, procetane and mixtures thereof;
• a heating oil comprising at least one additive selected from the group consisting of combustion promoter additives, cold-holding additives, flow-control additives, anti-corrosion additives, antioxidants, biocides, deodorants and mixtures thereof;
• kerosene comprising at least one additive selected from the group consisting of anti-static, antioxidant additives and mixtures thereof

The advantages of this composition in a hydrocarbon mixture in its various applications are described in the examples below, these results being given only to illustrate the invention and not to limit it.

EXAMPLE I

The present example describes the preparation of various compounds A according to the invention.

The reaction consists of a mono- or di-esterification of the anhydride function with a polyol or mono alcohol without catalyst according to the reagents used.

Thus, an alkylated diacid compound in acid or anhydride form can be reacted with an alcohol or polyol in a tetracol reactor equipped with an ascending condenser, a thermometer, a dropping funnel and a nitrogen inlet. .

By means of a dropping funnel, and with mechanical stirring, the alcohol or the polyol is dripped onto the previously heated acid or anhydride and maintained at 70.degree.

At the end of the addition, the sample is brought to the reflux temperature of the alcohol. The reactor is maintained at this temperature and under nitrogen flushing for a period of about five hours.

At the end of the reaction, the compound A thus obtained is distilled under vacuum in order to remove the water produced and / or the excess alcohol.

Different compounds A have been prepared. The products obtained by polyol reaction are in the form of diesters. Products obtained by mono reaction alcohol are in the form of half-esters. Compounds A are summarized in Table 1 below. <u> TABLE <b> I </ b></u> product anhydride Alcohol Anhydride / alcohol ratio A ₁ ODSA Ethylene glycol 1: 3 A ₂ ODSA ethanol 1: 2 A ₄ ODSA butanol 1: 2 A ₆ ODSA Step 1: ethanol 1: 2 Step 2: ethylene glycol 1: 2 A ₇ ODSA Ethanol / Diethylene glycol - 50/50 1: 2 1: 3 A ₈ OSA Ethylene glycol 1: 3 ODSA = octadecenyl succinic anhydride
OSA = octenyl succinic anhydride

EXAMPLE II

The present example aims to describe the lubricity performance of the compounds A _i in admixture with a compound B _i according to the invention, then in admixture with a third compound C _i .

All the additive tests were carried out in two types of gas oils GO1 and G02, the characteristics of which are given in Table II below. <u> TABLE II </ u> Characteristics GO1 GO2 MV15 (kg / m3) 818.4 835.4 Sulfur content (mg / kg) 8 6 Visco 40 ° C (mm2 / s) 2.13 2.45 Monoaromatic content 19.5 25.5 Diaromatic content 1.7 2.3 Polyaromatic content 0 0.1 ASTM D86 Initial point ° C 168.2 178.2 Point 5% v 190.2 198.7 Point 10% v 196.8 204 Point 20% v 210.7 216.2 Point 30% v 223.6 228.6 Point 40% v 235.8 241.5 Point 50% v 247 255 Point 60% v 257.6 268.2 Point 70% v 269.1 282.1 80% point 282.7 299.4 Point 90% v 303.1 325.9 Item 95% v 320.4 348.9 Period 335.7 352.5 V.distillé 98.5 mL 96.8 mL Residue 1.4 mL 2.8 mL losses 0.1 mL 0.4 mL

Of the compounds B _i of the invention, B ₁ is a mixture of long chain fatty acids containing 2% of a mixture of resin acids derived from pine oil commonly called Tall oil fatty acid.

The lubricity of the Ai / Bi mixtures was tested in two different gasols, GO ₁ and GO ₂ according to the ISO 12156-1 standard for each concentration in the gas oil of 100, 150 and 200 ppm.

The results showing the effectiveness of the compounds A _i and B ₁ are given in Table III below. <u> TABLE III </ u> Compound or mixture 100 ppm 150 ppm 200 ppm GO1 B1 445 μ m 427 μ m 407 μ m A1 (75% -pda in solvarex 10) 609 μ m 472 μ m 394 μ m B1 / A1 - 80/20 (comparative) 496 μ m 439 μ m 410 μ m B1 / A1 - 60/40 504 μ m 399 μ m 363 μ m B1 / A1 - 50/50 458 μ m 392 μ m 361 μ m B1 / A1 - 45/55 407 μ m 330 μ m 299 μ m B1 / A1 - 40/60 515 μ m 364 μ m 322 μ m B1 / A1 - 35/65 416 μ m 306 μ m 286 μ m B1 / A1 - 30/70 384 μ m 318 μ m 325 μ m GO2 B1 454 μ m 428 4 μ m 426 μ m B1 / A1 - 50/50 336 μ m 36 μ m 249 μ m

Since A1 is solid at room temperature, it is placed in an oven at 60 ° C. before formulation. For proportions greater than 50% of A ₁ , it is necessary to place the mixture for a few minutes in an oven at 60 ° C in order to homogenize it.

As a result, the maximum level of A ₁ in B ₁ is limited by the state of the mixture at room temperature. Indeed it seems that the maximum rate of A ₁ acceptable to have a liquid binary mixture at room temperature is between 80% (pasty mixture) and 60% (liquid but viscous).

Nevertheless, the results in Table III show a good lubricity efficiency of the mixtures A ₁ / B ₁ .

The best results are obtained with mixtures A ₁ / B ₁ - 50/50: better compromise between the HFRR efficiency and the ease of homogenization of the mixture.

However, in order to improve the viscosity of the A ₁ / B ₁ mixture, a compound C ₁ was introduced into these compositions.

The lubricity of the mixtures A _i / B _i / C _i , was tested in a gas oil GO ₁ for a concentration in gas oil of 200 ppm. Among potential C _i , C ₁ is a rapeseed methyl ester or EMC. The results relating to the mixtures A ₁ / B ₁ / C ₁ are given in Table IV below. <u> TABLE IV </ u> Mixed A1 B1 C1 HFRR ( μ m) Viscosity 40 ° C (mm2 / s) M1 40% 60% 0% 363 μ m 89.65 M 2 40% 60% 0% 355 μ m 99.54 M 3 40% 40% 20% 330 μ m 71.28 M4 70% 30 % 0% 291 μ m 564.14 M5 50% 30 % 20% 352 μ m 115.96 M6 40% 50% 10% 282 μ m 100 M7 55% 45% 0% 299 μ m 373.76 M8 55% 45% 0% 315 μ m 222.53 M9 60% 30 % 10% 287 μ m 251.18 M10 50% 40% 10% 239 μ m 142.15 M11 45% 50% 5% 275 μ m 175 M12 60% 35% 5% 280 μ m 288.34

The best compromise between viscosity (between 70 and 120mm ² / s at 40 ° C) and lubricity (<350μm) are obtained for the M ₇ and M ₁₁ mixtures, the viscosity of M ₈ being insufficient.

EXAMPLE III

The present example is intended to illustrate the lubricity efficiency of the other compounds A _i according to the invention, alone or in combination with Bi and C ₁ . Of the other Bi compounds, B ₂ is an ester resulting from the reaction of B ₁ with glycerol in a 1: 1 ratio and B ₃ is the reaction product of B ₁ with diethanolamine in a 1: 1 ratio. The results are given in Table V below. <u> TABLE V </ u> Compound 100 ppm 150 ppm 200 ppm GO1 B1 445 μ m 427 μ m 407 μ m A2 595 μ m 409 μ m 438 μ m B1 / A2- 50/50 455 μ m 403 μ m 327 μ m A4 560 μ m 488 μ m 374 μm B1 / A4- 50/50 457 μ m 426 μ m 327 μ m A6 581 μ m 494 μ m 313 μ m B1 / A6- 50/50 476 μ m 379 μ m 340 μ m A7 595 μ m 553 μ m 330 μ m B1 / A7 - 50/50 555 μ m 468 μ m 345 μ m AT 8 537 μ m 525 μ m 333 μ m B1 / A8 - 50/50 415 μ m 420 μ m 287 μ m B1 / A8 / C1 - 42/43/15 481 μ m 348 μ m 312 μ m B2 - - 320 μ m B3 - - 382 μ m B2 / A2-55 / 45 - - 290 μ m B3 / A2 -55/45 - - 310 μ m B3 / A1 / C1 - 42/43/15 - - 379 μ m B2 / A1 / C1 - 42/43/15 - - 380 μ m GO2. B1 454 μ m 428 μ m 426 μ m A2 488 μ m 385 μ m 385 μ m B1 / A2 - 50/50 459 μ m 377 μ m 369 μ m

As for A1, a synergistic effect is observed between the compounds B ₁ and Al, the addition of C ₁ improving the viscosity of the mixture if necessary.

EXAMPLE V

The purpose of this example is to illustrate the significant effect of the Ai / Bi mixture on conductivity and corrosion.

200 ppm of the mixture A _i / B _{i was introduced} into the diesel fuel GO ₁ . Conductivity measurements were made according to ASTM D2624-2 and corrosion measurements according to ASTM D 655.

The results are given in Tables VI and VII below. <u> TABLE VI </ u> Products tested Conductivity GO1 44 pS / m GO1 + 200 ppm Al (75% in solvarex) 367 pS / m GO1 + 100 ppm Al (75% in solvarex) 204 pS / m GO1 + 200 ppm B1 45 pS / m GO1 + 200 ppm B2 47 pS / m GO1 + 200 ppm B3 40 pS / m GO1 + 200 ppm C1 70 pS / m GO1 + 200 ppm B1 / A1 - 50/50 163 pS / m GO1 + 200 ppm B1 / A1 / C1 - 42/43/15 145 pS / m GO1 + 200 ppm B2 / A1 / C1- 42/43/15 104 pS / m GO1 + 200 ppm B3 / A1 / C1- 42/43/15 182 pS / m Corrosion test pure water GO1 E GO1 + 200 ppm A1 AT GO1 + 200 ppm B1 AT GO1 + 200 ppm B1 / A1 - 50/50 AT GO1 + 200 ppm B1 / A1 / C1- 42/43/15 AT GO1 + 200 ppm B2 / A1 / C1 - 42/43/15 AT GO1 + 200 ppm B3 / A1 / C1 - 42/43/15 AT E = corroded, A = no corrosion

Even if the efficiency in conductivity is good and if there is no corrosion with A ₁ alone, it is not the same for lubricity (see Table III of Example II).

On the other hand, the Bi bring only little conductivity for a strong lubricity.

To achieve the objectives of the invention, it is therefore to establish the best compromise between Ai, Bi and Ci, promoting both the lubricity and conductivity for an absence of corrosion. The best compromise is obtained for an A1 / B1 / C1 ratio corresponding to 43/42/15, the lubricity varying from 300 μm to 350 μm .

EXAMPLE VI

The purpose of this example is to illustrate the significant effect of the Al / Bi mixture on lubricity, conductivity and corrosion in kerosene containing less than 3000 ppm of sulfur. The results are given in Table VIII below. <u> TABLE VIII </ u> Trial WSIM Conductivity ASTM D2624 HFRR ( μ m) Kero 98 50 pS / m 808 μ m Kéro + A1 (200 ppm) 99 356 pS / m 440 μ m Kéro + A1 (100 ppm) 98 2046 pS / m 660 μ m Kéro + B1 (200 ppm) 95 56 pS / m 435 μ m Kero + B1 (100 ppm) <56 pS / m 516 μ m Kero + A1 / B1 / C1- (200 ppm) 42/43/15 48 164 pS / m 386 μ m

The effects of the composition according to the invention are also clearly visible for kerosines.

Claims (23)

1. Use of at least 50 ppm of a composition in a hydrocarbon mixture for improving lubricity, increasing conductivity and decreasing corrosivity, said composition comprising:

   a) from 40 to 70% by weight of at least a compound A of Formula (I) below:

   

   in which R₁ is an alkenyl group of 1-22 carbon atoms, and R₂ is hydrogen or vice-versa,
   and in which R₃ and R₄, identical or different, are chosen from the OH groups, in which R₃ and R₄ cannot be the OH group simultaneously, or deriving from a linear or branched monol or polyol group containing 1-20 carbon atoms having a functionality of 2 to 5 inclusive;

   b) and from 60 to 30% by weight of at least a compound B corresponding to a fatty acid of 16-24 carbon atoms, unsaturated or not, optionally in a mixture with a carboxylic acid comprising at least aromatic and/or olefinic polycycle or ring and/or their corresponding ester, amide or amine salts derivatives, taken alone or in a mixture.
2. Use according to claim 1, characterized in that the composition comprises at least 0.1% by weight of a compound C chosen from C₅-C₃₀ mono- and/or polycarboxylic acid esters.
3. Use according to claim 2, characterized in that the composition comprises from 30 to 60% by weight of at least a compound A, from 30 to 60% by weight of at least a compound B and from 5 to 20 % by weight of at least a compound C.
4. Use according to one of claims 1 to 3, characterized in that, in Formula (I) of compound A, R₃ and R₄, identical or different, are OR₅ with R₅ a group chosen from [(CH₂)_n-O]_m-H with n varying from 1-4 and m varying from 1-5; -[CH₂-CHOH]_p-CH₂-OH, with p varying from 1-3; -CH₂-CR₆R₇-OH, with R₆ and R₇ which can each be hydrogen, a methyl radical or a -CH₂OH radical.
5. Use according to one of claims 1 to 4, characterized in that, in Formula (I) of compound A, R₃ is OR₅ with R₅ a C₁-C₁₀ linear or branched alkyl group, optionally substituted by at least one OH group, and R₄ is OH or vice-versa.
6. Use according to one of claims 1 to 4, characterized in that, in Formula (I) of compound A, R₃ and R₄ are OR₅ groups, identical or different, with R₅ a C₁-C₁₀ linear or branched alkyl group, optionally substituted by at least one OH group.
7. Use according to one of claims 1 to 4, characterized in that, in Formula (I) of compound A, R₃ is OH or an OR₅ group with R₅ a C₁-C₁₀ linear or branched alkyl group, optionally substituted by at least one OH group, and R₄ is OR₅ with R₅ a -[(CH₂)_n-O]_m-H group with n varying from 1 to 4 and m varying from 1 to 5; -[CH₂-CHOH]_p-CH₂-OH, with p varying from 1 to 3; -CH₂-CR₆R₇-OH, with R₆ and R₇ which can each be hydrogen, a methyl radical or a -CH₂OH radical.
8. Use according to one of claims 1 to 3, characterized in that, in Formula (I) of compound A, the OR₅ groups are the groups -O-CH₂-CH₂-OH or -O-CH₂-CHOH-CH₂-OH or -O-CH₂-C(CH₃)(CH₂OH)-CH₂-OH or -O-CH₂-C(CH₂OH)(CH₂OH)-CH₂-OH.
9. Use according to one of claims 1 to 8, characterized in that the compound B comprises at least one saturated or unsaturated linear carboxylic acid and/or their esters, amide or amine salts derivatives, taken alone or in a mixture.
10. Use according to one of claims 1 to 9, characterized in that the compound B mainly comprises a mixture of oleic, linoleic, palmitic, stearic and isostearic acids and/or their esters, amide or amine salts derivatives, taken alone or in a mixture.
11. Use according to one of claims 1 to 10, characterized in that the compound B comprises a mixture of fatty acids of plant origin, from rapeseed, ricin, sunflower, maize, copra, pine or flax and/or their esters, amide or amine salts derivatives, taken alone or in a mixture.
12. Use according to one of claims 1 to 11, characterized in that the compound B is constituted by a mixture of fatty acids originating from the distillation of pine oils and/or their esters or amine salts derivatives.
13. Use according to one of claims 1 to 12, characterized in that the compound B comprises resin acids, including abietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, levopimaric acid and parastinic acid, and/ or their esters, amide or amines salt derivatives, taken alone or in a mixture.
14. Use according to one of claims 1 to 13, characterized in that the compound B is constituted by a mixture of fatty acids and resin acids originating from the distillation of vegetable oil, their esters, amide or amine salts derivatives.
15. Use according to one of claims 1 to 14, characterized in that the compound C is an ester of vegetable oil of rapeseed, ricin, sunflower, maize, copra, pine or flax.
16. Use according to one of claims 1 to 15 characterized in that the compound C is the methyl ester of rapeseed.
17. Hydrocarbonated mixture with a low sulphur content, below 50 ppm, mainly constituted of hydrocarbons originating from the distillation of crude oil, a gasoline, a gas oil or a kerosene and comprising at least 50 ppm of a composition such as defined in one of claims 1 to 16.
18. Hydrocarbonated mixture according to claim 17, characterized in that it comprises from 50 to 350 ppm of said composition.
19. Hydrocarbonated mixture according to claim 17 or 18, characterized by a sulphur content below 10 ppm.
20. Hydrocarbonated mixture according to one of claims 17 to 19 which is a gasoline comprising at least one additive chosen from the group consisting of antipinking, antifreeze, detergent, de-emulsifying, antioxidant, friction modifying, deposit reduction additives and their mixtures.
21. Hydrocarbonated mixture according to one of claims 17 to 19, which is a diesel fuel comprising at least one additive chosen from the group consisting of filterability, anti-foam, detergent, de-emulsifying additives, procetane additives and their mixtures.
22. Hydrocarbonated mixture according to one of claims 17 to 19, which is a domestic heating oil comprising at least one additive chosen from the group consisting of combustion promoting additives, low-temperature resistance additives, flow, anti-corrosion, antioxidant, biocide, reodorant additives and their mixtures.
23. Hydrocarbonated mixture according to one of claims 17 to 19, which is a kerosene comprising at least one additive chosen from the group consisting of anti-static, antioxidant additives and their mixtures.