EP1310547A1 - Fuel with low sulphur content for diesel engines - Google Patents
Fuel with low sulphur content for diesel engines Download PDFInfo
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- EP1310547A1 EP1310547A1 EP03003395A EP03003395A EP1310547A1 EP 1310547 A1 EP1310547 A1 EP 1310547A1 EP 03003395 A EP03003395 A EP 03003395A EP 03003395 A EP03003395 A EP 03003395A EP 1310547 A1 EP1310547 A1 EP 1310547A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1885—Carboxylic acids; metal salts thereof resin acid
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1886—Carboxylic acids; metal salts thereof naphthenic acid
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1888—Carboxylic acids; metal salts thereof tall oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
- C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
- C10L1/2286—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen triple bonds, e.g. nitriles
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
Definitions
- the present invention relates to a fuel containing a creaminess additive to improve lubricating properties of fuels, whether diesel or aviation fuel (jet fuel), and more particularly of low-content diesel fuels in sulfur.
- additives containing dimer acids such as those containing trimer acids, cannot be used in fuels for vehicles in which the fuel may come into contact with lubrication because these acids form by chemical reaction deposits that are sometimes insoluble in oil, but above all incompatible with commonly used detergents.
- US Patent 4,609,376 recommends the use anti-wear additives obtained from acid esters mono- and poly-carboxylic and polyhydric alcohols in fuels containing alcohols in their composition.
- US Patent 2,686,713 recommends the introduction of tall oil up to 60 ppm in diesel fuels to prevent rust from forming on surfaces metal in contact with these fuels.
- esters vegetable oils or the vegetable oils themselves in these fuels are also chosen route.
- esters vegetable oils or the vegetable oils themselves in these fuels are also chosen route.
- One of the major drawbacks of these esters is their low lubricity at a concentration of less than 0.5% by weight in fuels.
- patent application WO 95/33805 recommends the introduction of a cold-keeping additive consisting of nitrogenous additives comprising one or more NR 13 groups in which R 13 comprises from 12 to 24 atoms carbon, is linear, slightly branched or alicyclic and aromatic, the nitrogen group which can be linked by CO or CO 2 and form amine carboxylates or amides.
- the present invention aims to solve the problems encountered with the additives proposed by the prior art, that is to say to improve the lubricating power of desulfurized and flavored fuels, while remaining compatible with other additives, especially detergents, and lubricating oils, especially forming no deposits and reducing the cost, in particular by a lower additive content, well below 0.5%.
- the present invention relates to a fuel for diesel engine, sulfur content less than 500 ppm comprising a major part of at least one middle distillate from a direct distillation cut of crude oil, temperatures between 150 and 400 ° C and part minor lubricant additive containing acids monocarboxylic and polycyclic, the said fuel being characterized in that it contains at least 20 ppm of the additive consisting of a combination of at least one saturated or monocarboxylic aliphatic hydrocarbon unsaturated, of linear chain between 12 and 24 atoms carbon, and at least one hydrocarbon compound polycyclic, containing at least two cycles each formed from 5 to 6 atoms of which one at most is possibly a heteroatom such as nitrogen or oxygen and the others are carbon atoms, these two rings also having two carbon atoms in common, preferably vicinal, these said cycles being saturated or unsaturated, unsubstituted or substituted by at least one group chosen from the group formed by carboxylic groups, carboxylates amine, esters and nitriles, the
- the polycyclic hydrocarbon compound of said combination is a hydrocarbon compound of formula (I) below: with X designating the atoms of each cycle corresponding to 4 carbons, or 3 carbons and a heteroatom such as nitrogen or oxygen, with R 1 , R 2 , R 3 and R 4 , identical or different, designating either an atom of hydrogen, or hydrocarbon groups, each connected to at least one atom of one of the two rings, these hydrocarbon groups being chosen from alkyl groups consisting of 1 to 5 carbon atoms, aryl groups, hydrocarbon rings of 5 with 6 atoms, optionally containing a heteroatom such as oxygen or nitrogen, each cycle being formed by direct connection of two groups R i chosen from R 1 , R 2 , R 3 and R 4 , optionally via a hetero atom, the said ring being saturated or unsaturated, unsubstituted or substituted by an optionally olefinic aliphatic radical comprising from 1 to 4 carbon atoms
- the compound of formula (I) is chosen from group consisting of the natural resin acids obtained from the distillation residues of natural oils extracted from coniferous trees, especially conifers resinous, as well as amine carboxylates, esters and the nitriles of these acids.
- the acid is preferred. abietic, dihydroabietic acid, acid tetrahydroabietic, dehydroabietic acid, acid neoabietic, pimaric acid, levopimaric acid and parastrinic acid and their derivatives.
- the polycyclic hydrocarbon compound of said combination is a hydrocarbon compound of formula (II) below; in which at most one X in each cycle is a heteroatom such as nitrogen or oxygen, the other X being carbon atoms, in which R 1 , R 2 , R 3 and R 4, identical or different, are either a hydrogen atom or hydrocarbon groups, each connected to at least one atom from one of the two rings, these hydrocarbon groups being chosen from alkyl groups comprising from 1 to 5 atoms, aryl groups, hydrocarbon rings of 5 to 6 atoms, optionally containing a heteroatom such as oxygen or nitrogen, each ring being formed by direct connection of two groups R i chosen from R 1 , R 2 , R 3 and R 4 , optionally via a hetero atom, the said ring being saturated or unsaturated, unsubstituted or substituted by an optionally olefinic aliphatic radical comprising from 1 to 4 carbon atoms, and Z, connected to at least one X in each cycle is a hetero
- the aliphatic hydrocarbon monocarboxylic is in the form of acid, carboxylate amines and esters.
- the combination comprises from 1 to 50% by weight of at least one compound corresponding to at least one of the formulas (I) and (II), and from 50 to 99% by weight of at least one acid linear monocarboxylic, saturated or unsaturated, comprising 12 to 24 carbon atoms, these products being present under form of acid, carboxylate of amines or esters.
- amine carboxylates By amine carboxylates is meant the compounds resulting from the reaction of these acids with amines or primary, secondary and tertiary polyamines including from 1 to 8 carbon atoms per chain and the alkylene amines and primary, secondary or tertiary alkylene polyamines comprising from 2 to 8 carbon atoms.
- these amine salts are derived from selected amines in the group consisting of ethyl-2-hexylamine, N, N-dibutylamine, ethylenediamine, diethylenetriamine and tetraethylenepentamine.
- alkanol esters are preferred primary with 1 to 8 carbon atoms or polyalcohols from the group consisting of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, diethanolamine, triethanolamine and their derivatives.
- the fuel contains 50 to 1000 ppm of the oiliness additive.
- additives usually added in such fuels such as detergent additives, additives improving the index of cetane, demulsifying additives, anti-corrosion additives, additives improving cold coming, and odor modifying additives.
- This example describes the choice of additives in function of their solubility in a weak diesel sulfur.
- Each additive in test is diluted to 5% by weight in a diesel (GO) at 500 ppm sulfur, at room temperature.
- additives according to the invention are designated by Y and by C the comparative examples in Table I below.
- Additives Y consist, on the one hand, of a mixture of a combination of fatty acids containing by weight 50 to 55% oleic acid, 30 to 40% linoleic acid, 3 to 5% palmitic acid and 1 with 2% linolenic acid, and for another part in resin acids obtained by distillation of tall oil, by-product of the manufacture of wood pulp by the sulphate process.
- C 1 corresponds to pure oleic acid
- C 2 to rosin which is a mixture of resin acids corresponding to the distillation residue of pine gems
- C 3 is a mixture of dimer acids obtained by thermal dimerization and / or catalytic of unsaturated fatty acids.
- the test consists in imposing jointly with a ball of steel in contact with a stationary metal plate, a pressure corresponding to a weight of 200 g and a displacement alternating 1 mm at a frequency of 50 Hz.
- the ball in movement is lubricated by the composition to be tested.
- the temperature is maintained at 60 ° C for the duration of the test, i.e. 75 min.
- the lubricity is expressed as the average value of the footprint diameters wear of the ball on the plate.
- a small diameter wear generally less than 400 ⁇ m indicates good lubricity; conversely, a wear diameter important (greater than 400 ⁇ m) translates a power of as much more insufficient than the value of the wear diameter is high.
- Example I studies the compatibility of additives described in Example I with lubricants usually used in diesel engines according to the protocol described below.
- the additives of the invention, Y 1 and Y 2 give no deposit or cloudiness when the diesel fuel with 100 ppm additive is added to the oil.
- the purpose of this example is to describe additives oiliness adapted to be introduced into fuels according to the invention.
- amine carboxylates obtained by simple mixing at room temperature and at atmospheric pressure of Y 1 with an amine or polyamine according to the invention, thus allowing the neutralization of the carboxylic sites.
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- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Combustion & Propulsion (AREA)
- Liquid Carbonaceous Fuels (AREA)
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Abstract
Description
La présente invention concerne un carburant contenant un additif d'onctuosité pour améliorer les propriétés lubrifiantes des carburants, qu'il s'agisse de carburant diesel ou de carburant aviation (jet fuel), et plus particulièrement de carburants diesels à faible teneur en soufre.The present invention relates to a fuel containing a creaminess additive to improve lubricating properties of fuels, whether diesel or aviation fuel (jet fuel), and more particularly of low-content diesel fuels in sulfur.
Il est bien connu que les carburants diesels et les carburants aviations doivent posséder des aptitudes à la lubrification pour la protection des pompes, des systèmes d'injection et de toutes les parties en mouvement avec lesquels ces produits entrent en contact dans un moteur à combustion interne. Avec la volonté d'utiliser des produits de plus en plus purs et non polluants, notamment dépourvus de soufre, l'industrie du raffinage a été amenée à perfectionner de plus en plus ses procédés de traitement d'élimination des composés du soufre. Cependant on a observé qu'en perdant les composés soufrés on perdait également les composés aromatiques et polaires souvent associés, ce qui occasionnait une perte du pouvoir lubrifiant de ces carburants. Ainsi, en deçà de certaines teneurs, la suppression de composés soufrés dans la composition de ces produits favorise très sensiblement les phénomènes d'usure et de rupture de pièces en mouvement au niveau des pompes et des systèmes d'injection. Comme la réglementation de nombreux pays a imposé de limiter la teneur supérieure acceptable en composés soufrés dans les carburants à 0,05% en poids pour diminuer les émissions des voitures, camions ou autobus en gaz de combustion polluants, notamment dans les agglomérations urbaines, il est nécessaire de remplacer ces composés lubrifiants par d'autres composés non polluants au regard de l'environnement mais présentant un pouvoir lubrifiant suffisant pour éviter les risques d'usure. It is well known that diesel fuels and aviation fuels must have skills in lubrication for the protection of pumps, systems injection and all moving parts with which these products come into contact with in a internal combustion. With the desire to use products increasingly pure and non-polluting, especially devoid of sulfur, the refining industry was brought to improving their treatment processes more and more removal of sulfur compounds. However we observed that by losing the sulfur compounds we also lost the aromatic and polar compounds often associated, which caused a loss of the lubricating power of these fuels. Thus, below certain levels, the removal of sulfur compounds in the composition of these products very significantly promotes wear phenomena and rupture of moving parts at the pumps and injection systems. As the regulation of many countries imposed to limit the upper content acceptable as sulfur compounds in fuels at 0.05% by weight to reduce emissions from cars, trucks or buses with polluting combustion gases, particularly in urban agglomerations, it is necessary to replace these lubricating compounds by other non-polluting compounds with regard to the environment but presenting a power sufficient lubricant to avoid the risk of wear.
Pour résoudre ce problème, plusieurs types d'additifs ont déjà été proposés. Ainsi, on a ajouté aux gazoles des additifs anti-usures, connus pour certains dans le domaine des lubrifiants, du type des esters d'acides gras et des acides gras dimères non saturés, des amines aliphatiques, des esters d'acides gras et de diéthanolamine et des acides monocarboxyliques aliphatiques à chaíne longue tels que décrits dans les brevets US 2.252.889, US 4.185.594, US 4.204.481, US 4.208.190, US 4.428.182. La plupart de ces additifs présente un pouvoir lubrifiant suffisant mais à des concentrations bien trop élevées ce qui est très défavorable économiquement à l'achat. En outre, les additifs contenant des acides dimères, comme ceux contenant des acides trimères, ne peuvent être utilisés dans les carburants alimentant les véhicules dans lesquels le carburant peut être en contact avec l'huile de lubrification, car ces acides forment par réaction chimique des dépôts parfois insolubles dans l'huile, mais surtout incompatibles avec les détergents usuellement utilisés.To solve this problem, several types additives have already been proposed. So we added to diesel fuel additives anti-wear, known for some in the field of lubricants, of the fatty acid ester type and unsaturated dimer fatty acids, amines aliphatics, esters of fatty acids and diethanolamine and long chain aliphatic monocarboxylic acids as described in US Patents 2,252,889, US 4,185,594, US 4,204,481, US 4,208,190, US 4,428,182. The most of these additives have a lubricating power sufficient but at concentrations too high which is very economically unfavorable to purchase. In addition, additives containing dimer acids, such as those containing trimer acids, cannot be used in fuels for vehicles in which the fuel may come into contact with lubrication because these acids form by chemical reaction deposits that are sometimes insoluble in oil, but above all incompatible with commonly used detergents.
Le brevet US 4.609.376 préconise l'utilisation d'additifs anti-usures obtenus à partir d'esters d'acides mono- et poly-carboxyliques et d'alcools polyhydroxylés dans les carburants contenant des alcools dans leur composition.US Patent 4,609,376 recommends the use anti-wear additives obtained from acid esters mono- and poly-carboxylic and polyhydric alcohols in fuels containing alcohols in their composition.
Le brevet US 2.686.713 préconise l'introduction de tall oil jusqu'à 60 ppm dans les carburants diesel afin de prévenir la formation de rouille sur les surfaces métalliques en contact avec ces carburants.US Patent 2,686,713 recommends the introduction of tall oil up to 60 ppm in diesel fuels to prevent rust from forming on surfaces metal in contact with these fuels.
Une autre voie choisie est d'introduire des esters d'huiles végétales ou les huiles végétales elles-mêmes dans ces carburants pour améliorer leur pouvoir lubrifiant ou leur onctuosité. Parmi ceux-ci, on trouve les esters dérivés d'huiles de colza, de lin, de soja, de tournesol ou les huiles elles-mêmes (voir brevets EP 635.558 et EP 605.857). Un des inconvénients majeurs de ces esters est leur faible pouvoir lubrifiant à une concentration inférieure à 0,5 % en poids dans les carburants.Another chosen route is to introduce esters vegetable oils or the vegetable oils themselves in these fuels to improve their lubricity or their smoothness. Among these are derivative esters rapeseed, linseed, soybean, sunflower or oils themselves (see patents EP 635,558 and EP 605,857). One of the major drawbacks of these esters is their low lubricity at a concentration of less than 0.5% by weight in fuels.
Pour améliorer le pouvoir lubrifiant des gazoles, la demande de brevet WO 95/33805 préconise l'introduction d'un additif de tenue à froid constitué par des additifs azotés comprenant un à plusieurs groupements N-R13 dans lequel R13 comprend de 12 à 24 atomes de carbone, est linéaire, légèrement ramifié ou alicyclique et aromatique le groupement azoté pouvant être relié par CO ou CO2 et former des carboxylates d'amines ou des amides.To improve the lubricating power of gas oils, patent application WO 95/33805 recommends the introduction of a cold-keeping additive consisting of nitrogenous additives comprising one or more NR 13 groups in which R 13 comprises from 12 to 24 atoms carbon, is linear, slightly branched or alicyclic and aromatic, the nitrogen group which can be linked by CO or CO 2 and form amine carboxylates or amides.
La présente invention vise à résoudre les problèmes rencontrés avec les additifs proposés par l'art antérieur, c'est-à-dire à améliorer le pouvoir lubrifiant des carburants désulfurés et désaromatisés, tout en restant compatibles avec les autres additifs, notamment les détergents, et les huiles lubrifiantes, notamment en ne formant pas de dépôts et en diminuant le coût notamment par une teneur moindre en additif, nettement inférieure à 0,5%.The present invention aims to solve the problems encountered with the additives proposed by the prior art, that is to say to improve the lubricating power of desulfurized and flavored fuels, while remaining compatible with other additives, especially detergents, and lubricating oils, especially forming no deposits and reducing the cost, in particular by a lower additive content, well below 0.5%.
La présente invention a pour objet un carburant pour moteur diesel, à teneur en soufre inférieure à 500 ppm comprenant une majeure partie d'au moins un distillat moyen issu d'une coupe de distillation directe de pétrole brut, de températures comprise entre 150 et 400°C et une partie mineure d'un additif d'onctuosité contenant des acides monocarboxyliques et polycycliques, le dit carburant étant caractérisé en ce qu'il contient au moins 20 ppm de l'additif constitué par une combinaison d'au moins un hydrocarbure aliphatique monocarboxylique, saturé ou insaturé, de chaíne linéaire comprise entre 12 et 24 atomes de carbone, et au moins un composé hydrocarboné polycyclique, contenant au moins deux cycles formés chacun de 5 à 6 atomes dont l'un au plus est éventuellement un hétéroatome tel que l'azote ou l'oxygène et les autres sont des atomes de carbone, ces deux cycles ayant en outre deux atomes de carbone en commun, de préférence vicinaux, ces dits cycles étant saturés ou insaturés, non-substitués ou substitués par au moins un seul groupement choisi dans le groupe formé par les groupements carboxyliques, carboxylates d'amine, esters et nitriles, le carburant renfermant plus de 60 ppm d'additif lorsque la dite combinaison est le tall oil. The present invention relates to a fuel for diesel engine, sulfur content less than 500 ppm comprising a major part of at least one middle distillate from a direct distillation cut of crude oil, temperatures between 150 and 400 ° C and part minor lubricant additive containing acids monocarboxylic and polycyclic, the said fuel being characterized in that it contains at least 20 ppm of the additive consisting of a combination of at least one saturated or monocarboxylic aliphatic hydrocarbon unsaturated, of linear chain between 12 and 24 atoms carbon, and at least one hydrocarbon compound polycyclic, containing at least two cycles each formed from 5 to 6 atoms of which one at most is possibly a heteroatom such as nitrogen or oxygen and the others are carbon atoms, these two rings also having two carbon atoms in common, preferably vicinal, these said cycles being saturated or unsaturated, unsubstituted or substituted by at least one group chosen from the group formed by carboxylic groups, carboxylates amine, esters and nitriles, the fuel containing more than 60 ppm additive when the said combination is tall oil.
On s'est aperçu que le pouvoir lubrifiant apporté par l'additif d'onctuosité contenant une telle combinaison est bien supérieur à celui prévisible par ajout des pouvoirs lubrifiants de chacun de ses composants pris séparément. Ce résultat imprévisible traduit l'effet de synergie des différents composants de la dite combinaison au regard de la lubrification.We realized that the lubricating power provided by the oiliness additive containing such a combination is much higher than foreseeable by adding powers lubricants of each of its components taken separately. This unpredictable result reflects the synergistic effect of different components of the said combination with regard to the lubrication.
Selon un premier mode de réalisation du carburant selon l'invention, le composé hydrocarboné polycyclique de la dite combinaison est un composé hydrocarboné de formule (I) ci-après : avec X désignant les atomes de chaque cycle correspondant à 4 carbones, ou 3 carbones et un hétéroatome tel que l'azote ou l'oxygène, avec R1, R2, R3 et R4, identiques ou différents, désignant soit un atome d'hydrogène, soit des groupements hydrocarbonés, raccordés chacun à au moins un atome d'un des deux cycles, ces groupements hydrocarbonés étant choisis parmi les groupements alkyls constitués de 1 à 5 atomes de carbone, les groupements aryls, les cycles hydrocarbonés de 5 à 6 atomes, contenant éventuellement un hétéroatome tel que l'oxygène ou l'azote, chaque cycle étant formé par raccordement direct de deux groupements Ri choisis parmi R1, R2, R3 et R4, via éventuellement un hétéroatome, le dit cycle étant saturé ou insaturé, non substitué ou substitué par un radical aliphatique éventuellement oléfinique comprenant de 1 à 4 atomes de carbone, et Z est choisi dans le groupe constitué par les groupements carboxyliques, les carboxylates d'amines, les esters et les nitriles.According to a first embodiment of the fuel according to the invention, the polycyclic hydrocarbon compound of said combination is a hydrocarbon compound of formula (I) below: with X designating the atoms of each cycle corresponding to 4 carbons, or 3 carbons and a heteroatom such as nitrogen or oxygen, with R 1 , R 2 , R 3 and R 4 , identical or different, designating either an atom of hydrogen, or hydrocarbon groups, each connected to at least one atom of one of the two rings, these hydrocarbon groups being chosen from alkyl groups consisting of 1 to 5 carbon atoms, aryl groups, hydrocarbon rings of 5 with 6 atoms, optionally containing a heteroatom such as oxygen or nitrogen, each cycle being formed by direct connection of two groups R i chosen from R 1 , R 2 , R 3 and R 4 , optionally via a hetero atom, the said ring being saturated or unsaturated, unsubstituted or substituted by an optionally olefinic aliphatic radical comprising from 1 to 4 carbon atoms, and Z is chosen from the group consisting of carboxylic groups, carboxylate s of amines, esters and nitriles.
Dans un mode particulier de ce premier mode de réalisation, le composé de formule (I) est choisi dans le groupe constitué par les acides résiniques naturels obtenus à partir des résidus de distillation des huiles naturelles extraites des arbres résineux, notamment des conifères résineux, ainsi que les carboxylates d'amines, les esters et les nitriles de ces acides.In a particular mode of this first mode of embodiment, the compound of formula (I) is chosen from group consisting of the natural resin acids obtained from the distillation residues of natural oils extracted from coniferous trees, especially conifers resinous, as well as amine carboxylates, esters and the nitriles of these acids.
Parmi les acides résiniques, on préfère l'acide abiétique, l'acide dihydroabiétique, l'acide tétrahydroabiétique, l'acide dehydroabiétique, l'acide néoabiétique, l'acide pimarique, l'acide levopimarique et l'acide parastrinique et leurs dérivés.Among the resin acids, the acid is preferred. abietic, dihydroabietic acid, acid tetrahydroabietic, dehydroabietic acid, acid neoabietic, pimaric acid, levopimaric acid and parastrinic acid and their derivatives.
Dans un deuxième mode de réalisation de l'invention, le composé hydrocarboné polycyclique de la dite combinaison est un composé hydrocarboné de formule (II) ci-après; dans laquelle au plus un X de chaque cycle est un hétéroatome tel que l'azote ou l'oxygène, les autres X étant des atomes de carbone, dans laquelle R1, R2, R3 et R4, identiques ou différents, sont soit un atome d'hydrogène, soit des groupements hydrocarbonés, raccordés chacun à au moins un atome d'un des deux cycles, ces groupements hydrocarbonés étant choisis parmi les groupements alkyls comprenant de 1 à 5 atomes, les groupements aryls, les cycles hydrocarbonés de 5 à 6 atomes, contenant éventuellement un hétéroatome tel que l'oxygène ou l'azote, chaque cycle étant formé par raccordement direct de deux groupements Ri choisis parmi R1, R2, R3 et R4, via éventuellement un hétéroatome, le dit cycle étant saturé ou insaturé, non substitué ou substitué par un radical aliphatique éventuellement oléfinique comprenant de 1 à 4 atomes de carbone, et Z, raccordé à au moins un atome d'au moins un des deux cycles, est choisi dans le groupe constitué par les groupements carboxyliques, carboxylates d'amines, les esters et les nitriles.In a second embodiment of the invention, the polycyclic hydrocarbon compound of said combination is a hydrocarbon compound of formula (II) below; in which at most one X in each cycle is a heteroatom such as nitrogen or oxygen, the other X being carbon atoms, in which R 1 , R 2 , R 3 and R 4, identical or different, are either a hydrogen atom or hydrocarbon groups, each connected to at least one atom from one of the two rings, these hydrocarbon groups being chosen from alkyl groups comprising from 1 to 5 atoms, aryl groups, hydrocarbon rings of 5 to 6 atoms, optionally containing a heteroatom such as oxygen or nitrogen, each ring being formed by direct connection of two groups R i chosen from R 1 , R 2 , R 3 and R 4 , optionally via a hetero atom, the said ring being saturated or unsaturated, unsubstituted or substituted by an optionally olefinic aliphatic radical comprising from 1 to 4 carbon atoms, and Z, connected to at least one atom from at least one of the two rings, is chosen from the group constitute by carboxylic groups, carboxylates, amines, esters and nitriles.
Selon l'invention, l'hydrocarbure aliphatique monocarboxylique est sous forme d'acide, de carboxylate d'amines et d'esters.According to the invention, the aliphatic hydrocarbon monocarboxylic is in the form of acid, carboxylate amines and esters.
Dans un mode plus poussé de l'invention, la combinaison comprend de 1 à 50% en poids d'au moins un composé correspondant à au moins une des formules (I)et (II), et de 50 à 99% en poids d'au moins un acide monocarboxylique linéaire, saturé ou insaturé, comprenant de 12 à 24 atomes de carbones, ces produits étant présents sous forme d'acide, de carboxylate d'amines ou d'esters.In a more advanced mode of the invention, the combination comprises from 1 to 50% by weight of at least one compound corresponding to at least one of the formulas (I) and (II), and from 50 to 99% by weight of at least one acid linear monocarboxylic, saturated or unsaturated, comprising 12 to 24 carbon atoms, these products being present under form of acid, carboxylate of amines or esters.
Par carboxylates d'amines, on entend les composés résultant de la réaction de ces acides avec des amines ou polyamines primaires, secondaires et tertiaires comprenant de 1 à 8 atomes de carbone par chaíne et les alkylèneamines et alkylènepolyamines primaires, secondaires ou tertiaires comprenant de 2 à 8 atomes de carbone. Dans un mode préféré de l'invention, ces sels d'amines dérivent d'amines choisies dans le groupe constitué par l'éthyl-2-hexylamine, la N,N-dibutylamine, l'éthylènediamine, la diéthylènetriamine et la tétraéthylènepentamine.By amine carboxylates is meant the compounds resulting from the reaction of these acids with amines or primary, secondary and tertiary polyamines including from 1 to 8 carbon atoms per chain and the alkylene amines and primary, secondary or tertiary alkylene polyamines comprising from 2 to 8 carbon atoms. In a preferred mode of the invention, these amine salts are derived from selected amines in the group consisting of ethyl-2-hexylamine, N, N-dibutylamine, ethylenediamine, diethylenetriamine and tetraethylenepentamine.
Parmi les esters, on préfère les esters d'alcanols primaires comprenant de 1 à 8 atomes de carbone ou encore des polyalcool du groupe constitué par l'éthylèneglycol, le propylèneglycol, le glycérol, le triméthylolpropane, le pentaérythritol, la diéthanolamine, la triéthanolamine et leurs dérivés.Among the esters, alkanol esters are preferred primary with 1 to 8 carbon atoms or polyalcohols from the group consisting of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, diethanolamine, triethanolamine and their derivatives.
Dans un mode préféré de l'invention, le carburant contient de 50 à 1000 ppm de l'additif d'onctuosité.In a preferred embodiment of the invention, the fuel contains 50 to 1000 ppm of the oiliness additive.
Selon la présente invention, on peut ajouter au dit carburant au moins un additif du groupe des additifs usuellement ajoutés dans de tels carburants tels que les additifs détergents, les additifs améliorant l'indice de cétane, les additifs désémulsifiants, les additifs anti-corrosion, les additifs améliorant la venue à froid, et les additifs modificateurs d'odeur.According to the present invention, one can add to the said fuel at least one additive from the group of additives usually added in such fuels such as detergent additives, additives improving the index of cetane, demulsifying additives, anti-corrosion additives, additives improving cold coming, and odor modifying additives.
Pour expliciter les avantages de la présente invention au regard de l'art antérieur, des exemples sont donnés ci-après à titre illustratif mais non limitatif de la portée de l'invention revendiquée.To explain the advantages of this invention with regard to the prior art, examples are given below by way of illustration but not limiting of the scope of the claimed invention.
Le présent exemple décrit le choix des additifs en fonction de leur solubilité dans un gazole faiblement soufré.This example describes the choice of additives in function of their solubility in a weak diesel sulfur.
On dilue chaque additif en test à 5% poids dans un gazole (GO) à 500 ppm de soufre, à température ambiante.Each additive in test is diluted to 5% by weight in a diesel (GO) at 500 ppm sulfur, at room temperature.
On désigne par Y les additifs selon l'invention et
par C les exemples comparatifs dans le tableau I ci-après.
Les additifs Y consistent pour une part, en un mélange
d'une combinaison d'acides gras renfermant en poids 50 à 55
% d'acide oléique, 30 à 40 % d'acide linoléique,3 à 5 %
d'acide palmitique et 1 à 2 % d'acide linolénique, et pour
une autre part en acides résiniques obtenus par distillation
du tall oil, sous produit de fabrication de la pulpe de bois
par le procédé sulfate. Pour les exemples comparatifs, C1
correspond à l'acide oléique pur, C2 au colophane qui est un
mélange d'acides résiniques correspondant au résidu de
distillation des gemmes de pins et C3 est un mélange
d'acides dimères obtenus par dimérisation thermique et/ou
catalytique d'acides gras insaturés.
On constate d'après ce tableau qu'à l'exception des acides résiniques (C2), tous ces composés sont très solubles dans le gazole.It can be seen from this table that, with the exception of resin acids (C 2 ), all of these compounds are very soluble in diesel.
Le présent exemple étudie le pouvoir lubrifiant des additifs décrits dans l'exemple I.This example studies the lubricating power of additives described in Example I.
Le pouvoir lubrifiant de ces additifs a été mesuré dans les conditions de l'essai HFRR (High Frequency Reciprocating Rig) tel que décrit dans l'article SAE 932692 par J.W. HADLEY de l'université de Liverpool.The lubricity of these additives has been measured under the conditions of the HFRR test (High Frequency Reciprocating Rig) as described in article SAE 932692 by J.W. HADLEY of the University of Liverpool.
Le test consiste à imposer conjointement à une bille d'acier en contact avec un plateau métallique immobile, une pression correspondant à un poids de 200 g et un déplacement alternatif de 1 mm à une fréquence de 50 Hz. La bille en mouvement est lubrifiée par la composition à tester. La température est maintenue à 60°C pendant toute la durée de l'essai, c'est-à-dire 75 mn. Le pouvoir lubrifiant est exprimé par la valeur moyenne des diamètres de l'empreinte d'usure de la bille sur le plateau. Un faible diamètre d'usure (généralement inférieur à 400µm) indique un bon pouvoir lubrifiant ; à l'inverse, un diamètre d'usure important (supérieur à 400µm) traduit un pouvoir d'autant plus insuffisant que la valeur du diamètre d'usure est élevée. The test consists in imposing jointly with a ball of steel in contact with a stationary metal plate, a pressure corresponding to a weight of 200 g and a displacement alternating 1 mm at a frequency of 50 Hz. The ball in movement is lubricated by the composition to be tested. The temperature is maintained at 60 ° C for the duration of the test, i.e. 75 min. The lubricity is expressed as the average value of the footprint diameters wear of the ball on the plate. A small diameter wear (generally less than 400µm) indicates good lubricity; conversely, a wear diameter important (greater than 400µm) translates a power of as much more insufficient than the value of the wear diameter is high.
Le pouvoir lubrifiant des additifs a été mesuré sur
un gazole identique à celui de l'exemple I, chaque
échantillon testé ne contenant que 100 ppm d'additif. Les
résultats sont donnés dans le tableau II ci-après.
Ce tableau montre que les additifs (Y1 et Y2) selon l'invention ont un effet identique sinon meilleur que les acides dimères (C3). De plus, on constate que le mélange d'acides gras avec des acides résiniques a un pouvoir lubrifiant bien meilleur que ceux obtenus avec ces mêmes composés pris séparément, traduisant une synergie de ces composants entre eux.This table shows that the additives (Y 1 and Y 2 ) according to the invention have an identical effect if not better than the dimer acids (C 3 ). In addition, it is found that the mixture of fatty acids with resin acids has a much better lubricating power than those obtained with these same compounds taken separately, translating a synergy of these components between them.
Le présent exemple étudie la compatibilité des additifs décrits dans l'exemple I avec les lubrifiants utilisés usuellement dans les moteurs diesel selon le protocole décrit ci-après.This example studies the compatibility of additives described in Example I with lubricants usually used in diesel engines according to the protocol described below.
70 ml d'une huile moteur de basicité totale égale à 15 mg de KOH par gramme sont mélangés avec 700 ml de gazole à 500 ppm de soufre identique à celui de l'exemple I, dans lequel on rajoute 35 g d'additif. Chaque mélange ainsi constitué est placé dans une étuve à 50°C, puis on évalue visuellement la présence ou l'absence de dépôts, d'un précipité ou d'un trouble résultant d'une incompatibilité entre les additifs dits « d'onctuosité », au pouvoir lubrifiant suffisant, avec un lubrifiant moteur appelé KM2+ commercialisé par la société des Huiles Renault Diesel.70 ml of engine oil with total basicity equal to 15 mg of KOH per gram are mixed with 700 ml of diesel at 500 ppm of sulfur identical to that of Example I, in which is added 35 g of additive. Each mixture as well constituted is placed in an oven at 50 ° C, then evaluated visually the presence or absence of deposits, a precipitate or disorder resulting from incompatibility between so-called "oiliness" additives sufficient lubricant, with an engine lubricant called KM2 + marketed by the company of Huiles Renault Diesel.
Les résultats de compabilité sont rassemblés dans le
tableau III ci-après.
Les additifs de l'invention, Y1 et Y2 ne donnent ni dépôt, ni trouble lorsque que le gazole additivé à 100 ppm est ajouté à l'huile.The additives of the invention, Y 1 and Y 2 give no deposit or cloudiness when the diesel fuel with 100 ppm additive is added to the oil.
Le présent exemple vise à décrire des additifs d'onctuosité adaptés pour être introduits dans les carburants selon l'invention.The purpose of this example is to describe additives oiliness adapted to be introduced into fuels according to the invention.
Ce sont d'une part des esters obtenus en faisant réagir des alcools avec l'additif Y1 de l'exemple I dans un mélange équimolaire, à maintenir ce mélange à reflux entre 130 et 150°C sous pression atmosphérique, puis à distiller l'azéotrope eau/toluène.These are, on the one hand, esters obtained by reacting alcohols with the additive Y 1 of Example I in an equimolar mixture, in maintaining this mixture at reflux between 130 and 150 ° C. under atmospheric pressure, then in distilling l water / toluene azeotrope.
D'autre part, il s'agit de carboxylates d'amine obtenues par simple mélange à température ambiante et à pression atmosphérique de Y1 avec une amine ou polyamine selon l'invention, permettant ainsi la neutralisation des sites carboxyliques. On the other hand, they are amine carboxylates obtained by simple mixing at room temperature and at atmospheric pressure of Y 1 with an amine or polyamine according to the invention, thus allowing the neutralization of the carboxylic sites.
Ces additifs sont introduits dans un gazole tel que décrit dans l'exemple II à une concentration de 100 ppm.These additives are introduced into a diesel such as described in Example II at a concentration of 100 ppm.
Le tableau IV rassemble ci-après les résultats du
test d'usure décrit dans l'exemple II obtenus avec le gazole
ainsi dopé pour caractériser leur pouvoir lubrifiant.
D'après ces résultats, on confirme que les carburants dopés par de tels additifs selon l'invention, ont un bon pouvoir lubrifiant.From these results, it is confirmed that the fuels doped with such additives according to the invention have good lubricity.
Claims (12)
caractérisé en ce que le composé de formule (I) est choisi dans le groupe constitué par les acides résiniques naturels obtenus à partir des résidus de distillation des huiles naturelles extraites des arbres résineux, notamment des conifères résineux, les carboxylates d'amines, et les dérivés esters et nitriles de ces acides.Fuel according to one of claims 1 and 2
characterized in that the compound of formula (I) is chosen from the group consisting of natural resin acids obtained from the distillation residues of natural oils extracted from resinous trees, in particular resinous conifers, amine carboxylates, and ester and nitrile derivatives of these acids.
caractérisé en ce que les acides résiniques sont choisis dans le groupe constitué par l'acide abiétique, l'acide dihydroabiétique, l'acide tétrahydroabiétique, l'acide dehydroabiétique, l'acide néoabiétique, l'acide pimarique, l'acide lévopimarique, l'acide parastrinique et leurs dérivés.Fuel according to one of claims 1 to 3
characterized in that the resin acids are chosen from the group consisting of abietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, levopimaric acid, l parastrinic acid and their derivatives.
caractérisé en ce que l'hydrocarbure aliphatique monocarboxylique est sous forme d'acide, de carboxylate d'amines et/ou d'esters.Fuel according to one of claims 1 to 5
characterized in that the monocarboxylic aliphatic hydrocarbon is in the form of acid, amine carboxylate and / or esters.
caractérisé en ce qu'il comprend de 1 à 50% en poids d'au moins un composé correspondant à au moins une des formules (I) et (II), et de 50 à 99% en poids d'au moins un hydrocarbure aliphatique monocarboxylique linéaire, saturé ou insaturé, comprenant de 12 à 24 atomes de carbone.Fuel according to one of claims 1 to 6
characterized in that it comprises from 1 to 50% by weight of at least one compound corresponding to at least one of formulas (I) and (II), and from 50 to 99% by weight of at least one aliphatic hydrocarbon linear monocarboxylic, saturated or unsaturated, comprising from 12 to 24 carbon atoms.
caractérisé en ce que les carboxylates d'amines résultent de la réaction des ces acides avec des amines ou polyamines primaires, secondaires et tertiaires comprenant de 1 à 8 atomes de carbones par chaíne et les alkylèneamines et alkylènepolyamines primaires, secondaires, ou tertiaires comprenant de 2 à 8 atomes de carbone.Fuel according to one of claims 1 to 7
characterized in that the amine carboxylates result from the reaction of these acids with primary, secondary and tertiary amines or polyamines comprising from 1 to 8 carbon atoms per chain and the primary, secondary, or tertiary alkyleneamines and alkylene polyamines comprising from 2 to 8 carbon atoms.
caractérisé en ce que les esters résultent de la réaction de ces acides avec des alcools du groupe constitué par les alcools primaires comprenant de 1 à 8 atomes de carbone et les polyalcools du type éthylèneglycol, propylèneglycol, glycérol, triméthylolpropane, pentaérythritol, diéthanolamine et triéthanolamine.Fuel according to one of claims 1 to 7
characterized in that the esters result from the reaction of these acids with alcohols from the group consisting of primary alcohols comprising from 1 to 8 carbon atoms and polyalcohols of the ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, diethanolamine and triethanolamine type.
caractérisé en ce qu'il contient de 50 à 1000 ppm d'un additif d'onctuosité.Fuel according to one of claims 1 to 10
characterized in that it contains from 50 to 1000 ppm of a lubricity additive.
caractérisé en ce qu'il contient en outre au moins un additif du groupe des additifs usuellement ajoutés dans de tels carburants tels que les additifs détergents, les additifs améliorant l'indice de cétane, les additifs désémulsifiants, les additifs anti-corrosion, les additifs améliorant la venue à froid, et les additifs modificateurs d'odeur.Fuel according to one of claims 1 to 11
characterized in that it additionally contains at least one additive from the group of additives usually added in such fuels such as detergent additives, additives improving the cetane number, demulsifying additives, anti-corrosion additives, additives improving cold coming, and odor modifying additives.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9609662 | 1996-07-31 | ||
FR9609662A FR2751982B1 (en) | 1996-07-31 | 1996-07-31 | ONCTUOSITY ADDITIVE FOR ENGINE FUEL AND FUEL COMPOSITION |
EP97935651A EP0915944B1 (en) | 1996-07-31 | 1997-07-29 | Use of an additive for the improvement of lubricating properties of a fuel with low sulphur content for diesel engines |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP97935651A Division EP0915944B1 (en) | 1996-07-31 | 1997-07-29 | Use of an additive for the improvement of lubricating properties of a fuel with low sulphur content for diesel engines |
Publications (2)
Publication Number | Publication Date |
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EP1310547A1 true EP1310547A1 (en) | 2003-05-14 |
EP1310547B1 EP1310547B1 (en) | 2016-11-30 |
Family
ID=9494685
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97935651A Revoked EP0915944B1 (en) | 1996-07-31 | 1997-07-29 | Use of an additive for the improvement of lubricating properties of a fuel with low sulphur content for diesel engines |
EP03003395.5A Expired - Lifetime EP1310547B1 (en) | 1996-07-31 | 1997-07-29 | Fuel with low sulphur content for diesel engines |
EP03291021A Ceased EP1340801A1 (en) | 1996-07-31 | 1997-07-29 | Oiliness additive |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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EP97935651A Revoked EP0915944B1 (en) | 1996-07-31 | 1997-07-29 | Use of an additive for the improvement of lubricating properties of a fuel with low sulphur content for diesel engines |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP03291021A Ceased EP1340801A1 (en) | 1996-07-31 | 1997-07-29 | Oiliness additive |
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US (2) | US6592639B2 (en) |
EP (3) | EP0915944B1 (en) |
JP (1) | JP3129446B2 (en) |
KR (1) | KR100485452B1 (en) |
AR (1) | AR008413A1 (en) |
AT (1) | ATE252628T1 (en) |
AU (1) | AU3855497A (en) |
BR (1) | BR9711613A (en) |
DE (1) | DE69725726T2 (en) |
DK (2) | DK0915944T3 (en) |
ES (2) | ES2208940T3 (en) |
FR (1) | FR2751982B1 (en) |
HU (1) | HU223273B1 (en) |
ID (1) | ID19202A (en) |
MX (1) | MX222887B (en) |
MY (1) | MY121253A (en) |
NO (1) | NO990446L (en) |
PL (1) | PL186421B1 (en) |
PT (2) | PT1310547T (en) |
RU (1) | RU2165447C2 (en) |
SK (1) | SK285505B6 (en) |
WO (1) | WO1998004656A1 (en) |
ZA (1) | ZA976792B (en) |
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- 1997-07-29 ES ES97935651T patent/ES2208940T3/en not_active Expired - Lifetime
- 1997-07-29 US US09/147,604 patent/US6592639B2/en not_active Expired - Lifetime
- 1997-07-29 RU RU99104395/04A patent/RU2165447C2/en active
- 1997-07-29 DK DK97935651T patent/DK0915944T3/en active
- 1997-07-29 HU HU9903425A patent/HU223273B1/en active IP Right Grant
- 1997-07-29 EP EP97935651A patent/EP0915944B1/en not_active Revoked
- 1997-07-29 PT PT3003395T patent/PT1310547T/en unknown
- 1997-07-29 AU AU38554/97A patent/AU3855497A/en not_active Abandoned
- 1997-07-29 EP EP03003395.5A patent/EP1310547B1/en not_active Expired - Lifetime
- 1997-07-29 DE DE69725726T patent/DE69725726T2/en not_active Revoked
- 1997-07-29 KR KR10-1999-7000828A patent/KR100485452B1/en not_active IP Right Cessation
- 1997-07-29 AT AT97935651T patent/ATE252628T1/en not_active IP Right Cessation
- 1997-07-29 ES ES03003395.5T patent/ES2610592T3/en not_active Expired - Lifetime
- 1997-07-29 DK DK03003395.5T patent/DK1310547T3/en active
- 1997-07-29 EP EP03291021A patent/EP1340801A1/en not_active Ceased
- 1997-07-29 PT PT97935651T patent/PT915944E/en unknown
- 1997-07-29 JP JP10508571A patent/JP3129446B2/en not_active Expired - Lifetime
- 1997-07-29 SK SK127-99A patent/SK285505B6/en not_active IP Right Cessation
- 1997-07-29 PL PL97331372A patent/PL186421B1/en unknown
- 1997-07-29 BR BR9711613-0A patent/BR9711613A/en not_active IP Right Cessation
- 1997-07-30 ZA ZA9706792A patent/ZA976792B/en unknown
- 1997-07-30 MY MYPI97003481A patent/MY121253A/en unknown
- 1997-07-31 ID IDP972675A patent/ID19202A/en unknown
- 1997-07-31 AR ARP970103464A patent/AR008413A1/en not_active Application Discontinuation
-
1999
- 1999-01-29 NO NO990446A patent/NO990446L/en unknown
- 1999-02-18 MX MX9901648A patent/MX222887B/en active IP Right Grant
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2003
- 2003-05-29 US US10/446,851 patent/US7374589B2/en not_active Expired - Fee Related
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