EP1252269B1 - Multifunctional additive compositions enabling middle distillates to be operable in cold conditions - Google Patents

Multifunctional additive compositions enabling middle distillates to be operable in cold conditions Download PDF

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Publication number
EP1252269B1
EP1252269B1 EP00993628A EP00993628A EP1252269B1 EP 1252269 B1 EP1252269 B1 EP 1252269B1 EP 00993628 A EP00993628 A EP 00993628A EP 00993628 A EP00993628 A EP 00993628A EP 1252269 B1 EP1252269 B1 EP 1252269B1
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Prior art keywords
carbon atoms
fuel
formula
combustible
additive
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German (de)
French (fr)
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EP1252269A1 (en
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Franck Eydoux
Philippe Flores
Dominique Vichard
Laurent Germanaud
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Total Marketing Services SA
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Total France SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C10L10/16—Pour-point depressants

Definitions

  • the present invention relates to a new composition of multifunctional additives improving cold operability of middle distillates. She aims in particular the improvement of dispersing properties, anti-sedimentation and lowering point temperatures flow point and cloud point but also a improvement of the cetane of these distillates for a use as fuel for diesel engines and in fuels such as fuel oil for boilers.
  • Cold operability corresponds to a temperature limit at which middle distillates can be used without clogging problem. She is intermediate between cloud point temperature (ASTM D 2500-98) characteristic of the onset of crystallization of paraffins in the distillate and the pour point of the latter (ASTM D 97-96a).
  • paraffins are crystallized at bottom of the tank, they can be dragged starting in the fuel system and clogging in particular filters and prefilters placed upstream of the systems injection (pump and injectors). Likewise for storage domestic fuel oils, paraffins precipitate in the bottom tank and can be dragged and obstruct the pipes upstream of the pump and the supply system of the boiler (nozzle and filter). It is obvious that the presence of solids, such as paraffin crystals, prevents normal circulation of the middle distillate.
  • TLF additives Temporal Limit of Filterability
  • EP-A-0688796 describes an additive obtained by the reaction of a polyetheramine with a polymer containing groups derivatives of dicarboxylic acid anhydride, at least 1% of anhydride groups which have reacted with polyetheramine.
  • EP-A-02183293 describes an additive based on a copolymer octadecene and maleic anhydride reacted with diamine, however, no ration is indicated.
  • the copolymer of formula (I) is preferably a copolymer containing 45 65 mole of at least one olefin unit and 55 to 35 mole% at least one dicarboxylic unit.
  • dicarboxylics are preferably chosen from the group consisting of maleic anhydride, anhydride citraconic and fumaric acid, and olefin units chosen from linear or branched alkenyl units comprising from 1 to 30 carbon atoms.
  • the copolymer is chosen from copolymers maleic anhydride-octadecene, maleic anhydride-dodecene and maleic anhydride-hexadecene.
  • R 1 and R 2 are radicals preferably chosen from the group consisting of the dodecyl and octadecyl radicals and R 3 is chosen from alkyl groups comprising from 10 to 20 carbon atoms.
  • the alkylamines and polyalkylene polyamines of formula (II) are preferably chosen from the group comprising dibutylamine, didodecylamine, dioctadecylamine, N-alkylethylenediamines, N-alkylpropylenediamines, N-alkylbutylenediamines, N-alkyldiethylenetriamines, N-alkyldipropylenetriamines, N-alkyldibutylenetriamines, N-alkyltriethylenetetramines, N-alkyltripropylenetetramines, N-alkyltributylenetetramines, N-alkyltetraethylene pentamines, N-alkyltetrapropylenepentamines and N-alkyltributylenepentamines having an alkyl radical comprising from 12 to 22 carbon atoms, preferably N-dodecyldipropylenetri
  • a second object of the invention is a composition of additives comprising an additive of formula (I) and at least an additive chosen from filter additives and / or flow, procetane additives, promoters combustion and soot catalysts, detergents, lubricant additives, anti-wear and anti-foam additives, and other additives or additive compositions for improve cloud point, dispersion and paraffin sedimentation.
  • a third object according to the invention is a fuel, fuel and / or fuel oil containing a portion major hydrocarbon base made up of gasolines, middle distillates, synthetic fuels, animal or vegetable oils, esterified or not, and their mixtures, and a corresponding minor part from 50 to 1000 ppm to at least one multifunctional additive of formula (I).
  • This additive may be present in the fuel or fuel with at least one additive from the group consisting of procetane additives, catalytic promoters of combustion and soot, detergents, additives lubricity, anti-wear additives, anti-foam additives, anti-corrosion additives and other additives or additive compositions for improving the cloud point, dispersion and sedimentation of paraffins.
  • This example aims to show the effectiveness in filterability and flow of additives according to the invention to illustrate the intrinsic properties of additives of formula (III), (IV) and (V) when used alone and when used in formulation with others additives.
  • additive 1 consists of a copolymer comprising maleic anhydride units and octadecene units in a molar ratio 1/1, R 1 , R 2 , R ' 1 and R' 2 being identical and corresponding to dodecylamine radical.
  • additive 2 consists of a copolymer comprising maleic anhydride units and octadecene units in a molar ratio 1/1, R 1 and R ′ 1 being a hydrogen atom, R 2 a butyl radical and R ′ 2 being a dodecyl radical.
  • additive 3 consists of a copolymer comprising comprising maleic anhydride units and octadecene units in a molar ratio 1/1, R 1 is a hydrogen atom, R 2 being a ethylamine radical and R ′ 5 being a hexadecyl radical.
  • the above copolymers are generally obtained by chemical modification of an alpha-olefin / anhydride type copolymer maleic, the alpha-olefin being here octadecene.
  • the octadecene / maleic anhydride copolymer is synthesized in solution in a solvent preferably aromatic (for example toluene or xylene).
  • a solvent preferably aromatic (for example toluene or xylene).
  • the length of olefin chain ranges from 13 to 30 carbons, and this monomer is radically copolymerized (in a molar ratio varying from 0.4 to 0.6 with anhydride maleic, in bulk or in solution.
  • Priming is done thermally and preferably at temperatures between 60 and 140 ° C, and more precisely between 80 and 120 ° C.
  • two molar equivalents of amine are reacted on a molar equivalent of anhydride, without bringing the temperature to too high a value to not obtain a structure diamide.
  • the reaction temperature can vary from 20 ° C to 90 ° C, and preferably from 40 to 80 ° C. To get the ester we later reacts alcohol in proportions comparable.
  • the additives according to the invention provide a greater pour point gain than additives FI known. This gain is further increased when the additives 1,2 and 3 are combined with one of the FI additives.
  • the example presents the anti-sedimentation properties of the additives of formula (III), (IV) and (V) described in example 1 when they are introduced alone into the three gas oils 1, 2 and 3 at a content 0.025% by weight or in combination with two additives FI 1 and FI 2 at a concentration of 0.0125% by weight each.
  • A corresponds to very few sedimentation
  • B at stability
  • C at strong sedimentation visible to the eye.
  • additives 1, 2 and 3 provide an anti-sedimentation effect resulting in a change of category (C in A, or C in B) whether used alone or in combination mixture in each of the gas oils in the presence of an FI additive.
  • the present example illustrates the capacity of the additives 1, 2 and 3 of the invention to lower the cloud point of gas oils, this cloud point corresponding to the starting crystallization temperature (TCC) determined according to standard IP 389/90.
  • TCC crystallization temperature

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Detergent Compositions (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Beans For Foods Or Fodder (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Saccharide Compounds (AREA)

Abstract

The invention concerns a multifunctional additive enabling fuels to be operable in cold conditions, consisting of copolymers of at least a dicarboxylic compound with at least an olefin, and whereon are grafted nitrogenous functions and/or esters of general formula (1) wherein: R1 and R2, and R4 and R5, R3 and R6 are hydrogen or alkyl radicals, and x is selected among the amine salts and N-alkylpolyalkylenepolyamines and their monohydroxylated and polyhydroxylated derivatives, N-alkylpolyalkylenepolyamine alkylesters and esters, and alkylamines and N-alkylpolyalkylenepolyamines.

Description

La présente invention concerne une nouvelle composition d'additifs multifonctionnels améliorant l'opérabilité à froid des distillats moyens. Elle vise notamment l'amélioration des propriétés dispersantes, antisédimentation et l'abaissement des températures de point d'écoulement et de point de trouble, mais aussi une amélioration du cétane de ces distillats pour une utilisation comme carburant pour moteurs Diesel et dans les combustibles tels que les fiouls domestiques pour chaudières.The present invention relates to a new composition of multifunctional additives improving cold operability of middle distillates. She aims in particular the improvement of dispersing properties, anti-sedimentation and lowering point temperatures flow point and cloud point but also a improvement of the cetane of these distillates for a use as fuel for diesel engines and in fuels such as fuel oil for boilers.

L'opérabilité à froid correspond à une température limite à laquelle les distillats moyens peuvent être utilisés sans problème de colmatage. Elle est intermédiaire entre la température du point de trouble (ASTM D 2500-98) caractéristique du début de cristallisation des paraffines dans le distillat et le point d'écoulement de ce dernier (ASTM D 97-96a).Cold operability corresponds to a temperature limit at which middle distillates can be used without clogging problem. She is intermediate between cloud point temperature (ASTM D 2500-98) characteristic of the onset of crystallization of paraffins in the distillate and the pour point of the latter (ASTM D 97-96a).

Il est bien connu que la cristallisation des paraffines est un facteur limitatif de l'utilisation des distillats moyens. Aussi, il est important de préparer des carburants Diesel adaptés aux températures auxquelles ils seront utilisés dans les véhicules motorisés, c'est-à-dire au climat environnant. Généralement, une opérabilité à froid des carburants à -10°C est suffisante dans beaucoup de pays industrialisés. Mais dans d'autres pays, comme les pays nordiques, le Canada et les pays d'Asie du nord, on peut atteindre des températures d'utilisation des carburants bien inférieures à -20°C. Il en est de même pour les fiouls domestiques stockés à l'extérieur pour les maisons particulières et immeubles.It is well known that the crystallization of paraffins is a limiting factor in the use of middle distillates. Also, it is important to prepare Diesel fuels adapted to the temperatures at which they will be used in motorized vehicles, i.e. to the surrounding climate. Typically cold operability fuels at -10 ° C is sufficient in many countries industrialized. But in other countries, like countries countries, Canada and the countries of North Asia, we can achieve good fuel usage temperatures below -20 ° C. It is the same for fuel oils domestic stored outside for homes individuals and buildings.

Cette adéquation de l'opérabilité à froid des carburants Diesel est importante, notamment au démarrage à froid des moteurs. Si les paraffines sont cristallisées au fond du réservoir, elles peuvent être entraínées au démarrage dans le circuit de carburant et colmater notamment les filtres et préfiltres disposés en amont des systèmes d'injection (pompe et injecteurs). De même pour le stockage des fiouls domestiques, les paraffines précipitent en fond de cuve et peuvent être entraínées et obstruer les conduites en amont de la pompe et du système d'alimentation de la chaudière (gicleur et filtre). Il est évident que la présence de solides, tels que les cristaux de paraffines, empêche la circulation normale du distillat moyen.This adequacy of the cold operability of Diesel fuels is important, especially when starting up engine cold. If the paraffins are crystallized at bottom of the tank, they can be dragged starting in the fuel system and clogging in particular filters and prefilters placed upstream of the systems injection (pump and injectors). Likewise for storage domestic fuel oils, paraffins precipitate in the bottom tank and can be dragged and obstruct the pipes upstream of the pump and the supply system of the boiler (nozzle and filter). It is obvious that the presence of solids, such as paraffin crystals, prevents normal circulation of the middle distillate.

Pour améliorer leur circulation soit dans le moteur, soit vers les chaudières, plusieurs types d'additifs ont vu le jour.To improve their circulation either in the engine, either to the boilers, several types of additives have been the day.

Dans un premier temps, l'industrie pétrolière s'est attachée au développement des additifs favorisant la filtrabilité des carburants aux basses températures. Ces additifs, appelés additifs de TLF (Température Limite de Filtrabilité), ont pour rôle de limiter la taille des cristaux des paraffines formées. Ce type d'additifs, connu très largement par l'homme du métier, est actuellement systématiquement ajouté aux distillats moyens.The petroleum industry initially attached to the development of additives promoting filterability of fuels at low temperatures. These additives, called TLF additives (Temperature Limit of Filterability), have the role of limiting the size of paraffin crystals formed. This type of additive, known widely by those skilled in the art, is currently systematically added to middle distillates.

Pourtant ces additifs, bien que régulateurs de la taille des cristaux paraffiniques, ne peuvent pas empêcher la sédimentation des cristaux formés c'est-à-dire leur agglomération, notamment au fond des réservoirs des véhicules Diesel à l'arrêt ou dans les cuves de stockage des fiouls domestiques.However, these additives, although regulating the paraffinic crystal size, can not prevent the sedimentation of the crystals formed, that is to say their agglomeration, especially at the bottom of the reservoirs Diesel vehicles stationary or in the storage tanks of domestic fuel oils.

Aussi, dans un deuxième temps, l'industrie pétrolière s'est efforcée à développer des additifs antisédimentation, c'est-à-dire des dispersants, qui maintiennent les cristaux paraffiniques en suspension dans le distillat moyen ce qui évite qu'ils se déposent et s'agglomèrent entre eux. La demanderesse a notamment développé un tel additif décrit dans le brevet EP 0 674 689.Also, in a second step, the industry petroleum has endeavored to develop additives anti-sedimentation, i.e. dispersants, which keep paraffinic crystals suspended in the middle distillate which prevents them from settling and clump together. The plaintiff has in particular developed such an additive described in patent EP 0 674 689.

Néanmoins, l'action conjuguée des additifs TLF et antisédimentation n'a pas permis d'améliorer l'opérabilité à froid de tous les distillats moyens produits en raffinerie issus de tous les pétroles bruts connus.However, the combined action of the TLF additives and anti-sedimentation did not improve operability at cold of all middle distillates produced in refineries from all known crude oils.

C'est pourquoi l'industrie pétrolière a mis en oeuvre un troisième type d'additifs en vue d'abaisser la température d'opérabilité à froid des distillats moyens quels qu'ils soient y compris en dessous de -20°C, même si leur température de point de trouble est supérieure à -20°C. This is why the petroleum industry has implemented uses a third type of additive to lower the cold operability temperature of middle distillates whatever they are including below -20 ° C, even if their cloud point temperature is above -20 ° C.

C'est le cas des additifs décrits dans les brevets EP 0 722 481 et EP 0 832 172.This is the case of the additives described in the EP 0 patents 722 481 and EP 0 832 172.

EP-A-0688796 décrit un additif obtenu par la réaction d'une polyétheramine avec un polymère contenant des groupes dérivés d'anhydride d'acide dicarboxylique, au moins 1% des groupes anhydride ayant réagi avec la polyétheramine.EP-A-0688796 describes an additive obtained by the reaction of a polyetheramine with a polymer containing groups derivatives of dicarboxylic acid anhydride, at least 1% of anhydride groups which have reacted with polyetheramine.

EP-A-02183293 décrit un additif à, base d'un copolymère d'octadécène et d'anhydride maléique ayant réagi avec une diamine, aucun ration n'étant cependant indiqué.EP-A-02183293 describes an additive based on a copolymer octadecene and maleic anhydride reacted with diamine, however, no ration is indicated.

La présente invention vise un nouvel additif multifonctionnel permettant d'abaisser et de maintenir la température d'opérabilité à froid jusqu'à des températures au-delà de -20°C, mais aussi d'augmenter le cétane de ces distillats, sans aucune sédimentation des paraffines contenues dans les distillats moyens.
La présente invention a donc pour objet un combustible, carburant et/ou fioul, contenant une partie majeure d'une base hydrocarbonée constituée par les essences, les distillats moyens, les carburants de synthèse, les huiles animales ou végétales, estérifées ou non, et leurs mélanges, et une partie mineure de 50 à 1000ppm d'au moins un additif multifonctionnel d'opérabilité à froid des combustibles, cet additif étant constitué de copolymères d'au moins un composé dicarboxylique avec au moins une oléfine, et sur lequel sont greffées des fonctions azotées et/ou esters de formule générale (I) ci-après :

Figure 00030001
dans laquelle R1 et R2, identiques ou différents, sont des radicaux alkyles comprenant de 1 à 20 atomes de carbones, R3 et R6 identiques ou différents, sont l'hydrogène ou des radicaux alkyls comprenant de 1 à 30 atomes de carbone, avec R3 choisi parmi les groupements alkyls comprenant de 12 à 30 atomes de carbone quand R6 est l'hydrogène et inversement, R4 et R5, identiques ou différents, correspondent à l'hydrogène ou un radical alkyl comprenant de 1 à 22 atomes de carbone, n et m des nombres entiers variant de 1 à 50, X est choisi parmi :

  • i) les sels d'amine de type
    Figure 00040001
    dans lequel R'1 et R'2 identiques ou différents sont choisis parmi les groupements alkyles comprenant de 1 à 18 atomes de carbone, les alkylamines comprenant de 1 à 18 atomes de carbone et les N- alkylpolyalkylène-amines de formule (II) ;
    Figure 00040002
    avec R'3 et R'4, identiques ou différents, étant l'hydrogène ou un groupement alkyle linéaire ou ramifié comprenant de 1 à 22 atomes de carbone, et x, y et z des nombres entiers, x variant de 1 à 6 et y et z variant de 0 à 6, et les amines et polyamines mono et polyhydroxylées;
  • ii) les esters -OR'5, R'5 choisi parmi les radicaux alkyls comprenant de 1 à 30 atomes de carbone, et les N-alkylpolyalkylènepolyamines de formule (II);
  • iii) les alkylamines comprenant de 1 à 44 atomes de carbone; les N-alkylpolyalkylènepolyamines de formule (II); et lorsque R6 est l'hydrogène et R3 est choisi parmi les radicaux décyl, tétradécyl, hexadécyl, octadécyl et eicosyl, X est le groupe -NR"1R"2, dans lequel R"1 et R"2 identiques ou différents, sont choisis parmi les alkylamines comprenant de 1 à 22 atomes de carbone et les N-alkylpolyalkylènepolyamines du groupe comprenant les N-alkyldiéthylènetriamines, les N-alkyldipropylènetriamines, les N-alkyltriéthylènetétramines, les N-alkyltétraéthylènepentamines et les N-alkyltétra-propylènepentamines, ou alors R"1 et R"2 sont l'un un groupe alkyl de 12 à 18 atomes de carbone et l'autre est choisi parmi les alkylamines comprenant de 1 à 22 atomes de carbone et les N-alkylpolyalkylènepolyamines du groupe comprenant les N-alkyldiéthylènetriamines, les N-alkyldipropylènetriamines, les N-alkyltriéthylènetétramines, les N-alkyltétraéthylènepentamines et les N-alkyltétra-propylènepentamines;
    • le copolymère de formule (I) contenant de 45 à 65 % mole d'au moins un motif oléfine et de 55 à 35 % mole d'au moins un motif dicarboxylique.The present invention aims at a new multifunctional additive making it possible to lower and maintain the cold operability temperature up to temperatures above -20 ° C., but also to increase the cetane of these distillates, without any sedimentation. paraffins contained in middle distillates.
    The present invention therefore relates to a fuel, fuel and / or fuel oil, containing a major part of a hydrocarbon base constituted by gasolines, middle distillates, synthetic fuels, animal or vegetable oils, esterified or not, and their mixtures, and a minor part of 50 to 1000 ppm of at least one multifunctional additive for cold operability of fuels, this additive consisting of copolymers of at least one dicarboxylic compound with at least one olefin, and on which are grafted nitrogen and / or ester functions of general formula (I) below:
    Figure 00030001
    in which R 1 and R 2 , identical or different, are alkyl radicals comprising from 1 to 20 carbon atoms, R 3 and R 6 identical or different, are hydrogen or alkyl radicals comprising from 1 to 30 carbon atoms , with R 3 chosen from alkyl groups comprising from 12 to 30 carbon atoms when R 6 is hydrogen and vice versa, R 4 and R 5 , identical or different, correspond to hydrogen or an alkyl radical comprising from 1 to 22 carbon atoms, n and m whole numbers varying from 1 to 50, X is chosen from:
  • i) amine salts of the type
    Figure 00040001
    in which R ' 1 and R' 2, which are identical or different, are chosen from alkyl groups comprising from 1 to 18 carbon atoms, alkylamines comprising from 1 to 18 carbon atoms and N-alkylpolyalkylene-amines of formula (II);
    Figure 00040002
    with R ' 3 and R' 4 , identical or different, being hydrogen or a linear or branched alkyl group comprising from 1 to 22 carbon atoms, and x, y and z whole numbers, x varying from 1 to 6 and y and z varying from 0 to 6, and the mono and polyhydroxylated amines and polyamines;
  • ii) the esters -OR ' 5 , R' 5 chosen from alkyl radicals comprising from 1 to 30 carbon atoms, and N-alkylpolyalkylenepolyamines of formula (II);
  • iii) alkylamines comprising from 1 to 44 carbon atoms; the N-alkylpolyalkylene polyamines of formula (II); and when R 6 is hydrogen and R 3 is chosen from decyl, tetradecyl, hexadecyl, octadecyl and eicosyl radicals, X is the group -NR " 1 R" 2 , in which R " 1 and R" 2 are identical or different , are chosen from alkylamines comprising from 1 to 22 carbon atoms and N-alkylpolyalkylene polyamines from the group comprising N-alkyldiethylenetriamines, N-alkyldipropylenetriamines, N-alkyltriethylenetetramines, N-alkyltetraethylenepentamines and N-alkyltetrapentines then R " 1 and R" 2 are one an alkyl group of 12 to 18 carbon atoms and the other is chosen from alkylamines comprising from 1 to 22 carbon atoms and N-alkylpolyalkylene polyamines from the group comprising N- alkyldiethylenetriamines, N-alkyldipropylenetriamines, N-alkyltriethylenetetramines, N-alkyltetraethylenepentamines and N-alkyltetrapropylenepentamines;
    • the copolymer of formula (I) containing from 45 to 65 mol% of at least one olefin unit and from 55 to 35 mol% of at least one dicarboxylic unit.

    Des modes de réalisation particuliers correspondent aux revendications dépendantes 2 à 15. Particular embodiments correspond to dependent claims 2 to 15.

    On a constaté que ces additifs polyfonctionnels utilisés seuls ou en mélange présentaient de façon inattendue à la fois des propriétés de dispersion et d'anti-sédimentation supérieures aux additifs polyfonctionnels connus d'opérabilité à froid, un abaissement du point d'écoulement et également un abaissement des températures de filtrabilité (ou TLF) et de point de trouble des carburants, ainsi qu'une amélioration de l'indice de cétane.It has been found that these polyfunctional additives used alone or as a mixture unexpected both dispersing properties and anti-sedimentation superior to additives known polyfunctional cold operability, a lowering the pour point and also a lower filterability (or TLF) and fuel cloud point, as well as an improvement cetane number.

    Selon la présente invention, le copolymère de formule (I) est de préférence un copolymère contenant de 45 à 65 mole d'au moins un motif oléfine et de 55 à 35 % mole d'au moins un motif dicarboxylique. Les motifs dicarboxyliques sont choisis préférentiellement dans le groupe constitué par l'anhydride maléique, l'anhydride citraconique et l'acide fumarique, et les motifs oléfines choisis parmi les motifs alcényls linéaires ou ramifiés comprenant de 1 à 30 atomes de carbone. Dans un mode plus favorable, le copolymère est choisi parmi les copolymères anhydride maléïque-octadécène, anhydride maléïque-dodécène et anhydride maléïque-hexadécène.According to the present invention, the copolymer of formula (I) is preferably a copolymer containing 45 65 mole of at least one olefin unit and 55 to 35 mole% at least one dicarboxylic unit. The reasons dicarboxylics are preferably chosen from the group consisting of maleic anhydride, anhydride citraconic and fumaric acid, and olefin units chosen from linear or branched alkenyl units comprising from 1 to 30 carbon atoms. In a more fashion favorable, the copolymer is chosen from copolymers maleic anhydride-octadecene, maleic anhydride-dodecene and maleic anhydride-hexadecene.

    Dans le copolymère de formule (I), R1 et R2 sont des radicaux choisis de préférence dans le groupe constitué par les radicaux dodécyl et octadécyl et R3 est choisi parmi les groupements alkyles comprenant de 10 à 20 atomes de carbone.In the copolymer of formula (I), R 1 and R 2 are radicals preferably chosen from the group consisting of the dodecyl and octadecyl radicals and R 3 is chosen from alkyl groups comprising from 10 to 20 carbon atoms.

    Un premier additif selon l'invention est le copolymère de formule (III) ci-après:

    Figure 00070001
    dans laquelle R'1 et R'2 identiques ou différents sont choisis parmi les radicaux alkyles de 12 à 18 atomes de carbone, les alkylamines comprenant de 1 à 22 atomes de carbone et les N-alkylpolyalkylènepolyamines de formule (II) et les amines hydroxylées du groupe comprenant la diéthanolamine, la monoéthanolamine, la N-butylamine, la N-décyléthanolamine et la N-dodécyléthanolamine et leurs dérivés alcoxylés,

    • et R3 choisi parmi les radicaux décyl, tétradécyl, hexadécyl, octadécyl et eicosyl.
    A first additive according to the invention is the copolymer of formula (III) below:
    Figure 00070001
    in which R ' 1 and R' 2, which are identical or different, are chosen from alkyl radicals of 12 to 18 carbon atoms, alkylamines comprising from 1 to 22 carbon atoms and N-alkylpolyalkylenepolyamines of formula (II) and hydroxylated amines from the group comprising diethanolamine, monoethanolamine, N-butylamine, N-decylethanolamine and N-dodecylethanolamine and their alkoxylated derivatives,
    • and R 3 chosen from the decyl, tetradecyl, hexadecyl, octadecyl and eicosyl radicals.

    Un deuxième additif selon l'invention est le copolymère de formule (IV) ci-après :

    Figure 00070002
    dans laquelle

    • R'1 et R'2, identiques ou différents, sont choisis parmi les radicaux alkyls contenant de 1 22 atomes de carbone et les N-alkylpolyalkylènepolyamines du groupe comprenant les N-alkyldiéthylènetriamines, les N-alkyldipropylènetriamines, les N-alkyltriéthylènetétramines, les N-alkyltétraéthylènepentamines et les N-alkyltétra-propylènepentamines,
    • et R3 choisi parmi les radicaux décyl, tétradécylhexadécyl, octadécyl et eicosyl.
    A second additive according to the invention is the copolymer of formula (IV) below:
    Figure 00070002
    in which
    • R ' 1 and R' 2 , identical or different, are chosen from alkyl radicals containing from 12 to 22 carbon atoms and N-alkylpolyalkylene polyamines from the group comprising N-alkyldiethylenetriamines, N-alkyldipropylenetriamines, N-alkyltriethylenetetramines, N -alkyltetraethylenepentamines and N-alkyltetrapropylenepentamines,
    • and R 3 chosen from the decyl, tetradecylhexadecyl, octadecyl and eicosyl radicals.

    Un troisième additif selon l'invention est un copolymère de formule (V) ci-après :

    Figure 00070003
    dans laquelle

    • R'5 est choisi parmi les radicaux alkyls comprenant de 6 à 18 atomes de carbone et les N-alkylpolyalkylènepolyamines de formule (II) du groupe comprenant comprenant les N-alkyldiéthylènetriamines, les N-alkyldipropylènetriamines, les N-alkyltriéthylènetétramines, les N-alkyltétraéthylénepentamines et les N-alkyltétra-propylènepentamines,
    • et R3 choisi parmi les radicaux décyl, tétradécyl, hexadécyl, octadécyl et eicosyl.
    A third additive according to the invention is a copolymer of formula (V) below:
    Figure 00070003
    in which
    • R ' 5 is chosen from alkyl radicals comprising from 6 to 18 carbon atoms and N-alkylpolyalkylene polyamines of formula (II) from the group comprising N-alkyldiethylenetriamines, N-alkyldipropylenetriamines, N-alkyltriethylenetetramines, N-alkyltetraethylenepentamines and N-alkyltetrapropylenepentamines,
    • and R 3 chosen from the decyl, tetradecyl, hexadecyl, octadecyl and eicosyl radicals.

    Selon l'invention, les alkylamines et polyalkylènepolyamines de formule (II) sont choisies de préférence dans le groupe comprenant la dibutylamine, la didodécylamine, la dioctadécylamine, la N-alkyléthylènediamines, N-alkylpropylènediamines, N-alkylbutylènediamines, les N-alkyldiéthylènetriamines, les N-alkyldipropylènetriamines, les N-alkyldibutylènetriamines, les N-alkyltriéthylènetétramines, les N-alkyltripropylènetétramines, les N-alkyltributylènetétramines, les N-alkyltétraéthylènepentamines, les N-alkyltétrapropylènepentamines et les N-alkyltributylènepentamines présentant un radical alkyle comprenant de 12 à 22 atomes de carbone, de préférence la N-dodécyldipropylènetriamine, le N-octadécyldipropylènetriamine, la N-octadécyldiéthylène-triamine et la N-docosyldiéthylènetriamine.According to the invention, the alkylamines and polyalkylene polyamines of formula (II) are preferably chosen from the group comprising dibutylamine, didodecylamine, dioctadecylamine, N-alkylethylenediamines, N-alkylpropylenediamines, N-alkylbutylenediamines, N-alkyldiethylenetriamines, N-alkyldipropylenetriamines, N-alkyldibutylenetriamines, N-alkyltriethylenetetramines, N-alkyltripropylenetetramines, N-alkyltributylenetetramines, N-alkyltetraethylene pentamines, N-alkyltetrapropylenepentamines and N-alkyltributylenepentamines having an alkyl radical comprising from 12 to 22 carbon atoms, preferably N-dodecyldipropylenetriamine, N-octadecyldipropylenetriamine, N-octadecyldiethylene triamine and N-docosyldiethylenetriamine.

    Un deuxième objet de l'invention est une composition d'additifs comprenant un additif de formule (I) et au moins un additif choisi parmi les additifs de filtrablité et/ou d'écoulement, les additifs procétanes, les promoteurs catalytiques de combustion et de suie, les détergents, les additifs de lubrifiance, les additifs anti-usure et anti-mousse, et d'autres additifs ou compositions d'additifs pour améliorer le point de trouble, la dispersion et la sédimentation des paraffines.A second object of the invention is a composition of additives comprising an additive of formula (I) and at least an additive chosen from filter additives and / or flow, procetane additives, promoters combustion and soot catalysts, detergents, lubricant additives, anti-wear and anti-foam additives, and other additives or additive compositions for improve cloud point, dispersion and paraffin sedimentation.

    Parmi ces additifs, on peut citer particulièrement:

  • a) additif procétane, notamment (mais non limitativement) choisi parmi les nitrates d'alkyle, de préférence le nitrate de 2-éthylhexyle, les peroxydes d'aroyle, de préférence le peroxyde de benzyle, et les peroxydes d'alkyle, de préférence le peroxyde de ter-butyle.
  • b) additif de filtrabilité, notamment (mais non limitativement) choisi parmi les copolymères éthylène/acétate de vinyle (EVA), éthylène/propionate de vinyle (EVP), éthylène/éthanoate de vinyle (EVE), éthylène/méthacrylate de méthyle (EMMA), et éthylène/fumarate d'alkyle. Des exemples de tels additifs sont donnés dans les documents suivants: EP-A-0187488, FR-A-2490669, EP-A-0722481, EP-A-0832172.
  • c) additif anti-mousse, notamment (mais non limitativement) choisi parmi les polysiloxanes, les polysiloxanes oxyalkylés, et les amides d'acides gras issus d'huiles végétales ou animales. Des exemples de tels additifs sont donnés dans les documents suivants: EP-A-0861182, EP-A-0663000, EP-A-0736590.
  • d) additif détergent et/ou anti-corrosion, notamment (mais non limitativement) choisi dans le groupe constitué par les amines, les succinimides, les alkénylsuccinimides, les polyalkylamines, les polyalkyles polyamines et les polyétheramines. Des exemples de tels additifs sont donnés dans les documents suivants: EP-A-0938535.
  • e) additif de lubrifiance ou anti-usure, notamment (mais non limitativement) choisi dans le groupe constitué par les acides gras et leurs dérivés ester ou amide, notamment le monooléate de glycérol, et les dérivés d'acides carboxyliques mono- et polycycliques. Des exemples de tels additifs sont donnés dans les documents suivants: EP-A-0680506, EP-A-0860494, WO-A-9804656, EP-A-0915944, FR-A-2772783, FR-A-2772784.
  • f) additif de point de trouble, notamment (mais non limitativement) choisi dans le groupe constitué par les terpolymères oléfine à chaíne longue/ester (méth)acrylique /maléimide, et les polymères d'esters d'acides fumarique /maléique. Des exemples de tels additifs sont donnés dans les documents suivants: EP-A-0071513, EP-A-0100248, FR-A-2528051, FR-A-2528051, FR-A-2528423, EP-A-0112195, EP-A-0172758, EP-A-0271385, EP-A-0291367.
  • g) additif d'anti-sédimentation, notamment (mais non limitativement) choisi dans le groupe constitué par les copolymères acide (méth)acrylique/(méth)acrylate d'alkyle amidifié par une polyamine, les alkénylsuccinimides de polyamine, les dérivés d'acide phtalamique et d'amine grasse à double chaíne. Des exemples de tels additifs sont donnés dans les documents suivants: EP-A-0261959, EP-A-00593331, EP-A-0674689, EP-A-0327423, EP-A-0512889, EP-A-0832172.
  • h) additif polyfonctionnel d'opérabilité à froid choisi dans le groupe constitué par les polymères à base d'oléfine et de nitrate d'alkényle tels que décrits dans le EP 0 573 490.
    • Among these additives, there may be mentioned in particular:
  • a) procetane additive, in particular (but not limited to) chosen from alkyl nitrates, preferably 2-ethylhexyl nitrate, aroyl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide.
  • b) filterability additive, in particular (but not limited to) chosen from ethylene / vinyl acetate (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA) copolymers ), and ethylene / alkyl fumarate. Examples of such additives are given in the following documents: EP-A-0187488, FR-A-2490669, EP-A-0722481, EP-A-0832172.
  • c) anti-foam additive, in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils. Examples of such additives are given in the following documents: EP-A-0861182, EP-A-0663000, EP-A-0736590.
  • d) detergent and / or anti-corrosion additive, in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenyl succinimides, polyalkylamines, polyalkyl polyamines and polyetheramines. Examples of such additives are given in the following documents: EP-A-0938535.
  • e) lubricating or anti-wear additive, in particular (but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and derivatives of mono- and polycyclic carboxylic acids. Examples of such additives are given in the following documents: EP-A-0680506, EP-A-0860494, WO-A-9804656, EP-A-0915944, FR-A-2772783, FR-A-2772784.
  • f) cloud point additive, in particular (but not limited to) chosen from the group consisting of long chain olefin / (meth) acrylic / maleimide ester terpolymers, and polymers of fumaric / maleic acid esters. Examples of such additives are given in the following documents: EP-A-0071513, EP-A-0100248, FR-A-2528051, FR-A-2528051, FR-A-2528423, EP-A-0112195, EP- A-0172758, EP-A-0271385, EP-A-0291367.
  • g) anti-sedimentation additive, in particular (but not limited to) chosen from the group consisting of (meth) acrylic acid / alkyl (meth) acrylate copolymers amidified by a polyamine, polyamine alkenyl succinimides, derivatives of phthalamic acid and fatty amine with double chain. Examples of such additives are given in the following documents: EP-A-0261959, EP-A-00593331, EP-A-0674689, EP-A-0327423, EP-A-0512889, EP-A-0832172.
  • h) polyfunctional cold operability additive chosen from the group consisting of polymers based on olefin and alkenyl nitrate as described in EP 0 573 490.

    • Un troisième objet selon l'invention est un combustible, carburant et/ou fioul contenant une partie majeure de base hydrocarbonée constituée par les essences, les distillats moyens, les carburants de synthèse, les huiles animales ou végétales, estérifées ou non, et leurs mélanges, et une partie mineure correspondant de 50 à 1000 ppm à au moins un additif multifonctionnel de formule (I). Cet additif peut être présent dans le carburant ou combustible avec au moins un additif du groupe constitué par les additifs procétanes, les promoteurs catalytiques de combustion et de suie, les détergents, les additifs de lubrifiance, les additifs anti-usure, les additifs anti-mousse, les additifs anti-corrosion et d'autres additifs ou compositions d'additifs pour améliorer le point de trouble, la dispersion et la sédimentation des paraffines.A third object according to the invention is a fuel, fuel and / or fuel oil containing a portion major hydrocarbon base made up of gasolines, middle distillates, synthetic fuels, animal or vegetable oils, esterified or not, and their mixtures, and a corresponding minor part from 50 to 1000 ppm to at least one multifunctional additive of formula (I). This additive may be present in the fuel or fuel with at least one additive from the group consisting of procetane additives, catalytic promoters of combustion and soot, detergents, additives lubricity, anti-wear additives, anti-foam additives, anti-corrosion additives and other additives or additive compositions for improving the cloud point, dispersion and sedimentation of paraffins.

    Aux fins d'illustrer les avantages de la présente invention, des exemples sont donnés à titre non limitatif.For the purpose of illustrating the advantages of this invention, examples are given without limitation.

    EXEMPLE 1EXAMPLE 1

    Le présent exemple vise à montrer l'efficacité en filtrabilité et en écoulement des additifs selon l'invention en vue d'illustrer les propriétés intrinsèques des additifs de formule (III), (IV) et (V) lorsqu'ils sont utilisés seuls et lorsqu'ils sont utilisés en formulation avec d'autres additifs. This example aims to show the effectiveness in filterability and flow of additives according to the invention to illustrate the intrinsic properties of additives of formula (III), (IV) and (V) when used alone and when used in formulation with others additives.

    L'additif (III) référencé ci-après comme additif 1 est constitué d'un copolymère comprenant des motifs anhydride maléique et des motifs octadécène dans un rapport molaire 1/1, R1 , R2, R'1 et R'2 étant identiques et correspondant à radical dodécylamine.The additive (III) referenced below as additive 1 consists of a copolymer comprising maleic anhydride units and octadecene units in a molar ratio 1/1, R 1 , R 2 , R ' 1 and R' 2 being identical and corresponding to dodecylamine radical.

    L'additif (IV) référencé ci-après comme additif 2 est constitué d'un copolymère comprenant des motifs anhydride maléique et des motifs octadécène dans un rapport molaire 1/1, R1 et R'1 étant un atome d'hydrogène, R2 un radical butyl et R'2 étant un radical dodécyl.The additive (IV) referenced below as additive 2 consists of a copolymer comprising maleic anhydride units and octadecene units in a molar ratio 1/1, R 1 and R ′ 1 being a hydrogen atom, R 2 a butyl radical and R ′ 2 being a dodecyl radical.

    L'additif (V) référencé ci-après comme additif 3 est constitué d'un copolymère comprenant comprenant des motifs anhydride maléique et des motifs octadécène dans un rapport molaire 1/1,R1 est un atome d'hydrogène, R2 étant un radical éthylamine et R'5 étant un radical hexadécyl.The additive (V) referenced below as additive 3 consists of a copolymer comprising comprising maleic anhydride units and octadecene units in a molar ratio 1/1, R 1 is a hydrogen atom, R 2 being a ethylamine radical and R ′ 5 being a hexadecyl radical.

    Les copolymères ci-dessus sont généralement obtenus par modification chimique d'un copolymère de type alpha-oléfine/anhydride maléïque, l'alpha-oléfine étant ici l'octadécène.The above copolymers are generally obtained by chemical modification of an alpha-olefin / anhydride type copolymer maleic, the alpha-olefin being here octadecene.

    Le copolymère octadécène/anhydride maléïque est synthétisé en solution dans un solvant de préférence aromatique (par exemple toluène ou xylène). La longueur de chaíne de l'oléfine varie entre 13 et 30 carbones, et ce monomère est copolymérisé de manière radicalaire (dans un ratio molaire variant de 0,4 à 0,6 avec l'anhydride maléïque, en masse ou en solution. On utilise généralement un amorceur de type peroxyde , hydroperoxyde ou azonitrile afin de contrôler la masse moléculaire du polymère , et ce, dans des concentrations pondérales variant de 0,5 à 5% de la somme des monomères. L'amorçage se fait de manière thermique et de préférence à des températures comprises entre 60 et 140°C, et plus précisemment entre 80 et 120°C. Afin d'obtenir la structure dicarboxylée de type amide, sel d'amine, on fait réagir 2 équivalents molaire d'amine sur un équivalent molaire d'anhydride, sans porter la température à une valeur trop élevée pour ne pas obtenir de structure diamide. La température de réaction peut varier de 20°C à 90°C, et de préférence de 40 à 80°C. Pour obtenir l'ester on fait réagir ultérieurement un alcool dans des proportions comparables.The octadecene / maleic anhydride copolymer is synthesized in solution in a solvent preferably aromatic (for example toluene or xylene). The length of olefin chain ranges from 13 to 30 carbons, and this monomer is radically copolymerized (in a molar ratio varying from 0.4 to 0.6 with anhydride maleic, in bulk or in solution. We generally use a peroxide, hydroperoxide or azonitrile initiator in order to control the molecular weight of the polymer, and this, in weight concentrations varying from 0.5 to 5% of the sum of the monomers. Priming is done thermally and preferably at temperatures between 60 and 140 ° C, and more precisely between 80 and 120 ° C. To to obtain the dicarboxylated structure of amide, salt type of amine, two molar equivalents of amine are reacted on a molar equivalent of anhydride, without bringing the temperature to too high a value to not obtain a structure diamide. The reaction temperature can vary from 20 ° C to 90 ° C, and preferably from 40 to 80 ° C. To get the ester we later reacts alcohol in proportions comparable.

    Chaque additif est introduit dans trois gazoles différents de caractéristiques données dans le tableau I ci-après. ANALYSES Gazole 1 Gazole 2 Gazole 3 Point de trouble (°C) -5 -3 -1 Température Limite de Filtrabilité (°C) -6 -5. -2 Point d'écoulement (°C) -12 -12 -9 Température de cristallisation (°C) -8.9 -5.60 -9.85 Pourcentage de paraffine 14.8 11.5 10.8 Distillation/ point initial 168 178 176 Point à 5% volume 186 200 201 Point à 20% volume 212 220 222 Point à 40% volume 248 253 256 Point à 60% volume 272 278 282 Point à 80% volume 305 310 314 Point à 90% volume 340 362 356 Point final 354 370 363 Masse Volumique à 15°C 0.8355 0.08375 0.8483 Point éclair 65 71 70 Indice de Cétane 48.9 50.9 47.8 Each additive is introduced into three different diesel oils with characteristics given in Table I below. ANALYZES Diesel 1 Diesel 2 Diesel 3 Cloud point (° C) -5 -3 -1 Filterability Limit Temperature (° C) -6 -5. -2 Pour point (° C) -12 -12 -9 Crystallization temperature (° C) -8.9 -5.60 -9.85 Percentage of paraffin 14.8 11.5 10.8 Distillation / initial point 168 178 176 Point at 5% volume 186 200 201 20% volume point 212 220 222 Point at 40% volume 248 253 256 Point at 60% volume 272 278 282 80% volume point 305 310 314 90% volume point 340 362 356 Period 354 370 363 Density at 15 ° C 0.8355 0.08375 0.8483 Flash point 65 71 70 Cetane number 48.9 50.9 47.8

    Dans le tableau (II) ci-après, on donne les résultats obtenus en opérabilité à froid des additifs fonctionnels selon l'invention lorsqu'ils sont introduits à 0.025% en poids dans les trois gazoles du tableau (I).

    Figure 00130001
    In Table (II) below, the results obtained in cold operability of the functional additives according to the invention are given when they are introduced at 0.025% by weight in the three gas oils in Table (I).
    Figure 00130001

    On constate d'après ce tableau que quels que soient les additifs 1, 2 ou trois, on observe un gain systématique en température de point d'écoulement (PTE) quel que soit le gazole, et que le gain en température de filtrabilité (TLF) est surtout marqué sur les gazoles 2 et 3.We can see from this table that whatever additives 1, 2 or three, we observe a systematic gain in pour point temperature (PTE) whatever the diesel, and the gain in filterability temperature (TLF) is especially marked on diesel 2 and 3.

    Dans le tableau (II) ci-après sont rassemblés les résultats correspondant à l'utilisation de ces trois additifs dans les mêmes gazoles mais à une concentration de 00125% en poids , en combinaison avec deux additifs de filtrabilité (FI1 et FI2) classiquement utilisés en tenue au froid. Ces additifs FI1 et FI2 sont des copolymères ou des mélanges de copolymères de type éthylène / acétate de vinyle, généralement de masse moléculaire variant de 5000 à 50 000 et dont le taux en acétate de vinyle varie de 25% à 32% masse.

    Figure 00140001
    In table (II) below are collated the results corresponding to the use of these three additives in the same gas oils but at a concentration of 00125% by weight, in combination with two filterability additives (FI 1 and FI 2 ) conventionally used in cold weather. These additives FI 1 and FI 2 are copolymers or mixtures of copolymers of ethylene / vinyl acetate type, generally of molecular mass varying from 5000 to 50,000 and the vinyl acetate content of which varies from 25% to 32% by mass.
    Figure 00140001

    On constate d'après ce tableau et le tableau précédent, que les additifs selon l'invention apportent un gain en point d'écoulement plus important que les additifs FI connus. Ce gain est encore accru lorsque les additifs 1,2 et 3 sont combinés avec l'un des additifs FI.We see from this table and the table above, that the additives according to the invention provide a greater pour point gain than additives FI known. This gain is further increased when the additives 1,2 and 3 are combined with one of the FI additives.

    EXEMPLE 2 :EXAMPLE 2:

    L'exemple présente les propriétés d'anti-sédimentation des additifs de formule (III), (IV) et (V) décrits dans l'exemple 1 lorsqu'ils sont introduits seuls dans les trois gazoles 1, 2 et 3 à une teneur de 0.025% en poids ou en combinaison avec deux additifs FI1 et FI2 à une concentration de 0.0125% en poids chacun. The example presents the anti-sedimentation properties of the additives of formula (III), (IV) and (V) described in example 1 when they are introduced alone into the three gas oils 1, 2 and 3 at a content 0.025% by weight or in combination with two additives FI 1 and FI 2 at a concentration of 0.0125% by weight each.

    L'efficacité de ces additifs est déterminée en application de la norme NF M07-085 (95), par une quotation de la TLF et de la température de cristallisation commençante(TCC). Les résultats figurent dans le tableau IV ci-après. sédimentation [norme NF M07-085 (95)] Echantillon lecture visuelle delta TCC (°C) delta TLF (°C) "zone" Gazole 1 60 + C 22,5 17 C gazole 1 + additif "1" trouble 3,2 2 A Gazole 1 + Fl1 58 +C 22,8 18 C gazole 1 + Fl1 + additif "1" 114 + trouble 16,4 4 B Gazole 2 64 + C 24,2 19 C gazole 2 + additif "1" trouble 6,1 5 A Gazole 2 + Fl1 66 +C 21,0 19 C gazole 2 + Fl1 + additif "1" 187 + C 17,8 6 B Gazole 3 58 + C 23,4 19 C gazole 3 + additif "1" 232 + trouble 8,5 5 A Gazole 3 + Fl1 58 + C 23,0 19 C gazole 3 + Fl1 + additif "1" 136 + trouble 10,7 6 A gazole 1 + additif "2" trouble 5,5 5 A Gazole 1+Fl2 58 + C 22,8 18 C gazole 1 + Fl2 + additif "2" 150 + C 15,1 9 B gazole 2 + additif "2" 162 + C 11,2 8 B Gazole 2 + Fl2 66 + C 21,0 19 C gazole 2 + Fl2 + additif "2" 168 + C 9,7 10 B gazole 1 + additif "3" 236 + C 4,3 5 A gazole 1 + Fl2 + additif "3" 164 + trouble 10,2 13 B gazole 2 + additif "3" 172 + C 14,1 10 B gazole 2 + Fl2 + additif "3" 198 + C 15,3 8 B The effectiveness of these additives is determined in application of standard NF M07-085 (95), by a quotation of the TLF and of the starting crystallization temperature (TCC). The results are shown in Table IV below. sedimentation [standard NF M07-085 (95)] Sample visual reading delta TCC (° C) delta TLF (° C) "zoned" Diesel 1 60 + C 22.5 17 VS diesel 1 + additive "1" trouble 3.2 2 AT Diesel 1 + Fl 1 58 + C 22.8 18 VS diesel 1 + Fl 1 + additive "1" 114 + cloudy 16.4 4 B Diesel 2 64 + C 24.2 19 VS diesel 2 + additive "1" trouble 6.1 5 AT Diesel 2 + Fl 1 66 + C 21.0 19 VS diesel 2 + Fl 1 + additive "1" 187 + C 17.8 6 B Diesel 3 58 + C 23.4 19 VS diesel 3 + additive "1" 232 + trouble 8.5 5 AT Diesel 3 + Fl 1 58 + C 23.0 19 VS diesel 3 + Fl 1 + additive "1" 136 + cloudy 10.7 6 AT diesel 1 + additive "2" trouble 5.5 5 AT Diesel 1 + Fl 2 58 + C 22.8 18 VS diesel 1 + Fl 2 + additive "2" 150 + C 15.1 9 B diesel 2 + additive "2" 162 + C 11.2 8 B Diesel 2 + Fl 2 66 + C 21.0 19 VS diesel 2 + Fl 2 + additive "2" 168 + C 9.7 10 B diesel 1 + additive "3" 236 + C 4.3 5 AT diesel 1 + Fl 2 + additive "3" 164 + trouble 10.2 13 B diesel 2 + additive "3" 172 + C 14.1 10 B diesel 2 + Fl 2 + additive "3" 198 + C 15.3 8 B

    Dans ce tableau, A correspond à très peu de sédimentation, B à une stabilité et C à une forte sédimentation visible à l'oeil. In this table, A corresponds to very few sedimentation, B at stability and C at strong sedimentation visible to the eye.

    Des résultats contenus dans ce tableau, on peut conclure que les additifs 1, 2 et 3 apportent un effet antisédimentation se traduisant par un changement de catégorie (C en A, ou C en B) qu'ils soient utilisés seuls ou en mélange dans chacun des gazoles en présence d'un additif FI.From the results contained in this table, we can conclude that additives 1, 2 and 3 provide an anti-sedimentation effect resulting in a change of category (C in A, or C in B) whether used alone or in combination mixture in each of the gas oils in the presence of an FI additive.

    EXEMPLE 3EXAMPLE 3

    L'exemple présent illustre la capacité des additifs 1,2 et 3 de l'invention à abaisser le point de trouble des gazoles, ce point de trouble correspondant à La température de cristallisation commençante (TCC) déterminée selon la norme IP 389/90. Echantillon TCC (°C) Gazole 1 -8,6 gazole 1 + additif "1" -9,7 gazole 1 + additif "2" -10,0 Gazole 2 -4,1 gazole 2 + additif "1" -5,3 gazole 2 + additif "2" -5,2 The present example illustrates the capacity of the additives 1, 2 and 3 of the invention to lower the cloud point of gas oils, this cloud point corresponding to the starting crystallization temperature (TCC) determined according to standard IP 389/90. Sample TCC (° C) Diesel 1 -8.6 diesel 1 + additive "1" -9.7 diesel 1 + additive "2" -10.0 Diesel 2 -4.1 diesel 2 + additive "1" -5.3 diesel 2 + additive "2" -5.2

    On constate d'après ce tableau que les additifs 1, 2 et 3 favorisent l'abaissemnt de la température de cristallisation commençante (TCC) d'au moins 1 °C ce qui constitue pour l'homme du métier un gain appréciable.It can be seen from this table that the additives 1, 2 and 3 favor the lowering of the temperature starting crystallization (TCC) of at least 1 ° C which constitutes for the skilled person an appreciable gain.

    EXEMPLE 4EXAMPLE 4

    Le présent exemple illustre l'effet procétane amené par l'additif 3 de formule (III), utilisé tel quel ou en mélange avec du nitrate d'éthyl-2-hexyl cet effet étant mesuré en appliquant la norme ASTM-D613.This example illustrates the procetane effect brought about by additive 3 of formula (III), used as it is or in mixture with ethyl-2-hexyl nitrate this effect being measured by applying ASTM-D613.

    Les résultats sont donnés dans le tableau VI ci-après pour une concentration de 0.1 % en poids de nitrate d'alkyl et 0.025% en poids de l'additif 1. échantillon indice de cétane mesuré gain / gazole vierge gazole 1 48,9 - Gazole 1 + nitrate d'alkyle 53,5 4,6 Gazole 1 + additif "1" 51,5 2,6 gazole 1 + nitrate d'alkyle + additif "1" 55,0 6,1 gazole 2 50,9 - Gazole 2 + nitrate d'alkyle 54,9 4,0 Gazole 2 + additif "1" 53,6 2,7 gazole 2 + nitrate d'alkyle + additif "1" 56,7 5,8 The results are given in Table VI below for a concentration of 0.1% by weight of alkyl nitrate and 0.025% by weight of the additive 1. sample cetane number measured virgin gain / diesel diesel 1 48.9 - Diesel 1 + alkyl nitrate 53.5 4.6 Diesel 1 + additive "1" 51.5 2.6 diesel 1 + alkyl nitrate + additive "1" 55.0 6.1 diesel 2 50.9 - Diesel 2 + alkyl nitrate 54.9 4.0 Diesel 2 + additive "1" 53.6 2.7 diesel 2 + alkyl nitrate + additive "1" 56.7 5.8

    On confirme d'après ce tableau que les additifs selon l'invention ont bien un effet procétane puisqu'ils apportent un gain de 2,6 à 2,7. Cette amélioration est supérieure lorsque ces additifs selon l'invention sont introduit dans le gazole avec une autre additif de procétane.It is confirmed from this table that the additives according to the invention do have a procetane effect since they bring a gain of 2.6 to 2.7. This improvement is higher when these additives according to the invention are introduced into diesel with another additive of procetane.

    Claims (15)

    1. Combustible, fuel and/or fuel oil, containing a major part of a hydrocarbon base comprising petrols, middle distillates, synthetic fuels, animal or vegetable oils, esterified or not, and their mixtures, and a minor part, from 50 to 1000 ppm, of at least one multifunctional additive enabling fuels to be operable in cold conditions, this additive comprising copolymers of at least one dicarboxylic compound with at least one olefin, and whereon are grafted nitrogenous functions and/or esters of general formula (I) hereafter:
      Figure 00260001
      wherein: R1 and R2, identical or different, are hydrogen or alkyl radicals containing from 1 to 20 carbon atoms, R3 and R6, identical or different, are hydrogen or alkyl radicals containing from 1 to 30 carbon atoms, where R3 is selected among alkyl groups containing from 12 to 30 carbon atoms when R6 is hydrogen and vice versa, R4 and R5, identical or different, correspond to hydrogen or an alkyl radical containing from 1 to 22 carbon atoms, with n and m whole numbers varying between 1 and 50, and X is selected among:
      i) amine salts of the type
      Figure 00260002
      wherein R'1 and R'2, identical or different, are selected among alkyl groups containing from 1 to 18 carbon atoms, alkylamines containing from 1 to 18 carbon atoms, N-alkylpolyalkylene-amines of formula (II) hereafter:
      Figure 00260003
      wherein R'3 and R'4, identical or different, are hydrogen or a linear or branched alkyl group containing from 1 to 22 carbon atoms, and x, y and z whole numbers, x varying between 1 and 6 and y and z varying between 0 and 6, and mono- and poly-hydroxylated amines and polyamines;
      ii) esters -OR'5, R'5 selected among alkyl radicals containing from 1 to 30 carbon atoms and N-alkylpolyalkylene-polyamines of formula (II) ;
      iii) alkylamines containing from 1 to 44 carbon atoms ; N-alkylpolyalkylene-polyamines of formula (II); and when R6 is hydrogen the group - NR"1R"2 in which R"1 and R"2 , identical or different, are selected among alkylamines containing from 1 to 22 carbon atoms and N-alkylpolyalkylene-polyamines from the group comprising N-alkyldiethylene-triamines, N-alkyldipropylene-triamines, N-alkyltriethylene-tetramines, N-alkyltetraethylene-pentamines and N-alkyltetrapropylene-pentamines, or one of R"1 and R"2 is an alkyl group of 12 to 18 carbon atoms and the other is selected among alkylamines containing from 1 to 22 carbon atoms and N-alkylpolyalkylene-polyamines from the group comprising N-alkyldiethylene-triamines, N-alkyldipropylene-triamines, N-alkyltriethylene-tetramines, N-alkyltetraethylene-pentamines and N-alkyltetrapropylene-pentamines;
      the copolymer of formula (I) containing from 45 to 65 mole % of at least one olefin unit and from 55 to 35 mole % of at least one dicarboxylic unit.
    2. Combustible, fuel and/or fuel oil according to claim 1, characterized in that X is selected among:
      iii) alkylamines containing from 1 to 44 carbon atoms.
    3. Combustible, fuel and/or fuel oil according to claim 1 or 2, characterized in that the dicarboxylic units are selected among anhydride type units selected in the group comprising maleic anhydride, citraconic anhydride and fumaric acid, and olefin units selected among linear or branched alkenyl units containing from 1 to 30 carbon atoms.
    4. Combustible. fuel and/or fuel oil according to any of claims 1 to 3, characterized in that the copolymer is selected among the maleic anhydride - octadecene, maleic anhydride - dodecene and maleic anhydride - hexadecene copolymers.
    5. Combustible, fuel and/or fuel oil according to any of claims 1 to 4, characterized in that R1 and R2 are radicals selected among the group comprising dodecyl and octadecyl radicals and R3 is selected among alkyl groups containing from 4 to 20 carbon atoms.
    6. Combustible, fuel and/or fuel oil according to any of claims 1 to 5, characterized in that the copolymer is a compound of formula (III) hereafter:
      Figure 00280001
      wherein:
      R'1 and R'2, identical or different, are selected among alkyl radicals containing from 12 to 18 carbon atoms, alkyl- and N-alkyl-polyalkylene-polyamines of formula (II) and hydroxylated amines from the group comprising diethanolamine, monoethanolamine, N-butylamine, N-decylethanolamine and N-dodecylethanolamine and their alkoxylated derivatives ;
      and R3 is selected among decyl, tetradecyl, hexadecyl, octadecyl and eicosyl radicals.
    7. Combustible, fuel and/or fuel oil according to any of claims 1 to 5, characterized in that the copolymer is a compound of formula (IV) hereafter:
      Figure 00280002
      wherein:
      R"1 and R"2, identical or different, are selected among alkyl radicals containing from 12 to 18 carbon atoms, alkylamines containing from 1 to 22 carbon atoms and N-alkylpolyalkylene-polyamines from the group comprising N-alkyldiethylene-triamines, N-alkyldipropylene-triamines, N-alkyltriethylene-tretramines, N-alkyltetraethylene-pentamines and N-alkyltetrapolypropylene-pentamines.
      and R3 is selected among decyl, tetradecyl, hexadecyl, octadecyl and eicosyl radicals.
    8. Combustible, fuel and/or fuel oil according to any of claims 1 to 5, characterized in that the copolymer is a compound of formula (IV) hereafter:
      Figure 00290001
      wherein:
      -NR"1 R"2 is an alkylamine containing from 1 to 44 carbon atoms.
      and R3 is selected among decyl, tetradecyl, hexadecyl, octadecyl and eicosyl radicals.
    9. Combustible, fuel and/or fuel oil according to any of claims 1 to 5, characterized in that the copolymer is a compound of formula (IV) hereafter:
      Figure 00290002
      wherein:
      R"1 and R"2, identical or different, are selected among alkyl radicals with 12 to 18 carbon atoms.
      and R3 is selected among decyl, tetradecyl, hexadecyl, octadecyl and eicosyl radicals.
    10. Combustible, fuel and/or fuel oil according to any of claims 1 to 5, characterized in that the copolymer is a compound of formula (V) hereafter:
      Figure 00290003
      Figure 00300001
      wherein:
      R'5 is selected among alkyl radicals containing from 6 to 18 carbon atoms and N-alkylpolyalkylene-polyamines of formula (II) from the group comprising N-alkyldiethylene-triamines, N-alkyldipropylene-triamines, N-alkyltriethylene-tetramines, N-alkyltetraethylene-pentamines and N-alkyltetrapropylene-pentamines;
      and R'3 is selected among decyl, tetradecyl, hexadecyl, octadecyl and eicosyl radicals.
    11. Combustible, fuel and/or fuel oil according to any of claims 1 to 10, characterized in that the alkylamines and the N-alkylpolyalkylene-polyamines of formula (II) are selected among the group comprising dibutylamine, didodecylamine, dioctadecylamine, N-alkylethylene-diamines, N-alkylpropylene-diamines, N-alkylbutylene-diamines, N-alkyldiethylene-triamines, N-alkyldipropylene-triamines, N-alkyldibutylene-triamines, N-alkyltriethylene-tetramines, N-alkyltripropylene-tetramines, N-alkyltributylene-tetramines, N-alkyltetraethylene-pentamines, N-alkyltetrapropylene-pentamines and N-alkyltributylene-pentamines with an alkyl radical containing from 12 to 22 carbon atoms, preferably N-dodecyldipropylene-triamine, N-octadecyldipropylene-triamine, N-octadecyldiethylene-triamine and N-docosyldiethylene-triamine.
    12. Combustible, fuel and/or fuel oil according to claim 1, wherein the additive is a compound of formula (III) hereafter:
      Figure 00300002
      comprising a copolymer containing maleic anhydride units and octadecene units in a molar ratio of 1/1, wherein R1, R2, R'1 and R'2 are identical and correspond to a dodecylamine radical.
    13. Combustible, fuel and/or fuel oil according to claim 1, characterized in that the additive is a compound of formula (IV) hereafter:
      Figure 00310001
      comprising a copolymer containing maleic anhydride units and octadecene units in a molar ratio of 1/1, wherein R1 and R"1 are hydrogen atoms, R2 is a butyl radical and R"2 is a dodecyl radical.
    14. Combustible, fuel and/or fuel oil according to claim 1, wherein the additive is a compound of formula (V) hereafter:
      Figure 00310002
      comprising a copolymer containing maleic anhydride units and octadecene units in a molar ratio of 1/1, wherein R1 is a hydrogen atom, R2 is an ethylamine radical and R'5 is a hexadecyl radical.
    15. Combustible, fuel and/or fuel oil according to any of claims 1 to 14, characterized in that it contains at least one additive selected among filterability and/or flow additives, cetane number improvement additives, catalytic combustion and soot promoters, detergents, lubricating additives, anti-wear additives, anti-foaming additives, anti-corrosion additives and other additives or additive compositions for improving the cloud point, the dispersion and the sedimentation of paraffins.
    EP00993628A 1999-12-28 2000-12-27 Multifunctional additive compositions enabling middle distillates to be operable in cold conditions Expired - Lifetime EP1252269B1 (en)

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