EP1192239B1 - Multifunctional additive composition for cold process treatment of middle distillates - Google Patents

Multifunctional additive composition for cold process treatment of middle distillates Download PDF

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EP1192239B1
EP1192239B1 EP00922705A EP00922705A EP1192239B1 EP 1192239 B1 EP1192239 B1 EP 1192239B1 EP 00922705 A EP00922705 A EP 00922705A EP 00922705 A EP00922705 A EP 00922705A EP 1192239 B1 EP1192239 B1 EP 1192239B1
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composition
additive
chosen
weight
anhydride
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German (de)
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EP1192239A1 (en
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Franck Eydoux
Robert Leger
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Total Marketing Services SA
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TotalFinaElf France SA
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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
    • 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
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained

Definitions

  • the present invention relates to a new composition of multifunctional additives improving the cold operability of middle distillates, especially in during slow cooling processes during storage fuels and fuels at low temperatures. It aims in particular to improve the anti-sedimentation properties for application in fuels for Diesel engines and in fuels such as fuel oils domestic 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 2500-66) characteristic of the onset of crystallization of paraffins in the distillate and the pour point of the latter (ASTM D 97-66).
  • paraffins are crystallized at bottom of the tank, they can be dragged starting in the engine and clogging in particular the filters and prefilters arranged upstream of the injection systems (pump and injectors).
  • paraffins precipitate at the bottom of the tank and may be entrained and obstruct upstream pipes pump and boiler supply system (nozzle and filter). It is obvious that the presence of solids, such as paraffin crystals, prevents the normal circulation of the middle distillate.
  • TLF additives Temporal Limit of Filterability
  • the present invention relates to a composition multifunctional additives for lowering and maintain the cold operability temperature of middle distillates, so that during a stage of slow cooling during storage in a closed enclosure, up to temperatures above -20 ° C, we do not observe no sedimentation of the paraffins contained in the middle distillates.
  • the composition of additives is obtained by combining 50 to 80% AB and 20 to 50% by weight of the CD reaction product.
  • the composition of additives comprises from 50 to 80% by weight of a combination AB, CD in an AB / CD molar ratio varying from 0.2 to 4, and from 20 to 50% by weight of a mixture of AD, CB in a ratio AD / CB molar varying from 0.2 to 4.
  • the carboxylic compound (A) is preferably chosen in the group comprising dodecylmaleic anhydrides, dodecenylmaleic, hexadecylmaleic, hexadecenylmaleic octadecylmaleic, octadecenylmaleic, eicosylmaleic and éicosénylmaléique.
  • the polyalkyleneamine (B) is preferably chosen in the group comprising diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine and tetrapropylene.
  • the copolymer (C) is preferably a copolymer containing 45 to 65 mol% of at least one acid unit carboxylic and from 55 to 35 mol% of at least one ester unit alkylated.
  • the carboxylic acid units are chosen preferably among the units resulting from acids acrylic and methacrylic, and alkyl ester patterns among the patterns resulting from acrylic esters and methacrylics, and their derivatives.
  • the copolymer (C) is chosen from acrylic acid / methacrylic ester copolymers and methacrylic acid / acrylic ester copolymers containing 45 to 65 mole% of acid units and 55 to 35 mole% of ester patterns.
  • the N-alkylpolyalkylenepolyamine (D) is preference chosen from the group comprising N-alkylethylenediamines, N-alkylpropylenediamines, N-alkylbutylenediamines, N-alkyldiethylenetriamines, N-alkyldipropylenetriamines, N-alkyldibutylenetriamines, N-alkyltriethylenetetramines, N-alkyltripropylenetetramines and N-alkyltributylenetetramines having a alkyl radical comprising from 12 to 22 carbon atoms.
  • D is chosen from N-dodecyldipropylenetriamine, N-octadecyldipropylene triamine, N-octadecyldiethylenetriamine and N-docosyldiethylenetriamine.
  • a second object of the invention is a fuel containing a major part of middle distillate containing usually a filterability additive, and some minor, for example 50 to 1000 ppm of a composition Multifunctional cold operability additives for slow cooling.
  • This example presents the two methods of cooling implemented as well as the composition of diesel and additives tested.
  • the quench cooling method described in standard NFT M07-085, consists in pouring a sample of distillate in a graduated cylinder in volume and place for 24 hours in a refrigerated cabinet at one temperature generally set between -13 and -20 ° C, i.e. a temperature at least 1 ° C lower than its temperature cloud point, and at least 6 ° C higher than its pour point temperature.
  • the anti-sedimentation function of the additive compositions is therefore effective. If the upper phase is clear and a cloudy compaction appears at the bottom of the test tube, the sedimentation is important and the composition of additives ineffective in anti-sedimentation.
  • the slow cooling method is to introduce the sample of diesel fuel with or without additives into a cylinder graduated in volume, to place in a cabinet refrigerated at a temperature 10 ° C higher than the cloud point temperature of said diesel.
  • the sample is gradually cooled from this temperature from 1 to 3 ° C / hour, up to a final test temperature that can reach -15 to -20 ° C. Once the final temperature reached, the sample is kept for 24 hours at this temperature, then we do the visual rating already mentioned for the rapid quenching method, as well as the samples from the top and bottom of the test piece to determine the temperatures Tcc and TLF of these different phases. Interpretation of the results is identical to the rapid quenching method.
  • This example aims to show the difference between the quench cooling method and the method by slow cooling to 1 ° C per hour and therefore the interest to select additives reproducing the phenomenon of actual cooling of a stopped car tank and therefore the diesel cooling process.
  • composition of multifunctional additives is all the more effective the smaller the sum of the six differences on the three diesel fuels.
  • Ranking difference Tcc TLF gap difference Tcc TLF gap difference Tcc TLF gap Gi + TLF 21.2 11 17.8 10 19.7 10 89.7 11 AD 2.1 0 3.9 3 9.4 1 19.4 1 st AB 6.2 4 15.8 11 12.0 2 51 4 CD 2.2 6 7.2 3 12.7 4 35.1 2 CB 16.1 6 17.0 9 19.2 11 78.3 10 X 1 5.0 0 15.5 6 17.3 9 52.8 5 X 2 4.6 0 14.3 7 17.1 10 53 6 X 3 8.2 2 16.3 9 16.2 8 59.7 8 X 4 9.6 3 17.0 11 13.7 4 58.3 7 X 5 10.5 3 12.3 5 12.0 5 47.8 3 X 6 11.4 3 16.0 9 18.5 9 66.9 9 Slow method 1

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Beans For Foods Or Fodder (AREA)
  • Confectionery (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Detergent Compositions (AREA)

Abstract

The invention concerns a composition of mulifunctional additives for cold process treatment obtained by reacting carboxylic compounds with amine compounds, characterized in that it contains at least 50 wt. % of a mixture consisting of 10 to 90 wt. % of an additive (AB) of a carboxylic compound (A) selected among maleic and succinic anhydrides, corresponding acids and esters with a polyalkylamine (B) and 90 to 10 wt. % of an additive (CD) obtained by reacting a copolymer (C) obtained by reacting a first unsaturated carboxylic acid with an alkylated ester of a second unsaturated carboxylic acid, identical to or different from the first, of general formula (II) R1R2C=CR3COOR4 wherein R1 and R2, identical or different, being hydrogen, a linear or branched C1-C20 alkyl radical; R3 is hydrogen or a linear or branched alkyl group with not more than three carbon atoms and R4 is hydrogen or a C1-C25 radical, with N-alkylpolyalkylenepolyamine (D).

Description

La présente invention concerne une nouvelle composition d'additifs multifonctionnels améliorant l'opérabilité à froid des distillats moyens, notamment au cours des processus de refroidissement lent lors du stockage de combustibles et de carburants aux basses températures. Elle vise notamment l'amélioration des propriétés anti-sédimentation pour une application dans les carburants 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 the cold operability of middle distillates, especially in during slow cooling processes during storage fuels and fuels at low temperatures. It aims in particular to improve the anti-sedimentation properties for application in fuels for Diesel engines and in fuels such as fuel oils domestic 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 2500-66) caractéristique du début de cristallisation des paraffines dans le distillat et le point d'écoulement de ce dernier (ASTM D 97-66).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 2500-66) characteristic of the onset of crystallization of paraffins in the distillate and the pour point of the latter (ASTM D 97-66).

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 moteur 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 engine and clogging in particular the filters and prefilters arranged upstream of the injection systems (pump and injectors). Likewise for the storage of fuel oils domestic, paraffins precipitate at the bottom of the tank and may be entrained and obstruct upstream pipes pump and boiler supply system (nozzle and filter). It is obvious that the presence of solids, such as paraffin crystals, prevents the normal circulation of the middle distillate.

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 au-delà de -20°C, même si leur température de point de trouble est supérieure à -20°C. C'est le cas des additifs décrits dans les brevets EP 0 722 481 et EP 0 832 172. Cependant, l'ensemble de ces additifs montrent de bonnes propriétés d'opérabilité selon les régimes à froid par rapport à des mesures qui ont été faites par des trempes à froid, selon la norme NF M 07 085, des carburants et combustibles contenant de tels additifs. Cependant, si cette méthode permet de juger de l'efficacité des additifs, elle n'est pas rigoureusement représentative des phénomènes réels de refroidissement des carburants et des combustibles. Ainsi, l'amplitude et la vitesse de refroidissement sont variables selon les régions, et donc selon la température ambiante des véhicules. Un refroidissement lent est très favorable à la sédimentation progressive des paraffines, et donc il est nécessaire de trouver des solutions pour empêcher ce phénomène.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 above -20 ° C, even if their cloud point temperature is greater than -20 ° C. This is the case of the additives described in patents EP 0 722 481 and EP 0 832 172. However, all of these additives show good operability properties according to cold diets compared to measurements that have been made by cold quenching, according to standard NF M 07 085, fuels and fuels containing such additives. However, if this method allows to judge the effectiveness additives, it is not strictly representative real fuel cooling phenomena and fuels. So the amplitude and the speed of cooling vary by region, and therefore depending on the ambient temperature of the vehicles. A slow cooling is very favorable to sedimentation paraffins, and therefore it is necessary to find solutions to prevent this phenomenon.

La présente invention vise une composition d'additifs multifonctionnels permettant d'abaisser et de maintenir la température d'opérabilité à froid des distillats moyens, pour qu'au cours d'une étape de refroidissement lent au stockage dans une enceinte fermée, jusqu'à des températures au-delà de -20°C, on n'observe aucune sédimentation des paraffines contenues dans les distillats moyens.The present invention relates to a composition multifunctional additives for lowering and maintain the cold operability temperature of middle distillates, so that during a stage of slow cooling during storage in a closed enclosure, up to temperatures above -20 ° C, we do not observe no sedimentation of the paraffins contained in the middle distillates.

La présente invention a donc pour objet une composition d'additifs multifonctionnels d'opérabilité à froid des distillats moyens résultant de la réaction de composés carboxyliques avec des composés aminés caractérisée en ce qu'elle contient au moins 50 % en poids d'un mélange constitué par :

  • a) 10 à 90% en poids d'un additif (AB) résultant de la réaction d'au moins un composé carboxylique (A) choisi parmi les anhydrides alkylmaléiques et alkénylmaléiques et les anhydrides alkylsucciniques et alkénylsucciniques ayant de 4 à 32 atomes de carbone dans les radicaux alkyles et alkényles, les acides et les esters correspondant avec au moins une polyalkylèneamine (B) de formule générale (I) ci-après : NH2 -[(CH2)n-NH-]m-H où n est un nombre entier variant de 2 à 4 et m est un nombre entier variant de 1 à 4, le rapport molaire A/B étant compris entre 1 / m+1 et m+1, et de préférence entre 1 et 2,
  • b) et 90 à 10 % en poids d'un additif (CD) résultant de la réaction :
  • i) d'au moins un copolymère (C) résultant de la réaction d'au moins un premier acide carboxylique insaturé substitué ou non avec au moins un ester alkylé d'au moins un deuxième acide carboxylique insaturé substitué ou non, identique ou différent du premier, de formule générale (II) ci-après :
    Figure 00040001
    dans laquelle R1 et R2, identiques ou différents sont choisis dans le groupe constitué par l'hydrogène, et les groupements alkyles linéaires ou ramifiés comprenant de 1 à 20 atomes de carbone, R3 est l'hydrogène ou un groupement alkyle linéaire d'au plus trois atomes de carbone et R4 est l'hydrogène ou un groupement alkyle comprenant de 1 à 25 atomes de carbone,
  • ii) avec une N-alkylpolyalkylènepolyamine (D) de formule générale (III) ci-après : R5-NH-[-(CH2)p-NH-]q-H où R5 est un radical aliphatique saturé comprenant de 1 à 32 atomes de carbone, p est un nombre entier variant entre 2 et 4 et q est un nombre entier variant entre 1 et 4, le rapport molaire C/D variant entre 1 / q+1 et q+1, et de préférence variant entre 1 et 2.
    • The present invention therefore relates to a composition of multifunctional additives for cold operability of middle distillates resulting from the reaction of carboxylic compounds with amino compounds, characterized in that it contains at least 50% by weight of a mixture consisting through :
  • a) 10 to 90% by weight of an additive (AB) resulting from the reaction of at least one carboxylic compound (A) chosen from alkylmaleic and alkenylmaleic anhydrides and alkylsuccinic and alkenylsuccinic anhydrides having from 4 to 32 carbon atoms in the alkyl and alkenyl radicals, the acids and the esters corresponding with at least one polyalkyleneamine (B) of general formula (I) below: NH 2 - [(CH 2 ) n -NH-] m -H where n is an integer varying from 2 to 4 and m is an integer varying from 1 to 4, the molar ratio A / B being between 1 / m +1 and m + 1, and preferably between 1 and 2,
  • b) and 90 to 10% by weight of an additive (CD) resulting from the reaction:
  • i) of at least one copolymer (C) resulting from the reaction of at least one first unsaturated carboxylic acid substituted or not with at least one alkyl ester of at least one second unsaturated carboxylic acid substituted or not, identical or different from first, of general formula (II) below:
    Figure 00040001
    in which R 1 and R 2 , identical or different, are chosen from the group consisting of hydrogen, and linear or branched alkyl groups comprising from 1 to 20 carbon atoms, R 3 is hydrogen or a linear alkyl group d '' at most three carbon atoms and R 4 is hydrogen or an alkyl group comprising from 1 to 25 carbon atoms,
  • ii) with an N-alkylpolyalkylenepolyamine (D) of general formula (III) below: R 5 -NH - [- (CH 2 ) p -NH-] q -H where R 5 is a saturated aliphatic radical comprising from 1 to 32 carbon atoms, p is an integer varying between 2 and 4 and q is an integer varying between 1 and 4, the C / D molar ratio varying between 1 / q +1 and q + 1, and preferably varying between 1 and 2.

    • La combinaison de ces deux produits de réaction (AB) et (CD) dans la composition selon l'invention, a permis d'améliorer très significativement l'opérabilité à froid des carburants et combustibles dans lesquels on les incorpore pour un refroidissement lent par rapport à l'efficacité de ces produits pris séparément.The combination of these two reaction products (AB) and (CD) in the composition according to the invention, has made it possible to significantly improve the cold operability of fuels and combustibles in which they are incorporated for slow cooling compared to the efficiency of these products taken separately.

    Pour comparer l'efficacité de cette composition d'additifs avec les additifs connus de l'art antérieur, la demanderesse a mis au point un nouveau test dérivé de la norme NFT M 07 085 dans laquelle la procédure rapide de refroidissement par trempe a été remplacée par un refroidissement lent et contrôlé de la température, par exemple de 1 à 3 degré par minute, jusqu'à une température de palier, par exemple -20°C.To compare the effectiveness of this composition of additives with the additives known from the prior art, the plaintiff has developed a new test derived from the standard NFT M 07 085 in which the rapid procedure for quench cooling has been replaced by a slow and controlled temperature cooling, by example 1 to 3 degrees per minute, up to a temperature level, for example -20 ° C.

    De façon plus précise, l'additif selon l'invention est constitué :

    • de 50 à 100% en poids de la combinaison contenant de 20 à 80% en poids de l'additif AB et de 80 à 20 % en poids de l'additif CD,
    • et 0 à 50% en poids d'une combinaison des additifs AD et CB obtenus par réaction de A et de D dans un rapport molaire variant entre 0,2 et 4, et de B avec C dans un rapport molaire variant entre 0,2 et 4, A, B,C et D ayant été préalablement définis pour les additifs multifonctionnels AB et CD.
    More specifically, the additive according to the invention consists of:
    • from 50 to 100% by weight of the combination containing from 20 to 80% by weight of the additive AB and from 80 to 20% by weight of the additive CD,
    • and 0 to 50% by weight of a combination of the additives AD and CB obtained by reaction of A and D in a molar ratio varying between 0.2 and 4, and of B with C in a molar ratio varying between 0.2 and 4, A, B, C and D having been previously defined for the multifunctional additives AB and CD.

    Dans un premier mode de réalisation, la composition d'additifs est obtenue par combinaison de 50 à 80 % AB et de 20 à 50% en poids du produit de réaction CD.In a first embodiment, the composition of additives is obtained by combining 50 to 80% AB and 20 to 50% by weight of the CD reaction product.

    Dans un deuxième mode de réalisation, la composition d'additifs comprend de 50 à 80 % en poids d'une combinaison AB,CD dans un rapport molaire AB/CD variant de 0,2 à 4, et de 20 à 50% en poids d'un mélange de AD,CB dans un rapport molaire AD/CB variant de 0,2 à 4.In a second embodiment, the composition of additives comprises from 50 to 80% by weight of a combination AB, CD in an AB / CD molar ratio varying from 0.2 to 4, and from 20 to 50% by weight of a mixture of AD, CB in a ratio AD / CB molar varying from 0.2 to 4.

    Le composé carboxylique (A) est de préférence choisi dans le groupe comprenant les anhydrides dodécylmaléique, dodécénylmaléique, hexadécylmaléique, hexadécénylmaléique octadécylmaléique, octadécénylmaléique, éicosylmaléique et éicosénylmaléique.The carboxylic compound (A) is preferably chosen in the group comprising dodecylmaleic anhydrides, dodecenylmaleic, hexadecylmaleic, hexadecenylmaleic octadecylmaleic, octadecenylmaleic, eicosylmaleic and éicosénylmaléique.

    La polyalkylèneamine (B) est choisie de préférence dans le groupe comprenant la diéthylènetriamine, la dipropylènetriamine, la triéthylènetétramine, la tripropylènetétramine, la tétraéthylènepentamine et la tétrapropylènepentamine.The polyalkyleneamine (B) is preferably chosen in the group comprising diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine and tetrapropylene.

    Le copolymère (C) est de préférence un copolymère contenant de 45 à 65 % mole d'au moins un motif acide carboxylique et de 55 à 35 % mole d'au moins un motif ester alkylé. Les motifs acides carboxyliques sont choisis préférentiellement parmi les motifs résultant d'acides acrylique et méthacrylique, et les motifs esters alkylés parmi les motifs résultant d'esters acryliques et méthacryliques, et de leur dérivés. Dans un mode plus favorable, le copolymère (C) est choisi parmi les copolymères acide acrylique/esters méthacryliques et les copolymères acide méthacrylique/esters acryliques contenant 45 à 65 % mole de motifs acide et de 55 à 35 % mole de motifs ester.The copolymer (C) is preferably a copolymer containing 45 to 65 mol% of at least one acid unit carboxylic and from 55 to 35 mol% of at least one ester unit alkylated. The carboxylic acid units are chosen preferably among the units resulting from acids acrylic and methacrylic, and alkyl ester patterns among the patterns resulting from acrylic esters and methacrylics, and their derivatives. In a more fashion favorable, the copolymer (C) is chosen from acrylic acid / methacrylic ester copolymers and methacrylic acid / acrylic ester copolymers containing 45 to 65 mole% of acid units and 55 to 35 mole% of ester patterns.

    La N-alkylpolyalkylènepolyamine (D) est de préférence choisie dans le groupe comprenant les N-alkyléthylènediamines, N-alkylpropylènediamines, N-alkylbutylènediamines, les N-alkyldiéthylènetriamines, les N-alkyldipropylènetriamines, les N-alkyldibutylènetriamines, les N-alkyltriéthylènetétramines, les N-alkyltripropylènetétramines et les N-alkyltributylènetétramines présentant un radical alkyle comprenant de 12 à 22 atomes de carbone. De préférence, D est choisi parmi la N-dodécyldipropylènetriamine, le N-octadécyldipropylène triamine, la N-octadécyldiéthylènetriamine et la N-docosyldiéthylènetriamine. The N-alkylpolyalkylenepolyamine (D) is preference chosen from the group comprising N-alkylethylenediamines, N-alkylpropylenediamines, N-alkylbutylenediamines, N-alkyldiethylenetriamines, N-alkyldipropylenetriamines, N-alkyldibutylenetriamines, N-alkyltriethylenetetramines, N-alkyltripropylenetetramines and N-alkyltributylenetetramines having a alkyl radical comprising from 12 to 22 carbon atoms. Of preferably, D is chosen from N-dodecyldipropylenetriamine, N-octadecyldipropylene triamine, N-octadecyldiethylenetriamine and N-docosyldiethylenetriamine.

    Un deuxième objet de l'invention est un carburant contenant une partie majeure de distillat moyen contenant généralement un additif de filtrabilité, et une partie mineure, par exemple de 50 à 1000 ppm d'une composition d'additifs multifonctionnels d'opérabilité à froid pour refroidissement lent.A second object of the invention is a fuel containing a major part of middle distillate containing usually a filterability additive, and some minor, for example 50 to 1000 ppm of a composition Multifunctional cold operability additives for slow cooling.

    On ne sortirait pas du cadre de l'invention, si à ce carburant était ajouté des additifs procétanes, des détergents, des additifs de point d'écoulement et de point de trouble, des additifs antimousse, désémulsifiants, anticorrosion et antioxydants.It would not go beyond the scope of the invention, if at this fuel was added procetane additives, detergents, pour point and point additives cloudiness, defoamers, demulsifiers, anticorrosion and antioxidants.

    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 présente les deux méthodes de refroidissement mises en oeuvre ainsi que la composition des gazoles et des additifs testés.This example presents the two methods of cooling implemented as well as the composition of diesel and additives tested.

    La méthode par refroidissement par trempe décrite dans la norme NFT M07-085, consiste à verser un échantillon de distillat dans une éprouvette graduée en volume et à la placer pendant 24 heures, dans une armoire réfrigérée à une température fixée généralement entre -13 et -20°C, soit à une température inférieure d'au moins 1°C à sa température de point de trouble, et supérieure d'au moins 6°C à sa température de point d'écoulement.The quench cooling method described in standard NFT M07-085, consists in pouring a sample of distillate in a graduated cylinder in volume and place for 24 hours in a refrigerated cabinet at one temperature generally set between -13 and -20 ° C, i.e. a temperature at least 1 ° C lower than its temperature cloud point, and at least 6 ° C higher than its pour point temperature.

    Après 24 heures, on observe dans l'éprouvette l'aspect du distillât(trouble, légèrement trouble, clair et limpide) et le volume des cristaux de paraffines décantés dans le fond de l'éprouvette.After 24 hours, we observe in the test tube the appearance of the distillate (cloudy, slightly cloudy, clear and clear) and the volume of decanted paraffin crystals in the bottom of the test tube.

    Si la phase supérieure est restée trouble, les cristaux de paraffines sont restés en suspension, la fonction anti-sédimentation des compositions d'additifs est donc efficace. Si la phase supérieure est limpide et un tassement trouble apparaít en fond d'éprouvette, la sédimentation est importante et la composition d'additifs inefficace en anti-sédimentation. If the upper phase remained cloudy, the paraffin crystals remained in suspension, the anti-sedimentation function of the additive compositions is therefore effective. If the upper phase is clear and a cloudy compaction appears at the bottom of the test tube, the sedimentation is important and the composition of additives ineffective in anti-sedimentation.

    Pour une approche plus quantitative de la sédimentation, on prélève des volumes égaux du haut et du bas de l'éprouvette pour déterminer la température de cristallisation commençante (Tcc) déterminée par la méthode ACD (analyse calorimétrique différentielle) et la température limite de filtrabilité (TLF). Les résultats sont comparés aux valeurs initiales préalablement mesurées, un écart minimal de température indiquant un maximum d'homogénéité et donc une action dispersante maximale de la composition d'additifs.For a more quantitative approach to sedimentation, we take equal volumes from the top and bottom of the test tube to determine the temperature of beginning crystallization (Tcc) determined by the method ACD (differential scanning calorimetry) and the filterability limit temperature (TLF). The results are compared to the initial values previously measured, a minimum temperature difference indicating maximum homogeneity and therefore a maximum dispersing action of the composition of additives.

    La méthode de refroidissement lent consiste à introduire l'échantillon de gazole additivé ou non dans une éprouvette graduée en volume, à la placer dans une armoire réfrigérée à une température supérieure de 10°C à la température de point de trouble du dit gazole. L'échantillon est refroidi progressivement de cette température de 1 à 3°C/heure, jusqu'à une température finale du test pouvant atteindre -15 à -20°C. Une fois la température finale atteinte, l'échantillon est maintenu pendant 24 heures à cette température, puis on effectue la cotation visuelle déjà mentionnée pour la méthode rapide par trempe, ainsi que les prélèvements des phases en haut et bas de l'éprouvette pour déterminer les températures Tcc et TLF de ces différentes phases. L'interprétation des résultats est identique à la méthode rapide par trempe.The slow cooling method is to introduce the sample of diesel fuel with or without additives into a cylinder graduated in volume, to place in a cabinet refrigerated at a temperature 10 ° C higher than the cloud point temperature of said diesel. The sample is gradually cooled from this temperature from 1 to 3 ° C / hour, up to a final test temperature that can reach -15 to -20 ° C. Once the final temperature reached, the sample is kept for 24 hours at this temperature, then we do the visual rating already mentioned for the rapid quenching method, as well as the samples from the top and bottom of the test piece to determine the temperatures Tcc and TLF of these different phases. Interpretation of the results is identical to the rapid quenching method.

    Trois gazoles, G1, G2 et G3 ont été testés : leurs caractéristiques sont données avant et après dopage par un un additif de filtrabilité de type copolymère éthylène-acétate de vinyle dans le tableau I ci-après. ANALYSES G1 G2 G3 Point de trouble en °C -3 -7 -6 Température limite de filtrabilité en °C -3 -7 -7 Point d'écoulement en °C -15 -12 -12 Tempérture de cristallisaton commençante en °C -5.63 -8.57 -9.86 Pourcentage de paraffine 11.5 14.8 11.4 % de paraffine < à C13 0.9 1.7 1.2 % C13-17 8.7 10.0 8.4 % C18-23 1.9 3.1 1.8 % C24-24+ 0 0 0 Distillation : Point initial 176 162 176 Point à 5 % volume 199 185 200 Point à 10 % volume 208 194 213 Point à 20 % volume 222 212 230 Point à 30 % volume 238 230 243 Point à 40 % volume 252 246 256 Point à 50 % volume 264 260 269 Point à 60 % volume 277 274 282 Point à 70 % volume 291 287 296 Point à 80 % volume 310 304 314 Point à 90 % volume 338 325 338 Point à 95% volume 361 340 356 Point final 371 354 362 Masse voluminique à 15° C en kg/l 0.8372 0.8352 0.8413 Point éclair en °C 70 65 69 Indice de cétane 50.9 48.9 60.5 Gi + TLF(ppm) 250 250 125 Température limite de filtrabilité en °C -17 -16 -18 Point d'écoulement en °C -27 -24 -24 Three gas oils, G 1 , G 2 and G 3 were tested: their characteristics are given before and after doping with a filterability additive of the ethylene-vinyl acetate copolymer type in Table I below. ANALYZES G 1 G 2 G 3 Cloud point in ° C -3 -7 -6 Filterability limit temperature in ° C -3 -7 -7 Pour point in ° C -15 -12 -12 Starting crystallization temperature in ° C -5.63 -8.57 -9.86 Percentage of paraffin 11.5 14.8 11.4 % of paraffin <to C13 0.9 1.7 1.2 % C13-17 8.7 10.0 8.4 % C18-23 1.9 3.1 1.8 % C24-24 + 0 0 0 Distillation: Initial point 176 162 176 Point at 5% volume 199 185 200 Point at 10% volume 208 194 213 Point at 20% volume 222 212 230 Point at 30% volume 238 230 243 Point at 40% volume 252 246 256 Point at 50% volume 264 260 269 Point at 60% volume 277 274 282 Point at 70% volume 291 287 296 80% volume point 310 304 314 90% volume point 338 325 338 95% volume point 361 340 356 Period 371 354 362 Density at 15 ° C in kg / l 0.8372 0.8352 0.8413 Flash point in ° C 70 65 69 Cetane number 50.9 48.9 60.5 Gi + TLF (ppm) 250 250 125 Filterability limit temperature in ° C -17 -16 -18 Pour point in ° C -27 -24 -24

    Les additifs selon l'invention X1 à X6 sont décrits dans le tableau II ci - après : les valeurs correspondent aux pourcentages massiques de chacun des composés AD, BC, CD et AB introduit dans les formulations Xi. ADDITIF AD AB CD CB Rapport molaire 2 2 2 2 X1 50 50 X2 40 10 10 40 X3 25 25 25 25 X4 80 20 X5 20 80 X6 25 25 25 25    avec :

  • A = anhydride octadécylmaléique
  • B = diéthylènetriamine
  • C = coplymère acide acrylique/méthacrylates (60% mole de motifs acide, 20% mole de motifs méthacrylate de lauryle et 20% mole de motifs méthacrylate de stéaryle)
  • D = N-dodécyldipropylènetriamine
    • The additives according to the invention X 1 to X 6 are described in Table II below: the values correspond to the percentages by mass of each of the compounds AD, BC, CD and AB introduced into the formulations X i . ADDITIVE AD AB CD CB Molar ratio 2 2 2 2 X 1 50 50 X 2 40 10 10 40 X 3 25 25 25 25 X 4 80 20 X 5 20 80 X 6 25 25 25 25 with:
  • A = octadecylmaleic anhydride
  • B = diethylenetriamine
  • C = acrylic acid / methacrylate copolymer (60 mole of acid units, 20% mole of lauryl methacrylate units and 20% mole of stearyl methacrylate units)
  • D = N-dodecyldipropylenetriamine

    • Ces échantillons Xi sont introduits à une teneur de 200 ppm dans les gazoles G1 et G2, et à 100 ppm dans le gazole G3.These samples X i are introduced at a content of 200 ppm in the gas oils G 1 and G 2 , and at 100 ppm in the gas oil G 3 .

    EXEMPLE IIEXAMPLE II

    Le présent exemple vise à montrer la différence entre la méthode de refroidissement par trempe et la méthode par refroidissement lent à 1°C par heure et donc l'intérêt de sélectionner des additifs reproduisant le phénomène de refroidissement réel d'un réservoir de voiture à l'arrêt et donc du processus de refroidissement du gazole.This example aims to show the difference between the quench cooling method and the method by slow cooling to 1 ° C per hour and therefore the interest to select additives reproducing the phenomenon of actual cooling of a stopped car tank and therefore the diesel cooling process.

    Les résultats de ces essais utilisant les procédures de refroidissement décrites dans l'exemple I sont donnés dans le tableau III ci-après. On apprécie l'efficacité de ces additifs en calculant la somme des écarts entre d'une part la température de filtrabilité (TLF), avant essai de sédimentation, et celle du prélèvement du bas de l'éprouvette après essai de sédimentation , et d'autre part la somme des écarts entre les températures de cristallisation commençant(Tcc) des prélèvements haut et bas dans l'éprouvette après l'essai de sédimentation.The results of these tests using the procedures cooling systems described in Example I are given in Table III below. We appreciate the effectiveness of these additives by calculating the sum of the differences between one share the filterability temperature (TLF), before testing sedimentation, and that of the bottom sample the test tube after sedimentation test, and on the other hand the sum of the differences between the temperatures of starting crystallization (Tcc) of the high and low samples in the test tube after the sedimentation test.

    La composition d'additifs multifonctionnels est d'autant plus efficace que la somme des six écarts sur les trois gazoles est la plus faible. Méthode classique NFT M 07-085. G1 G2 G3 Sommes des écarts en °C Classement écart Tcc écart TLF écart Tcc écart TLF écart Tcc écart TLF Gi + TLF 21.2 11 17.8 10 19.7 10 89.7 11 AD 2.1 0 3.9 3 9.4 1 19.4 1er AB 6.2 4 15.8 11 12.0 2 51 4 CD 2.2 6 7.2 3 12.7 4 35.1 2 CB 16.1 6 17.0 9 19.2 11 78.3 10 X1 5.0 0 15.5 6 17.3 9 52.8 5 X2 4.6 0 14.3 7 17.1 10 53 6 X3 8.2 2 16.3 9 16.2 8 59.7 8 X4 9.6 3 17.0 11 13.7 4 58.3 7 X5 10.5 3 12.3 5 12.0 5 47.8 3 X6 11.4 3 16.0 9 18.5 9 66.9 9 Méthode lente 1°C/heure G1 G2 G3 Sommes des écarts en °C Classement écart Tcc écart TLF écart Tcc écart TLF écart Tcc écart TLF Gi + TLF 25.1 14 21.8 13 22.5 14 110.4 11 AD 19.1 15 20.3 14 21.9 14 104.3 8 AB 21.8 15 20.6 16 20.5 14 107.9 9 CD 22.1 15 20.2 15 20.3 11 103.6 7 CB 22.3 13 21.7 14 22.3 15 108.3 10 X1 15.4 9 18.0 11 9 1 63.4 1er X2 20.4 13 20.1 16 17.1 10 96.6 5 X3 21.2 12 20.3 16 14.8 6 90.3 3 X4 22.1 16 20.5 17 13.1 7 95.7 4 X5 21.1 13 20.4 15 12.5 6 88 2 X6 21.2 19 20.8 16 16.9 9 102.9 6 The composition of multifunctional additives is all the more effective the smaller the sum of the six differences on the three diesel fuels. Conventional method NFT M 07-085. G 1 G 2 G 3 Sum of deviations in ° C Ranking difference Tcc TLF gap difference Tcc TLF gap difference Tcc TLF gap Gi + TLF 21.2 11 17.8 10 19.7 10 89.7 11 AD 2.1 0 3.9 3 9.4 1 19.4 1 st AB 6.2 4 15.8 11 12.0 2 51 4 CD 2.2 6 7.2 3 12.7 4 35.1 2 CB 16.1 6 17.0 9 19.2 11 78.3 10 X 1 5.0 0 15.5 6 17.3 9 52.8 5 X 2 4.6 0 14.3 7 17.1 10 53 6 X 3 8.2 2 16.3 9 16.2 8 59.7 8 X 4 9.6 3 17.0 11 13.7 4 58.3 7 X 5 10.5 3 12.3 5 12.0 5 47.8 3 X 6 11.4 3 16.0 9 18.5 9 66.9 9 Slow method 1 ° C / hour G 1 G 2 G 3 Sum of deviations in ° C Ranking difference Tcc TLF gap difference Tcc TLF gap difference Tcc TLF gap Gi + TLF 25.1 14 21.8 13 22.5 14 110.4 11 AD 19.1 15 20.3 14 21.9 14 104.3 8 AB 21.8 15 20.6 16 20.5 14 107.9 9 CD 22.1 15 20.2 15 20.3 11 103.6 7 CB 22.3 13 21.7 14 22.3 15 108.3 10 X 1 15.4 9 18.0 11 9 1 63.4 1 st X 2 20.4 13 20.1 16 17.1 10 96.6 5 X 3 21.2 12 20.3 16 14.8 6 90.3 3 X 4 22.1 16 20.5 17 13.1 7 95.7 4 X 5 21.1 13 20.4 15 12.5 6 88 2 X 6 21.2 19 20.8 16 16.9 9 102.9 6

    On constate d'après ce tableau que le classement des additifs est notablement modifié lorsque le mode de refroidissement varie. En effet, les formules Xi sont plus efficaces que les produits de réaction AD, AB, CD et CB lorsqu'on les soumet à un refroidissement lent de 1°C par heure.It can be seen from this table that the classification of additives is significantly modified when the cooling mode varies. In fact, the formulas X i are more effective than the reaction products AD, AB, CD and CB when they are subjected to a slow cooling of 1 ° C. per hour.

    Claims (11)

    1. A multifunctional additive composition for the cold operability of middle distillates resulting from the reaction of carboxylic compounds with amine compounds, characterized in that it contains at least 50% by weight of a mixture consisting of:
      a) 10% to 90% by weight of an additive (AB) from at least one carboxylic compound (A) chosen from alkylmaleic and alkenylmaleic anhydrides and alkylsuccinic and alkenylsuccinic anhydrides containing from 4 to 32 carbon atoms in the alkyl and alkenyl radicals, the corresponding acids and esters with at least one amine compound (B) chosen from the polyalkylamines of general formula (I) below: NH2-[(CH2)n-NH-]m-H in which n is an integer ranging from 2 to 4 and m is an integer ranging from 1 to 4, the molar ratio A/B being between 1 / m+1 and m+1, and preferably between 1 and 2,
      b) and 90% to 10% by weight of an additive (CD) :
      i) of at least one copolymer (C) resulting from the reaction of at least one first unsaturated carboxylic acid which may be unsubstituted or substituted with at least one alkyl ester of at least one second substituted or unsubstituted unsaturated carboxylic acid, which may be identical to or different from the first, of general formula (II) below:
      Figure 00180001
      in which R1 and R2, which may be identical or different, are chosen from the group consisting of hydrogen and linear or branched alkyl groups containing from 1 to 20 carbon atoms, R3 is hydrogen or a linear alkyl group of not more than 3 carbon atoms and R4 is hydrogen or an alkyl group containing from 1 to 25 carbon atoms,
      ii) with an N-alkylpolyalkylenepolyamine (D) of general formula (III) below: R5-NH-[-(CH2)p-NH-]q-H in which R5 is a saturated aliphatic radical comprising from 12 to 22 carbon atoms, p is an integer ranging between 2 and 4 and q is an integer ranging between 1 and 4, the molar ratio C/D ranging between 1 / q+1 and q+1, and preferably ranging between 1 and 2.
    2. The composition as claimed in claim 1, characterized in that it consists of:
      50% to 100% by weight of the combination containing from 20% to 80% by weight of an additive AB and from 80% to 20% by weight of an additive CD, and
      0% to 50% by weight of a combination of additives AD and CB obtained by reacting A and D in a molar ratio ranging between 0.2 and 4 and of B with C in a molar ratio ranging between 0.2 and 4.
    3. The composition as claimed in claims 1 and 2, characterized in that it is obtained by combination of 50% to 80% of an additive AB and 20% to 50% by weight of an additive CD.
    4. The composition as claimed in claims 1 and 2, characterized in that it comprises from 50% to 80% by weight of a combination AB,CD in an AB/CD molar ratio ranging from 0.2 to 4, and from 20% to 50% by weight of a combination AD,CB in an AD/CB molar ratio ranging from 0.2 to 4.
    5. The composition as claimed in claims 1 to 4, characterized in that the carboxylic compound (A) is chosen from the group consisting of dodecylmaleic anhydride, dodecenylmaleic anhydride, hexadecylmaleic anhydride, hexadecenylmaleic anhydride, octadecylmaleic anhydride, octadecenylmaleic anhydride, eicosylmaleic anhydride and eicosenylmaleic anhydride.
    6. The composition as claimed in claims 1 to 5, characterized in that the polyalkyleneamine (B) is chosen from the group comprising diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine and tetrapropylenepentamine.
    7. The composition as claimed in claims 1 to 6, characterized in that the copolymer (C) is chosen from copolymers containing from 45 mol% to 65 mol% of at least one carboxylic acid unit and from 55 mol% to 35 mol% of at least one alkyl ester unit, the carboxylic acid units are chosen from acrylic acid and methacrylic acid units, and the alkyl ester units are chosen from acrylic esters and methacrylic esters units, and derivatives thereof.
    8. The composition as claimed in claim 7, characterized in that the copolymer (C) is chosen from acrylic acid/methacrylic ester copolymers and methacrylic acid/acrylic ester copolymers containing 45 mol% to 65 mol% of carboxylic acid units and from 55 mol% to 35 mol% of ester units.
    9. The composition as claimed in claims 1 to 8, characterized in that the N-alkylpolyalkylenepolyamine (D) is a compound from the group consisting of N-alkylethylenediamines, N-alkylpropylenediamines, N-alkylbutylenediamines, N-alkyldiethylenetriamines, N-alkyldipropylenetriamines, N-alkyldibutylenetriamines, N-alkyltriethylenetetramines, N-alkyltripropylenetetramines and N-alkyltributylenetetramines with an alkyl radical containing from 12 to 22 carbon atoms.
    10. The composition as claimed in claim 9, characterized in that the N-alkylpolyalkylenepolyamine D is chosen from the group comprising N-dodecyldipropylenetriamine, N-octadecyldipropylenetriamine, N-octadecyldiethylenetriamine and N-docosyldiethylenetriamine.
    11. A fuel containing a majority of middle distillate, optionally containing a filterability additive, and a minority, for example from 50 to 1 000 ppm, of a multifunctional additive composition as claimed in one of claims 1 to 10.
    EP00922705A 1999-04-26 2000-04-21 Multifunctional additive composition for cold process treatment of middle distillates Expired - Lifetime EP1192239B1 (en)

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    FR2735494B1 (en) * 1995-06-13 1997-10-10 Elf Antar France BIFUNCTIONAL COLD-RESISTANT ADDITIVE AND FUEL COMPOSITION
    CA2189918C (en) * 1995-11-13 2005-01-25 Richard Mark Scott Dispersant additives
    US5755834A (en) * 1996-03-06 1998-05-26 Exxon Chemical Patents Inc. Low temperature enhanced distillate fuels
    GB9610363D0 (en) * 1996-05-17 1996-07-24 Ethyl Petroleum Additives Ltd Fuel additives and compositions
    DE19622052A1 (en) * 1996-05-31 1997-12-04 Basf Ag Paraffin dispersants for petroleum middle distillates

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    SK285752B6 (en) 2007-07-06
    CA2367927A1 (en) 2000-11-02
    PL192234B1 (en) 2006-09-29
    JP2002543237A (en) 2002-12-17
    ATE232233T1 (en) 2003-02-15
    KR100657047B1 (en) 2006-12-12
    FR2792646B1 (en) 2001-07-27
    PL352553A1 (en) 2003-08-25
    PT1192239E (en) 2003-06-30
    ES2192175T3 (en) 2003-10-01
    DE60001368T2 (en) 2003-11-27
    EP1192239A1 (en) 2002-04-03
    WO2000065000A1 (en) 2000-11-02
    CA2367927C (en) 2008-06-17
    DK1192239T3 (en) 2003-05-26
    DE60001368D1 (en) 2003-03-13
    US6623536B1 (en) 2003-09-23
    CZ296126B6 (en) 2006-01-11
    SI1192239T1 (en) 2003-06-30
    CZ20013842A3 (en) 2002-05-15
    KR20020050755A (en) 2002-06-27
    SK15132001A3 (en) 2002-05-09
    FR2792646A1 (en) 2000-10-27

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