EP0071513A2 - Additives for use as pour point dispersants for middle distillate hydrocarbons, and compositions of middle distillate hydrocarbons containing said additives - Google Patents
Additives for use as pour point dispersants for middle distillate hydrocarbons, and compositions of middle distillate hydrocarbons containing said additives Download PDFInfo
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- EP0071513A2 EP0071513A2 EP82401335A EP82401335A EP0071513A2 EP 0071513 A2 EP0071513 A2 EP 0071513A2 EP 82401335 A EP82401335 A EP 82401335A EP 82401335 A EP82401335 A EP 82401335A EP 0071513 A2 EP0071513 A2 EP 0071513A2
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- additive
- compound
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- carbon atoms
- middle distillate
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
Definitions
- the invention relates to new nitrogen additives which can be used as agents for lowering the cloud point of hydrocarbon middle distillates (fuel oil, diesel fuels), as well as the middle distillate compositions containing said additives.
- the petroleum distillates concerned by the invention consist of middle distillates (fuel oils, diesel oils) whose distillation interval (standard ASTM D 86-67) is between 150 ° C and 450 ° C.
- This class of chemical compounds also has an effect on other properties of middle distillates (in particular gas oils), by modifying the behavior of the medium which contains the precipitated paraffins.
- the compounds recommended in the invention have a significant action on the limit filterability temperature and the flow temperature.
- the additives of the invention can be defined as products with an average molecular mass of approximately 300 to 10,000, resulting from the condensation of at least one compound comprising a primary amine function corresponding to one of the following general formulas (I) and (II): and on at least one dicarboxylic compound which will be defined later.
- R generally represents a monovalent saturated aliphatic radical, comprising from 1 to 30 carbon atoms;
- Z may, depending on the case, be an oxygen atom or represent a divalent group of the type - NR '-, R' may be either a hydrogen atom or a monovalent aliphatic radical;
- n is an integer from 2 to 4, and
- m can be zero or an integer from 1 to 4.
- the compounds of formula (I) above may consist of primary amines of formula NH 2 R l_ (in this case, in formula (I), Z represents the -NH- group, and the value of m is zero) .
- the radical R 1 is linear and contains from 12 to 30, and more particularly from 16 to 25 carbon atoms.
- these amines mention may be made of: dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine and docosylamine. Hexadecylamine and octadecylamine being preferred.
- the compounds of formula (I) can also consist of polyamines derived from saturated aliphatic amines corresponding to the formula: which corresponds to the general formula (I) in which Z represents the group -NH-; m can have a value of 1 to 4 and n a value of 2 to 4, preferably 3.
- the radical R 1 is linear and contains from 12 to 30 and more particularly from 16 to 25 carbon atoms.
- N-dodecyl diamino-1,3 propane N-tetradecyl diamino-1,3 propane, N-hexa- dec y l diamino-1,3 propane, N-octadecyl diamino -1.3 propane, N-eicosyl diamino-1,3 propane, N-docosyl diamino-1,3 propane, N-hexadecyldipropylene triamine, N-octadecyl dipropylene triamine, N-eicosyldipropylene triamine and N- docosyldipropylene triamine.
- N-docosyl-, N-eicosyl-, N-octadecyl-, N-hexadecyl- or N-dodecyl-diamino 1,3 propane, as well as N-hexadecyl- and N-octadecyl are used.
- the compounds of formula (I) can also consist of polyamines corresponding to the formula: where R 2 and R 3 , identical or different, are each an alkyl radical having from 1 to 24 and preferably from 8 to 22 carbon atoms, R 2 and R 3 containing together the two preferably from 16 to 32 carbon atoms ; n has a value of 2 to 4 and m a value of 1 to 4.
- the compounds of formula (I) considered in the invention can consist of ether-amines corresponding more particularly to the formula: which corresponds to the general formula (I) in which Z is an oxygen atom; preferably, the radical R 4 is linear and contains from 12 to 24 carbon atoms, m is an integer from 1 to 4 and n is an integer from 1 to 4, preferably 2 or 3.
- ether-amines which may be mentioned as specific compounds: 2-methoxy-ethylamine, 3-methoxy-propylamine, 4-methoxy-butylamine, 3-ethylpropylamine, 3-octyloxy-propylamine, 3-decyloxy-propylamine , 3-hexadecyloxy-propylamine, 3-eicosyloxy-propylamine, 3-docosyloxy-propylamine, N- (3-octyloxy-propyl) diamino-1,3 propane, N- (3-decyloxy-propyl) diamino-1, 3 propane, (2,4,6,4-trimethyl decyl) oxy-3 propylamine and N - [(2,4,6,6-trimethyl decyl) oxy-3 propyl diamino-1,3 propane.
- the compound with a primary amine function involved in the preparation of the additives of the invention may also consist of an amino alcohol of formula (II): where R 5 represents a divalent saturated aliphatic radical, linear or branched, preferably linear, containing from 1 to 18 and preferably from 10 to 18 carbon atoms.
- the dicarboxylic compounds on which the condensation of a compound of formula (1) or of a compound of formula (II) as described above is carried out are more particularly chosen from anhydrides of a, ⁇ - aliphatic dicarboxylic acids and preferably unsaturated, such as for example maleic anhydride, alkylmaleic anhydrides, for example methylmaleic anhydride (or citraconic) or also among alkenyl succinic anhydrides, for example those obtained by the action of at least one olefin-a preferably linear (for example having 10 to 30 carbon atoms) on maleic anhydride. Mention may be made more specifically of n-octadecenyl succinic anhydride or dodecenyl succinic anhydride. It is of course possible to use mixtures of two (or more) of these compounds.
- polyalkenyl succinic anhydrides such as for example polyisobutenyl succinic anhydrides, whose molecular mass is between 500 and 2000 and, preferably, between 1000 and 1700. Preparation of this type anhydride is well known in the prior art.
- the primary amine-functional compounds of formulas (I) and (II) are usually used in an amount of 1.02 to 1.2 moles, preferably 1.05 to 1.1 moles, per mole of dicarboxylic compound. It is also possible to bring into play a slight defect in the compound with primary amine function (I) or (II), up to 0.9 mole per mole of dicarboxylic compound. The proportion is therefore, in general, from 0.9 to 1.2 mole / mole.
- dicarboxylic compounds e.g. acid dicarboxyli q ues, ester or preferably anhydrides
- condensation of compounds of formula (I) and / or (II), dicarboxylic compounds can be performed without solvent, but preferably used a more consistent solvent particularly in an aromatic or naphtheno-aromatic hydrocarbon with a boiling point of between 70 ° and 250 ° C for example: toluene, xylenes, diisopropylbenzene or even an petroleum fraction having the appropriate distillation range.
- the reaction time, after addition of the reactants is for example between 1 and 8 hours and preferably between 3 and 6 hours.
- the additives considered in the invention are particularly advantageous for improving the cloud point of petroleum middle distillates (in particular diesel fuels), that is to say for reducing the temperature of appearance of the first crystals of n-paraffins contained in them. this.
- the additives considered in the invention which are effective in improving the cloud point of middle distillates have, on the other hand, the property of inhibiting the sedimentation of n-paraffins in middle distillates. at rest, to improve the limit filterability temperature and the flow temperature and to inhibit corrosion of the metal surfaces in contact with these distillates.
- the concentration range of the additive from 20 g to 2000 g per tonne, it is possible to observe a lowering of the filterability temperature which can go for example up to 12 ° C., a lowering of the pour point of up to 20 ° C, a reduction in the proportion of sedimented paraffins and a marked anticorrosion effect observed in particular on ferrous metals.
- middle distillate compositions of the invention it is possible to add the additives directly to the middle distillate by a simple mixing operation.
- the “mother solutions” can contain, for example, from 20 to 60% by weight of additives.
- Additive I was analyzed after evaporation of the solvent. Its number molecular mass, measured by tonometry, is 1800. The infrared spectrum in thin layer shows the existence of bands imides at 1700 and 1780 cm -1 , secondary amide at 1635 and 1560 cm -1 and secondary amine at 3300 cm -1 .
- Additives II to VII have the same bands as Additive I. Their molecular weights are between 1500 and 3000.
- additives are used, at a rate of 0.1% by weight in the same two gas oils as above, which differ essentially from each other in the nature of the starting dicarboxylic compound.
- the additive used is additive I already used previously.
- test pieces are hermetically sealed, then left to stand in a cold room at -10 ° C for one week.
- Paraffins are in 85% of the total volume. They are better dispersed and easier to transport.
- the TLFs are determined according to standard NF M 07 - 042
- Product I was used in the two gas oils No. 1 and No. 2 already described above, at a concentration of 0.01% by weight.
- the two non-additive diesel no. 1 and no. 2 give rusty test pieces at 100% of their surface and the two gas oils containing 0.01% by weight of additive give intact test pieces with 0% rust.
- a solution consisting of 294 g (3 moles) of maleic anhydride dissolved in 500 g of xylene is introduced into a 3 1 reactor, fitted with a Dean and Stark water separation system and good stirring. . Keeping the temperature of this solution between 30 and 40 ° C, there is added, in 1.5 h, a solution obtained from 1230 g (3 moles) of N, N-didodecyldiamino 1.3 propane and 1000 g xylene. The whole is heated for 3 hours at the reflux of xylene, time during which 55 g of water are collected evacuated from the reaction medium. The reaction product constitutes additive VIII which is in solution in xylene at a concentration very close to 50% by weight.
- the condensation product constitutes additive IX, the concentration of which in xylene is adjusted to obtain a value of 50% by weight.
- a polyisobutenyl succinic anhydride with a mass close to 1200 is used, having 0.90 anhydride function per 1000 g.
- 1200 g (1 mole) of this polyisobutenyl succinic anhydride is condensed on a mixture of products consisting of 289 g (0.5 mole) of N, N-dioctadecyldiamino-1,3 propane and 40.8 g / 0.4 mol) of N, N-dimethyldiamino-1,3 propane dissolved in xylene.
- the reaction product constitutes additive X, its weight concentration in xylene is adjusted to 50% by weight.
- the additive XIa was analyzed after evaporation of the solvent. Its number molecular mass, measured by tonometry, is 500. The infrared spectrum in thin layer shows the existence of imide bands at 1700 and 1780 cm -1 , secondary amide at 1635 and 1560 cm -1 and ether at 1100 cm -1 .
- Additives XII to XVI have the same infrared absorption bands as those of additive XI, their molecular weights are between 600 and 3000.
- Example 12 the same preparation method is used as that described in Example 12, while maintaining similar molar ratios, but using different amino compounds.
- Example 12 These examples are carried out according to the procedure described in Example 12, while maintaining molar ratios between the reactants identical to that given in Example 12.
- Condensation is carried out (trimethyl-2,4-6 decyl) oxy-3 propylamine on a polyisobutenyl succinic anhydride of mass approximately 1000, having 0.675 anhydrous function per 1000 g, which provides the additive XIV.
- the alkenyl succinic anhydride used in Example 16 is condensed, ethanolamine, using a mol / del ratio between ethanolamine and the anhydride content of the alkenyl succinic anhydride used. This gives additive XVI.
- the additives are obtained in solution in xylene, the amount of which is adjusted so as to obtain solutions of additives at 50% by weight in xylene.
- 0.1% by weight of the additive XI is introduced into the second test piece.
- the two test pieces are hermetically sealed and then left to stand in a cold room at -10 ° C for one week.
- Paraffins are in 85% of the total volume. They are better dispersed and easier to transport.
- the product XIa was used in the two gas oils G 1 and G 2 already described previously at a concentration of 0.01% by weight.
- the corrosion test consists of studying corrosion by synthetic seawater, of cylindrical steel or polished iron specimens, according to standard ASTM D 665 modified as follows: the temperature is 32.2 ° C. and the duration of 20 hours.
- the two non-additive G 1 and G 2 gas oils give rusty test pieces at 100% of their surface and the two gas oils containing 0.01% by weight of additive give intact test pieces with 0% rust.
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Abstract
On décrit des additifs utilisables notamment pour abaisser le point de trouble des distillats moyens, qui consistent en des produits de masse molaire de 300 à 10.000 résultant de la réaction d'au moins un composé à fonction amine primaire sur un composé dicarboxylique choisi parmi l'anhydride maléique, les anhydrides alkylmaléiques, les anhydrides alcénylsucciniques et les anhydrides polyalcénylsucciniques, les acides et les esters d'alcoyle inférieur correspondants. Le composé à fonction amine primaire peut répondre à la formule générale R - Z [ (CH2 ‶? NH ]? H où R est un radical alkyle, Z peut représenter - NH -, -NR' - (R' étant un radical alkyle), ou -O-: n est un nombre entier de 2 à 4; et m peut être zéro ou un nombre entier de 1 à 4; ou à la formule générale HOCH2 - R<5> - NH2 où R<5> est un radical alcoylène. Ces additifs peuvent être ajoutés aux distillats moyens (en particulier aux gazoles) à des concentrations de 20 à 2.000 g/tonne.Additives are described which can be used in particular for lowering the cloud point of middle distillates, which consist of products with a molar mass of 300 to 10,000 resulting from the reaction of at least one compound with a primary amine function on a dicarboxylic compound chosen from maleic anhydride, alkylmaleic anhydrides, alkenylsuccinic anhydrides and polyalkenylsuccinic anhydrides, acids and corresponding lower alkyl esters. The compound with primary amine function can correspond to the general formula R - Z [(CH2 ‶? NH]? H where R is an alkyl radical, Z can represent - NH -, -NR '- (R' being an alkyl radical) , or -O-: n is an integer from 2 to 4; and m can be zero or an integer from 1 to 4; or to the general formula HOCH2 - R <5> - NH2 where R <5> is a alkylene radical These additives can be added to middle distillates (in particular to diesel fuels) at concentrations of 20 to 2,000 g / tonne.
Description
L'invention concerne de nouveaux additifs azotés utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures (fuel -oils, gazoles), ainsi que les compositions de distillats moyens renfermant les dits additifs.The invention relates to new nitrogen additives which can be used as agents for lowering the cloud point of hydrocarbon middle distillates (fuel oil, diesel fuels), as well as the middle distillate compositions containing said additives.
Les distillats de pétrole concernés par l'invention consistent en des distillats moyens (fuel -oils, gazoles) dont l'intervalle de distillation (norme ASTM D 86-67) se situe entre 150°C et 450°C.The petroleum distillates concerned by the invention consist of middle distillates (fuel oils, diesel oils) whose distillation interval (standard ASTM D 86-67) is between 150 ° C and 450 ° C.
Les gazoles considérés plus particulièrement ont un intervalle de distillation allant d'une température initiale comprise entre 160°C et 190°C à une température finale comprise entre 350°C et 390°C.The diesel oils considered more particularly have a distillation interval ranging from an initial temperature between 160 ° C and 190 ° C to a final temperature between 350 ° C and 390 ° C.
Il existe sur le marché un grand nombre de produits préconisés pour améliorer la température limite de filtrabilité et le point d'écoulement des coupes pétrolières riches en paraffines, tels que par exemple :
- - les polymères à base d'oléfines à longue chaîne,
- - les copolymères à base d'alpha-oléfines,
- - les copolymères éthylène-acétate de vinyle,
- - les N-acylaminoéthylesters de polymères contenant des acides, ou encore :
- - des composés halocarbonés.
- - polymers based on long chain olefins,
- - copolymers based on alpha-olefins,
- - ethylene-vinyl acetate copolymers,
- - N-acylaminoethyl esters of polymers containing acids, or also:
- - halocarbon compounds.
Ces produits agissent sur les phénomènescinétiques de cristallisation et modifient la taille des cristaux, permettant l'emploi de la suspension à une température plus basse sans colmatage des canalisations et des filtres. Les produits mentionnés ci-dessus ne modifient pas la température à laquelle apparaissent les premiers cristaux de paraffine. En effet, il a été considéré jusqu'à présent que cette température était une donnée dépendant du poids moléculaire et de la formule des paraffines et de la nature du solvant.These products act on kinetic phenomena of crystallization and modify the size of the crystals, allowing the use of the suspension at a lower temperature without clogging of the pipes and filters. The products mentioned above do not modify the temperature at which the first paraffin crystals appear. In fact, it has hitherto been considered that this temperature is a given depending on the molecular weight and the formula of the paraffins and on the nature of the solvent.
L'abaissement du point de trouble des distillats moyens (notamment des gazoles) par un additif, présenterait un intérêt important pour les raffineurs, car il permettrait, sans modifier le schéma de distillation, de respecter les spécifications qui évoluent actuellement dans le sens d'une plus grande sévérité.Lowering the cloud point of middle distillates (in particular diesel) by an additive, would be of great interest to refiners, because it would allow, without modifying the distillation scheme, to comply with the specifications which are currently evolving in the direction of greater severity.
On a maintenant découvert que certains composés chimiques, dont une définition est donnée plus loin, ont, lorsqu'ils sont ajoutés aux distillats moyens, la propriété de ne laisser apparaître les premiers cristaux de paraffines qu'à une température plus basse que celle à laquelle ces cristaux apparaîtraient en l'absence de tels additifs. Cette propriété est d'autant plus inattendue qu'elle se conserve après plusieurs cycles de réchauffage et de refroidissement et se manifeste par un mécanisme qui n'est pas encore expliqué.We have now discovered that certain chemical compounds, a definition of which is given below, have, when added to middle distillates, the property of allowing the first paraffin crystals to appear only at a temperature lower than that at which these crystals would appear in the absence of such additives. This property is all the more unexpected since it is preserved after several heating and cooling cycles and manifests itself by a mechanism which has not yet been explained.
Cette classe de composés chimiques présente également un effet sur d'autres propriétés des distillats moyens (notamment des gazoles), en modifiant le comportement du milieu qui contient les paraffines précipitées.This class of chemical compounds also has an effect on other properties of middle distillates (in particular gas oils), by modifying the behavior of the medium which contains the precipitated paraffins.
Ainsi, les composés préconisés dans l'invention ont une action importante sur la température limite de filtrabilité et la température d'écoulement.Thus, the compounds recommended in the invention have a significant action on the limit filterability temperature and the flow temperature.
Lorsque les cristaux de paraffines dont la formation est provoquée par le refroidissement sont apparus, leur tendance naturelle est de se rassembler par gravité dans la partie basse. Ce phénomène, généralement connu sous le terme de sédimentation, provoque le bouchage des canalisations et des filtres et est préjudiciable à la bonne utilisation des distillats moyens et notamment des gazoles. Les composés chimiques préconisés dans l'invention peuvent diminuer notablementWhen the paraffin crystals whose formation is caused by cooling have appeared, their natural tendency is to gather by gravity in the lower part. This phenomenon, generally known as sedimentation, causes clogging of pipes and filters and is detrimental to the proper use of middle distillates and in particular diesel. The chemical compounds recommended in the invention can significantly decrease
la vitesse de sédimentation des paraffines formées par refroidissement des gazoles et autres distillats moyens.the rate of sedimentation of the paraffins formed by cooling the gas oils and other middle distillates.
Enfin, les produits préconisés pour leurs propriétés mentionnées ci-dessus confèrent en outre aux gazoles et distillats moyens auxquels ils sont ajoutés, des propriétés anti-corrosion sur les surfaces métalliques.Finally, the products recommended for their properties mentioned above also confer on the gas oils and middle distillates to which they are added, anti-corrosion properties on metal surfaces.
D'une manière générale, les additifs de l'invention peuvent être définis comme des produits de masse moléculaire moyenne d'environ 300 à 10 000, résultantde la condensation d'au moins un composé comprenant une fonction amine primaire répondant à l'une des formules générales suivantes (I) et (II) :
Dans la formule (I), R représente en général un radical aliphatique saturé monovalent, comprenant de 1 à 30 atomes de carbone ; Z peut, suivant les cas, être un atome d'oxygène ou représenter un groupement divalent du type - NR' -, R' pouvant être soit un atome d'hydrogène, soit un radical aliphatique monovalent ; n est un nombre entier de 2 à 4, et m peut avoir la valeur zéro ou être un nombre entier de 1 à 4.In formula (I), R generally represents a monovalent saturated aliphatic radical, comprising from 1 to 30 carbon atoms; Z may, depending on the case, be an oxygen atom or represent a divalent group of the type - NR '-, R' may be either a hydrogen atom or a monovalent aliphatic radical; n is an integer from 2 to 4, and m can be zero or an integer from 1 to 4.
Les composés de formule (I) ci-dessus peuvent consister en des amines primaires de formule Rl_NH2 (dans ce cas, dans la formule (I), Z représente le groupement -NH-, et la valeur de m est zéro).The compounds of formula (I) above may consist of primary amines of formula NH 2 R l_ (in this case, in formula (I), Z represents the -NH- group, and the value of m is zero) .
De préférence, le radical R1 est linéaire et renferme de 12 à 30, et plus particulièrement de 16 à 25 atomes de carbone. Comme exemples spécifiques de ces amines, on peut citer : la dodécylamine, la tétradécylamine, l'hexadécylamine, l'octadécylamine, l'éicosylamine et la docosylamine. L'hexadécylamine et l'octadécylamine étant préférées.Preferably, the radical R 1 is linear and contains from 12 to 30, and more particularly from 16 to 25 carbon atoms. As specific examples of these amines, mention may be made of: dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine and docosylamine. Hexadecylamine and octadecylamine being preferred.
Les composés de formule (I) peuvent encore consister en des polyamines dérivées d'amines aliphatiques saturées répondant à la formule :
De préférence, le radical R1 est linéaire et renferme de 12 à 30 et plus particulièrement de 16 à 25 atomes de carbone.Preferably, the radical R 1 is linear and contains from 12 to 30 and more particularly from 16 to 25 carbon atoms.
Comme composés spécifiques, on peut citer : le N-dodécyl diamino-1,3 propane, le N-tétradécyl diamino-1,3 propane, le N-hexa- décyl diamino-1,3 propane, le N-octadécyl diamino-1,3 propane, le N-éicosyl diamino-1,3 propane, le N-docosyl diamino-1,3 propane, la N-hexadécyldipropylène triamine, la N-octadécyl dipropylène triamine, la N-éicosyldipropylène triamine et la N-docosyldipropylène triamine.As specific compounds, there may be mentioned: N-dodecyl diamino-1,3 propane, N-tetradecyl diamino-1,3 propane, N-hexa- dec y l diamino-1,3 propane, N-octadecyl diamino -1.3 propane, N-eicosyl diamino-1,3 propane, N-docosyl diamino-1,3 propane, N-hexadecyldipropylene triamine, N-octadecyl dipropylene triamine, N-eicosyldipropylene triamine and N- docosyldipropylene triamine.
Le plus avantageusement, on utilise les N-docosyl-, N-eicosyl-, N-octadécyl-, N-hexadécyl- ou encore N-dodécyl-diamino 1,3 propane, ainsi que la N-hexadécyl- et la N-octadécyl- dipropylène - triamine.Most advantageously, N-docosyl-, N-eicosyl-, N-octadecyl-, N-hexadecyl- or N-dodecyl-diamino 1,3 propane, as well as N-hexadecyl- and N-octadecyl are used. - dipropylene - triamine.
Les composés de formule (I) peuvent également consister en des polyamines répondant à la formule :
Comme composés spécifiques, on peut citer le N, N-diéthyl-diamino-1,2 éthane, le N,N-diisopropyldiamino-1,2 éthane, le N,N-dibutyl-diamino-1,2 éthane, le N,N- diéthyl-diamino-1,4 butane, le N,N-diméthyl--diamino-1,3 propane, le N,N -diéthyl-diamino-1,3 propane, le N,N-dioctyl-diamino-1,3 propane, le N,N-didécyldiamino-1,3 propane, le N,N didodécyl-diamino-1,3 propane, le N,N-ditétradécyl-diamino-1,3 propane, le N,N-dihexadécyldiamino-1,3 propane, le N,N-diocta- décyldiamino-1,3 propane, la N,N-didodécyldipropylènetriamine, la N,N-ditétradécyldipropylène triamine, la N,N-dihexadécyldipropylène triamine et la N,N-dioctadécyldipropylènetriamine.As specific compounds, mention may be made of N, N-diethyl-diamino-1,2 ethane, N, N-diisopropyldiamino-1,2 ethane, N, N-dibutyl-diamino-1,2 ethane, N, 1,4-N-diethyl-diamino-butane, N, N-dimethyl-1,3-diamino propane, N, N-1,3-diamino-diamino propane, N, N-dioctyl-diamino-1 , 3 propane, N, N-didécyldiamino-1,3 propane, N, N didodécyl-diamino-1,3 propane, N, N-ditétradécyl-diamino-1,3 propane, N, N-dihexadécyldiamino- 1,3 propane, N, N-diocta-decyldiamino-1,3 propane, N, N-didodécyldipropylènetriamine, N, N-ditétradécyldipropylène triamine, N, N-dihexadécyldipropylène triamine and N, N-dioctadécyldipropylénnetriamine.
Enfin les composés de formule (I) considérés dans l'invention peuvent consister en des éther-amines répondant plus particulièrement à la formule :
Parmi les éther-amines, on peut citer comme composés spécifiques : la méthoxy-2 éthylamine, la méthoxy-3 propylamine, la méthoxy-4 butylamine, l'éthoxy-3 propylamine, l'octyloxy-3 propylamine, la décyloxy-3 propylamine, l'hexadécyloxy-3 propylamine, l'éicosyloxy-3 propylamine, la docosyloxy-3 propylamine, le N-(octyloxy-3 propyl) diamino-1,3 propane, le N-(décyloxy-3 propyl) diamino-1,3 propane, la (triméthyl-2,4,6 décyl) oxy-3 propylamine et le N-[(triméthyl-2,4,6 décyl) oxy-3 propyl diamino-1,3 propane.Among the ether-amines which may be mentioned as specific compounds: 2-methoxy-ethylamine, 3-methoxy-propylamine, 4-methoxy-butylamine, 3-ethylpropylamine, 3-octyloxy-propylamine, 3-decyloxy-propylamine , 3-hexadecyloxy-propylamine, 3-eicosyloxy-propylamine, 3-docosyloxy-propylamine, N- (3-octyloxy-propyl) diamino-1,3 propane, N- (3-decyloxy-propyl) diamino-1, 3 propane, (2,4,6,4-trimethyl decyl) oxy-3 propylamine and N - [(2,4,6,6-trimethyl decyl) oxy-3 propyl diamino-1,3 propane.
Le compose à fonction amine primaire mis en jeu dans la préparation des additifs de l'invention peut aussi consister en un aminoalcool de formule (II) :
Comme exemples spécifiques, on peut citer :
- la monoéthanolamine, l'amino-1 propanol-3, l'amino-1 butanol-4, l'amino-1 pentanol-5, l'amino-1 hexanol-6, l'amino -1 heptanol-7, l'amino-1 octanol-8, l'amino- ldécanol-10, l'amino-1 undécanol- 11, l'amino-1 tridécanol-13, l'amino-1 tétradécanol-14, l'amino-1 hexadécanol-16, l'amino-2 méthyl-2 propanol-1, l'amino-2 butanol-1 et l'amino-2 pentanol-1.
- monoethanolamine, amino-1 propanol-3, amino-1 butanol-4, amino-1 pentanol-5, amino-1 hexanol-6, amino -1 heptanol-7, amino-1 octanol-8, amino-ldecanol-10, amino-1 undecanol- 11, amino-1 tridecanol-13, amino-1 tetradecanol-14, amino-1 hexadecanol-16 , 2-amino-2-methyl propanol-1, 2-amino butanol-1 and 2-amino pentanol-1.
Il doit être entendu que, sans sortir du cadre de l'invention, il est possible de mettre en jeu un ou plusieurs composés répondant à la formule (I) et/ou un ou plusieurs composés répondant à la formule (II).It should be understood that, without departing from the scope of the invention, it is possible to bring into play one or more compounds corresponding to formula (I) and / or one or more compounds corresponding to formula (II).
Les composés dicarboxyliques sur lesquels on effectue la condensation d'un composé de formule (1) ou d'un composé de formule (II ) tels que décrits précédemment, sont plus particulièrement choisis parmi les anhydrides d'acides a ,β - dicarboxyliques aliphatiques et de préférence insaturés, tels que par exemple l'anhydride maléique, les anhydrides alkylmaléiques, par exemple l'anhydride méthylmaléique (ou citraconique) ou encore parmi les anhydrides alcényl-succiniques, par exemple ceux obtenus par action d'au moins une oléfine-a de préférence linéaire (ayant par exemple de 10 à 30 atomes de carbone) sur l'anhydride maléique. On peut mentionner plus spécifiquement l'anhydride n-octadécényl succinique ou l'anhydride dodécényl-succinique. Il est possible, bien entendu, d'utiliser des mélanges de deux (ou plus) de ces composés.The dicarboxylic compounds on which the condensation of a compound of formula (1) or of a compound of formula (II) as described above is carried out, are more particularly chosen from anhydrides of a, β - aliphatic dicarboxylic acids and preferably unsaturated, such as for example maleic anhydride, alkylmaleic anhydrides, for example methylmaleic anhydride (or citraconic) or also among alkenyl succinic anhydrides, for example those obtained by the action of at least one olefin-a preferably linear (for example having 10 to 30 carbon atoms) on maleic anhydride. Mention may be made more specifically of n-octadecenyl succinic anhydride or dodecenyl succinic anhydride. It is of course possible to use mixtures of two (or more) of these compounds.
On peut également, dans le cadre de l'invention, utiliser des anhydrides polyalcényl-succiniques, comme par exemple des anhydrides polyisobuténylsucciniques, dont la masse moléculaire est comprise entre 500 et 2000 et, préférentiellement, entre 1000 et 1700. La préparation de ce type d'anhydride est bien connue de l'art antérieur.It is also possible, within the framework of the invention, to use polyalkenyl succinic anhydrides, such as for example polyisobutenyl succinic anhydrides, whose molecular mass is between 500 and 2000 and, preferably, between 1000 and 1700. Preparation of this type anhydride is well known in the prior art.
Au lieu des anhydrides mentionnés ci-dessus, il est possible d'utiliser les acides dicarboxyliques correspondants, ainsi que les diesters d'alkyle légers de ceux-ci (tels que, par exemple, les esters de méthyle, éthyle, propyle et butyle).Instead of the anhydrides mentioned above, it is possible to use the corresponding dicarboxylic acids, as well as the light alkyl diesters thereof (such as, for example, methyl, ethyl, propyl and butyl esters) .
Les composés à fonction amine primaire de formules (I) et (II) sont habituellement utilisés à raison de 1,02 à 1,2 mole, de préférence de 1,05 à 1,1 mole, par mole de composé dicarboxylique. On peut également mettre en jeu un léger défaut de composé à fonction amine primaire (I) ou (II), jusqu'à 0,9 mole par mole de composé dicarboxylique. La proportion est donc, en général, de 0,9 à 1,2 mole/mole.The primary amine-functional compounds of formulas (I) and (II) are usually used in an amount of 1.02 to 1.2 moles, preferably 1.05 to 1.1 moles, per mole of dicarboxylic compound. It is also possible to bring into play a slight defect in the compound with primary amine function (I) or (II), up to 0.9 mole per mole of dicarboxylic compound. The proportion is therefore, in general, from 0.9 to 1.2 mole / mole.
La condensation des composés de formule (I) et/ou (II), sur les composés dicarboxyliques (par exemple acides dicarboxyliques, esters, ou de préférence anhydrides) peut être faite sans solvant, mais de préférence on utilisera un solvant consistant plus particulièrement en un hydrocarbure aromatique ou naphténo-aromatique de point d'ébullition compris entre 70° et 250°C par exemple : le toluène, les xylènes, le diisopropylbenzène ou bien encore une coupe pétrolière ayant l'intervalle de distillation approprié.The condensation of compounds of formula (I) and / or (II), dicarboxylic compounds (e.g. acid dicarboxyli q ues, ester or preferably anhydrides) can be performed without solvent, but preferably used a more consistent solvent particularly in an aromatic or naphtheno-aromatic hydrocarbon with a boiling point of between 70 ° and 250 ° C for example: toluene, xylenes, diisopropylbenzene or even an petroleum fraction having the appropriate distillation range.
Pour préparer les compositions d'additifs considérées dans l'in- ventim, on peut dans la pratique procéder de la manière suivante : Dans un réacteur contenant le composé dicarboxylique, et en maintenant le température entre 30°C et 80°C, on introduit peu à peu le composé de formule (I) et/ou (Il). On élève ensuite la température à 120° C - 200° C en éliminant les produits volatils formés (eau ou alcools), soit par entraînement avec un courant de gaz inerte, soit par distillation azéotropique avec le solvant choisi ; la concentration en matière sèche est par exemple de 40 à 70 %, le plus souvent voisine de 60 %.In order to prepare the additive compositions considered in the invention, it is possible in practice to proceed as follows: In a reactor containing the dicarboxylic compound, and maintaining the temperature between 30 ° C. and 80 ° C., the following are introduced: little by little the compound of formula (I) and / or (II). The temperature is then raised to 120 ° C - 200 ° C by eliminating the volatile products formed (water or alcohols), either by entrainment with a stream of inert gas, or by azeotropic distillation with the chosen solvent; the dry matter concentration is for example 40 to 70%, most often close to 60%.
La durée de réaction,.après addition des réactifs, est comprise par exemple entre 1 et 8 heures et de préférence entre 3 et 6 heures.The reaction time, after addition of the reactants, is for example between 1 and 8 hours and preferably between 3 and 6 hours.
Les additifs considérés dans l'invention sont particulièrement intéressants pour améliorer le point de trouble des distillats moyens du pétrole Notamment des gazoles) c'est-à-dire pour diminuer la température d'apparition des premiers cristaux de n-paraffines contenues dans ceux-ci.The additives considered in the invention are particularly advantageous for improving the cloud point of petroleum middle distillates (in particular diesel fuels), that is to say for reducing the temperature of appearance of the first crystals of n-paraffins contained in them. this.
Bien que le mécanisme d'action de ces additifs sur la température d'apparition des cristaux de paraffines dans les distillats moyens n'ait pas encore été clairement élucidé, on observe une nette amélioration du point de trouble des distillats moyens traités par ces additifs, lorsqu'ils sont ajoutés à des concentrations allant par exemple de 20 à 2 000 g par tonne de distillat moyen. Les concentrations préférées vont de 100 à 2000 g/t. L'abaissement du point de trouble peut aller par exemple jusqu'à 5° C, quelquefois davantage.Although the mechanism of action of these additives on the temperature of appearance of paraffin crystals in middle distillates has not yet been clearly elucidated, there is a marked improvement in the cloud point of the middle distillates treated with these additives, when added at concentrations ranging, for example, from 20 to 2,000 g per tonne of middle distillate. Preferred concentrations range from 100 to 2000 g / t. The lowering of the cloud point can go for example up to 5 ° C, sometimes more.
De plus, il est remarquable de constater que les additifs considérés dans l'invention qui sont efficaces sur l'amélioration du point de trouble des distillats moyens ont d'autre part la propriété d'inhiber la sédimentation des n-paraffines dans les distillats moyens au repos, d'améliorer la température limite de filtrabilité etla température d'écoulement et d'inhiber la corrosion des surfaces métalliques en contact avec ces distillats.In addition, it is remarkable to note that the additives considered in the invention which are effective in improving the cloud point of middle distillates have, on the other hand, the property of inhibiting the sedimentation of n-paraffins in middle distillates. at rest, to improve the limit filterability temperature and the flow temperature and to inhibit corrosion of the metal surfaces in contact with these distillates.
Ainsi, dans la gamme de concentration de l'additif, de 20 g à 2 000 g par tonne, il est possible d'observer un abaissement de la température de filtrabilité pouvant aller par exemple jusqu'à 12° C, un abaissement du point d'écoulement pouvant aller jusqu'à 20° C, une diminution de la proportion de paraffines sédimentées et un effet anticorrosion net observé en particulier sur les métaux ferreux.Thus, in the concentration range of the additive, from 20 g to 2000 g per tonne, it is possible to observe a lowering of the filterability temperature which can go for example up to 12 ° C., a lowering of the pour point of up to 20 ° C, a reduction in the proportion of sedimented paraffins and a marked anticorrosion effect observed in particular on ferrous metals.
Pour formuler les compositions de distillats moyens de l'invention, il est possible d'ajouter les additifs directement au distillat moyen par une simple opération de mélange.To formulate the middle distillate compositions of the invention, it is possible to add the additives directly to the middle distillate by a simple mixing operation.
Il est cependant souvent avantageux de les introduire sous la forme de "solutions mères" préparées au préalable dans les solvants déjà mentionnés plus haut.It is however often advantageous to introduce them in the form of "mother solutions" prepared beforehand in the solvents already mentioned above.
Les "solutions mères" peuvent contenir par exemple de 20 à 60 % en poids d'additifs.The "mother solutions" can contain, for example, from 20 to 60% by weight of additives.
Les exemples suivants illustrent l'invention et ne doivent en aucune manière être considérés comme limitatifs.The following examples illustrate the invention and should in no way be taken as limiting.
On introduit dans un réacteur de 20 1 muni d'une bonne agitation 2.700g d'une polyamine commerciale (contenant un mélange, environ 27 % de palmityl 1,3 propane-diamine et 70 % de stéaryl 1,3 propane-diamine ayant un équivalent de 370 g pour une amine primaire) et 2.700 g de xylène, on dissout l'amine à 50°C et on refroidit ensuite à 30°C, on rajoute une solution de 699 g d'anhydride maléique dissout dans 1.050 g de xylène en maintenant la température intérieure à 40°C ; l'addition dure une heure, on chauffe ensuite pendant 3 H à reflux de xylène, la température intérieure est de 144°C, on élimine par distillation 157 g d'eau correspondant à 128 g d'eau de réaction et 29 g d'eau contenue dans l'amine ; à la fin de la réaction on distille 500 g de xylène pour obtenir une solution à 50 % en poids de l'additif I dans le xylène.2.700 g of a commercial polyamine (containing a mixture, approximately 27% of palmityl 1,3 propane-diamine and 70% of stearyl 1,3 propane-diamine having a equivalent of 370 g for a primary amine) and 2,700 g of xylene, the amine is dissolved at 50 ° C and then cooled to 30 ° C, a solution of 699 g of maleic anhydride dissolved in 1,050 g of xylene is added maintaining the interior temperature at 40 ° C; the addition lasts one hour, then heated for 3 hours at xylene reflux, the internal temperature is 144 ° C., 157 g of water are removed by distillation corresponding to 128 g of reaction water and 29 g of water contained in the amine; at the end of the reaction, 500 g of xylene are distilled to obtain a 50% by weight solution of the additive I in xylene.
L'additif I a été analysé après évaporation du solvant. Sa masse moléculaire en nombre, mesurée par tonométrie, est de 1800. Le spectre infra-rouge en couche mince montre l'existence de bandes imides à 1700 et 1780 cm-1, amide secondaire à 1635 et 1560 cm-1 et amine secondaire à 3300 cm-1.Additive I was analyzed after evaporation of the solvent. Its number molecular mass, measured by tonometry, is 1800. The infrared spectrum in thin layer shows the existence of bands imides at 1700 and 1780 cm -1 , secondary amide at 1635 and 1560 cm -1 and secondary amine at 3300 cm -1 .
Les additifs II à VII présentent les mêmes bandes que l'additif I. Leurs masses moléculaires sont comprises entre 1500 et 3000.Additives II to VII have the same bands as Additive I. Their molecular weights are between 1500 and 3000.
On teste l'activité de cet additif I dans deux coupes de gazole d'origine Aramco dont les caractéristiques sont indiquées au tableau I ci-après.
L'effet de l'additif I sur l'abaissement du point de trouble de chacune des deux coupes de gazole, en fonction de la concentration en additif, déterminé suivant la méthode NF T 60 105, est montré au tableau II ci-après.
Dans cet exemple, on utilise à 0,1 % en poids dans les deux coupes de gazole utilisées dans l'exemple 1, des additifs qui diffèrent principalement par la nature de l'amine de départ, la méthode de préparation étant la même que dans l'exemple 1.
- Additif I : produit utilisé dans l'exemple 1
- Additif II : produit de la condensation sur l'anhydride maléique de la N-stéaryl-dipropylène triamine ;
- Additif III : produit de la condensation sur l'anhydride maléique de la stéaryl-amine.
- Additive I: product used in Example 1
- Additive II: product of condensation on the maleic anhydride of N-stearyl-dipropylene triamine;
- Additive III: produces condensation on the maleic anhydride of stearylamine.
Les résultats sont indiqués au tableau III ci-après.
On constate que l'effet d'abaissement du point de trouble est le plus important dans le cas de l'additif I, dans lequel l'amine de départ est un mélange de deux N-alkyl 1,3 propane diamines.It is found that the effect of lowering the cloud point is most significant in the case of additive I, in which the starting amine is a mixture of two N-alkyl 1,3 propane diamines.
Dans cet exemple, on utilise à raison de 0,1 % en poids dans les deux mêmes gazoles que précédemment, des additifs qui diffèrent essentiellement par la longueur de la chaîne alkyle de l'amine de départ :
- Ainsi on utilise :
- Additif I : produit utilisé dans l'exemple 1
- Additif IV : produit de la condensation sur l'anhydride maléique de la N-béhényl 1,3 propane diamine (béhényl = C22)
- Additif V : produit de la condensation sur l'anhydride maléique de la N-lauryl,3 propane diamine (lauryl = C12)
- So we use:
- Additive I: product used in Example 1
- Additive IV: product of condensation on the maleic anhydride of N-behenyl 1,3 propane diamine (be h en y l = C 22 )
- Additive V: product of condensation on the maleic anhydride of N-lauryl, 3 propane diamine (lauryl = C 12 )
Les résultats des déterminations du point de trouble sont indiqués au tableau IV ci-après.
Dans cet exemple, on utilise, à raison de 0,1 % en poids dans les deux mêmes gazoles que précédemment, des additifs qui diffèrent entre eux essentiellement par la nature du composé dicarboxylique de départ.In this example, additives are used, at a rate of 0.1% by weight in the same two gas oils as above, which differ essentially from each other in the nature of the starting dicarboxylic compound.
Ainsi on utilise :
- Additif I : produit utilisé dans l'exemple 1, dérivant de l'anhydride maléique
- Additif VI : produit de la condensation de la N-stéaryl 1,3 propane diamine sur l'anhydride méthylmaléique (citraconique)
- Additif VII : produit de la condensation de la N-stéaryl 1,3 propane diamine sur l'anhydride n-octadécenyl succinique.
- Additive I: product used in Example 1, derived from maleic anhydride
- Additive VI: product of the condensation of N-stearyl 1,3 propane diamine on methylmaleic anhydride (citraconic)
- Additive VII: product of the condensation of N-stearyl 1,3 propane diamine on n-octadecenyl succinic anhydride.
Les points de trouble déterminés sont indiqués au tableau V ci-après :
Dans cet exemple, on a testé l'action inhibitrice d'un additif, selon l'invention, sur la sédimentation des n-paraffines cristallisant dans une coupe de gazole maintenue au repos à basse température.In this example, the inhibitory action of an additive according to the invention was tested on the sedimentation of n-paraffins crystallizing in a fraction of diesel fuel kept at rest at low temperature.
L'additif utilisé est l'additif I déjà utilisé précédemment.The additive used is additive I already used previously.
Deux éprouvettes de 100 cm3 sont remplies d'une coupe gazole caractérisée par l'intervalle de distillation PI = 186°C, PF = 385°C - (gazole n° 2 déjà utilisé précédemment).Two 100 cm3 test tubes are filled with a diesel cut characterized by the distillation interval PI = 186 ° C, PF = 385 ° C - (diesel n ° 2 already used previously).
Dans la première éprouvette, on n'introduit pas d'additif.In the first test tube, no additive is introduced.
Dans la deuxième éprouvette, on introduit 0,1 % en poids de l'additif 1.0.1% by weight of the additive 1 is introduced into the second test piece.
Les deux éprouvettes sont bouchées hermétiquement, puis laissées au repos en chambre froide à -10°C pendant une semaine.The two test pieces are hermetically sealed, then left to stand in a cold room at -10 ° C for one week.
Au bout d'une semaine, le degré de sédimentation des paraffines ayant précipité, exprimé par le volume de la phase supérieure limpide, est noté dans le tableau suivant :After one week, the degree of sedimentation of the precipitated paraffins, expressed by the volume of the clear upper phase, is noted in the following table:
Pour le gazole additivé, il n'y a que 15 % de phase supérieure limpide. Les paraffines sont dans 85 % du volume total. Elles sont mieux dispersées et plus faciles à véhiculer.For the additive diesel, there is only 15% of clear upper phase. Paraffins are in 85% of the total volume. They are better dispersed and easier to transport.
Dans cet exemple, on teste l'effet d'un additif selon l'invention sur la température limite de filtrabilité (TLF) des deux coupes de gazole déjà décrites précédemment.In this example, the effect of an additive according to the invention is tested on the limit filterability temperature (TLF) of the two diesel fuel cuts already described above.
Les TLF sont déterminées suivant la norme NF M 07 - 042
Dans cet exemple, on teste l'effet anti-corrosion de l'additif I de l'exemple 1 .In this example, the anti-corrosion effect of the additive I of example 1 is tested.
Le produit I a été utilisé dans les deux gazoles n° 1 et n° 2 déjà décrits précédemment, à la concentration de 0,01 % en poids.Product I was used in the two gas oils No. 1 and No. 2 already described above, at a concentration of 0.01% by weight.
Le test de corrosion consiste à étudier la corrosion par de l'eau de mer synthétique, d'éprouvettes cylindriques en acier ou en fer poli selon la norme ASTM D 665 modifiée de la façon suivante :
- La température est de 32,2°C et la durée : 20 heures
- The temperature is 32.2 ° C and the duration: 20 hours
Les deux gazoles n° 1 et n° 2 non additivés donnent des éprouvettes rouillées à 100 % de leur surface et les deux gazoles contenant 0,01% en poids d'additif donnent des éprouvettes intactes à 0 % de rouille.The two non-additive diesel no. 1 and no. 2 give rusty test pieces at 100% of their surface and the two gas oils containing 0.01% by weight of additive give intact test pieces with 0% rust.
Dans cet exemple on teste l'effet de l'additif I selon l'invention sur le point d'écoulement de coupes gazoles. Les points d'écoulement sont déterminés suivant la norme française NFT 60105 ; l'additif est essayé à 0,1 % en poids. Les résultats sont indiqués au tableau VIII ci-après.In this example, the effect of the additive I according to the invention is tested on the point of flow of diesel cuts. Pour points are determined according to French standard NFT 60105; the additive is tested at 0.1% by weight. The results are shown in Table VIII below.
Dans un réacteur de 3 1, muni d'un système de séparation d'eau de Dean et Stark et d'une bonne agitation, on introduit une solution constituée par 294 g (3 moles) d'anhydride maléique dissous dans 500 g de xylène. En maintenant la température de cette solution entre 30 et 40° C, on y ajoute, en 1,5 h, une solution obtenue à partir de 1230 g (3 moles) de N,N-didodécyldiamino 1,3 propane et de 1000 g de xylène. L'ensemble est porté pendant 3 heures au reflux du xylène, temps pendant lequel on recueille 55 g d'eau évacués hors du milieu réactionnel. Le produit de la réaction constitue l'additif VIII qui se trouve en solution dans le xylène à une concentration très voisine de 50 % en poids.A solution consisting of 294 g (3 moles) of maleic anhydride dissolved in 500 g of xylene is introduced into a 3 1 reactor, fitted with a Dean and Stark water separation system and good stirring. . Keeping the temperature of this solution between 30 and 40 ° C, there is added, in 1.5 h, a solution obtained from 1230 g (3 moles) of N, N-didodecyldiamino 1.3 propane and 1000 g xylene. The whole is heated for 3 hours at the reflux of xylene, time during which 55 g of water are collected evacuated from the reaction medium. The reaction product constitutes additive VIII which is in solution in xylene at a concentration very close to 50% by weight.
En suivant un mode opératoire identique à celui de l'exemple 9, on procède à la condensation de 532 g (2 moles) d'anhydride dodécénylsuc- cinique sur 820 g (2 moles) de N,N-didodécyldiamino-1,3 propane.Following a procedure identical to that of Example 9, 532 g (2 moles) of dodecenylsuccinic anhydride are condensed on 820 g (2 moles) of N, N-didodecyldiamino-1,3 propane .
Le produit de la condensation constitue l'additif IX, dont la concentration dans le xylène est ajustée pour obtenir une valeur de 50 % en poids.The condensation product constitutes additive IX, the concentration of which in xylene is adjusted to obtain a value of 50% by weight.
Dans cet exemple, on utilise un anhydride polyisobutényl-succinique de masse voisine de 1200, présentant 0,90 fonction anhydride pour 1000 g. En suivant le mode opératoire de l'exemple 9, on condense 1200 g (1 mole) de cet anhydride polyisobutényl-succinique sur un mélange de produits constitué par 289 g (0,5 mole) de N,N-dioctadécyldiamino-1,3 propane et 40,8 g/0,4 mole) de N,N-diméthyldiamino-1,3 propane en solution dans du xylène. Le produit de la réaction constitue l'additif X, sa concentration pondérale dans le xylène est ajustée à 50 % en poids.In this example, a polyisobutenyl succinic anhydride with a mass close to 1200 is used, having 0.90 anhydride function per 1000 g. Following the procedure of Example 9, 1200 g (1 mole) of this polyisobutenyl succinic anhydride is condensed on a mixture of products consisting of 289 g (0.5 mole) of N, N-dioctadecyldiamino-1,3 propane and 40.8 g / 0.4 mol) of N, N-dimethyldiamino-1,3 propane dissolved in xylene. The reaction product constitutes additive X, its weight concentration in xylene is adjusted to 50% by weight.
On a testé l'effet des additifs VIII, IX et X ainsi obtenus sur le point de trouble (déterminé selon la norme NF T 60-105), la température limite de filtrabilité (déterminée selon la norme NF M 07-042) et le point d'écoulement (déterminé selon la norme NF T 60-105) des deux gazoles n° 1 et n° 2, la concentration des additifs étant, dans chaque cas, de 0,1 % en poids.The effect of the additives VIII, IX and X thus obtained was tested on the cloud point (determined according to standard NF T 60-105), the filterability limit temperature (determined according to standard NF M 07-042) and the pour point (determined according to standard NF T 60-105) of the two gas oils n ° 1 and n ° 2, the concentration of the additives being, in each case, of 0.1% by weight.
Les résultats sont rassemblés dans le tableau IX ci-après
On introduit dans un réacteur de 3 1 muni d'une bonne agitation 294 g (3 moles) d'anhydride maléique dissout dans 500 g de xylène et on refroidit à 30°C. On rajoute une solution de 797 g (3,1 moles) de (triméthyl-2,4,6 décyl)oxy-3 propylamine, dans 324 g de xylène, en maintenant la température inférieure à 40°C. L'addition dure une heure, on chauffe ensuite pendant 3 heures à reflux du xylène. La température intérieure est de 144°C. On élimine par distillation 67 g d'eau correspondant à 54 g d'eau de réaction et 13 g d'eau contenue dans l'amine ; à la fin de la réaction, on dilue par 200 g de xylène pour obtenir une solution à 50% en poids de l'additif XI dans le xylène.294 g (3 moles) of maleic anhydride dissolved in 500 g of xylene are introduced into a 3 l reactor fitted with good stirring and the mixture is cooled to 30 ° C. A solution of 797 g (3.1 moles) of (trimethyl-2,4,6 decyl) oxy-3 propylamine is added to 324 g of xylene, keeping the temperature below 40 ° C. The addition lasts one hour, then heated for 3 hours at reflux of xylene. The indoor temperature is 144 ° C. 67 g of water are removed by distillation, corresponding to 54 g of reaction water and 13 g of water contained in the amine; at the end of the reaction, diluted with 200 g of xylene to obtain a 50% by weight solution of the additive XI in xylene.
L'additif XIa été analysé après évaporation du solvant. Sa masse moléculaire en nombre, mesurée par tonométrie, est de 500. Le spectre infra-rouge en couche mince montre l'existence de bandes imides à 1700 et 1780 cm-1, amide secondaire à 1635 et 1560 cm-1 et éther à 1100 cm-1.The additive XIa was analyzed after evaporation of the solvent. Its number molecular mass, measured by tonometry, is 500. The infrared spectrum in thin layer shows the existence of imide bands at 1700 and 1780 cm -1 , secondary amide at 1635 and 1560 cm -1 and ether at 1100 cm -1 .
Les additifs XII à XVI,dont la préparation est donnée dans les exemples suivants, présentent les mêmes bandes d'absorption infra-rouge que celles de l'additif XI, leurs masses moléculaires sont comprises entre 600 et 3000.Additives XII to XVI, the preparation of which is given in the following examples, have the same infrared absorption bands as those of additive XI, their molecular weights are between 600 and 3000.
Dans ces exemples, on utilise le même mode de préparation que celui décrit dans l'exemple 12, en conservant des rapports molaires similaires, mais en utilisant des composés aminés différents.In these examples, the same preparation method is used as that described in Example 12, while maintaining similar molar ratios, but using different amino compounds.
L'additif XII es- obtenu par condensation de l'anhydride maléique sur le N- [ (triméthyl-2,4-6, décyl)oxy-3]propyl diamino-1,3 propane.Additive XII es - obtained by condensation of maleic anhydride on N- [(trimethyl-2,4-6, decyl) oxy-3] propyl diamino-1,3 propane.
Le produit de condensation sur l'anhydride maléique d'un mélange renfermant en moles, 55 % d'éthanolamine et 45% d'une coupe commerciale de N-alkyl propylènediamines, dont les chaînes alkyles consistent en environ 27% de chaine en C16 et 72% de chaine en C18 (masse moléculaire équivalente : 370 pour une fonction amine primaire) conduit à l'additif XIII.The condensation product on maleic anhydride of a mixture containing in moles, 55% ethanolamine and 45% of a commercial cut of N-alkyl propylenediamines, the alkyl chains of which consist of approximately 27% of C 16 chain and 72% of C 18 chain (equivalent molecular mass: 370 for a primary amine function) leads to the additive XIII.
Ces exemples sont conduits suivant le mode opératoire décrit dans l'exemple 12,en maintenant des rapports molaires entre les réactifs identiques à celui donné dans l'exemple 12.These examples are carried out according to the procedure described in Example 12, while maintaining molar ratios between the reactants identical to that given in Example 12.
On procède à la condensation de la (triméthyl-2,4-6 décyl)oxy-3 propylamine sur un anhydride polyisobutényl-succinique de masse environ 1000, présentant 0,675 fonction anhydre pour 1000 g,ce qui fournit l'additif XIV.Condensation is carried out (trimethyl-2,4-6 decyl) oxy-3 propylamine on a polyisobutenyl succinic anhydride of mass approximately 1000, having 0.675 anhydrous function per 1000 g, which provides the additive XIV.
La (triméthyl-2,4-6 décyl)oxy-3 propylamine est condensée sur l'anhydride alcényl succinique obtenu par réaction, en quantités équimoléculaires, d'anhydride maléique sur une coupe d'oléfines-a linéaires, renfermant approximativement 49% d'oléfine en C20, 42% en C22 et 9% en C24. Le résultat de cette condensation fournit l'additif XV.(Trimethyl-2,4-6 decyl) oxy-3 propylamine is condensed on alkenyl succinic anhydride obtained by reaction, in equimolecular amounts, of maleic anhydride on a section of linear olefins-a, containing approximately 49% d olefin C 20 , 42% C 22 and 9% C 24 . The result of this condensation provides the additive XV.
On condense sur l'anhydride alcénylsuccinique utilisé dans l'exemple 16, de l'éthanolamine, en utilisant un rapport molaire del/lentre l'éthanolamine et la teneur en anhydride de l'anhydride alcénylsuccinique utilisé. On obtient ainsi l'additif XVI.The alkenyl succinic anhydride used in Example 16 is condensed, ethanolamine, using a mol / del ratio between ethanolamine and the anhydride content of the alkenyl succinic anhydride used. This gives additive XVI.
Dans les exemples qui précèdent, les additifs sont obtenus en solution dans le xylène dont on ajuste la quantité de façon à obtenir des solutions d'additifs à 50% en poids dans le xylène.In the above examples, the additives are obtained in solution in xylene, the amount of which is adjusted so as to obtain solutions of additives at 50% by weight in xylene.
On teste l'activité de ces compositions d'additifs en les incorporant a raison de 0,1 % en poids d'additif par rapport au gazole, aux deux coupes de gazoles d'origine ARAMCO, désignées par G1 et G2, dont les caractéristiques ont été indiquées plus haut.The activity of these additive compositions is tested by incorporating them at a rate of 0.1% by weight of additive relative to the diesel fuel, into the two diesel fuel cuts of ARAMCO origin, designated by G 1 and G 2 , of which the characteristics have been indicated above.
Pour chacune des compositions ainsi formées, trois déterminations ont été effectuées :
- - le point de trouble suivant la méthode NF T 60-105
- - la température limite de filtrabilité (TLF) par la méthode NF M 07-042
- - le point d'écoulement par la méthode NF T 60-105.
- - the cloud point according to the NF T 60-105 method
- - the filterability limit temperature (TLF) by the NF M 07-042 method
- - the pour point by the NF T 60-105 method.
Les résultats de ces déterminations sont rassemblées dans le tableau X ci-après :
Dans cet exemple, on a testé l'action inhibitrice d'un additif selon l'invention, sur la sédimentation des n-paraffines cristallisant dans une coupe de gazole maintenue au repos à basse température.In this example, the inhibiting action of an additive according to the invention was tested on the sedimentation of n-paraffins crystallizing in a fraction of diesel fuel kept at rest at low temperature.
Deux éprouvettes de 100 cm3 sont remplies d'une coupe gazole caractérisée par l'intervalle de distillation PI - 186°C, PF = 385°C (gazole G2 déjà utilisé précédemment).Two 100 cm3 test tubes are filled with a diesel cut characterized by the distillation interval PI - 186 ° C, PF = 385 ° C (diesel G 2 already used previously).
Dans la première éprouvette, on n'introduit pas d'additif.In the first test tube, no additive is introduced.
Dans la deuxième éprouvette, on introduit 0,1% en poids de l'additif XI. Les deux éprouvettes sont bouchées hermétiquement puis laissées au repos en chambre froide à -10°C pendant une semaine.0.1% by weight of the additive XI is introduced into the second test piece. The two test pieces are hermetically sealed and then left to stand in a cold room at -10 ° C for one week.
Au bout d'une semaine , le degré de sédimentation des paraffines ayant précipité, exprimé par le volume de la phase supérieure limpide, est noté dans le tableau suivant :
Toutes les paraffines précipitées se retrouvent donc dans 50% du volume dans le gazole non additivé, ce qui rend la partie inférieure plus difficile à utiliser par colmatage des pompes, filtres et canalisations.All of the precipitated paraffins are therefore found in 50% of the volume in the non-additive diesel, which makes the lower part more difficult to use by clogging the pumps, filters and pipes.
Pour le gazole additivé, il n'y a que 15% de phase supérieure limpide. Les paraffines sont dans 85% du volume total. Elles sont mieux dispersées et plus faciles à véhiculer.For the additive diesel, there is only 15% of clear upper phase. Paraffins are in 85% of the total volume. They are better dispersed and easier to transport.
Dans cet exemple, on teste l'effet anti-corrosion de l'additif XI de l'exemple 12.In this example, the anti-corrosion effect of the additive XI of example 12 is tested.
Le produit XIa été utilisé dans les deux gazoles G1 et G2 déjà décrits précédemment à la concentration de 0,01% en poids.The product XIa was used in the two gas oils G 1 and G 2 already described previously at a concentration of 0.01% by weight.
Le test de corrosionconsiste à étudier la corrosion par l'eau de mer synthétique, d'éprouvettes cylindriques en acier ou en fer poli, selon la norme ASTM D 665 modifiée de la façon suivante : la température est de 32,2°C et la durée de 20 heures.The corrosion test consists of studying corrosion by synthetic seawater, of cylindrical steel or polished iron specimens, according to standard ASTM D 665 modified as follows: the temperature is 32.2 ° C. and the duration of 20 hours.
Les deux gazoles G1 et G2 non additivés donnent des éprouvettes rouillées à 100% de leur surface et les deux gazoles contenant 0,01 % en poids d'additif donnent des éprouvettes intactes à 0% de rouille.The two non-additive G 1 and G 2 gas oils give rusty test pieces at 100% of their surface and the two gas oils containing 0.01% by weight of additive give intact test pieces with 0% rust.
Claims (12)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8114870A FR2510598A1 (en) | 1981-07-30 | 1981-07-30 | USE OF NITROGEN ADDITIVES AS DISORDERS OF HYDROCARBON MEDIUM DISTILLATE DISORDER POINT AND HYDROCARBON MEDIUM DISTILLATE COMPOSITIONS COMPRISING SUCH ADDITIVES |
| FR8114870 | 1981-07-30 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0071513A2 true EP0071513A2 (en) | 1983-02-09 |
| EP0071513A3 EP0071513A3 (en) | 1983-04-27 |
| EP0071513B1 EP0071513B1 (en) | 1986-11-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82401335A Expired EP0071513B1 (en) | 1981-07-30 | 1982-07-16 | Additives for use as pour point dispersants for middle distillate hydrocarbons, and compositions of middle distillate hydrocarbons containing said additives |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4652273A (en) |
| EP (1) | EP0071513B1 (en) |
| JP (1) | JPS58108297A (en) |
| CA (1) | CA1192519A (en) |
| DE (1) | DE3274368D1 (en) |
| DK (1) | DK158993C (en) |
| FI (1) | FI75361C (en) |
| FR (1) | FR2510598A1 (en) |
| NO (1) | NO158142C (en) |
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| FR2539754A1 (en) * | 1983-01-25 | 1984-07-27 | Inst Francais Du Petrole | Nitrogenous additives usable as cloud point lowering agents for hydrocarbon middle distillates and hydrocarbon middle distillate compositions containing the said additives. |
| EP0086049B1 (en) * | 1982-02-03 | 1986-12-17 | The Lubrizol Corporation | Compositions for use in alcohol and alcohol containing fuels |
| GR880100284A (en) * | 1987-04-29 | 1989-01-31 | Nalco Chemical Co | Hydrocarbon fuel cleansing means |
| FR2633638A1 (en) * | 1988-06-29 | 1990-01-05 | Inst Francais Du Petrole | FORMULATIONS OF NITROGEN ADDITIVES FOR MOTOR FUELS AND MOTOR FUELS CONTAINING THEM |
| EP0411811A1 (en) * | 1989-08-03 | 1991-02-06 | Texaco Development Corporation | Process for producing ORI control additives |
| GB2242190A (en) * | 1990-03-24 | 1991-09-25 | Abm Chemicals Limited | Biocidal amines |
| EP0593331A1 (en) * | 1992-10-09 | 1994-04-20 | Institut Francais Du Petrole | Amines phosphates having a terminal imide cycle, their preparation and their use as additives for motor-fuels |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4895578A (en) * | 1987-04-29 | 1990-01-23 | Nalco Chemical Company | Hydrocarbon fuel detergent |
| US4874395A (en) * | 1988-09-02 | 1989-10-17 | Nalco Chemical Company | Amine neutralized alkenylsuccinic anhydride propylene glycol adducts as corrosion inhibitors for hydrocarbon fuels |
| US4981493A (en) * | 1989-01-27 | 1991-01-01 | Texaco Inc. | ORI-Inhibited and deposit-resistant motor fuel composition |
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| FR2925916B1 (en) * | 2007-12-28 | 2010-11-12 | Total France | VINYL ETHYLENE / UNSATURATED TERPOLYMER / UNSATURATED ESTERS AS AN ADDITIVE TO ENHANCE COLD LIQUID HYDROCARBONS LIKE MEDIUM DISTILLATES AND FUELS OR COMBUSTIBLES |
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| WO2022241203A1 (en) | 2021-05-13 | 2022-11-17 | Ecolab Usa Inc. | Synthetic lubricity additives for hydrocarbon fuels |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1197418A (en) * | 1958-01-07 | 1959-12-01 | Socony Mobil Oil Co Inc | Improved mineral oils and in particular anti-rust oils |
| US2982630A (en) * | 1958-12-24 | 1961-05-02 | Socony Mobil Oil Co Inc | N-alkanol succinamic acid deicer |
| US3035907A (en) * | 1956-06-14 | 1962-05-22 | Gulf Research Development Co | Hydrocarbon composition containing an itaconic acid-amine reaction product |
| US3046102A (en) * | 1958-10-06 | 1962-07-24 | Socony Mobil Oil Co Inc | Stabilized distillate fuel oil |
| US3068082A (en) * | 1957-08-15 | 1962-12-11 | Monsanto Chemicals | Rust inhibited hydrocarbon fuel |
| US3172853A (en) * | 1965-03-09 | Chs chj x c chax c chx | ||
| FR1416295A (en) * | 1963-12-05 | 1965-10-29 | Armour & Co | Motor fuels |
| GB1021183A (en) * | 1961-08-18 | 1966-03-02 | Lubrizol Corp | Oil-soluble nitrogen-containing products and process for preparing same |
| US3444082A (en) * | 1966-02-07 | 1969-05-13 | Chevron Res | Acid-amide pour point depressants |
| FR2018439A1 (en) * | 1968-09-19 | 1970-05-29 | Exxon Research Engineering Co | |
| FR2095403A5 (en) * | 1969-12-10 | 1972-02-11 | Inst Francais Du Petrole | |
| US3905781A (en) * | 1972-10-30 | 1975-09-16 | Texaco Inc | Carburetor detergent and corrosion inhibiting motor fuel compositions |
| FR2354346A1 (en) * | 1976-06-07 | 1978-01-06 | Texaco Development Corp | LUBRICATING OIL COMPOSITION |
| US4144036A (en) * | 1978-03-27 | 1979-03-13 | Texaco Inc. | Detergent fuel composition |
| US4234435A (en) * | 1979-02-23 | 1980-11-18 | The Lubrizol Corporation | Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation |
| EP0034968A1 (en) * | 1980-02-15 | 1981-09-02 | Institut Français du Pétrole | N-substituted succinimides, their preparation and their use as additives for fuels |
| US4326987A (en) * | 1980-02-25 | 1982-04-27 | Petrolite Corporation | Reaction products of alkyl and alkenyl succinic acids and ether diamines |
| EP0074199A2 (en) * | 1981-09-01 | 1983-03-16 | The Lubrizol Corporation | Acylated ether amine and lubricants and fuels containing the same |
| EP0100248A1 (en) * | 1982-06-04 | 1984-02-08 | Institut Français du Pétrole | Copolymers with functional nitrogen groups used especially as cloud point reduction additives of middle distillate hydrocarbons, and middle distillate hydrocarbon compositions containing the same |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3018173A (en) * | 1957-04-26 | 1962-01-23 | Universal Oil Prod Co | Stabilization of hydrocarbons |
| FR1318311A (en) * | 1961-03-31 | 1963-02-15 | California Research Corp | New polyamide detergent and set point lowering for lubricants and fuels |
| US3272746A (en) * | 1965-11-22 | 1966-09-13 | Lubrizol Corp | Lubricating composition containing an acylated nitrogen compound |
| US3681038A (en) * | 1970-03-09 | 1972-08-01 | Universal Oil Prod Co | Middle distillate |
| US3877888A (en) * | 1970-03-09 | 1975-04-15 | Universal Oil Prod Co | Middle distillate |
| FR2178775A1 (en) * | 1972-04-06 | 1973-11-16 | Texaco Development Corp | Asparagine deriv gasoline additive - inhibiting and removing carburettor deposits |
| GB1469512A (en) * | 1973-07-05 | 1977-04-06 | Dunlop Ltd | Assembly of a wheel rim a pneumatic tyre and means for en closing lubricant within the inflation chamber of the tyre |
| US3974526A (en) * | 1973-07-06 | 1976-08-17 | Dardik Irving I | Vascular prostheses and process for producing the same |
| US3955940A (en) * | 1975-01-06 | 1976-05-11 | Exxon Research And Engineering Company | Middle distillate petroleum oils containing cold flow improving additives |
| IL47062A (en) * | 1975-04-10 | 1979-07-25 | Yeda Res & Dev | Process for diminishing antigenicity of tissues to be usedas transplants by treatment with glutaraldehyde |
| US4177041A (en) * | 1978-09-22 | 1979-12-04 | Texaco Inc. | Carburetor detergents |
-
1981
- 1981-07-30 FR FR8114870A patent/FR2510598A1/en active Granted
-
1982
- 1982-07-16 DE DE8282401335T patent/DE3274368D1/en not_active Expired
- 1982-07-16 EP EP82401335A patent/EP0071513B1/en not_active Expired
- 1982-07-28 NO NO822591A patent/NO158142C/en not_active IP Right Cessation
- 1982-07-28 DK DK337682A patent/DK158993C/en not_active IP Right Cessation
- 1982-07-30 FI FI822674A patent/FI75361C/en not_active IP Right Cessation
- 1982-07-30 JP JP57134636A patent/JPS58108297A/en active Granted
- 1982-07-30 CA CA000408447A patent/CA1192519A/en not_active Expired
-
1985
- 1985-05-23 US US06/737,133 patent/US4652273A/en not_active Expired - Lifetime
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3172853A (en) * | 1965-03-09 | Chs chj x c chax c chx | ||
| US3035907A (en) * | 1956-06-14 | 1962-05-22 | Gulf Research Development Co | Hydrocarbon composition containing an itaconic acid-amine reaction product |
| US3068082A (en) * | 1957-08-15 | 1962-12-11 | Monsanto Chemicals | Rust inhibited hydrocarbon fuel |
| FR1197418A (en) * | 1958-01-07 | 1959-12-01 | Socony Mobil Oil Co Inc | Improved mineral oils and in particular anti-rust oils |
| US3046102A (en) * | 1958-10-06 | 1962-07-24 | Socony Mobil Oil Co Inc | Stabilized distillate fuel oil |
| US2982630A (en) * | 1958-12-24 | 1961-05-02 | Socony Mobil Oil Co Inc | N-alkanol succinamic acid deicer |
| GB1021183A (en) * | 1961-08-18 | 1966-03-02 | Lubrizol Corp | Oil-soluble nitrogen-containing products and process for preparing same |
| FR1416295A (en) * | 1963-12-05 | 1965-10-29 | Armour & Co | Motor fuels |
| US3444082A (en) * | 1966-02-07 | 1969-05-13 | Chevron Res | Acid-amide pour point depressants |
| FR2018439A1 (en) * | 1968-09-19 | 1970-05-29 | Exxon Research Engineering Co | |
| FR2095403A5 (en) * | 1969-12-10 | 1972-02-11 | Inst Francais Du Petrole | |
| US3905781A (en) * | 1972-10-30 | 1975-09-16 | Texaco Inc | Carburetor detergent and corrosion inhibiting motor fuel compositions |
| FR2354346A1 (en) * | 1976-06-07 | 1978-01-06 | Texaco Development Corp | LUBRICATING OIL COMPOSITION |
| US4144036A (en) * | 1978-03-27 | 1979-03-13 | Texaco Inc. | Detergent fuel composition |
| US4234435A (en) * | 1979-02-23 | 1980-11-18 | The Lubrizol Corporation | Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation |
| EP0034968A1 (en) * | 1980-02-15 | 1981-09-02 | Institut Français du Pétrole | N-substituted succinimides, their preparation and their use as additives for fuels |
| US4326987A (en) * | 1980-02-25 | 1982-04-27 | Petrolite Corporation | Reaction products of alkyl and alkenyl succinic acids and ether diamines |
| EP0074199A2 (en) * | 1981-09-01 | 1983-03-16 | The Lubrizol Corporation | Acylated ether amine and lubricants and fuels containing the same |
| EP0100248A1 (en) * | 1982-06-04 | 1984-02-08 | Institut Français du Pétrole | Copolymers with functional nitrogen groups used especially as cloud point reduction additives of middle distillate hydrocarbons, and middle distillate hydrocarbon compositions containing the same |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0086049B1 (en) * | 1982-02-03 | 1986-12-17 | The Lubrizol Corporation | Compositions for use in alcohol and alcohol containing fuels |
| FR2539754A1 (en) * | 1983-01-25 | 1984-07-27 | Inst Francais Du Petrole | Nitrogenous additives usable as cloud point lowering agents for hydrocarbon middle distillates and hydrocarbon middle distillate compositions containing the said additives. |
| US5814110A (en) * | 1986-09-24 | 1998-09-29 | Exxon Chemical Patents Inc. | Chemical compositions and use as fuel additives |
| GR880100284A (en) * | 1987-04-29 | 1989-01-31 | Nalco Chemical Co | Hydrocarbon fuel cleansing means |
| FR2633638A1 (en) * | 1988-06-29 | 1990-01-05 | Inst Francais Du Petrole | FORMULATIONS OF NITROGEN ADDITIVES FOR MOTOR FUELS AND MOTOR FUELS CONTAINING THEM |
| EP0353116A1 (en) * | 1988-06-29 | 1990-01-31 | Institut Français du Pétrole | Recipes of nitrogenous additives for engine fuels, and engine fuels containing them |
| EP0411811A1 (en) * | 1989-08-03 | 1991-02-06 | Texaco Development Corporation | Process for producing ORI control additives |
| GB2242190A (en) * | 1990-03-24 | 1991-09-25 | Abm Chemicals Limited | Biocidal amines |
| US5449386A (en) * | 1992-10-09 | 1995-09-12 | Institut Francais Du Petrole | Amine phosphates having a terminal cyclic imide |
| EP0593331A1 (en) * | 1992-10-09 | 1994-04-20 | Institut Francais Du Petrole | Amines phosphates having a terminal imide cycle, their preparation and their use as additives for motor-fuels |
| WO1994013758A1 (en) * | 1992-12-17 | 1994-06-23 | Institut Francais Du Petrole | Middle petroleum distillate composition containing a paraffin settling speed limiter |
| FR2699550A1 (en) * | 1992-12-17 | 1994-06-24 | Inst Francais Du Petrole | Medium petroleum distillate composition containing nitrogen additives which can be used as agents for limiting the sedimentation rate of paraffins. |
| US6860908B2 (en) | 1992-12-17 | 2005-03-01 | Institut Francais du Pétrole | Petroleum middle distillate composition containing a substance for limiting the paraffin sedimentation rate |
| FR2699551A1 (en) * | 1992-12-18 | 1994-06-24 | Inst Francais Du Petrole | New amine phosphate(s) contg. terminal imide gp. |
| WO2010073233A2 (en) | 2008-12-23 | 2010-07-01 | Total Raffinage Marketing | Diesel fuel for a diesel engine with high carbon from renewable sources and oxygen contents |
| WO2011001352A1 (en) | 2009-07-03 | 2011-01-06 | Total Raffinage Marketing | Ethylene/vinyl acetate/unsaturated esters terpolymer as an additive for improving the resistance to cold of liquid hydrocarbons such as middle distillates and fuels |
| WO2012085865A1 (en) | 2010-12-23 | 2012-06-28 | Total Raffinage Marketing | Modified alkyl-phenol-aldehyde resins, use thereof as additives for improving the properties of liquid hydrocarbon fuels in cold conditions |
| WO2012107454A1 (en) | 2011-02-08 | 2012-08-16 | Total Raffinage Marketing | Liquid compositions for marking liquid hydrocarbon-based fuels and combustibles, fuels and combustibles containing the same and process for detecting the markers |
| WO2013007738A1 (en) | 2011-07-12 | 2013-01-17 | Total Raffinage Marketing | Additive compositions that improve the stability and the engine performances of diesel fuels |
| WO2013092533A1 (en) | 2011-12-21 | 2013-06-27 | Total Raffinage Marketing | Additive compositions that improve the lacquering resistance of superior quality diesel or biodiesel fuels |
| WO2013120985A1 (en) | 2012-02-17 | 2013-08-22 | Total Raffinage Marketing | Additives for improving the resistance to wear and to lacquering of diesel or biodiesel fuels |
| WO2013189868A1 (en) | 2012-06-19 | 2013-12-27 | Total Marketing Services | Additive compositions and use thereof for improving the cold properties of fuels and combustibles |
| WO2014029770A1 (en) | 2012-08-22 | 2014-02-27 | Total Marketing Services | Additives that improve the wear resistance and lacquering resistance of diesel or biodiesel fuels |
| WO2014173844A1 (en) | 2013-04-25 | 2014-10-30 | Total Marketing Services | Additive for improving the oxidation-stability and/or storage-stability of liquid hydrocarbon fuels or oxidizers |
| EP3144059A1 (en) | 2015-09-16 | 2017-03-22 | Total Marketing Services | Method for preparing microcapsules by double emulsion |
| WO2017046344A1 (en) | 2015-09-16 | 2017-03-23 | Total Marketing Services | Method for preparing microcapsules by double emulsion |
| WO2018033684A1 (en) | 2016-08-18 | 2018-02-22 | Total Marketing Services | Method for manufacturing a lubricity additive for fuel having a low sulfur content |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1192519A (en) | 1985-08-27 |
| DK337682A (en) | 1983-01-31 |
| DK158993B (en) | 1990-08-13 |
| FI822674A0 (en) | 1982-07-30 |
| DK158993C (en) | 1991-01-21 |
| FR2510598A1 (en) | 1983-02-04 |
| JPH0251478B2 (en) | 1990-11-07 |
| US4652273A (en) | 1987-03-24 |
| EP0071513B1 (en) | 1986-11-20 |
| FI822674L (en) | 1983-01-31 |
| FI75361C (en) | 1988-06-09 |
| NO158142C (en) | 1988-07-20 |
| FI75361B (en) | 1988-02-29 |
| JPS58108297A (en) | 1983-06-28 |
| NO822591L (en) | 1983-01-31 |
| EP0071513A3 (en) | 1983-04-27 |
| DE3274368D1 (en) | 1987-01-08 |
| FR2510598B1 (en) | 1985-01-18 |
| NO158142B (en) | 1988-04-11 |
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