EP0071513B1 - 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 PDF

Info

Publication number
EP0071513B1
EP0071513B1 EP82401335A EP82401335A EP0071513B1 EP 0071513 B1 EP0071513 B1 EP 0071513B1 EP 82401335 A EP82401335 A EP 82401335A EP 82401335 A EP82401335 A EP 82401335A EP 0071513 B1 EP0071513 B1 EP 0071513B1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
compound
composition according
additive
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82401335A
Other languages
German (de)
French (fr)
Other versions
EP0071513A2 (en
EP0071513A3 (en
Inventor
Paul Maldonado
Robert Leger
Choua Cohen
Bernard Sillion
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Elf Antar France
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Elf France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN, Elf France SA filed Critical IFP Energies Nouvelles IFPEN
Publication of EP0071513A2 publication Critical patent/EP0071513A2/en
Publication of EP0071513A3 publication Critical patent/EP0071513A3/en
Application granted granted Critical
Publication of EP0071513B1 publication Critical patent/EP0071513B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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 middle hydrocarbon distillates (fuel oils, gas oils), the cloud point of which is lowered by adding nitrogen additives.
  • the petroleum distillates concerned by the invention consist of middle distillates (fuel oils, gas oils) whose distillation range (standard ASTM D 86-67) is between 150 ° C and 450 ° 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.
  • US Patent 2,982,630 describes a gasoline additive consisting of an alkenyl succinamic N-ethanol acid obtained by reaction of equimolar proportions of alkenyl succinic acid anhydride and ethanolamine. The reaction is carried out under conditions such that no water of condensation is formed. Therefore, no imide groups are formed. In a different manner, in the present application, volatile products (water) are eliminated, with the formation of imide groups.
  • the additives are used in middle distillates (gas oils, fuel oils) and not in gasolines.
  • Patent FR 1,197,418 describes additives used in particular in fuel oils (fuel oils) and consisting in particular of amide acids such as succinamic acids and maleamic acids. It is mentioned that the formation of cyclic imides is avoided (page 3, column 1, lines 25-27).
  • 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 middle petroleum distillate compositions of the invention may be. defined as comprising a major proportion of middle petroleum distillate and a minor proposal, sufficient to lower the cloud point thereof, of an additive consisting of a product of average molecular weight of approximately 300 to 10,000 resulting from the reaction of at least one aliphatic dicarboxylic compound chosen from maleic and alkylmaleic anhydrides, alkenylsuccinic anhydrides having from 10 to 30 carbon atoms in the alkenyl radical, dicarboxylic acids and corresponding light alkyl diesters, and at least one compound having a function primary amine corresponding to one of the general formulas: where R represents a monovalent saturated aliphatic radical of 1 to 30 carbon atoms, Z is chosen from the groups -NR'- in which R 'represents a hydrogen atom or a monovalent saturated aliphatic radical of 1 to 30 carbon atoms, n is an integer from 2 to 4, m is zero or an integer from 1 to 4; and R 5 represents
  • the compounds of formula (I) below can consist of primary amines of formula R I- NH P (in this case, in formula (I), Z represents the group -NH-, 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 (1) 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-hexadecyl 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 24 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 dicarboxylic compounds on which the condensation of a compound of formula (I) or of a compound of formula (II) as described above is carried out are more particularly chosen from maleic anhydride, alkylmaleic anhydrides, for example l 'methylmaleic (or citraconic) anhydride or also among alkenyl succinic anhydrides, for example those obtained by the action of at least one olefin-a preferably linear (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.
  • 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 a primary amine function (I) or (II), up to 0.9 mole per mole of dicarboxylic compound. The proportion is therefore from 0.9 to 1.2 moles / mole, as indicated above.
  • the condensation of the compounds of formula (I) and / or (II), on the dicarboxylic compounds can be carried out without solvent, but preferably a solvent consisting more particularly of 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.
  • a solvent consisting more particularly of 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 reagents, 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 gas oils), that is to say to reduce the temperature of appearance of the first crystals of n-paraffins contained in those -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 point of 'flow of up to 20 ° C, a decrease in the proportion of sedimented paraffins and a clear 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 1 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 imide bands 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.
  • the additive derived from a diamine with an alkyl chain of 12 carbon atoms is clearly less effective than those which derive from a diamine with a longer alkyl chain: 16, 18 or 22 carbon atoms.
  • 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 the additive 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 1 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 I reactor, fitted with a Dean and Stark water separation system and good stirring. . Maintaining 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 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 X in xylene.
  • Additive X was analyzed after evaporation of the solvent.
  • the thin layer infrared spectrum shows the existence of imide bands at 1700 and 1780 cm- '.
  • Example 11 This example is carried out according to the procedure described in Example 11, while maintaining molar ratios between the reactants identical to that given in Example 11.
  • Ethanolamine 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% of C 20 olefin, 42% of C 22 and 9% C 24 .
  • a molar ratio of 1/1 is used between ethanolamine and the anhydride groups of alkenyl succinic anhydride. The result of this condensation provides the additive XI.
  • This additive is obtained in solution in xylene, the amount of which is adjusted so as to obtain a 50% by weight solution in xylene.

Landscapes

  • 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)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Description

L'invention concerne des distillates moyens d'hydrocarbures (fuel-oils, gazoles), dont le point de trouble est abaissé par adjonction d'additifs azotés.The invention relates to middle hydrocarbon distillates (fuel oils, gas oils), the cloud point of which is lowered by adding nitrogen 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. 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 petroleum distillates concerned by the invention consist of middle distillates (fuel oils, gas oils) whose distillation range (standard ASTM D 86-67) is between 150 ° C and 450 ° 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.
There are a large number of products on the market recommended to improve the limit filterability temperature and the pour point of petroleum fractions rich in paraffins, such as for example:
  • -polymers based on long chain olefins.
  • -alpha-olefin-based copolymers,
  • - 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 distillates 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 (especially 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.

Des additifs voisins de ceux considérés dans la présente demande et définis plus loin ont été décrit dans l'art antérieur. On indique ci-après comment l'invention se distingue de l'enseignement des documents antérieurs les plus proches.Additives similar to those considered in the present application and defined below have been described in the prior art. It is indicated below how the invention differs from the teaching of the closest prior documents.

Le brevet US 3,035,907 décrit des additifs qui peuvent être utilisés notamment dans les fuel-oils et les carburants Diesel et qui sont obtenus par amidation de l'acide itaconique par une mono-ou une diamine primaire ou secondaire. L'acide itaconique (ou méthylène succinique) ne fait pas partie des acides alcénylsucciniques qui seront considérés dans la présente demande, et dont les radicaux alcényles renfermant de 10 à 30 atomes de carbone.US Pat. No. 3,035,907 describes additives which can be used in particular in fuel oils and diesel fuels and which are obtained by amidation of itaconic acid with a primary or secondary mono or diamine. Itaconic acid (or methylene succinic) is not one of the alkenyl succinic acids which will be considered in the present application, and whose alkenyl radicals containing from 10 to 30 carbon atoms.

Par ailleurs, dans ce document antérieur, on s'arrête à la formation d'amides, alors que, compte tenu des conditions opératoires mises en oeuvre dans la préparation des additifs .utilisés dans l'invention, ceux-ci renferment une proportion substantielle de fonctions imides.Furthermore, in this prior document, the formation of amides is stopped, whereas, taking into account the operating conditions used in the preparation of the additives used in the invention, these contain a substantial proportion of imide functions.

Le brevet US 3,046,102 décrit des additifs pour fuel-oils consistant en particulier en des acides amiques formés entre l'acide itaconique et une amine aliphatique, primaire ou secondaire. La réaction est une amidation. En outre, comme pour le document précédent, l'acide itaconique ne fait pas partie des acides alcénylsucciniqùes considérés dans l'invention.US Patent 3,046,102 describes additives for fuel oils consisting in particular of amino acids formed between itaconic acid and an aliphatic amine, primary or secondary. The reaction is an amidation. In addition, as for the previous document, itaconic acid is not one of the alkenyl succinic acids considered in the invention.

Le brevet US 2,982,630 décrit un additif pour essence consistant en un acide N-éthanol alcényl- succinamique obtenue par réaction de proportions équimolaires d'anhydride d'acide alcénylsuccinique et d'éthanolamine. La réaction est menée dans des conditions telles qu'on ne forme pas d'eau de condensation. Il ne se forme donc pas de groupements imides. De manière différente, dans la présente demande, des produits volatils (eau) sont éliminés, avec formation de groupements imides. De plus, les additifs sont utilisés dans des distillats moyens (gazoles, fuel-oils) et non dans des essences.US Patent 2,982,630 describes a gasoline additive consisting of an alkenyl succinamic N-ethanol acid obtained by reaction of equimolar proportions of alkenyl succinic acid anhydride and ethanolamine. The reaction is carried out under conditions such that no water of condensation is formed. Therefore, no imide groups are formed. In a different manner, in the present application, volatile products (water) are eliminated, with the formation of imide groups. In addition, the additives are used in middle distillates (gas oils, fuel oils) and not in gasolines.

Le brevet FR 1.197.418 décrit des additifs utilisés notamment dans les huiles combustibles (fuel-oils) et consistant en particulier en des acides amidiques tels que les acides succinamiques et les acides maléamiques. Il est mentionné que l'on évite la formation d'imides cycliques, (page 3, colonne 1, lignes 25-27).Patent FR 1,197,418 describes additives used in particular in fuel oils (fuel oils) and consisting in particular of amide acids such as succinamic acids and maleamic acids. It is mentioned that the formation of cyclic imides is avoided (page 3, column 1, lines 25-27).

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 naturelleest de se rassembler par gravité dans la partie basse. Ce phénomène, généralement connu dans le term 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 notablement la vitesse de sédimentation des paraffines formées par refroidissement des gazoles et autres distillats moyens.When the paraffin crystals whose formation is caused by cooling have appeared, their natural tendency is to collect by gravity in the lower part. This phenomenon, generally known in the term of sedimentation, causes clogging of the pipes and filters and is detrimental to the proper use of middle distillates and in particular diesel. Compounds chemicals recommended in the invention can significantly reduce the rate of sedimentation of paraffins formed by cooling 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 compositions de distillats moyens de pétrole de l'invention peuvent être. définies comme comprenant une proportion majeure de distillat moyen de pétrole et une proposition mineure, suffisante pour en abaisser le point de trouble, d'un additif consistant en un produit de masse moléculaire moyenne d'environ 300 à 10.000 résultant de la réaction d'au moins un composé dicarboxylique aliphatique choisi parmi les anhydrides maléiques et alkylmaléiques, les anhydrides alcénylsucciniques ayant de 10 à 30 atomes de carbone dans le radical alcényl, les acides dicarboxyliques et les diesters d'alkyles légers correspondants, et d'au moins un composé à fonction amine primaire répondant à l'une des formules générales:

Figure imgb0001
Figure imgb0002
où R représente un radical aliphatique saturé monovalent de 1 à 30 atomes de carbone, Z est choisi parmi les groupements -NR'- dans lesquels R' représente un atome d'hydrogène ou un radical aliphatique saturé monovalent de 1 à 30 atomes de carbone, n est un nombre entier de 2 à 4, m est zéro ou un nombre entier de 1 à 4; et R5 représente un radical aliphatique saturé divalent de 1 à 18 atomes de carbone; ledit composé à fonction amine primaire étant utilisé en une proportion de 0,9 à 1,2 mole par mole dudit composé dicarboxylique et ladite réaction étant effectuée à une température de 120 à 200°C, pendant un temps suffisant pour former la quantité théorique de produits volatils consistant en eau et/ou en alcool, qui sont éliminés.Generally, the middle petroleum distillate compositions of the invention may be. defined as comprising a major proportion of middle petroleum distillate and a minor proposal, sufficient to lower the cloud point thereof, of an additive consisting of a product of average molecular weight of approximately 300 to 10,000 resulting from the reaction of at least one aliphatic dicarboxylic compound chosen from maleic and alkylmaleic anhydrides, alkenylsuccinic anhydrides having from 10 to 30 carbon atoms in the alkenyl radical, dicarboxylic acids and corresponding light alkyl diesters, and at least one compound having a function primary amine corresponding to one of the general formulas:
Figure imgb0001
Figure imgb0002
 where R represents a monovalent saturated aliphatic radical of 1 to 30 carbon atoms, Z is chosen from the groups -NR'- in which R 'represents a hydrogen atom or a monovalent saturated aliphatic radical of 1 to 30 carbon atoms, n is an integer from 2 to 4, m is zero or an integer from 1 to 4; and R 5 represents a divalent saturated aliphatic radical of 1 to 18 carbon atoms; said compound with primary amine function being used in a proportion of 0.9 to 1.2 mole per mole of said dicarboxylic compound and said reaction being carried out at a temperature of 120 to 200 ° C, for a time sufficient to form the theoretical amount of volatile products consisting of water and / or alcohol, which are eliminated.

Les composés de formule (I) ci-dessous peuvent consister en des amines primaires de formule RI-NHP (dans ce cas, dans la formule (I), Z représente le groupement-NH-, et la valeur de m est zéro).The compounds of formula (I) below can consist of primary amines of formula R I- NH P (in this case, in formula (I), Z represents the group -NH-, 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:

Figure imgb0003
qui correspond à la formule générale (1) dans laquelle Z représente le groupement -NH-; m peut avoir une valeur de 1 à 4 et n une valeur de 2 à 4, de préférence 3.The compounds of formula (I) can also consist of polyamines derived from saturated aliphatic amines corresponding to the formula:
Figure imgb0003
 which corresponds to the general formula (1) 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.

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-hexadécyl 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. 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.As specific compounds, there may be mentioned: N-dodecyl diamino-1,3 propane, N-tetradecyl diamino-1,3 propane, N-hexadecyl 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. 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:

Figure imgb0004
où R2 et R3, identiques ou différents, sont chacun un radical alkyle ayant de 1 à 24 et de préférence de 8 à 24 atomes de carbone, R2 et R3 renfermant à eux deux de préférence de 16 à 32 atomes de carbone; n a une valeur de 2 à 4 et m une valeur de 1 à 4.The compounds of formula (I) can also consist of polyamines corresponding to the formula:
Figure imgb0004
 where R 2 and R 3 , identical or different, are each an alkyl radical having from 1 to 24 and preferably from 8 to 24 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.

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-dioctadécyldiamino-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, N-diethyl-diamino-1,4-butane, N, N-dimethyl-diamino-1,3 propane, N, N-diethyl-diamino-1,3 propane, N, N-dioctyl-diamino-1, 3 propane, N, N-didécyldiamino-1,3 propane, N, N didodécyl-diamino-1,3 propane, N, N-ditétradécyl-1,3-propane, N, N-dihexadécyldiamino-1 , 3 propane, N, N-dioctadecyldiamino-1,3 propane, N, N-didodecyldipropylenetriamine, N, N-ditetradecyldipropylene triamine, N, N-dihexadecyldipropylene triamine and N, N-dioctadecyldipropylenetriamine.

Le composé à fonction amine primaire mis en jeu dans la préparation des additifs de l'invention peut aussi consister en un aminoalcool de formule (II):

Figure imgb0005
où R5 représente un radical aliphatique saturé divalent, linéaire ou ramifié, de préférence linéaire, renfermant de 1 à 18 et de préférence de 10 à 18 atomes de carbone. Comme exemples spécifiques, on peut citer:

  • la monoéthanolamine, l'amino-1 propanol-3, 1'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-1 décanol-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
The compound with primary amine function involved in the preparation of the additives of the invention can also consist of an amino alcohol of formula (II):
Figure imgb0005
 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. As specific examples, we can cite:
  • 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-1 decanol-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 (I) ou d'un composé de formule (II) tels que décrits précédemment, sont plus particulièrement choisis parmi 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 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 (I) or of a compound of formula (II) as described above is carried out, are more particularly chosen from maleic anhydride, alkylmaleic anhydrides, for example l 'methylmaleic (or citraconic) anhydride or also among alkenyl succinic anhydrides, for example those obtained by the action of at least one olefin-a preferably linear (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.

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 de 0,9 à 1,2 mole/mole, comme indiqué précédemment.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 a primary amine function (I) or (II), up to 0.9 mole per mole of dicarboxylic compound. The proportion is therefore from 0.9 to 1.2 moles / mole, as indicated above.

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 the compounds of formula (I) and / or (II), on the dicarboxylic compounds (for example dicarboxylic acids, esters, or preferably anhydrides) can be carried out without solvent, but preferably a solvent consisting more particularly of 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'invention, 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 (II). On élevèe 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., little is introduced at 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 heurs.The reaction time, after addition of the reagents, 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 gas oils), that is to say to reduce the temperature of appearance of the first crystals of n-paraffins contained in those -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 égé 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 2000 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 2000 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 et la 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 2000 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 point of 'flow of up to 20 ° C, a decrease in the proportion of sedimented paraffins and a clear 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" préparés au préalable dans les solvents déjà mentionnés plus haut.It is however often advantageous to introduce them in the form of "stock 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.

Exemple 1Example 1

On introduit dans un réacteur de 20 I muni d'une bonne agitation 2.700 g d'une polyamine commerciale (contenant un mélange, environ 27% de palmityl 1,3- propane-diamine et 70 % de stéaryl 1,3 propanediamine 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 propanediamine having an equivalent) are introduced into a 20 I reactor fitted with good stirring. 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 1 a été analysé après évaporation du solvant. Sa masse moléculaire en nombre, mesurée par tonomètrie, 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 1 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 imide bands 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.

Figure imgb0006
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 Il ci-après.
Figure imgb0007
 The activity of this additive I is tested in two cuts of diesel fuel of Aramco origin, the characteristics of which are indicated in Table I below.
Figure imgb0006
 The effect of the additive I on the lowering of the cloud point of each of the two cuts of diesel, as a function of the concentration of additive, determined according to the NF T 60 105 method, is shown in Table II below.
Figure imgb0007

Exemple 2Example 2

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 Il : 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.
In this example, 0.1% by weight is used in the two gas oil fractions used in Example 1, additives which differ mainly in the nature of the starting amine, the method of preparation being the same as in Example 1.
  • Additive I: product used in Example 1
  • Additive II: produces 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.

Figure imgb0008
The results are shown in Table III below.
Figure imgb0008

On constante que l'effet d'abaissement du point de trouble est le plus important dans le cas de l'additif I, dans lequel l'amide 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 important in the case of additive I, in which the starting amide is a mixture of two N-alkyl 1,3 propane diamines.

Exemple 3Example 3

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)
In this example, 0.1% by weight is used in the same two gas oils as above, of additives which differ essentially by the length of the alkyl chain of the starting amine:
  • 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 (behenyl = 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.

Figure imgb0009
The results of the cloud point determinations are shown in Table IV below.
Figure imgb0009

On remarque que l'additif dérivant d'une diamine à chaîne alkyle de 12 atomes de carbone est nettement moins efficice que ceux qui dérivent de diamine à chaîne alkyle plus longue: 16,18 ou 22 atomes de carbone.It is noted that the additive derived from a diamine with an alkyl chain of 12 carbon atoms is clearly less effective than those which derive from a diamine with a longer alkyl chain: 16, 18 or 22 carbon atoms.

Exemple 4Example 4

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 1 : 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.
So we use:
  • Additive 1: 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:

Figure imgb0010
The cloud points determined are indicated in Table V below:
Figure imgb0010

Exemple 5Example 5

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 maintenu 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 déjà utilisé précédemment.The additive used is the additive 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 I.In the second test tube, 0.1% by weight of the additive I is introduced.

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 degrée de sédimentation des paraffines ayant précipité, exprimé par le volume de la phase supérieure limpide, est noté dans le tableau suivant:

Figure imgb0011
After a week, the degree of sedimentation of the precipitated paraffins, expressed by the volume of the clear upper phase, is noted in the following table:
Figure imgb0011

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.

Exemple 6Example 6

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 07-042The TLFs are determined according to standard NF M 07-042

Figure imgb0012
Figure imgb0012

Exemple 7 Example 7

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 1 a été utilisé dans les deux gazoles n° 1 et n° 2 déjà décrits précédemment, à la concentration de 0,01 % en poids.Product 1 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 corrosion test consists in studying corrosion by synthetic sea water, 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: 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.

Exemple 8Example 8

Dans cet exemple on test l'effet de l'additif 1 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.

Figure imgb0013
In this example, the effect of the additive 1 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.
Figure imgb0013

Exemple 9Example 9

Dans un réacteur de 3 I, 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 I reactor, fitted with a Dean and Stark water separation system and good stirring. . Maintaining 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.

Exemple 10 .Example 10.

En suivant un mode opératoire identique à celui de l'exemple 9, on procédé à la condensation de 532 g (2 moles) d'anhydride dodécénylsuccinique sur 820 g (2 moles) de N,N-didodécyldiamino-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.Following a procedure identical to that of Example 9, the condensation of 532 g (2 moles) of dodecenylsuccinic anhydride is carried out on 820 g (2 moles) of N, N-didodecyldiamino-1,3 propane. The condensation product constitutes additive IX, the concentration of which in xylene is adjusted to obtain a value of 50% by weight.

On a testé l'effet des additifs VIII et IX 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 and IX 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 point d flow (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.

Figure imgb0014
The results are collated in Table IX below.
Figure imgb0014

Exemple 11Example 11

On introduit dans un réacteur de 3 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 ajoute une solution dans 324 g de xylène d'un mélange de 55% en moles d'éthanolamine et 45% en moles d'une coupe commerciale de N-alkyl propylènediamines, dont les chaînes alkyles consistent en environ 27% de chaîne en C16 et 72% de chaîne en C'8 (masse moléculaire équivalent: 370 pour une fonction amine primaire), la quantité globale d'équivalents amines primaires étant de 3, I, la température étant maintenu inférieure à 40°C.294 g (3 moles) of maleic anhydride dissolved in 500 g of xylene are introduced into a reactor of 3 with good stirring and the mixture is cooled to 30 ° C. A solution in 324 g of xylene of a mixture of 55 mol% of ethanolamine and 45 mol% of a commercial cut of N-alkyl propylenediamines is added, the alkyl chains of which consist of approximately 27% of C chain 16 and 72% of chain in C '8 (equivalent molecular mass: 370 for a primary amine function), the overall amount of primary amine equivalents being 3, I, the temperature being kept below 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 67g d'eau correspondant à 54g d'eau de réaction et 13g d'eau contenu dans l'amine; à la fin de la réaction, on dilue par 200g de xylène pour obtenir une solution à 50% en poids de l'additif X dans le xylène.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 X in xylene.

L'additif X a été analysé après évaporation du solvant. Le spectre infra-rouge en couche mince montre l'existence de bandes imides à 1700 et 1780 cm-'.Additive X was analyzed after evaporation of the solvent. The thin layer infrared spectrum shows the existence of imide bands at 1700 and 1780 cm- '.

Exemple 12Example 12

Cet exemple est conduit suivant le mode opératoire décrit dans l'exemple 11, en maintenant des rapports molaires entre les réactifs identiques à celui donné dans l'exemple 11.This example is carried out according to the procedure described in Example 11, while maintaining molar ratios between the reactants identical to that given in Example 11.

De l'éthanolamine 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. On utilise un rapport molaire de 1/1 entre l'éthanolamine et les groupements anhydrides de l'anhydride alcénylsuccinique. Le résultat de cette condensation fournit l'additif XI.Ethanolamine 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% of C 20 olefin, 42% of C 22 and 9% C 24 . A molar ratio of 1/1 is used between ethanolamine and the anhydride groups of alkenyl succinic anhydride. The result of this condensation provides the additive XI.

Cet additif est obtenu en solution dans le xylène dont on ajuste la quantité de façon à obtenir une solution à 50% en poids dans le xylène.This additive is obtained in solution in xylene, the amount of which is adjusted so as to obtain a 50% by weight solution in xylene.

On teste l'activité des compositions d'additifs préparées dans les exemples 11 et 12 en les incorporant à raison de 0,1 % en poids d'additif par rapport au gazole, aux deux coupes de gazoles d'origine ARAMCO, désignées par G, et G2, dont les caractéristiques ont été indiquées plus haut.The activity of the additive compositions prepared in Examples 11 and 12 is tested by incorporating them in an amount of 0.1% by weight of additive relative to the diesel fuel, into the two cuts of diesel oils of ARAMCO origin, designated by G , and G 2 , the characteristics of which 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.
For each of the compositions thus formed, three determinations were made:
  • -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:

Figure imgb0015
The results of these determinations are collated in Table X below:
Figure imgb0015

Claims (12)

1. Oil middle distillate composition, characterized as comprising a major proportion of oil middle distillate and a minor proportion, sufficient to decrease the cloud point of said distillate, of an additive consisting of a material having an average molecular weight of about 300 to 10,000 and resulting from the reaction of at least one aliphatic dicarboxylic compound selected from the maleic and alkylmaleic anhydrides, the alkenylsuccinic anhydrides having 10 to 30 carbon atoms in the alkenyl radical, the corresponding dicarboxylic acids and lower alkyl diesters, with at least one compound having a primary amine function, complying with one of the general formulas:
Figure imgb0026
and
Figure imgb0027
wherein R represents a monovalent saturated aliphatic radical of 1 to 30 carbon atoms, Z is selected form the-NR'-groups, wherein R' is a hydrogen atom or a monovalent saturated aliphatic radical containing 1 to 30 carbon atoms, n is an integer from 2 to 4, m is zero or an integer from 1 to 4; and R5 represents a divalent saturated aliphatic radical having 1 to 18 carbon atoms; said compound having a primary amine function being used in a proportion of 0.9 to 1.2 mole per mole of said dicarboxylic compound and said reaction being effected at a temperature of 120 to 200°C for a sufficient time to form the theoretical amount of volatile products consisting of water and/or alcohol, which are eliminated.
2. A composition according to claim 1, characterized in that said compound having a primary amine function (I) consists of at least one mono-amine of the formula RI NH2 where R' represents a linear alkyl radical of 12 to 30 carbon atoms.
3. A composition according to claim 1, characterized in that said compound having a primary amine function (1) consists of a least one polyamine of the formula
Figure imgb0028
wherein R1 represents a linear alkyl radical with 12 to 30 carbon atoms, n is an integer from 2 to 4 and m an integer from 1 to 4.
4. A composition according to claim 1, characterized in that said compund having a primary amine function (I) consists of at least one polyamine of the formula
Figure imgb0029
wherein R2 and R3 are each a linear alkyl radical of 8 to 24 carbon atoms, R2 and R3 together comprising from 16 to 32 carbon atoms, n is an integer from 2 to 4 and m is an integer from 1 to 4.
5. A composition according to claim 1, characterized in that said compound having a primary amine function (II) consists of at least one amino-alcohol of the formula:
Figure imgb0030
where R5 represents a linear alkylene radical of 1 to 18 carbon atoms.
6. A composition according to one of claims 1 to 5, characterized in that said aliphatic dicarboxylic compound is selected from maleic anhydride, methylmateic anhydride and the n-octadecenyl and dodecenyl succinic anhydrides.
7. A composition according to one of claims 1 to 6, characterized in that said reaction is performed in a hydrocarbon solvent having a boiling point between 70 and 250°C.
8. A composition according to one of claims 1 to 7, characterized in that said reaction comprises admixing, at a temperature of 30 to 80°C, said dicarboxylic compound with said compound of formula (I) or (II) and heating the resultant mixture at a temperature of 120 to 200°C for 1 to 8 hours.
9. A composition, characterized in that said middle distillate has a distillation range between 150 and 450°C.
10. A composition according to claim 9, characterized in that said middle distillate consists of a gas oil cut having a distillation range from an initial temperature of 160 to 190°C to a final temperature of 350 to 390°C.
11. A composition according to one of claims 1 to 10, characterized in that the proportion of said additive is from 20 to 2000 g/ton.
12. A composition according to claim 11, characterized in that the proportion of said additive is about 1000 g/ton.
EP82401335A 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 Expired EP0071513B1 (en)

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 EP0071513A2 (en) 1983-02-09
EP0071513A3 EP0071513A3 (en) 1983-04-27
EP0071513B1 true EP0071513B1 (en) 1986-11-20

Family

ID=9261024

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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994013758A1 (en) 1992-12-17 1994-06-23 Institut Francais Du Petrole Middle petroleum distillate composition containing a paraffin settling speed limiter

Families Citing this family (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN158027B (en) * 1982-02-03 1986-08-16 Lubrizol Corp
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
US4863487A (en) * 1987-04-29 1989-09-05 Nalco Chemical Company Hydrocarbon fuel detergent
US4895578A (en) * 1987-04-29 1990-01-23 Nalco Chemical Company Hydrocarbon fuel detergent
FR2633638B1 (en) * 1988-06-29 1991-04-19 Inst Francais Du Petrole FORMULATIONS OF NITROGEN ADDITIVES FOR ENGINE FUELS AND THE ENGINE FUELS CONTAINING THE SAME
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
US5147414A (en) * 1989-08-03 1992-09-15 Texaco Inc. Process for producing ori control additives
US4997456A (en) * 1989-09-11 1991-03-05 Ethyl Petroleum Additives, Inc. Fuel compositions
US5122616A (en) * 1989-09-11 1992-06-16 Ethyl Petroleum Additives, Inc. Succinimides
US5312555A (en) * 1990-02-16 1994-05-17 Ethyl Petroleum Additives, Inc. Succinimides
US6488723B2 (en) * 1990-03-05 2002-12-03 Alfred Richard Nelson Motor fuel additive composition and method for preparation thereof
AU660608B2 (en) * 1990-03-05 1995-07-06 Polar Molecular Corporation Motor fuel additive composition and method for preparation thereof
GB2242190A (en) * 1990-03-24 1991-09-25 Abm Chemicals Limited Biocidal amines
FR2699551B1 (en) * 1992-12-18 1995-03-17 Inst Francais Du Petrole Formulations containing an amine phosphate and a paraffin germination additive.
DE69309842T2 (en) * 1992-10-09 1997-10-16 Inst Francais Du Petrole Amine phosphates with an imide end ring, their production and their use as additives for motor fuels
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
FR2792646B1 (en) * 1999-04-26 2001-07-27 Elf Antar France COMPOSITION OF MULTI-FUNCTIONAL COLD OPERABILITY ADDITIVES FOR MEDIUM DISTILLATES
US20090158643A1 (en) * 2004-06-02 2009-06-25 Polar Molecular Corporation Motor fuel additive composition
US20050268534A1 (en) * 2004-06-02 2005-12-08 Polar Molecular Corporation Motor fuel additive composition
US20050268537A1 (en) * 2004-06-02 2005-12-08 Polar Molecular Corporation Motor fuel additive composition
US20090158642A1 (en) * 2004-06-02 2009-06-25 Polar Molecular Corporation Motor fuel additive composition
US20050268531A1 (en) * 2004-06-02 2005-12-08 Polar Molecular Corporation Motor fuel additive composition
US20050268532A1 (en) * 2004-06-02 2005-12-08 Polar Molecular Corporation Motor fuel additive composition
US20050268533A1 (en) * 2004-06-02 2005-12-08 Polar Molecular Corporation Motor fuel additive composition
FR2925909B1 (en) * 2007-12-26 2010-09-17 Total France BIFUNCTIONAL ADDITIVES FOR LIQUID HYDROCARBONS OBTAINED BY GRAFTING FROM COPOLYMERS OF ETHYLENE AND / OR PROPYLENE AND VINYL ESTERS
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
FR2940314B1 (en) 2008-12-23 2011-11-18 Total Raffinage Marketing GASOLINE FUEL FOR DIESEL ENGINE HAVING HIGH CARBON CONTENT OF RENEWABLE ORIGIN AND OXYGEN
EP2230226B1 (en) * 2009-03-18 2017-01-18 Infineum International Limited Additives for fuel oils
FR2943678B1 (en) 2009-03-25 2011-06-03 Total Raffinage Marketing LOW MOLECULAR WEIGHT (METH) ACRYLIC POLYMERS, FREE FROM SULFUR, METAL AND HALOGEN COMPOUNDS AND LOW RESIDUAL MONOMER RATES, PREPARATION METHOD AND USES THEREOF
FR2947558B1 (en) 2009-07-03 2011-08-19 Total Raffinage Marketing TERPOLYMER AND ETHYLENE / VINYL ACETATE / UNSATURATED ESTERS AS ADDITIVES TO ENHANCE COLD LIQUID HYDROCARBONS LIKE MEDIUM DISTILLATES AND FUELS OR COMBUSTIBLES
FR2969620B1 (en) 2010-12-23 2013-01-11 Total Raffinage Marketing MODIFIED ALKYLPHENOL ALDEHYDE RESINS, THEIR USE AS ADDITIVES IMPROVING THE COLD PROPERTIES OF LIQUID HYDROCARBON FUELS AND FUELS
FR2971254B1 (en) 2011-02-08 2014-05-30 Total Raffinage Marketing LIQUID COMPOSITIONS FOR MARKING LIQUID HYDROCARBON FUELS AND FUELS, FUELS AND FUELS CONTAINING THEM, AND METHOD OF DETECTING MARKERS
CA2831157C (en) 2011-04-13 2019-08-27 Basf Se Amine and diamine compounds and their use for inverse froth flotation of silicate from iron ore
FR2977895B1 (en) 2011-07-12 2015-04-10 Total Raffinage Marketing ADDITIVE COMPOSITIONS ENHANCING STABILITY AND MOTOR PERFORMANCE OF NON-ROAD GASES
FR2984918B1 (en) 2011-12-21 2014-08-01 Total Raffinage Marketing ADDITIVE COMPOSITIONS ENHANCING LACQUERING RESISTANCE OF HIGH-QUALITY DIESEL OR BIODIESEL FUEL
FR2987052B1 (en) 2012-02-17 2014-09-12 Total Raffinage Marketing ADDITIVES ENHANCING WEAR AND LACQUERING RESISTANCE OF GASOLINE OR BIOGAZOLE FUEL
FR2991992B1 (en) 2012-06-19 2015-07-03 Total Raffinage Marketing ADDITIVE COMPOSITIONS AND THEIR USE TO ENHANCE THE COLD PROPERTIES OF FUELS AND FUELS
US9145340B2 (en) 2012-08-13 2015-09-29 Verdesian Life Sciences, Llc Method of reducing atmospheric ammonia in livestock and poultry containment facilities
FR2994695B1 (en) 2012-08-22 2015-10-16 Total Raffinage Marketing ADDITIVES ENHANCING WEAR AND LACQUERING RESISTANCE OF GASOLINE OR BIOGAZOLE FUEL
US9961922B2 (en) 2012-10-15 2018-05-08 Verdesian Life Sciences, Llc Animal feed and/or water amendments for lowering ammonia concentrations in animal excrement
FR3005061B1 (en) 2013-04-25 2016-05-06 Total Raffinage Marketing ADDITIVE FOR IMPROVING THE STABILITY OF OXIDATION AND / OR STORAGE OF LIQUID HYDROCARBON FUELS OR FUELS
US11254620B2 (en) 2013-08-05 2022-02-22 Verdesian Life Sciences U.S., Llc Micronutrient-enhanced polymeric seed coatings
TW201522390A (en) 2013-08-27 2015-06-16 特級肥料產品公司 Polyanionic polymers
CA2923561C (en) 2013-09-05 2022-05-03 Verdesian Life Sciences, Llc Polymer-boric acid compositions
FR3017875B1 (en) 2014-02-24 2016-03-11 Total Marketing Services COMPOSITION OF ADDITIVES AND PERFORMANCE FUEL COMPRISING SUCH A COMPOSITION
FR3017876B1 (en) 2014-02-24 2016-03-11 Total Marketing Services COMPOSITION OF ADDITIVES AND PERFORMANCE FUEL COMPRISING SUCH A COMPOSITION
CA2945823C (en) 2014-05-21 2022-04-26 Verdesian Life Sciences, Llc Polymer soil treatment compositions including humic acids
WO2015179552A1 (en) 2014-05-22 2015-11-26 Verdesian Life Sciences, Llc Polymeric compositions
EP3144059A1 (en) 2015-09-16 2017-03-22 Total Marketing Services Method for preparing microcapsules by double emulsion
FR3055135B1 (en) 2016-08-18 2020-01-10 Total Marketing Services METHOD FOR MANUFACTURING A LUBRICANT ADDITIVE FOR LOW SULFUR FUEL.
WO2022241203A1 (en) 2021-05-13 2022-11-17 Ecolab Usa Inc. Synthetic lubricity additives for hydrocarbon fuels

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (28)

* Cited by examiner, † Cited by third party
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
US3018173A (en) * 1957-04-26 1962-01-23 Universal Oil Prod Co Stabilization of hydrocarbons
US3068082A (en) * 1957-08-15 1962-12-11 Monsanto Chemicals Rust inhibited hydrocarbon fuel
BE568954A (en) * 1958-01-07
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
FR1318311A (en) * 1961-03-31 1963-02-15 California Research Corp New polyamide detergent and set point lowering for lubricants and fuels
US3087936A (en) * 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
FR1416295A (en) * 1963-12-05 1965-10-29 Armour & Co Motor fuels
US3272746A (en) * 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
GB1140171A (en) * 1966-02-07 1969-01-15 Chevron Res Substituted succinamic acids and their use as pour point depressants
GB1241327A (en) * 1968-09-19 1971-08-04 Exxon Research Engineering Co Fuel or lubricating oil compositions
FR2095403A5 (en) * 1969-12-10 1972-02-11 Inst Francais Du Petrole
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
US3905781A (en) * 1972-10-30 1975-09-16 Texaco Inc Carburetor detergent and corrosion inhibiting motor fuel compositions
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
GB1531945A (en) * 1976-06-07 1978-11-15 Texaco Development Corp Alkenylsuccinic acid or anhydride/amine condensation products and lubricating oil compositions containing them
US4144036A (en) * 1978-03-27 1979-03-13 Texaco Inc. Detergent fuel composition
US4177041A (en) * 1978-09-22 1979-12-04 Texaco Inc. Carburetor detergents
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
FR2476119B1 (en) * 1980-02-15 1985-07-26 Inst Francais Du Petrole N-SUBSTITUTED SUCCINIMIDE ETHERS, THEIR PREPARATION AND THEIR USE AS FUEL ADDITIVES
US4326987A (en) * 1980-02-25 1982-04-27 Petrolite Corporation Reaction products of alkyl and alkenyl succinic acids and ether diamines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994013758A1 (en) 1992-12-17 1994-06-23 Institut Francais Du Petrole Middle petroleum distillate composition containing a paraffin settling speed limiter

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
EP0071513A2 (en) 1983-02-09
JPH0251478B2 (en) 1990-11-07
US4652273A (en) 1987-03-24
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

Similar Documents

Publication Publication Date Title
EP0071513B1 (en) Additives for use as pour point dispersants for middle distillate hydrocarbons, and compositions of middle distillate hydrocarbons containing said additives
EP0100248B1 (en) Copolymers with functional nitrogen groups used especially as cloud point reduction additives of middle distillate hydrocarbons, and middle distillate hydrocarbon compositions containing the same
EP0112195B1 (en) Copolymers with functional nitrogens used especially as cloud point reduction additives of middle distillate hydrocarbons, and middle distillate hydrocarbon compositions containing the same
EP0674689B1 (en) Middle petroleum distillate composition containing a paraffin settling speed limiter
CA1321444C (en) Polymers with nitrogen-containing functions derived from insaturated polymers and their use as pour point lowering additives of hydrocarbon middle distillates
FR2528423A1 (en) Nitrogen contg. additives reducing cloud pt. of middle distillates - obtd. by reacting aliphatic di:carboxylic cpd., of e.g. (alkyl)maleic anhydride, with amide cpds.
CA1327597C (en) Polymers derived from insaturated polyesters by addition of a amine functional group, and their use as additives to modify the properties at room temperature of middle distallatesof petroleum
EP0291367B1 (en) Polymers containing nitrogen, their preparation and their use as additives for improving flow properties of middle distillate hydrocarbons
EP0593331B1 (en) Amines phosphates having a terminal imide cycle, their preparation and their use as additives for motor-fuels
EP0172758B1 (en) Additive compositions, especially to improve the cold filtration properties of petroleum middle distillates
CA1200341A (en) Copolymers with nitrogen-containng functions useful for instance as additives that lower the turbidity point of hydrocarbons middle distillates; hydrocarbons middle distillates compositions containing said copolymers
EP1252269B1 (en) Multifunctional additive compositions enabling middle distillates to be operable in cold conditions
EP0353116B1 (en) Recipes of nitrogenous additives for engine fuels, and engine fuels containing them
FR2528435A1 (en) Additive lowering middle distillate cloud pt. - is reaction prod. of polymerised unsaturated carboxylic acid or its ester with amine
EP0349369B1 (en) Composition obtained from hydroxy-imidazolines and polyamines, and their use as fuel additives
FR2539754A1 (en) Nitrogenous additives usable as cloud point lowering agents for hydrocarbon middle distillates and hydrocarbon middle distillate compositions containing the said additives.
EP0627483B1 (en) Additives formulated for motor-fuels containing at least one alkoxylated imidazo-oxazole compound
US6860908B2 (en) Petroleum middle distillate composition containing a substance for limiting the paraffin sedimentation rate
FR2633637A1 (en) Compositions obtained from hydroxyimidazolines and polyamines and their use as fuel additives

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE GB IT LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): BE DE GB IT LU NL SE

17P Request for examination filed

Effective date: 19831017

ITF It: translation for a ep patent filed

Owner name: ST. ASSOC. MARIETTI & PIPPARELLI

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE GB IT LU NL SE

REF Corresponds to:

Ref document number: 3274368

Country of ref document: DE

Date of ref document: 19870108

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
EPTA Lu: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 82401335.3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19970723

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19970903

Year of fee payment: 16

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980716

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980731

BERE Be: lapsed

Owner name: ELF FRANCE

Effective date: 19980731

Owner name: INSTITUT FRANCAIS DU PETROLE

Effective date: 19980731

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20010627

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20010709

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20010731

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20010813

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20020715

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20020716

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Effective date: 20020715

EUG Se: european patent has lapsed

Ref document number: 82401335.3

NLV7 Nl: ceased due to reaching the maximum lifetime of a patent

Effective date: 20020716