EP0674689B1 - Middle petroleum distillate composition containing a paraffin settling speed limiter - Google Patents

Middle petroleum distillate composition containing a paraffin settling speed limiter Download PDF

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Publication number
EP0674689B1
EP0674689B1 EP94902004A EP94902004A EP0674689B1 EP 0674689 B1 EP0674689 B1 EP 0674689B1 EP 94902004 A EP94902004 A EP 94902004A EP 94902004 A EP94902004 A EP 94902004A EP 0674689 B1 EP0674689 B1 EP 0674689B1
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Prior art keywords
compound
additive
reaction
carbon atoms
composition according
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German (de)
French (fr)
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EP0674689A1 (en
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Despina Vassilakis
Robert Leger
Alain Forestiere
Jean Gaillard
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Elf Antar France
IFP Energies Nouvelles IFPEN
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Elf Antar France
IFP Energies Nouvelles IFPEN
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/222Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/143Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/221Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/222Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224Amides; Imides carboxylic acid amides, imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/234Macromolecular compounds
    • C10L1/238Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/234Macromolecular compounds
    • C10L1/238Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2381Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds polyamides; polyamide-esters; polyurethane, polyureas
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/04Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1608Well defined compounds, e.g. hexane, benzene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/195Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic

Definitions

  • the invention relates to middle hydrocarbon distillates (fuel oils, gas oils), in which the decantation of paraffins is slowed down by the addition of nitrogenous additives. It also relates to a method for slowing the decantation or sedimentation of paraffins of a middle hydrocarbon distillate by adding a minor proportion of at least one nitrogenous additive.
  • the petroleum distillates concerned by the invention consist of middle distillates (fuel oils, gas oils) containing paraffins whose distillation range (ASTM D 86-67 standard) is between 150 ° C and 450 ° C.
  • the gas 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.
  • the products recommended in the present invention for their properties also confer on diesel oils and other middle distillates to which they are added, anti-corrosion properties on metal surfaces.
  • compositions of petroleum middle distillates according to the present invention can be defined as comprising a major proportion of petroleum middle distillate and a minor proportion sufficient to limit the rate of sedimentation of the paraffins which it contains, at least one additive consisting of a product with an average molecular weight of approximately 300 to 10,000 resulting from the reaction of at least one aliphatic dicarboxylic compound chosen from anhydrides maleic and alkyl maleic, alkenyl succinic anhydrides having from 10 to 32 carbon atoms in the alkenyl radical, dicarboxylic acids and the corresponding light alkyl diesters, and at least one compound having a primary amine function corresponding to the general formula (I ): where R 1 represents a monovalent saturated aliphatic radical having from 1 to 32 carbon atoms, Z is chosen from the groups -NR'- in which R 'represents a hydrogen atom or a monovalent saturated aliphatic radical having from 1 to 32 atoms carbon, n is an integer from 2 to 4,
  • the present invention also relates to a method for reducing the rate of sedimentation of paraffins contained in a mixture of hydrocarbons comprising the introduction into this mixture of hydrocarbons of a minor amount sufficient to reduce the rate of sedimentation of paraffins, at least at least one additive consisting of a product with an 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, alkenyl succinic anhydrides having from 10 to 30 carbon atoms in the alkenyl radical, the dicarboxylic acids and the corresponding light alkyl diesters, and of at least one compound with a primary amine function corresponding to the general formula (I): in which Z, R1, n and m have the definition given above, said compound with primary amine function being used in a proportion of 0.3 to 0.8 mole per mole of said dicarboxylic compound and said reaction being carried out at a temperature from 120 to 200 ° C, and
  • the compounds of formula (I) can 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 ma a value of 2 to 4 and n is equal to 3; R 1 is preferably a linear monovalent saturated aliphatic radical having from 12 to 32 carbon atoms and more particularly from 16 to 24 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 are used, and preferably dipropylene triamines such as N-hexadecyl- or N-octadecyl-dipropylene-triamine.
  • the compounds of formula (I) can also consist of polyamines corresponding to the formula: which corresponds to the general formula (I) in which Z represents the group -NR 2 R 3 where R 2 and R 3 , identical or different, have the same definition as R 1 and are each preferably an alkyl radical having from 1 to 24 and preferably from 6 to 24 carbon atoms, R 2 and R 3 containing together preferably from 12 to 32 carbon atoms; n has a value of 2 to 4, preferably 3 and m a value of 1 to 4, preferably of 2 to 4.
  • the dicarboxylic compounds on which the condensation of a compound of formula (I) is carried out as described above are more particularly chosen from maleic anhydride, alkylmaleic anhydrides, for example methylmaleic anhydride (or citraconic) or also from alkenyl succinic anhydrides, for example those obtained by the action of at least one olefin, preferably linear, (for example having 10 to 32 carbon atoms) on maleic anhydride.
  • olefin preferably linear, (for example having 10 to 32 carbon atoms) on maleic anhydride.
  • n-octadecenyl succinic anhydride or dodecenyl succinic anhydride It is of course possible to use mixtures of two (or more) of these compounds
  • the compounds with a primary amine function of formula (I) are usually used in an amount of 0.3 to 0.8 mole, preferably from 0.4 to 0.7 mole, per mole of dicarboxylic compound.
  • the condensation of the compounds of formula (I) on the dicarboxylic compounds can be carried out without solvent, but preferably a hydrocarbon solvent with a boiling point of between 70 ° C. will be used. and 250 ° C., more particularly consisting of an aromatic or naphtheno-aromatic hydrocarbon, for example: toluene, xylenes, diisopropylbenzene or alternatively a 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 slowing down the settling of paraffins in middle petroleum distillates (in particular gas oils).
  • concentration range of the additive from 20 g to 2000 g / t, it is possible to observe a reduction in the proportion of sedimented paraffins of up to 100% under the conditions of the tests described in the patent EP- B-71513 but also under more severe temperature conditions of 5 to 10 ° C. In addition, a clear anticorrosion effect is 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.
  • compositions of middle petroleum distillates (for example gas oils) of the invention may also contain other additives, in particular other additives intended to improve the cold behavior, for example additives lowering the pour point and additives lowering the filterability limit temperature of middle distillates (for example diesel).
  • the present invention also relates to the use of at least one compound of formula (I): in which Z, R 1 , n and m have the definition given above, in a proportion of 20 to 2000 parts per million of the total weight of the composition, as an additive reducing the rate of sedimentation of paraffins in a hydrocarbon composition consisting of a major proportion of a middle distillate of paraffin-containing hydrocarbons. It also relates to the use of at least one compound of general formula (I) above in a proportion of 20 to 2,000 parts per million of the total weight of the composition, as an anticorrosion additive in a hydrocarbon composition consisting in a major proportion of a middle distillate of hydrocarbons containing paraffins.
  • At least one compound of formula (I) consisting of at least one polyamine having one of the formulas below: R 1 -NH - [(CH 2 ) n -NH-] m H in which R1, R2, R3, n and m have the definition given above.
  • Additive I was analyzed after evaporation of the solvent. Its number average 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 . This additive is that described in Example 1 of patent EP-B-71513.
  • Example 1 is repeated using the amine N-stearyldipropylene triamine in a proportion of 0.75 mole of amine per mole of anhydride.
  • the reactor is kept at the reflux temperature of xylene for 3 hours 30 minutes, at the end of which there is no longer any elimination of water.
  • the amount of xylene is adjusted to obtain a 50% by weight solution of the additive II in xylene.
  • Additive II was analyzed after evaporation of the solvent. Its number average molecular mass measured by tonometry is 1600. 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 .
  • Example 2 is repeated using the amine N-stearyldipropylene triamine and the anhydride N-octadecenyl succinic anhydride in a proportion of 0.70 mole of amine per mole of anhydride.
  • the reactor is maintained at the reflux temperature of xylene for 4 hours at the end of which there is no longer any removal of water.
  • the amount of xylene is adjusted to obtain a 50% by weight solution of the additive III in xylene.
  • Additive III was analyzed after evaporation of the solvent. Its number average molecular mass measured by tonometry is 1700. The infrared spectrum in thin layer shows the existence of imide bands at 1700 and 1780 cm -1 , secondary amide at 1365 and 1560 cm -1 and secondary amine at 3300 cm -1 .
  • Example 2 is repeated using the amine N-stearyldipropylene triamine and the anhydride N-octadecenyl succinic anhydride in a proportion of 0.5 mole of amine per mole of anhydride.
  • the reactor is maintained at the xylene reflux temperature for 3 hours, at the end of which there is no longer any removal of water.
  • the amount of xylene is adjusted to obtain a 50% by weight solution of the additive IV in xylene.
  • Additive IV was analyzed after evaporation of the solvent. Its number average molecular mass measured by tonometry is 1650. The infrared spectrum in thin layer shows the existence of imide bands at 1700 and 1780 cm -1 , secondary amide at 1365 and 1560 cm -1 and secondary amine at 3300 cm -1 .
  • Two 250 cm 3 test tubes are filled with No. 1 diesel fuel.
  • no additive is introduced in the first test tube.
  • 0.1% by weight of one of the additives is introduced into the second test piece.
  • the 2 test pieces are hermetically sealed, then left to stand in a cold room at -15 ° C for 24 hours. After 24 hours, the degree of sedimentation of the paraffins that have precipitated is expressed by the volumes of the different phases (quantity of sediment, phase slightly cloudy, cloudy phase, clear or limpid phase) in the test tube.
  • the quality of the upper phase is decisive for the anti-sedimentation efficiency of the product: when the upper phase is cloudy, a large proportion of paraffins has remained in suspension. When this phase is clear, almost all of the paraffins have sedimented. With a slightly cloudy upper phase, the anti-sedimentation efficiency is intermediate.
  • Tables II and III relate to the results obtained with the additive I.
  • Tables IV and V relate to the results obtained with the additive II
  • Tables VI and VII relate to the results obtained with the additives III and IV.
  • TABLE II Test tube N ° 1 Test tube N ° 2 Commercial diesel N ° 1 as is Commercial diesel N ° 1 + additive I 50 ml sedimented 100 ml sedimented + + 200 ml clear 150 ml slightly cloudy Test tube N ° 1 Test tube N ° 2
  • Commercial diesel N ° 2 as is Commercial diesel N ° 2 + additive I 60 ml sedimented 70 ml sedimented + + 190 ml clear 180 ml clear
  • the additive IV manages to ensure the best homogeneity of the diesel fuel in cold storage.
  • the additive is used in the two gas oils No. 1 and No. 2 already described above at a concentration of 0.01% by weight.
  • the corrosion test consists in 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 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 one of the additives described above give 0% intact test pieces. rust.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract

A middle petroleum distillate composition containing a major proportion of middle petroleum distillate and a minor proportion of an additive in a sufficient amount to limit the settling speed of paraffins contained in said middle distillate. Said additive consists of a product resulting from a reaction between at least one aliphatic dicarboxylic compound and at least one primary amine functional compound of general formula (I), wherein R<1> is a monovalent saturated aliphatic radical, Z is selected from -NR'- groupings in which R' is a hydrogen atom or a monovalent saturated aliphatic radical, n is an integer between 2 and 4, and m is an integer between 1 and 4; said primary amine functional compound being used in a ratio of 0.3-0.8 mols per mol of said dicarboxylic compound.

Description

L'invention concerne des distillats moyens d'hydrocarbures (fuel-oils, gazoles), dans lesquels la décantation des paraffines est ralentie par adjonction d'additifs azotés. Elle concerne également une méthode pour ralentir la décantation ou sédimentation des paraffines d'un distillat moyen d'hydrocarbures par adjonction d'une proportion mineure d'au moins un additif azoté.The invention relates to middle hydrocarbon distillates (fuel oils, gas oils), in which the decantation of paraffins is slowed down by the addition of nitrogenous additives. It also relates to a method for slowing the decantation or sedimentation of paraffins of a middle hydrocarbon distillate by adding a minor proportion of at least one nitrogenous additive.

Les distillats de pétrole concernés par l'invention consistent en des distillats moyens (fuel-oils, gazoles) contenant des paraffines 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) containing paraffins whose distillation range (ASTM D 86-67 standard) is between 150 ° C and 450 ° C. The gas 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
  • 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 phénomènes cinétiques 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.These products act on the 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.

Il existe aussi sur le marché des additifs qui abaissent le point de trouble des coupes pétrolières, en modifiant la température à laquelle apparaissent les premiers cristaux de paraffines.There are also additives on the market which lower the cloud point of petroleum cuts by modifying the temperature at which the first paraffin crystals appear.

L'abaissement du point de trouble des distillats moyens (notamment des gazoles) par un additif, présente un intérêt important pour les raffineurs, car il permet 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, is of great interest to refiners, because it allows without modifying the distillation scheme, to meet the specifications, which are currently evolving in the direction of greater severity.

Par ailleurs, 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 à basse température.Furthermore, when 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 at low temperature.

La classe de composés chimiques décrits dans le brevet EP-B-71513 comme additifs permettant d'abaisser le point de trouble des distillats moyens d'hydrocarbures et ayant une action importante sur la température limite de filtrabilité et sur la température d'écoulement sont également décrits comme ayant une action sur la vitesse de sédimentation des paraffines formées par refroidissement des gazoles et autres distillats moyens.The class of chemical compounds described in patent EP-B-71513 as additives making it possible to lower the cloud point of middle hydrocarbon distillates and having a significant action on the limit filterability temperature and on the flow temperature are also described as having an action on the rate of sedimentation of paraffins formed by cooling of gas oils and other middle distillates.

Les additifs considérés dans la présente demande et définis plus loin, sont voisins des additifs décrits dans le brevet EP-B-71513 et appartiennent à la même classe de composés chimiques. De façon surprenante, on a découvert que dans la classe de composés chimiques décrite de façon générique dans le brevet EP-B-71513, certains d'entre eux, qui n'ont pas été décrits dans ce document, présentent des propriétés bien supérieures en ce qui concerne leur action sur la vitesse de sédimentation des paraffines et sont des additifs dits d'anti-sédimentation plus efficaces dans des conditions de test plus sévères.The additives considered in the present application and defined below are close to the additives described in patent EP-B-71513 and belong to the same class of chemical compounds. Surprisingly, it has been discovered that in the class of chemical compounds described generically in patent EP-B-71513, some of them, which have not been described in this document, have much superior properties in with regard to their action on the sedimentation rate of paraffins and are so-called anti-sedimentation additives which are more effective under more severe test conditions.

Enfin, les produits, préconisés dans la présente invention pour leurs propriétés notamment d'anti-sédimentation mentionnées ci-dessus, confèrent en outre aux gazoles et d'autres distillats moyens auxquels ils sont ajoutés, des propriétés anti-corrosion sur les surfaces métalliques.Finally, the products recommended in the present invention for their properties, in particular the anti-sedimentation properties mentioned above, also confer on diesel oils and other middle distillates to which they are added, anti-corrosion properties on metal surfaces.

A noter qu'ont déjà été décrits dans l'art antérieur (brevet US-A-2 638 450) comme additifs inhibiteurs de corrosion dans les huiles minérales, les essences et autres produits légers du pétrole, des dérivés de polyalkylènepolyamines N-alkylées et d'anhydrides d'acides alcènylsucciniques. Ces composés sont obtenus en deux étapes :

  • 1) Alkylation d'une polyalkylènepolyamine à l'aide d'un halogènure d'alkyle comportant de 4 à 31 atomes de carbone. La polyalkylènepolyamine alkylée obtenue de cette façon peut avoir une structure extrêmement variable, la présence de dérivés de C-alkylation et de dérivés de N-alkylation étant admise.
  • 2) Réaction de la polyalkylènepolyamine alkylée avec de l'anhydride d'un acide alcènylsuccinique. Le rapport molaire de la polyamine à l'anhydride dépend du taux d'alkylation de la polyamine, c'est-à-dire du rapport molaire polyamine/halogénure d'alkyle mis en oeuvre à la phase d'alkylation; il peut être inférieur ou égal à 1.
Note that have already been described in the prior art (US Pat. No. 2,638,450) as corrosion inhibiting additives in mineral oils, gasolines and other light petroleum products, N-alkylated polyalkylene polyamine derivatives and alkenyl succinic acid anhydrides. These compounds are obtained in two stages:
  • 1) Alkylation of a polyalkylene polyamine using an alkyl halide containing from 4 to 31 carbon atoms. The alkylated polyalkylene polyamine obtained in this way can have an extremely variable structure, the presence of C-alkylation derivatives and of N-alkylation derivatives being admitted.
  • 2) Reaction of the alkylated polyalkylene polyamine with anhydride of an alkenyl succinic acid. The molar ratio of the polyamine to the anhydride depends on the degree of alkylation of the polyamine, that is to say of the molar ratio of polyamine / alkyl halide used in the alkylation phase; it can be less than or equal to 1.

En raison de l'alkylation préalable de la polyamine qui donne vraisemblablement naissance à des dérivés de C-alkylation et à des dérivés de N-alkylation des divers groupes amino, ces additifs sont différents des composés dont l'emploi est revendiqué dans la présente demande. En outre, ce document antérieur enseigne l'utilisation de ces produits comme agent anticorrosion pour des dérivés pétroliers dont il n'est pas dit qu'ils donnent lieu au phénomène de cristallisation des paraffines. Ce document ne fait d'ailleurs aucune référence à ce problème particulier.Due to the prior alkylation of the polyamine which presumably gives rise to C-alkylation derivatives and to N-alkylation derivatives of the various amino groups, these additives are different from the compounds whose use is claimed in the present application . In addition, this prior document teaches the use of these products as an anti-corrosion agent for petroleum derivatives which are not said to give rise to the phenomenon of crystallization of paraffins. This document also makes no reference to this particular problem.

D'une manière générale, les compositions de distillats moyens de pétrole selon la présente invention peuvent être définies comme comprenant une proportion majeure de distillat moyen de pétrole et une proportion mineure suffisante pour limiter la vitesse de sédimentation des paraffines qu'il contient, d'au moins 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 32 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 la formule générale (I):

Figure imgb0001
où R1 représente un radical aliphatique saturé monovalent ayant de 1 à 32 atomes de carbone, Z est choisi parmi les groupements -NR'- dans lesquels R' représente un atome d'hydrogène ou un radical aliphatique saturé monovalent ayant de 1 à 32 atomes de carbone, n est un nombre entier de 2 à 4, m est un nombre entier de 1 à 4 ; ledit composé à fonction amine primaire étant utilisé en une proportion de 0,3 à 0,8 mole par mole dudit composé dicarboxylique et ladite réaction étant effectuée à une température de 120 à 200 °C, et étant poursuivie jusqu'à la fin du dégagement des produits volatils consistant en eau et/ou en alcool formés au cours de la réaction. Le plus souvent la réaction est poursuivie pendant un temps suffisant pour former la quantité théorique de produits volatils consistant en eau et/ou en alcool, qui sont éliminés.In general, the compositions of petroleum middle distillates according to the present invention can be defined as comprising a major proportion of petroleum middle distillate and a minor proportion sufficient to limit the rate of sedimentation of the paraffins which it contains, at least one additive consisting of a product with an average molecular weight of approximately 300 to 10,000 resulting from the reaction of at least one aliphatic dicarboxylic compound chosen from anhydrides maleic and alkyl maleic, alkenyl succinic anhydrides having from 10 to 32 carbon atoms in the alkenyl radical, dicarboxylic acids and the corresponding light alkyl diesters, and at least one compound having a primary amine function corresponding to the general formula (I ):
Figure imgb0001
where R 1 represents a monovalent saturated aliphatic radical having from 1 to 32 carbon atoms, Z is chosen from the groups -NR'- in which R 'represents a hydrogen atom or a monovalent saturated aliphatic radical having from 1 to 32 atoms carbon, n is an integer from 2 to 4, m is an integer from 1 to 4; said compound with primary amine function being used in a proportion of 0.3 to 0.8 mole per mole of said dicarboxylic compound and said reaction being carried out at a temperature of 120 to 200 ° C, and being continued until the end of the release volatile products consisting of water and / or alcohol formed during the reaction. Most often the reaction is continued for a time sufficient to form the theoretical amount of volatile products consisting of water and / or alcohol, which are removed.

La présente invention concerne également une méthode pour diminuer la vitesse de sédimentation des paraffines contenues dans un mélange d'hydrocarbures comprenant l'introduction dans ce mélange d'hydrocarbures d'une quantité mineure suffisante pour réduire la vitesse de sédimentation des paraffines, d'au moins 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 las 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 la formule générale (I) :

Figure imgb0002
dans laquelle Z, R1, n et m ont la définition donnée ci-avant, ledit composé à fonction amine primaire étant utilisé en une proportion de 0,3 à 0,8 mole par mole dudit composé dicarboxylique et ladite réaction étant effectuée à une température de 120 à 200°C, et étant poursuivie jusqu'à la fin du dégagement des produits volatils consistant en eau et/ou en alcool formés au cours de la réaction.The present invention also relates to a method for reducing the rate of sedimentation of paraffins contained in a mixture of hydrocarbons comprising the introduction into this mixture of hydrocarbons of a minor amount sufficient to reduce the rate of sedimentation of paraffins, at least at least one additive consisting of a product with an 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, alkenyl succinic anhydrides having from 10 to 30 carbon atoms in the alkenyl radical, the dicarboxylic acids and the corresponding light alkyl diesters, and of at least one compound with a primary amine function corresponding to the general formula (I):
Figure imgb0002
in which Z, R1, n and m have the definition given above, said compound with primary amine function being used in a proportion of 0.3 to 0.8 mole per mole of said dicarboxylic compound and said reaction being carried out at a temperature from 120 to 200 ° C, and being continued until the end of the evolution of volatile products consisting of water and / or alcohol formed during the reaction.

Les composés de formule (I) peuvent consister en des polyamines dérivées d'amines aliphatiques saturées répondant à la formule :

Figure imgb0003
qui correspond à la formule générale (I) 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 m a une valeur de 2 à 4 et n est égal à 3 ; R1 est de préférence un radical aliphatique saturé monovalent linéaire ayant de 12 à 32 atomes de carbone et plus particulièrement de 16 à 24 atomes de carbone.The compounds of formula (I) can consist of polyamines derived from saturated aliphatic amines corresponding to the formula:
Figure imgb0003
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 ma a value of 2 to 4 and n is equal to 3; R 1 is preferably a linear monovalent saturated aliphatic radical having from 12 to 32 carbon atoms and more particularly from 16 to 24 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, et de préférence des dipropylène triamines comme la N-hexadécyl- ou 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 are used, and preferably dipropylene triamines such as N-hexadecyl- or N-octadecyl-dipropylene-triamine.

Les composés de formule (I) peuvent également consister en des polyamines répondant à la formule :

Figure imgb0004
qui correspond à la formule générale (I) dans laquelle Z représente le groupement -NR2R3 où R2 et R3, identiques ou différents, ont la même définition que R1 et sont chacun de préférence un radical alkyle ayant de 1 à 24 et de préférence de 6 à 24 atomes de carbone, R2 et R3 renfermant à eux deux de préférence de 12 à 32 atomes de carbone ; n a une valeur de 2 à 4, de préférence 3 et m une valeur de 1 à 4, de préférence de 2 à 4.The compounds of formula (I) can also consist of polyamines corresponding to the formula:
Figure imgb0004
which corresponds to the general formula (I) in which Z represents the group -NR 2 R 3 where R 2 and R 3 , identical or different, have the same definition as R 1 and are each preferably an alkyl radical having from 1 to 24 and preferably from 6 to 24 carbon atoms, R 2 and R 3 containing together preferably from 12 to 32 carbon atoms; n has a value of 2 to 4, preferably 3 and m a value of 1 to 4, preferably of 2 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, et comme composés spécifiques préférés la N,N-didodécyldipropylène triamine, la N,N-ditétradécyl-dipropylène triamine, la N,N-dihexadécyldipropylène triamine et la N,N-dioctadécyldipropylène triamine.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-diamino-1,3 propane, N, N-dihexadécyldiamino- 1,3 propane, N, N-dioctadécyldiamino-1,3 propane, and as preferred specific compounds N, N-didodécyldipropylène triamine, N, N-ditétradécyl-dipropylène triamine, N, N-dihexadécyldipropylène triamine and N , N-dioctadecyldipropylene triamine.

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).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).

Les composés dicarboxyliques sur lesquels on effectue la condensation d'un composé de formule (I) 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 alcénylsucciniques, par exemple ceux obtenus par action d'au moins une oléfine, de préférence linéaire, (ayant par exemple 10 à 32 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 composésThe dicarboxylic compounds on which the condensation of a compound of formula (I) is carried out as described above, are more particularly chosen from maleic anhydride, alkylmaleic anhydrides, for example methylmaleic anhydride (or citraconic) or also from alkenyl succinic anhydrides, for example those obtained by the action of at least one olefin, preferably linear, (for example having 10 to 32 carbon atoms) on maleic anhydride. There may be mentioned more specifically 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 formule (I) sont habituellement utilisés à raison de 0,3 à 0,8 mole, de préférence de 0,4 à 0,7 mole, par mole de composé dicarboxylique.The compounds with a primary amine function of formula (I) are usually used in an amount of 0.3 to 0.8 mole, preferably from 0.4 to 0.7 mole, per mole of dicarboxylic compound.

La condensation des composés de formule (I) 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 hydrocarboné de point d'ébullition compris entre 70°C et 250°C, consistant plus particulièrement en un hydrocarbure aromatique ou naphténo-aromatique, 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) on the dicarboxylic compounds (for example dicarboxylic acids, esters, or preferably anhydrides) can be carried out without solvent, but preferably a hydrocarbon solvent with a boiling point of between 70 ° C. will be used. and 250 ° C., more particularly consisting of an aromatic or naphtheno-aromatic hydrocarbon, for example: toluene, xylenes, diisopropylbenzene or alternatively a 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 la température entre 30 °C et 80 °C, on introduit peu à peu le composé de formule (I). 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 %.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). 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 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 ralentir la décantation de paraffines dans les distillats moyens du pétrole (notamment des gazoles).The additives considered in the invention are particularly advantageous for slowing down the settling of paraffins in middle petroleum distillates (in particular gas oils).

Bien que le mécanisme d'action de ces additifs sur la vitesse de sédimentation des cristaux de paraffines dans les distillats moyens n'ait pas encore été clairement élucidé, on observe un net ralentissement de la décantation des paraffines dans les distillats moyens traités par ces additifs, lorsqu'ils sont ajoutés à des concentrations allant par exemple de 20 à 2000 grammes par tonne (g/t) de distillat moyen. Les concentrations préférées vont de 100 à 2000 g/t.Although the mechanism of action of these additives on the rate of sedimentation of paraffin crystals in middle distillates has not yet been clearly elucidated, a marked slowing down of the decantation of paraffins in the middle distillates treated with these additives, when added at concentrations ranging, for example, from 20 to 2000 grams per tonne (g / t) of middle distillate. Preferred concentrations range from 100 to 2000 g / t.

De plus, il est remarquable de constater que les additifs considérés dans l'invention qui ont la propriété d'inhiber la sédimentation des n-paraffines dans les distillats moyens au repos, inhibent aussi 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 have the property of inhibiting the sedimentation of n-paraffins in middle distillates at rest, also inhibit the corrosion of metal surfaces in contact with these distillates.

Dans la gamme de concentration de l'additif, de 20 g à 2000 g/t, il est possible d'observer une diminution de la proportion de paraffines sédimentées allant jusqu'à 100 % dans les conditions des tests décrits dans le brevet EP-B-71513 mais aussi dans des conditions de température plus sévères de 5 à 10° C. De plus, un effet anticorrosion net est observé en particulier sur les métaux ferreux.In the concentration range of the additive, from 20 g to 2000 g / t, it is possible to observe a reduction in the proportion of sedimented paraffins of up to 100% under the conditions of the tests described in the patent EP- B-71513 but also under more severe temperature conditions of 5 to 10 ° C. In addition, a clear anticorrosion effect is 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 solvants déjà mentionnés plus haut. Les "solutions mères" peuvent contenir par exemple de 20 à 60 % en poids d'additifs.However, it is often advantageous to introduce them in the form of "stock solutions" prepared beforehand in the solvents already mentioned above. The "mother solutions" can contain, for example, from 20 to 60% by weight of additives.

Les compositions de distillats moyens de pétrole (par exemple gazoles) de l'invention peuvent également renfermer d'autres additifs, en particulier d'autres additifs destinés à améliorer le comportement à froid par exemple des additifs abaissant le point d'écoulement et des additifs abaissant la température limite de filtrabilité des distillats moyens (par exemple des gazoles).The compositions of middle petroleum distillates (for example gas oils) of the invention may also contain other additives, in particular other additives intended to improve the cold behavior, for example additives lowering the pour point and additives lowering the filterability limit temperature of middle distillates (for example diesel).

La présente invention concerne aussi l'utilisation d'au moins un composé de formule (I) :

Figure imgb0005
dans laquelle Z, R1, n et m ont la définition donnée ci-avant, en une proportion de 20 à 2 000 parties par millions du poids total de la composition, en tant qu'additif réduisant la vitesse de sédimentation des paraffines dans une composition hydrocarbonée consistant en une proportion majeure d'un distillat moyen d'hydrocarbures contenant des paraffines. Elle concerne également l'utilisation d'au moins un composé de formule générale (I) ci-avant en une proportion de 20 à 2 000 parties par million du poids total de la composition, en tant qu'additif anticorrosion dans une composition hydrocarbonée consistant en une proportion majeure d'un distillat moyen d'hydrocarbures contenant des paraffines.The present invention also relates to the use of at least one compound of formula (I):
Figure imgb0005
in which Z, R 1 , n and m have the definition given above, in a proportion of 20 to 2000 parts per million of the total weight of the composition, as an additive reducing the rate of sedimentation of paraffins in a hydrocarbon composition consisting of a major proportion of a middle distillate of paraffin-containing hydrocarbons. It also relates to the use of at least one compound of general formula (I) above in a proportion of 20 to 2,000 parts per million of the total weight of the composition, as an anticorrosion additive in a hydrocarbon composition consisting in a major proportion of a middle distillate of hydrocarbons containing paraffins.

Dans ce cadre, on peut utiliser avantageusement au moins un composé de formule (I) consistant en au moins une polyamine ayant l'une des formules ci-après :

        R1-NH-[(CH2)n-NH-] m H

Figure imgb0006
dans lesquelles R1, R2, R3, n et m ont la définition donnée ci-avant.In this context, it is advantageous to use at least one compound of formula (I) consisting of at least one polyamine having one of the formulas below:

R 1 -NH - [(CH 2 ) n -NH-] m H

Figure imgb0006
in which R1, R2, R3, n and m have the definition given above.

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 1 (comparatif)Example 1 (comparative)

On introduit dans un réacteur de 20 l muni d'une bonne agitation 2.700 g d'une polyamine commerciale (contenant un mélange formé d'environ 27 % de palmityl 1,3-propane-diamine et d'environ 70 % de stéaryl 1,3 propanediamine, ledit mélange ayant un équivalent de 370 g pour un groupe 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 la température de reflux du xylène, la température intérieure du réacteur 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 de départ ; 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 formed of approximately 27% palmityl 1,3-propane diamine and approximately 70% stearyl 1) are introduced into a 20 l reactor fitted with good stirring. 3 propanediamine, said mixture having an equivalent of 370 g for a primary amine group) 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 while maintaining the internal temperature at 40 ° C; the addition lasts one hour, the mixture is then heated for 3 hours at the reflux temperature of xylene, the internal temperature of the reactor 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 starting 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 moyenne 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. Cet additif est celui décrit dans l'exemple 1 du brevet EP-B-71513.Additive I was analyzed after evaporation of the solvent. Its number average 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 . This additive is that described in Example 1 of patent EP-B-71513.

Exemple 2Example 2

On répète l'exemple 1 en utilisant comme amine le N-stéaryldipropylène-triamine en une proportion de 0,75 mole d'amine par mole d'anhydride. On maintient le réacteur à la température de reflux du xylène pendant 3 heures 30 au bout desquelles il n'y a plus d'élimination d'eau. On ajuste la quantité de xylène pour obtenir une solution à 50 % en poids de l'additif Il dans le xylène.Example 1 is repeated using the amine N-stearyldipropylene triamine in a proportion of 0.75 mole of amine per mole of anhydride. The reactor is kept at the reflux temperature of xylene for 3 hours 30 minutes, at the end of which there is no longer any elimination of water. The amount of xylene is adjusted to obtain a 50% by weight solution of the additive II in xylene.

L'additif II a été analysé après évaporation du solvant. Sa masse moléculaire moyenne en nombre mesurée par tonométrie est de 1600. 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 II was analyzed after evaporation of the solvent. Its number average molecular mass measured by tonometry is 1600. 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 .

Exemple 3Example 3

On répète l'exemple 2 en utilisant comme amine la N-stéaryldipropylène-triamine et comme anhydride l'anhydride N-octadécényl succinique en une proportion de 0,70 mole d'amine par mole d'anhydride. On maintient le réacteur à la température de reflux du xylène pendant 4 heures au bout desquelles il n'y a plus d'élimination d'eau. On ajuste la quantité de xylène pour obtenir une solution à 50 % en poids de l'additif III dans le xylène.Example 2 is repeated using the amine N-stearyldipropylene triamine and the anhydride N-octadecenyl succinic anhydride in a proportion of 0.70 mole of amine per mole of anhydride. The reactor is maintained at the reflux temperature of xylene for 4 hours at the end of which there is no longer any removal of water. The amount of xylene is adjusted to obtain a 50% by weight solution of the additive III in xylene.

L'additif III a été analysé après évaporation du solvant. Sa masse moléculaire moyenne en nombre mesurée par tonométrie est de 1700. Le spectre infra-rouge en couche mince montre l'existence de bandes imides à 1700 et 1780 cm-1, amide secondaire à 1365 et 1560 cm-1 et amine secondaire à 3300 cm-1.Additive III was analyzed after evaporation of the solvent. Its number average molecular mass measured by tonometry is 1700. The infrared spectrum in thin layer shows the existence of imide bands at 1700 and 1780 cm -1 , secondary amide at 1365 and 1560 cm -1 and secondary amine at 3300 cm -1 .

Exemple 4Example 4

On répète l'exemple 2 en utilisant comme amine la N-stéaryldipropylène-triamine et comme anhydride l'anhydride N-octadécényl succinique en une proportion de 0,5 mole d'amine par mole d'anhydride. On maintient le réacteur à la température de reflux du xylène pendant 3 heures au bout desquelles il n'y a plus d'élimination d'eau. On ajuste la quantité de xylène pour obtenir une solution à 50 % en poids de l'additif IV dans le xylène.Example 2 is repeated using the amine N-stearyldipropylene triamine and the anhydride N-octadecenyl succinic anhydride in a proportion of 0.5 mole of amine per mole of anhydride. The reactor is maintained at the xylene reflux temperature for 3 hours, at the end of which there is no longer any removal of water. The amount of xylene is adjusted to obtain a 50% by weight solution of the additive IV in xylene.

L'additif IV a été analysé après évaporation du solvant. Sa masse moléculaire moyenne en nombre mesurée par tonométrie est de 1650. Le spectre infra-rouge en couche mince montre l'existence de bandes imides à 1700 et 1780 cm-1, amide secondaire à 1365 et 1560 cm-1 et amine secondaire à 3300 cm-1.Additive IV was analyzed after evaporation of the solvent. Its number average molecular mass measured by tonometry is 1650. The infrared spectrum in thin layer shows the existence of imide bands at 1700 and 1780 cm -1 , secondary amide at 1365 and 1560 cm -1 and secondary amine at 3300 cm -1 .

Exemple 5Example 5

On teste l'action inhibitrice de l'additif I et des additifs Il à IV selon l'invention sur la sédimentation des n-paraffines cristallisant dans deux gazoles hiver commerciaux, dont les caractéristiques sont indiquées au tableau I ci-après : TABLEAU I Gazole commercial N° 1 Gazole commercial N° 2 Densité à 15 °C 0,844 0,843 Distillation ASTM D 86-67 Point Initial 172 166 5 % 200 190 10 % 213 199 20% 231 214 30 % 246 228 40 % 260 242 50 % 273 257 60 % 286 269 70 % 300 285 80 % 314 305 90 % 332 336 95 % 343 359 Point Final 359 373 % N-paraffines 10,1 10,0 Point de trouble - 6 - 6 T. L. F. - 15 - 16 Point d'écoulement - 27 - 30 The inhibitory action of the additive I and of the additives II to IV according to the invention is tested on the sedimentation of n-paraffins crystallizing in two commercial winter gas oils, the characteristics of which are indicated in table I below: TABLE I Commercial diesel N ° 1 Commercial diesel N ° 2 Density at 15 ° C 0.844 0.843 Distillation ASTM D 86-67 Initial point 172 166 5% 200 190 10% 213 199 20% 231 214 30 % 246 228 40% 260 242 50% 273 257 60% 286 269 70% 300 285 80% 314 305 90% 332 336 95% 343 359 Period 359 373 % N-paraffins 10.1 10.0 Cloud point - 6 - 6 TLF - 15 - 16 Pour point - 27 - 30

Ces gazoles commerciaux contiennent 500 ppm en poids d'un améliorant de point d'écoulement du type polymère éthylène-acétate de vinyle (EVA).These commercial gas oils contain 500 ppm by weight of a pour point improver of the ethylene vinyl acetate (EVA) type.

Deux éprouvettes de 250 cm3 sont remplies de gazole n°1. Dans la première éprouvette, on n'introduit pas d'additif. Dans la deuxième éprouvette, on introduit 0,1 % en poids de l'un des additifs.Two 250 cm 3 test tubes are filled with No. 1 diesel fuel. In the first test tube, no additive is introduced. 0.1% by weight of one of the additives is introduced into the second test piece.

Les 2 éprouvettes sont bouchées hermétiquement, puis laissées au repos en chambre froide à -15°C pendant 24 H. Au bout de 24 heures, le degré de sédimentation des paraffines ayant précipité est exprimé par les volumes des différentes phases (quantité sédimentée, phase légèrement trouble, phase trouble, phase claire ou limpide) dans l'éprouvette.The 2 test pieces are hermetically sealed, then left to stand in a cold room at -15 ° C for 24 hours. After 24 hours, the degree of sedimentation of the paraffins that have precipitated is expressed by the volumes of the different phases (quantity of sediment, phase slightly cloudy, cloudy phase, clear or limpid phase) in the test tube.

On constate les résultats suivants donnés dans les tableaux II,IV et VI ci-après.The following results are noted given in Tables II, IV and VI below.

Le même test est effectué avec le gazole n°2, à -20°C pendant 24 H. Les résultats sont portés sur les tableaux III, V et VII ci-après.The same test is carried out with diesel No. 2, at -20 ° C for 24 hours. The results are shown in Tables III, V and VII below.

La qualité de la phase supérieure est déterminante pour l'efficacité anti-sédimentation du produit : lorsque la phase supérieure est trouble, une grande proportion de paraffines est restée en suspension. Lorsque cette phase est claire, la quasi totalité des paraffines a sédimenté. Avec une phase supérieure légèrement trouble, l'efficacité anti-sédimentation est intermédiaire.The quality of the upper phase is decisive for the anti-sedimentation efficiency of the product: when the upper phase is cloudy, a large proportion of paraffins has remained in suspension. When this phase is clear, almost all of the paraffins have sedimented. With a slightly cloudy upper phase, the anti-sedimentation efficiency is intermediate.

Si l'on considère à présent la quantité de paraffines sédimentées : plus la phase supérieure est déparaffinée, plus la phase sédimentée est dense, ce qui rend la pompabilité du gazole difficile. On ne peut comparer les quantités de paraffines sédimentées que si elles sont de densité équivalente, c'est-à-dire si les phases supérieures sont de même nature.If we now consider the quantity of sedimented paraffins: the more the dewaxed upper phase, the denser the sedimented phase, which makes pumpability of diesel difficult. The quantities of sedimented paraffins can only be compared if they are of equivalent density, that is to say if the upper phases are of the same nature.

Les tableaux Il et III concernent les résultats obtenus avec l'additif I. Les tableaux IV et V concernent les résultats obtenus avec l'additif Il Les tableaux VI et VII concernent les résultats obtenus avec les additifs III et IV. TABLEAU II Eprouvette N° 1 Eprouvette N° 2 Gazole commercial N° 1 tel quel Gazole commercial N° 1 +additif I 50 ml sédimenté 100 ml sédimenté + + 200 ml clair 150 ml légèrement trouble TABLEAU III Eprouvette N° 1 Eprouvette N° 2 Gazole commercial N° 2 tel quel Gazole commercial N° 2 +additif I 60 ml sédimenté 70 ml sédimenté + + 190 ml clair 180 ml clair Tables II and III relate to the results obtained with the additive I. Tables IV and V relate to the results obtained with the additive II Tables VI and VII relate to the results obtained with the additives III and IV. TABLE II Test tube N ° 1 Test tube N ° 2 Commercial diesel N ° 1 as is Commercial diesel N ° 1 + additive I 50 ml sedimented 100 ml sedimented + + 200 ml clear 150 ml slightly cloudy Test tube N ° 1 Test tube N ° 2 Commercial diesel N ° 2 as is Commercial diesel N ° 2 + additive I 60 ml sedimented 70 ml sedimented + + 190 ml clear 180 ml clear

On constate que l'additif I exemplifié dans EP-B-71513 pour son efficacité anti-sédimentation à -10°C est moins efficace à -15°C et pas efficace à -20°C. TABLEAU IV Eprouvette N° 1 Eprouvette N° 2 Gazole commercial N° 1 tel quel Gazole commercial N° 1+additif II 50 ml sédimenté 55 ml sédimenté + + 200 ml clair 195 ml légèrement trouble TABLEAU V Eprouvette N° 1 Eprouvette N° 2 Gazole commercial N° 2 tel quel Gazole commercial N° 2 +additif II 60 ml sédimenté 80 ml sédimenté + + 190 ml clair 170 ml légèrement trouble It is noted that the additive I exemplified in EP-B-71513 for its anti-sedimentation efficiency at -10 ° C is less effective at -15 ° C and not effective at -20 ° C. TABLE IV Test tube N ° 1 Test tube N ° 2 Commercial diesel N ° 1 as is Commercial diesel N ° 1 + additive II 50 ml sedimented 55 ml sedimented + + 200 ml clear 195 ml slightly cloudy Test tube N ° 1 Test tube N ° 2 Commercial diesel N ° 2 as is Commercial diesel N ° 2 + additive II 60 ml sedimented 80 ml sedimented + + 190 ml clear 170 ml slightly cloudy

L'efficacité anti-sédimentation de l'additif Il est supérieure à celle de l'additif I, notamment à -20°C. TABLEAU VI Eprouvette N° 1 Eprouvette N° 2 Eprouvette N° 3 Gazole N° 1 tel quel Gazole N° 1 +additif III Gazole N° 1 +additif IV 50 ml sédimenté 40 ml sédimenté 2 ml sédimenté + + + 200 ml clair 210 ml trouble 248 ml trouble TABLEAU VII Eprouvette N° 1 Eprouvette N° 2 Eprouvette N° 3 Gazole N° 2 tel quel Gazole N° 2 +additif III Gazole N° 2 +additif IV 60 ml sédimenté 110 ml sédimenté 10 ml sédimenté + + + 190 ml clair 140 ml trouble 240 ml trouble The anti-sedimentation efficiency of additive II is higher than that of additive I, especially at -20 ° C. TABLE VI Test tube N ° 1 Test tube N ° 2 Test tube N ° 3 Diesel N ° 1 as is Diesel N ° 1 + additive III Diesel N ° 1 + additive IV 50 ml sedimented 40 ml sedimented 2 ml sedimented + + + 200 ml clear 210 ml cloudy 248 ml cloudy Test tube N ° 1 Test tube N ° 2 Test tube N ° 3 Diesel N ° 2 as is Diesel N ° 2 + additive III Diesel N ° 2 + additive IV 60 ml sedimented 110 ml sedimented 10 ml sedimented + + + 190 ml clear 140 ml cloudy 240 ml cloudy

Une meilleure dispersion des paraffines est obtenue avec l'additif III par rapport à l'additif II, mais le ratio des réactifs est un facteur important pour l'efficacité anti-sédimentation des additifs : l'additif IV parvient à assurer la meilleure homogénéité des gazoles au stockage à froid.A better dispersion of the paraffins is obtained with the additive III compared to the additive II, but the ratio of the reagents is an important factor for the anti-sedimentation efficiency of the additives: the additive IV manages to ensure the best homogeneity of the diesel fuel in cold storage.

Exemple 6Example 6

On teste l'effet anticorrosion des additifs I à IV décrits ci-avant.The anti-corrosion effect of the additives I to IV described above is tested.

L'additif est utilisé dans les deux gazoles n° 1 et n° 2 déjà décrits précédemment à la concentration de 0,01% en poids.The additive is 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 ia façon suivante : la température est de 32,2 °C et la durée de 20 heures.The corrosion test consists in 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 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 de l'un des additifs décrits ci-avant 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 one of the additives described above give 0% intact test pieces. rust.

Claims (10)

  1. A petroleum middle distillate composition comprising a major proportion of a petroleum middle distillate containing paraffins and whose distillation range (ASTM D 86-87) is between 150 and 450°C and a minor proportion of at least one additive consisting of a product with an average molecular weight of about 300 to 10,000 resulting from the reaction of at least one aliphatic dicarboxylic compound (a) selected from maleic and alkylmaleic anhydrides, alkenyl succinic anhydrides containing 10 to 32 carbon atoms in the alkenyl radical, and the corresponding dicarboxylic acids and lower alkyl diesters, and at least one compound with primary amine function (b) having the general formula (I):
    Figure imgb0015
    where R1 represents a monovalent saturated aliphatic radical containing 1 to 32 carbon atoms, Z is selected from the amino groups -NR'- where R' represents a hydrogen atom or a monovalent saturated aliphatic radical containing 1 to 32 carbon atoms, n is a whole number from 2 to 4, and m is whole number from 1 to 4; characterized in that, in order that the additive exhibits a sufficient efficiency in the control of the sedimentation of paraffins, said compound with primary amine junction (b) is used in a proportion of 0.3 to 0.8 moles per mole of said dicarboxylic compound (a); and said reaction is carried out at a temperature of 120°C to 200°C, and continued until all the volatile products consisting of water and/or alcohol formed during the reaction have evolved.
  2. A composition according to claim 1 characterized in that the additive used results from the reaction of 0.4 to 0.7 mole of compound (b) per mole of compound (a).
  3. A composition according to anyone of claims 1 and 2 characterized in that the compound with primary amine junction (b) consists of at least one polyamine with formula :
    Figure imgb0016
    which corresponds to general formula (I) where Z represents the -NH- group, m is 1 to 4, n is 2 to 4, and R1 is a linear monovalent saturated aliphatic radical containing 12 to 32 carbon atoms.
  4. A composition according to anyone of claims 1 and 2 characterized in that the compound with primary amine junction (b) consists of at least one polyamine with formula :
    Figure imgb0017
    which corresponds to general formula (I) where R1-Z- represents the group -NR2R3 where R2 and R3, which may be identical or different, are each an alkyl radical containing 1 to 24 carbon atoms, n is 2 to 4 and m mis 1 to 4.
  5. A composition according to any one of claims 1 to 4, characterized in that the dicarboxylic compound (a) is selected from the group consisting of maleic anhydride, methylmaleic anhydride, n-octadecenyl succinic anhydride and dodecenyl succinic anhydride.
  6. A composition according to any one of claims 1 to 5, characterized in that the reaction is carried out in a hydrocarbon solvent with a boiling oint between 70°C and 250°C and comprises mixing said dicarboxylic compound (a) with said compound (b) with formula (I) at a temperature of 30°C to 80°C and heating the resulting mixture to a temperature of 120°C to 200°C for a period of 1 to 8 hours.
  7. A composition according to any one of claims 1 to 6, characterized in that the middle distillate is a gaz oil cut with a distillation range from an initial boiling point of 160°c to 190°C to a cut point of 350°C to 390°C.
  8. A composition according to any one of claims 1 to 7 characterized in that proportion of said additive is 20 to 2000 grams per ton of middle distillate.
  9. A method for limiting the sedimentation rate of the paraffins contained in a petroleum middle distillate containing paraffins and the distillation range of which (ASTM D 86-67) is between 150°C and 450°C, characterised in that it comprises introducing into said middle distillate a minor efficient proportion of at least one additive consisting of a product with an average molecular weight of about 300 to 10,000 resulting from the reaction of at least one aliphatic dicarboxylic compound (a) selected from maleic and alkylmaleic anhydrides, alkenyl succinic anhydrides containing 10 to 32 carbon atoms in the alkenyl radical and the corresponding dicarboxylic acids and lower alkyl diesters, and at least one compound with a primary amine junction (b) with general formula (I) :

            R1-Z[-(CH2)n-NH-]m H

    where R1 represents a monovalent saturated aliphatic radical containing 1 to 32 carbon atoms, Z is selected from the amino groups -NR'- where R' represents a hydrogen atom or a monovalent saturated aliphatic radical containing 1 to 32 carbon atoms, n is a whole number from 2 to 4, and m is whole number from 1 to 4; whereby said compound with primary amine is used in a proportion of 0.3 to 0.8 moles per mole of said dicarboxylic compound (a); and said reaction is carried out at a temperature of 120°C to 200°C, and continued until all the volatile products consisting of water and/or alcohol formed during the reaction have evolved.
  10. A composition according to claim 9, characterised in that the additive used is produced by reacting 0.4 to 0.7 mole of compound (b) per mole of compound (a).
EP94902004A 1992-12-17 1993-12-08 Middle petroleum distillate composition containing a paraffin settling speed limiter Expired - Lifetime EP0674689B1 (en)

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FR9215358A FR2699550B1 (en) 1992-12-17 1992-12-17 Composition of petroleum middle distillate containing nitrogenous additives usable as agents limiting the rate of sedimentation of paraffins.
PCT/FR1993/001212 WO1994013758A1 (en) 1992-12-17 1993-12-08 Middle petroleum distillate composition containing a paraffin settling speed limiter

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CA2146573C (en) 2006-06-06
ATE153053T1 (en) 1997-05-15
NO952393L (en) 1995-06-16
DK0674689T3 (en) 1997-07-28
JPH08507315A (en) 1996-08-06
DE69310766D1 (en) 1997-06-19
KR950704453A (en) 1995-11-20
NO309729B1 (en) 2001-03-19
DE69310766T2 (en) 1997-08-28
JP3650781B2 (en) 2005-05-25
ES2105607T3 (en) 1997-10-16
FR2699550A1 (en) 1994-06-24
GR3023626T3 (en) 1997-08-29
KR100287514B1 (en) 2001-05-02
CA2146573A1 (en) 1994-06-23
FR2699550B1 (en) 1995-01-27
NO952393D0 (en) 1995-06-16
EP0674689A1 (en) 1995-10-04

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