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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Lubricants (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Polyesters Or Polycarbonates (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 1981
  • 1981-07-30 FR FR8114870A patent/FR2510598A1/fr active Granted
• 1982
  • 1982-07-16 DE DE8282401335T patent/DE3274368D1/de not_active Expired
  • 1982-07-16 EP EP82401335A patent/EP0071513B1/fr not_active Expired
  • 1982-07-28 NO NO822591A patent/NO158142C/no not_active IP Right Cessation
  • 1982-07-28 DK DK337682A patent/DK158993C/da not_active IP Right Cessation
  • 1982-07-30 CA CA000408447A patent/CA1192519A/fr not_active Expired
  • 1982-07-30 FI FI822674A patent/FI75361C/fi not_active IP Right Cessation
  • 1982-07-30 JP JP57134636A patent/JPS58108297A/ja active Granted
• 1985
  • 1985-05-23 US US06/737,133 patent/US4652273A/en not_active Expired - Lifetime

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