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 new nitrogen additives which can be used as agents for lowering the cloud point of hydrocarbon middle distillates (fuel oil, diesel fuels), as well as the middle distillate compositions containing said additives.
• the petroleum distillates concerned by the invention consist of middle distillates (fuel oils, diesel oils) whose distillation interval (standard ASTM D 86-67) is between 150 ° C and 450 ° C.
• This class of chemical compounds also has an effect on other properties of middle distillates (in particular gas oils), by modifying the behavior of the medium which contains the precipitated paraffins.
• the compounds recommended in the invention have a significant action on the limit filterability temperature and the flow temperature.
• the additives of the invention can be defined as products with an average molecular mass of approximately 300 to 10,000, resulting from the condensation of at least one compound comprising a primary amine function corresponding to one of the following general formulas (I) and (II): and on at least one dicarboxylic compound which will be defined later.
• R generally represents a monovalent saturated aliphatic radical, comprising from 1 to 30 carbon atoms;
• Z may, depending on the case, be an oxygen atom or represent a divalent group of the type - NR '-, R' may be either a hydrogen atom or a monovalent aliphatic radical;
• n is an integer from 2 to 4, and
• m can be zero or an integer from 1 to 4.
• the compounds of formula (I) above may consist of primary amines of formula NH 2 R l_ (in this case, in formula (I), Z represents the -NH- group, and the value of m is zero) .
• the radical R 1 is linear and contains from 12 to 30, and more particularly from 16 to 25 carbon atoms.
• these amines mention may be made of: dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine and docosylamine. Hexadecylamine and octadecylamine being preferred.
• the compounds of formula (I) can also consist of polyamines derived from saturated aliphatic amines corresponding to the formula: which corresponds to the general formula (I) in which Z represents the group -NH-; m can have a value of 1 to 4 and n a value of 2 to 4, preferably 3.
• the radical R 1 is linear and contains from 12 to 30 and more particularly from 16 to 25 carbon atoms.
• N-dodecyl diamino-1,3 propane N-tetradecyl diamino-1,3 propane, N-hexa- dec y l diamino-1,3 propane, N-octadecyl diamino -1.3 propane, N-eicosyl diamino-1,3 propane, N-docosyl diamino-1,3 propane, N-hexadecyldipropylene triamine, N-octadecyl dipropylene triamine, N-eicosyldipropylene triamine and N- docosyldipropylene triamine.
• N-docosyl-, N-eicosyl-, N-octadecyl-, N-hexadecyl- or N-dodecyl-diamino 1,3 propane, as well as N-hexadecyl- and N-octadecyl are used.
• the compounds of formula (I) can also consist of polyamines corresponding to the formula: where R 2 and R 3 , identical or different, are each an alkyl radical having from 1 to 24 and preferably from 8 to 22 carbon atoms, R 2 and R 3 containing together the two preferably from 16 to 32 carbon atoms ; n has a value of 2 to 4 and m a value of 1 to 4.
• the compounds of formula (I) considered in the invention can consist of ether-amines corresponding more particularly to the formula: which corresponds to the general formula (I) in which Z is an oxygen atom; preferably, the radical R 4 is linear and contains from 12 to 24 carbon atoms, m is an integer from 1 to 4 and n is an integer from 1 to 4, preferably 2 or 3.
• ether-amines which may be mentioned as specific compounds: 2-methoxy-ethylamine, 3-methoxy-propylamine, 4-methoxy-butylamine, 3-ethylpropylamine, 3-octyloxy-propylamine, 3-decyloxy-propylamine , 3-hexadecyloxy-propylamine, 3-eicosyloxy-propylamine, 3-docosyloxy-propylamine, N- (3-octyloxy-propyl) diamino-1,3 propane, N- (3-decyloxy-propyl) diamino-1, 3 propane, (2,4,6,4-trimethyl decyl) oxy-3 propylamine and N - [(2,4,6,6-trimethyl decyl) oxy-3 propyl diamino-1,3 propane.
• the compound with a primary amine function involved in the preparation of the additives of the invention may also consist of an amino alcohol of formula (II): where R 5 represents a divalent saturated aliphatic radical, linear or branched, preferably linear, containing from 1 to 18 and preferably from 10 to 18 carbon atoms.
• the dicarboxylic compounds on which the condensation of a compound of formula (1) or of a compound of formula (II) as described above is carried out are more particularly chosen from anhydrides of a, ⁇ - aliphatic dicarboxylic acids and preferably unsaturated, such as for example maleic anhydride, alkylmaleic anhydrides, for example methylmaleic anhydride (or citraconic) or also among alkenyl succinic anhydrides, for example those obtained by the action of at least one olefin-a preferably linear (for example having 10 to 30 carbon atoms) on maleic anhydride. Mention may be made more specifically of n-octadecenyl succinic anhydride or dodecenyl succinic anhydride. It is of course possible to use mixtures of two (or more) of these compounds.
• polyalkenyl succinic anhydrides such as for example polyisobutenyl succinic anhydrides, whose molecular mass is between 500 and 2000 and, preferably, between 1000 and 1700. Preparation of this type anhydride is well known in the prior art.
• the primary amine-functional compounds of formulas (I) and (II) are usually used in an amount of 1.02 to 1.2 moles, preferably 1.05 to 1.1 moles, per mole of dicarboxylic compound. It is also possible to bring into play a slight defect in the compound with primary amine function (I) or (II), up to 0.9 mole per mole of dicarboxylic compound. The proportion is therefore, in general, from 0.9 to 1.2 mole / mole.
• dicarboxylic compounds e.g. acid dicarboxyli q ues, ester or preferably anhydrides
• condensation of compounds of formula (I) and / or (II), dicarboxylic compounds can be performed without solvent, but preferably used a more consistent solvent particularly in an aromatic or naphtheno-aromatic hydrocarbon with a boiling point of between 70 ° and 250 ° C for example: toluene, xylenes, diisopropylbenzene or even an petroleum fraction having the appropriate distillation range.
• the reaction time, after addition of the reactants is for example between 1 and 8 hours and preferably between 3 and 6 hours.
• the additives considered in the invention are particularly advantageous for improving the cloud point of petroleum middle distillates (in particular diesel fuels), that is to say for reducing the temperature of appearance of the first crystals of n-paraffins contained in them. this.
• the additives considered in the invention which are effective in improving the cloud point of middle distillates have, on the other hand, the property of inhibiting the sedimentation of n-paraffins in middle distillates. at rest, to improve the limit filterability temperature and the flow temperature and to inhibit corrosion of the metal surfaces in contact with these distillates.
• the concentration range of the additive from 20 g to 2000 g per tonne, it is possible to observe a lowering of the filterability temperature which can go for example up to 12 ° C., a lowering of the pour point of up to 20 ° C, a reduction in the proportion of sedimented paraffins and a marked anticorrosion effect observed in particular on ferrous metals.
• middle distillate compositions of the invention it is possible to add the additives directly to the middle distillate by a simple mixing operation.
• the “mother solutions” can contain, for example, from 20 to 60% by weight of additives.
• Additive I was analyzed after evaporation of the solvent. Its number molecular mass, measured by tonometry, is 1800. The infrared spectrum in thin layer shows the existence of bands imides at 1700 and 1780 cm -1 , secondary amide at 1635 and 1560 cm -1 and secondary amine at 3300 cm -1 .
• Additives II to VII have the same bands as Additive I. Their molecular weights are between 1500 and 3000.
• additives are used, at a rate of 0.1% by weight in the same two gas oils as above, which differ essentially from each other in the nature of the starting dicarboxylic compound.
• the additive used is additive I already used previously.
• test pieces are hermetically sealed, then left to stand in a cold room at -10 ° C for one week.
• Paraffins are in 85% of the total volume. They are better dispersed and easier to transport.
• the TLFs are determined according to standard NF M 07 - 042
• Product I was used in the two gas oils No. 1 and No. 2 already described above, at a concentration of 0.01% by weight.
• the two non-additive diesel no. 1 and no. 2 give rusty test pieces at 100% of their surface and the two gas oils containing 0.01% by weight of additive give intact test pieces with 0% rust.
• a solution consisting of 294 g (3 moles) of maleic anhydride dissolved in 500 g of xylene is introduced into a 3 1 reactor, fitted with a Dean and Stark water separation system and good stirring. . Keeping the temperature of this solution between 30 and 40 ° C, there is added, in 1.5 h, a solution obtained from 1230 g (3 moles) of N, N-didodecyldiamino 1.3 propane and 1000 g xylene. The whole is heated for 3 hours at the reflux of xylene, time during which 55 g of water are collected evacuated from the reaction medium. The reaction product constitutes additive VIII which is in solution in xylene at a concentration very close to 50% by weight.
• the condensation product constitutes additive IX, the concentration of which in xylene is adjusted to obtain a value of 50% by weight.
• a polyisobutenyl succinic anhydride with a mass close to 1200 is used, having 0.90 anhydride function per 1000 g.
• 1200 g (1 mole) of this polyisobutenyl succinic anhydride is condensed on a mixture of products consisting of 289 g (0.5 mole) of N, N-dioctadecyldiamino-1,3 propane and 40.8 g / 0.4 mol) of N, N-dimethyldiamino-1,3 propane dissolved in xylene.
• the reaction product constitutes additive X, its weight concentration in xylene is adjusted to 50% by weight.
• the additive XIa was analyzed after evaporation of the solvent. Its number molecular mass, measured by tonometry, is 500. The infrared spectrum in thin layer shows the existence of imide bands at 1700 and 1780 cm -1 , secondary amide at 1635 and 1560 cm -1 and ether at 1100 cm -1 .
• Additives XII to XVI have the same infrared absorption bands as those of additive XI, their molecular weights are between 600 and 3000.
• Example 12 the same preparation method is used as that described in Example 12, while maintaining similar molar ratios, but using different amino compounds.
• Example 12 These examples are carried out according to the procedure described in Example 12, while maintaining molar ratios between the reactants identical to that given in Example 12.
• Condensation is carried out (trimethyl-2,4-6 decyl) oxy-3 propylamine on a polyisobutenyl succinic anhydride of mass approximately 1000, having 0.675 anhydrous function per 1000 g, which provides the additive XIV.
• the alkenyl succinic anhydride used in Example 16 is condensed, ethanolamine, using a mol / del ratio between ethanolamine and the anhydride content of the alkenyl succinic anhydride used. This gives additive XVI.
• the additives are obtained in solution in xylene, the amount of which is adjusted so as to obtain solutions of additives at 50% by weight in xylene.
• 0.1% by weight of the additive XI is introduced into the second test piece.
• the two test pieces are hermetically sealed and then left to stand in a cold room at -10 ° C for one week.
• Paraffins are in 85% of the total volume. They are better dispersed and easier to transport.
• the product XIa was used in the two gas oils G 1 and G 2 already described previously at a concentration of 0.01% by weight.
• the corrosion test consists of studying corrosion by synthetic seawater, of cylindrical steel or polished iron specimens, according to standard ASTM D 665 modified as follows: the temperature is 32.2 ° C. and the duration of 20 hours.
• the two non-additive G 1 and G 2 gas oils give rusty test pieces at 100% of their surface and the two gas oils containing 0.01% by weight of additive give intact test pieces with 0% rust.

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

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Cited By (23)

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Citations (19)

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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/de 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 FI FI822674A patent/FI75361C/fi not_active IP Right Cessation
  • 1982-07-30 CA CA000408447A patent/CA1192519A/fr not_active Expired
  • 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

Patent Citations (19)

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