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
  • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
• • 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
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups

Definitions

• the invention relates to the combined use of additives having synergistic properties on the cold filterability of middle petroleum distillates, in particular diesel fuels. It also relates to the compositions of petroleum middle distillates comprising these combinations of additives.
• branched polyethylene in middle distillates does not make it possible to obtain satisfactory properties of cold filterability; the same applies to various copolymers based on ethylene and another co-monomer such as, for example, vinyl acetate, olefins-a, esters or diesters having an olefinic double bond.
• French patent FR 2 347 435 describes the synergistic action of an alkyl-aromatic derivative associated either with a hydrogenated 1,4-polybutadiene or with a hydrogenated copolymer of 1,4-butadiene and a second dialkene compound.
• US Patent 2,917,375 describes the synergistic properties of microcrystalline paraffin waxes mixed with acrylic and / or methacrylic polymers.
• US Patent 4,140,492 cites the synergistic action of two compounds: the first results from the action of boron compounds on Mannich bases of phenolic compounds, the second can be an amorphous hydrocarbon or a hydrogenated polybutadiene.
• compositions in which one of the constituents is an ethylene copolymer.
• US Patent 3,640,691 associates a paraffinic minor fraction, containing n-paraffins of 24 to 40 carbon atoms, with ethylene / vinyl acetate copolymers.
• French patent FR 2 061 457 combines two copolymers, of different molecular weights, based on ethylene and vinyl acetate.
• Japanese patent JP 57 209 995 describes a synergistic action between a residual heavy oil and a copolymer of ethylene and of carboxylic acid ester having ethylenic bonds.
• European patent EP 074 208 describes a synergistic action on the limit temperature of filterability of fuel oils between, on the one hand, a copolymer of ethylene and alkoxy-alkyl (meth) acrylate and, on the other hand , an ethylene copolymer associated either with a vinyl ester or with an alkyl ester of an unsaturated acid.
• compositions in which one of the constituents is polyethylene.
• US Pat. No. 3,640,824 associates a highly branched polyethylene of molecular mass in number greater than 6,000 with a microcrystalline wax, and / or with naphthalene, and / or with asphaltenes.
• US Patent 3,166,387 describes the synergistic action of low molecular weight polyethylene associated with a secondary or tertiary amine salt of carboxylic acid.
• additives added to diesel fuel cuts, for example at concentrations of the order of 0.1% by weight, have shown a favorable action, mainly on the cloud point thereof, but also on their limiting temperature. filterability, as well as their flow temperature.
• middle petroleum distillates having, according to the distillation standard ASTM-D-1160, ranges of initial temperatures from 160 to 235 ° C and final temperatures from 355 to 440 ° C, (reduced to atmospheric pressure) by the use of certain combinations of products which will be described below.
• the constituent (B) more particularly has a number average molecular weight of 1,000 to 10,000.
• the copolymers considered for the formation of component (B) more particularly comprise a proportion of 15 to 40 mol% of units derived from olefins -a from 20 to 70 mol% of units derived from compound a, p-dicarboxytic unsaturated and from 15 to 40 mol% of units derived from an alkyl ester of unsaturated monocarboxylic acid.
• the linear olefins-a used in the composition of the polymers contain for example from 16 to 30 carbon atoms.
• mixtures of linear a-olefins of 20 to 24 carbon atoms, of 24 to 28 carbon atoms are used, or alternatively sections containing approximately 20% by weight of ⁇ -olefins of at most 28 carbon atoms and about 80% by weight of olefins-a of 30 carbon atoms or more.
• the unsaturated a, p-dicarboxytic compounds used in the composition of the copolymer are more particularly dicarboxylic acids such as maleic acid, or alkylmaleic acids, for example methylmaleic (or citraconic) acid.
• These compounds can also consist of alkyl diesters of these dicarboxylic acids, in particular methyl, ethyl or propylic diesters, or alternatively of the anhydrides corresponding to these dicarboxylic acids.
• Anhydrides will be preferred, and more particularly maleic anhydride.
• the alkyl esters of unsaturated monocarboxylic acids are more particularly the acrylates and alkyl methacrylates of 4 to 30 carbon atoms, for example butyl, ethylhexyl, decyl, dodecyl, hexadecyl acrylates, octadecyl and eicosyl. Mention may also be made of the acrylates and methacrylates of industrial alcohol fractions containing on average 12 carbon atoms (lauryl acrylate and methacrylate) or 18 carbon atoms (stearyl acrylate and methacrylate), as well as more alcohol fractions heavy, rich in alcohols having 20 or 22 carbon atoms.
• the vinyl esters of saturated aliphatic monocarboxylic acids are more particularly vinyl esters of monocarboxylic acids of 2 to 22 carbon atoms.
• the compound with a primary amine function which is condensed with the copolymers described above to form the constituent (B) of the additive compositions of the invention can correspond to one of the following two general formulas:
• R 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 -NH- or -NR'-, R 'being a monovalent aliphatic radical, preferably linear, comprising from 1 to 30 carbon atoms and preferably of 12 to 24 carbon atoms, n is an integer from 2 to 4, and m can have the value zero, when Z is NH, or be an integer from 1 to 4, in all cases.
• the compounds of formula (I) above can consist of primary amines of formula R-NH 2 (in this case, in formula (I), Z represents the group -NH-, and the value of m is zero) .
• the radical R is linear and contains from 12 to 24 carbon atoms.
• these amines mention may be made of: dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine and docosylamine.
• 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 is linear and contains from 12 to 24 carbon atoms.
• the compounds of formula (I) can also consist of polyamines corresponding to the formula: corresponding to the general formula (I) where Z represents -N R'- and where R and R ', identical or different, are each an alkyl radical having from 1 to 24 and preferably from 8 to 24 carbon atoms, R and R 'containing both of them preferably from 16 to 32 carbon atoms; n has a value of 2 to 4 and m a value of 1 to 4.
• N, N-diethyl-1,2-diamino ethane N, N-diisopropyldiamino-1,2 ethane, N, N-dibutyl diamino-1,2 ethane, N, N- 1,4-diethyl-diamino 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-didodécyldiamino-1,3 propane, N, N-dissetradécyl-diamino-1,3 propane, N, N-dihexadécyldiamino-1,3 ' propane, N, N-dioctadecyl
• the compounds of formula (I) 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 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, (trimethyl-2,4,6 decyl) oxy-3 propylamine and N - [(trimethyl-2,4,6 decyl) oxy-3 propyl] diamino-1,3 propane.
• the compound with a primary amine function involved in the preparation of component B of the additive compositions of the invention may also consist of an amino alcohol of formula (II): where R "represents a divalent saturated, linear or branched, preferably linear, preferably linear aliphatic radical containing from 1 to 18 carbon atoms.
• the preparation of the constituents (B) of the additive compositions of the invention is generally carried out in two stages: first the terpolymers are prepared, then the condensation of the compound of formula (I) is carried out thereon and / or (II).
• the terpolymers can be prepared, in the first step, according to conventional radical polymerization methods, for example in the presence of an initiator of the azobisisobutyronitrile or peroxide type, in solution in a hydrocarbon solvent, such as for example cyclohexane, 'isooctane, dodecane, benzene, toluene, xylene, or diisopropylbenzene or even tetrahydrofuran or dioxane.
• a hydrocarbon solvent such as for example cyclohexane, 'isooctane, dodecane, benzene, toluene, xylene, or diisopropylbenzene or even tetrahydrofuran or dioxane.
• relatively high boiling hydrocarbon fractions such as kerosene or diesel
• the amount of solvent used will generally be such that the concentration by weight of dry matter is between 25 and 70% and preferably in the vicinity of 60%.
• the copolymerization reaction in the presence of the radical initiator, is carried out at a temperature of 70 to 200 ° C and preferably from 80 to 130 ° C. Depending on the operating conditions, the duration of the reaction can range from 2 to 14 hours.
• a solution of copolymers is obtained in the form of a viscous liquid of light yellow color.
• the compound of formula (I) or (II) is condensed on the copolymer formed in the first step, according to any usual method.
• the compound of formula (I) or (II) is generally added in a molar proportion corresponding substantially to the proportion of diacid, of diester, or of unsaturated anhydride brought into play in the preparation of the copolymer.
• This proportion can be for example from 0.9 to 1.1 mole of compound (I) or (II) per mole of dicarboxylic compound. It is also possible to provide for a greater defect in the compound of formula (I) or (II). It is then possible to use a proportion as low as, for example, 0.5 mole per mole of dicarboxylic compound used in the copolymer.
• the reaction is carried out by heating the mixture to a temperature of between 75 and 130 ° C, preferably between 80 and 100 ° C, the duration of the reaction being between approximately 1 and 6 hours, a duration of the order of 2 hours is generally sufficient.
• the reaction of the products of formula (I) or (II) on the units (b) of the copolymer gives rise to imide groups (succinimides), this reaction being accompanied by the formation of water or alcohol depending on the nature of the functions dicarboxylates of (b) (diacid, anhydride or diester). It is possible, if desired, to remove the volatile products formed from the reaction mixture, either by entrainment with an inert gas such as nitrogen, or by azeotropic distillation with the chosen solvent.
• an inert gas such as nitrogen
• Another particular mode of synthesis of the constituents (B) of the additive compositions considered in the invention may consist, in certain cases, in carrying out the radical copolymerization of one or more alkyl esters of unsaturated monocarboxylic acids with a mixture olefins-a and N-substituted maleimides, the latter being obtained by prior reaction of the compounds of formula (I) or (II) with maleic anhydride or one of its abovementioned derivatives.
• the additive compositions of the invention comprising at least one component (A) and at least one component (B) as defined above, are used in particular to improve the cold filterability properties of middle distillates of petroleum with respect to which each of the constituents (A) and (B) used in isolation has only a very reduced effect. It therefore seems that each of the constituents (A) and (B) exerts on the properties of the other a synergistic action, the mechanism of which has not been clearly elucidated.
• this action manifests itself appreciably when the ratio between the weight quantities of the constituents (A) and (B) is between 1/20 and 20/1 and, preferably, from 1/5 to 5/1.
• the combinations of additives (A) and (B) are generally added to these gas oil cuts at overall weight concentrations, between 20 and 2,000 ppm, and more particularly between 50 and 500 ppm.
• To formulate the diesel fuel compositions of the invention it is possible to add the constituents (A) and (B) directly to the diesel fuel by a simple mixing operation.
• the solvent (s) can consist, for example, of solvents of aromatic character, such as for example toluene, xylenes, di-isopropylbenzene, an petroleum fraction of aromatic character having the desired distillation range.
• the “mother solutions” can contain, for example, from 20 to 60% by weight of additives.
• the additive compositions of the invention which are effective in contrast to the conventional additives in enlarged cuts, that is to say those having for example a distillation range of 160 - 370 ° C and more, on the one hand are always so if they are used in a "narrow" cut whose distillation range is for example 225 ° C - 360 ° C and more, that is to say an enlarged cut which has suppressed the light fraction (kerosene), on the other hand simultaneously inhibit the sedimentation of n- paraffins in gas oils doped at rest, although the n-paraffins are constituted by the heaviest n-paraffins of the distillable fraction of the crude.
• compositions of the invention therefore make it possible to considerably improve the cold filterability properties of middle petroleum distillates, thus making it possible to use as gas oils and fuels cuts of distillates with a higher boiling end point, which represents a obvious economic interest.
• gas oil cuts used are those which appear in Table I; they are characterized according to the distillation ASTM-D-1160; their density is also indicated in table I. One of them is a narrow section, another is an enlarged section; the others are intermediate cuts. They are designated by G1, ... G6.
• concentrations of components (A) and (B) of the additives are expressed in weight proportions of pure products, expressed in parts per million (ppm), it being understood that the compositions can be used in the diluted state.
• TLF filterability limit temperature
• a condensation product of a terpolymer and a fatty amine was used, which will be called B 1 .
• the number average molecular weight of the terpolymer is 2470.
• Fat amine is a cut of primary imines whose alkyl chains contain in approximate molar proportions: 1% of C 14 , 28% of C 16 and 71% of C 18 . It is used at the rate of 1 molar equivalent.
• the amine is condensed on the terpolymer by heating at 90 ° C for two hours.
• the filterability limit temperature of each of the diesel fuel cuts without additives or additives was determined as indicated in Table II below (The TLFs are in ° C).
• the overall concentration of additives A 1 + B 1 is 100 ppm in diesel.
• Table III gives the results of the TLF determinations for the various tests; The values obtained for the G 4 diesel cut in example 1 are also given in this table (tests 1a, 1b, 1d, 1e).
• the gas oil G 1 described in table I is used.
• the overall additive concentration is varied; Table IV shows the results obtained for the TLF.
• Additives 1 and 2 correspond to conventional commercial additives.
• Additive 3 corresponds to the composition of the additive of the invention, as described in Example 3.
• test pieces are hermetically sealed and then left to stand in a cold room at -10 ° C for one week.
• Table VII indicates the compositions chosen for the constituents (B).
• the terpolymer is formed by a molar equivalent of each of the three unsaturated compounds: olefins-a, maleic anhydride, ester of unsaturated acid. On this terpolymer is condensed a molar equivalent of the compound with primary amine function.

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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)
• Compositions Of Macromolecular Compounds (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Lubricants (AREA)

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• 1984
  • 1984-07-10 FR FR8410979A patent/FR2567536B1/fr not_active Expired
• 1985
  • 1985-06-28 AT AT85401312T patent/ATE31424T1/de not_active IP Right Cessation
  • 1985-06-28 CA CA000485848A patent/CA1262406A/fr not_active Expired
  • 1985-06-28 DE DE8585401312T patent/DE3561206D1/de not_active Expired
  • 1985-06-28 EP EP85401312A patent/EP0172758B1/fr not_active Expired
  • 1985-07-08 NO NO852742A patent/NO852742L/no unknown
  • 1985-07-08 DK DK311685A patent/DK311685A/da not_active Application Discontinuation
  • 1985-07-10 JP JP15334485A patent/JPS6136397A/ja active Granted
  • 1985-07-10 US US06/753,507 patent/US4664676A/en not_active Expired - Fee Related
  • 1985-07-10 IN IN524/MAS/85A patent/IN165554B/en unknown

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