EP0485773B1 - Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées - Google Patents

Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées Download PDF

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EP0485773B1
EP0485773B1 EP91118116A EP91118116A EP0485773B1 EP 0485773 B1 EP0485773 B1 EP 0485773B1 EP 91118116 A EP91118116 A EP 91118116A EP 91118116 A EP91118116 A EP 91118116A EP 0485773 B1 EP0485773 B1 EP 0485773B1
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Prior art keywords
copolymers
alkyl
mol
meth
copolymer
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German (de)
English (en)
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EP0485773A1 (fr
Inventor
Gerd Dr. Konrad
Bernd Dr. Wenderoth
Klaus Dr. Barthold
Erich Dr. Schwartz
Hans-Juergen Raubenheimer
Heinrich Dr. Hartmann
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BASF SE
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BASF SE
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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
    • C10L1/234—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
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular 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
    • C10L1/1973—Macromolecular 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 present invention relates to petroleum middle distillates which contain small amounts of a conventional flow improver based on ethylene and copolymers of ethylenically unsaturated carboxylic acid esters of long-chain n-alkanols and ethylenically unsaturated dicarboxylic acid derivatives and which are characterized by improved flow properties in the cold.
  • Middle distillates such as gas oils, diesel oils or heating oils, which are obtained from petroleum by distillation, have different paraffin contents depending on the origin of the crude oil and the processing method in the refinery.
  • the proportion of long-chain n-paraffins in particular determines the cold flow behavior of such distillates.
  • the n-paraffins Upon cooling, the n-paraffins separate out as platelet-shaped, interlocking crystals that build up a three-dimensional network (house of cards structure), in which large quantities of still liquid distillate are enclosed and immobilized.
  • the crystallization of the n-paraffins is parallel to a decrease in fluidity and an increase in viscosity. This makes it difficult to supply middle distillates to the combustion units, the failed paraffins clog upstream filters, so that in extreme cases the supply can completely stop.
  • ethylene copolymers especially copolymers of ethylene and unsaturated esters, such as those e.g. are described in DE-A 21 02 469 or EP-A 84 148.
  • DE-A 16 45 785 discloses the use of polymers with unbranched, saturated side chains with at least 18 carbon atoms to lower the pour point of heating oil containing wax.
  • DE-A 25 31 234 recommends the addition of alternating copolymers containing maleic acid diamide or maleimide structures as stabilizers in mineral oils, i.e. the carboxyl groups are completely reacted with amines to give the diamides or imides.
  • reaction products of monoamines with maleic anhydride polymers to the corresponding imides are also described, wherein when using less than one mole of amine per mole of maleic anhydride unit, remaining carboxyl groups are converted into metal salts by neutralization.
  • alkyl vinyl ether and monovinyl hydrocarbons are preferably used.
  • FR-A2 592 658 describes mixtures of an ethylene polymer and a reaction product of a primary amine with a copolymer of e.g. Acrylic acid alkyl esters, diisobutene and maleic anhydride and their use as an additive to middle distillates.
  • EP-A 283 293 discloses the use of polymers with at least one amide group from a secondary amine and a carboxyl group as an additive to middle distillates.
  • the polymers can include by copolymerization of unsaturated esters with maleic anhydride and subsequent reaction with the secondary amine.
  • the unsaturated ester monomers include Dialkyl fumarates and vinyl acetate are described.
  • the copolymers B consist of 10 to 95 mol%, preferably 40 to 95 mol% and particularly preferably 60 to 90 mol-1% of alkyl (meth) acrylates and 5 to 90 mol%, preferably 5 to 60 mol% and particularly preferably 10 to 40 mol% from the olefinically unsaturated dicarboxylic acid derivatives.
  • the weight ratio of flow improver A to copolymer B is between 40:60 and 95: 5, preferably between 60:40 and 95: 5 and particularly preferably between 70:30 and 90:10.
  • alkyl groups of the alkyl (meth) acrylates consist of 1 to 26, preferably 4 to 22 and particularly preferably 8 to 18 carbon atoms. They are preferably straight-chain and unbranched. However, up to 20% by weight of cyclic and / or branched portions can also be present.
  • alkyl (meth) acrylates examples include n-octyl (meth) acrylate, n-decyl (meth) arylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate and n-octadecyl (meth) acrylate and mixtures thereof.
  • ethylenically unsaturated dicarboxylic acids are maleic acid, tetrahydrophthalic acid, citraconic acid and itaconic acid or their anhydrides and fumaric acid.
  • Maleic anhydride is preferred.
  • R 1 is a straight-chain or branched alkyl radical having 1 to 30, preferably 8 to 26 and particularly preferably 16 to 24 carbon atoms and R 1 is hydrogen or C 1 - to Cao-alkyl, preferably hydrogen or C 8 - to C 26 Alkyl and particularly preferably hydrogen or C 16 to C 24 alkyl, where R 1 and R 2 together can also form a 5 to 6-membered ring which optionally contains a heteroatom from the group consisting of oxygen, nitrogen and sulfur.
  • morpholine piperidine, 2-ethylhexylamine, n-octadecylamine, oleylamine, tallow fatty amine, N-methyloctadecylamine and preferably behenylamine, dibehenylamine and hydrogenated ditallow fatty amine may be mentioned.
  • Examples of flow improvers A are the polymers already mentioned, described in DE-A 21 02 469 and EP-A 84 148, such as copolymers of ethylene with vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate or with esters of (meth) acrylic acid, which can be derived from alkanols with 1 to 12 carbon atoms.
  • Mixtures of several copolymers of ethylene and vinyl acetate (EP-A 261 951, additive A), copolymers of ethylene with ⁇ -olefins (EP-A261 957, additive D) and the mixtures specified in DE-A 36 24 147 are also suitable Terpolymers of ethylene, vinyl acetate and diisobutene with oxidized polyethylene wax. Copolymers of ethylene with vinyl acetate or vinyl propionate or ethylhexyl acrylate are particularly preferred.
  • the alkyl (meth) acrylates are easily accessible. They can be obtained by the known esterification processes. For example, a solution of (meth) acrylic acid and an alkanol or a mixture of different alkanols is heated in an organic solvent with the addition of the usual polymerization inhibitors, e.g. Hydroquinone derivatives and esterification catalysts such as sulfuric acid, p-toluenesulfonic acid or acidic ion exchangers at the boil and remove the water of reaction formed by azeotropic distillation.
  • the esterification products can usually be used unpurified for the polymerization. If a purer ester is required, this can be obtained by washing the ester solution with alkaline agents and water and by distillation.
  • alkyl (meth) acrylates are the reaction of (meth) acrylic acid chloride or anhydride with the corresponding alkanols and the reaction of lower (meth) acrylic acid esters known as transesterification with the corresponding C 8 to C ls alkanols with addition acidic or basic catalysts and distillative removal of the lower alkanol.
  • the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, for example maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride, since the anhydrides generally copolymerize better with the (meth) acrylates.
  • the anhydride groups of the copolymers can then be reacted directly with the amines.
  • the reaction of the polymers with the amines takes place at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours.
  • the amine is in amounts of about one to two moles per mole of polymerized dicarboxylic anhydride, i.e. about 0.9 to 2.1 mol / mol applied. The use of larger or smaller amounts is possible, but has no advantage. If more than two moles are used, free amine is present. If amounts less than one mole are used, there is no complete conversion to the monoamide and a correspondingly reduced effect is obtained.
  • the amide / ammonium salt structure is built up from two different amines.
  • a copolymer of lauryl acrylate and maleic anhydride can first be reacted with a secondary amine such as hydrogenated ditallow fatty amine to give the amide, after which the free carboxyl group derived from the anhydride can be reacted with another amine, e.g. 2-ethylhexylamine is neutralized to the ammonium salt.
  • a secondary amine such as hydrogenated ditallow fatty amine
  • another amine e.g. 2-ethylhexylamine is neutralized to the ammonium salt.
  • the reverse procedure is also conceivable: First the reaction with ethylhexylamine to form the monoamide, then with ditallow fatty amine to the ammonium salt.
  • At least one amine is preferably used which has at least one straight-chain, unbranched alkyl group with more than 16 carbon atoms. It is immaterial whether this amine is present in the structure of the amide structure or as the ammonium salt of dicarboxylic acid.
  • the copolymers B are prepared by known batch or continuous polymerization processes such as bulk, suspension, precipitation or solution polymerization and initiation with customary radical donors such as acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxidicylate, 2,2'-dodecarboxylate, tert.
  • customary radical donors such as acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxidicylate, 2,2'-dodecarboxylate, tert.
  • -Azobis (4-methoxy-2,4-dimethylvaleronitrile), tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permaleinate, 2,2'-azobis (isobutyronitrile), bis- ( tert-butyl peroxide) cyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl peracetate, dicumyl peroxide, di-tert-amyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide and mixtures with one another.
  • these initiators are used in amounts of 0.1 to 20% by weight, preferably 0.2 to 15% by weight, based on the monomers.
  • the polymerization is generally carried out at temperatures of 40 to 400 ° C, preferably 70 to 300 ° C, with the use of solvents with boiling temperatures below the polymerization temperature is advantageously carried out under pressure.
  • the polymerization is conveniently carried out in the absence of air, i.e. if it is not possible to work under boiling conditions, e.g. performed under nitrogen or carbon dioxide, since oxygen delays the polymerization.
  • the reaction can be accelerated by using redox coinitiators such as benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, manganese, iron, nickel and chromium.
  • the amounts usually used are 0.1 to 2000 ppm by weight, preferably 0.1 to 1000 ppm by weight.
  • regulators are, for example, allyl alcohols, such as but-1-en-3-ol, organic mercapto compounds, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan, which are generally used in amounts of 0.1 to 10 wt .-%.
  • allyl alcohols such as but-1-en-3-ol
  • organic mercapto compounds such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n
  • Equipment suitable for the polymerization is e.g. Conventional stirred kettles with, for example, anchor, blade, impeller or multi-stage impulse countercurrent stirrers and for the continuous production of stirred kettle cascades, tubular reactors and static mixers.
  • the simplest method of polymerization is bulk polymerization.
  • the monomers are polymerized in the presence of an initiator and in the absence of solvents.
  • all monomers are mixed in the desired composition and a small part, e.g. about 5 to 10%, in the reactor before, heated to the desired polymerization temperature with stirring and metered in the remaining monomer mixture and the initiator and optionally coinitiator and regulator evenly within 1 to 10 hours, preferably 2 to 5 hours. It is expedient to meter in the initiator and the coinitiator separately in the form of solutions in a small amount of a suitable solvent.
  • the copolymer can then be converted directly into the melt or after being taken up in a suitable solvent to the flow improver according to the invention.
  • a continuous high-pressure process which permits space-time yields of 1 to 50 kg of polymer per liter of reactor and hour is also suitable for producing the desired copolymers.
  • Polymerisa tion apparatus for example, a pressure vessel, a pressure vessel cascade, a pressure tube or a pressure vessel with a downstream reaction tube, which is provided with a static mixer, can be used.
  • the monomers of (meth) acrylic acid esters and unsaturated dicarboxylic acids or their anhydrides are preferably polymerized in at least two polymerization zones connected in series.
  • One reaction zone can consist of a pressure-tight vessel, the other of a heatable static mixer. You get sales of more than 99%.
  • a copolymer of (meth) acrylic acid esters and maleic anhydride can be prepared, for example, by continuously feeding the monomers and a suitable initiator to a reactor or two reaction zones connected in series, for example a reactor cascade, and the reaction product after a residence time of from 2 to 60, preferably from 5 to 30 minutes, continuously discharged from the reaction zone at temperatures between 200 and 400 ° C.
  • the polymerization is expediently carried out at pressures of more than 1 bar, preferably between 1 and 200 bar.
  • the copolymers obtained have solids contents of over 99% and can then be further converted to the corresponding amides or amide / ammonium salts.
  • copolymers B Another simple method for producing the copolymers B is solution polymerization. It is carried out in solvents in which the monomers and the copolymers formed are soluble. All solvents that meet this requirement and that do not react with the monomers are suitable for this. For example, these are toluene, xylene, ethylbenzene, cumene, high-boiling aromatic mixtures such as Solvesso® 100, 150 and 200, aliphatic and cycloaliphatic hydrocarbons such as e.g.
  • n-Hexane cyclohexane, methylcyclohexane, n-octane, iso-octane, paraffin oils, Shellsol® TD, T and Ksie as well as tetrahydrofuran and dioxane, tetrahydrofuran and dioxane being particularly suitable for achieving low molecular weight copolymers.
  • solvent and part of the monomer mixture e.g. about 5 to 20%
  • the monomers can also be metered in individually at different rates.
  • the concentrations of the monomers to be polymerized are between 10 and 80% by weight, preferably 30 and 70% by weight.
  • the solid copolymer can easily be obtained by evaporating the solvent.
  • Solution polymerization is the preferred form of preparation for the copolymers of (meth) acrylates and dicarboxylic acid (anhydrides).
  • polymers A and B should be present together in the form of a concentrate, since the use of 2 concentrates - one each for polymer A and polymer B - makes handling more difficult. Due to the possible incompatibility of the polymers A and B, phase separation can occur when the two polymers are mixed in a common solvent. This can optionally be suppressed by suitable solvents and / or additives. Suitable are e.g.
  • Alkanols such as iso-butanol, n-hexanol, 2-ethylhexanol, iso-decanol and their adducts with ethylene oxide, propylene oxide and / or butylene oxide as well as half esters or diesters of dicarboxylic acids with alkanols or (oligo) alkylene oxide semi-ethers such as mono- or dibutyl phthalate, mono- or Di-2-ethylhexyl phthalate or di (2-methoxyethyl) phthalate.
  • Another method of avoiding possible phase separation is to graft copolymer B at least in part onto the flow improver.
  • Bulk or solution polymerization is preferably used for the grafting.
  • the polymerization can be carried out according to the "batch" or feed procedure.
  • the total amount of flow improver A to be grafted is initially introduced together with the monomers and initiator and, if appropriate, coinitiator and regulator are metered in.
  • the total amount of flow improver A to be grafted is optionally introduced together with some of the monomers and the rest of the monomers, initiator and, if appropriate, coinitiator and regulator are metered in. After the end of the polymerization, the reaction with the amines then takes place.
  • the copolymer B As already mentioned, it is not necessary to graft the copolymer B onto the entire proportion of the flow improver A. For example, at a ratio A: B of 90:10, for reasons of space-time yield, the copolymer B will only be grafted to a proportion of 2 to 20% by weight of the total amount of A. With an A: B ratio of 40:60, however, in a proportion of 30 to 100% by weight of the total amount of A.
  • copolymer B may also be present in the concentrates described.
  • the K values (according to H. Fikentscher, Celulosechemie Volume 13, pages 58 to 64 and 71 to 74 (1932)), determined in 2% (w / v) xylene solution of the copolymers B, are between 10 and 50, preferably between 10 to 40 and particularly preferably between 13 and 30.
  • the particularly preferred range corresponds to molecular weights between approximately 5000 and 25,000 g / mol (number average values, determined by gel permeation chromatography against polystyrene standards).
  • the additives A and B according to the invention are added to the petroleum middle distillates in amounts of altogether 50 to 5000 ppm, preferably 100 to 2000 ppm.
  • the middle distillates according to the invention containing small amounts of a flow improver A and a copolymer B, can, depending on the intended use, other additives or additives such as dispersants, anti-foam additives, corrosion inhibitors, antioxidants, dyes and others. contain.
  • Example 3 As in Example 3, but instead of lauryl acrylate, an n-alkyl acrylate mixture, prepared from a commercially available fatty alcohol mixture of the following composition, was used.
  • a clear, light yellow, viscous, approximately 50% by weight polymer solution was obtained.
  • the K value of the polymer was 23.8; the molar ratio of acrylate to maleic anhydride is approximately 80:20.
  • the reaction was carried out by adding the appropriate amount of the amine to the above polymer solutions and stirring at 100 ° C. until the anhydride band had disappeared in the infrared spectrum.
  • Example 18 As in Example 18, but with 76 g of the polymer solution from Example 16, 121.1 g of FI (A) and 121.1 g of Solvesso® 150.
  • Example 7 25 g of a 50% by weight polymer solution according to Example 7 were stirred with 0.99 g of 2-ethylhexylamine and 0.99 g of Solvesso® 150 at 40 ° C. for 30 minutes. The polymer is thereby converted into the amide / ammonium salt.
  • the monoamide is formed by means of amine A, the ammonium salt with 2-ethylhexylamine.
  • the flow improvers FI (A) and FI (B) are commercially available products, e.g. the Keroflux® brands from BASF.

Claims (8)

1. Distillat moyen de pétrole brut ayant des propriétés d'écoulement au froid améliorées, contenant de faibles quantités
A) d'un agent d'amélioration de l'écoulement traditionnel à base d'éthylène et
B) d'un copolymère constitué de 10 à 95% en moles d'un ou plusieurs acrylates d'alkyle ou méthacrylates d'alkyle avec des chaînes alkyle en C1-C26 et de 5 à 90% en moles d'un ou plusieurs acides dicarboxyliques à insaturation éthylénique ou de leurs anhydrides, le copolymère ayant ensuite réagi avec une ou plusieurs amines primaires ou secondaires pourformer le monoamide ou l'amide/sel d'ammonium de l'acide dicarboxylique, et le rapport pondéral de A à B étant compris entre 40 à 60 et 95 à 5.
2. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce que les copolymères B se composent de 40 à 95% en moles de (méth)acrylates d'alkyle et de 5 à 60% en moles de dérivés d'acides dicarboxyliques à insaturation éthylénique.
3. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce que les (méth)acrylates d'alkyle portent des groupements alkyle en C4-C22 à chaîne droite non ramifiée.
4. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce que les acides dicarboxyliques à insaturation éthylénique ou leurs dérivés dans les copolymères B sont ensuite transformés en monoamides avec des alkylamines primaires ou secondaires avec au moins une chaîne hydrocarbonée non ramifiée d'au moins 16 atomes de carbone.
5. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce que les acides dicarboxyliques à insaturation éthylénique ou leurs dérivés dans les copolymères B sont ensuite transformés en amide/sel d'ammonium avec des alkylamines primaires ou secondaires avec au moins une chaîne hydrocarbonée non ramifiée d'au moins 16 atomes de carbone.
6. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce que l'agent d'amélioration traditionnel se compose de copolymères, d'éthylène avec de l'acétate de vinyle, du propionate de vinyle ou de l'acrylate d'éthylhexyle.
7. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce que les copolymères sont greffés à 0-100% sur l'agent d'amélioration de l'écoulement traditionnel.
8. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce qu'il contient l'agent d'amélioration A et les copolymères B en quantités représentant ensemble de 50 à 5000 ppm.
EP91118116A 1990-11-14 1991-10-24 Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées Revoked EP0485773B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT91118116T ATE101639T1 (de) 1990-11-14 1991-10-24 Erdoelmitteldestillate mit verbesserten fliesseigenschaften in der kaelte.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4036225 1990-11-14
DE4036225A DE4036225A1 (de) 1990-11-14 1990-11-14 Erdoelmitteldestillate mit verbesserten fliesseigenschaften in der kaelte

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EP0485773A1 EP0485773A1 (fr) 1992-05-20
EP0485773B1 true EP0485773B1 (fr) 1994-02-16

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EP91118116A Revoked EP0485773B1 (fr) 1990-11-14 1991-10-24 Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées

Country Status (8)

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US (1) US5178641A (fr)
EP (1) EP0485773B1 (fr)
AT (1) ATE101639T1 (fr)
CA (1) CA2055416A1 (fr)
DE (2) DE4036225A1 (fr)
ES (1) ES2049071T3 (fr)
FI (1) FI915128A (fr)
NO (1) NO914445L (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018054892A1 (fr) 2016-09-21 2018-03-29 Basf Se Terpolymères d'anhydride de l'acide maléique, d'acrylates et d'alpha-oléfines, en particulier destinés à être utilisés comme agent d'amélioration de l'écoulement de pétrole

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4241948A1 (de) * 1992-12-12 1994-06-16 Hoechst Ag Pfropfpolymerisate, ihre Herstellung und Verwendung als Stockpunkterniedriger und Fließverbesserer für Rohöle, Rückstandsöle und Mitteldestillate
AU680915B2 (en) * 1993-07-27 1997-08-14 Shell Internationale Research Maatschappij B.V. Polymeric flow improver additives
EP0673990A1 (fr) * 1994-03-22 1995-09-27 Shell Internationale Researchmaatschappij B.V. Compositions d'huile d'hydrocarbure à proprietés améliorées d'écoulement à froid
FR2735494B1 (fr) * 1995-06-13 1997-10-10 Elf Antar France Additif bifonctionnel de tenue a froid et composition de carburant
US6179458B1 (en) 1996-11-01 2001-01-30 E. I. Du Pont De Nemours And Company Forming a solution of fluids having low miscibility and large-scale differences in viscosity
BR9713405A (pt) 1996-11-22 2000-01-25 Clariant Gmbh Aditivos para inibir a formação de hidratos gasosos.
CN1067712C (zh) * 1998-08-13 2001-06-27 中国石油化工总公司 柴油流动改进剂组合物
EA009104B1 (ru) * 2003-10-22 2007-10-26 Лейна Полимер Гмбх Присадка в качестве компонента композиции минерального нефтетоплива
DE10349851B4 (de) * 2003-10-25 2008-06-19 Clariant Produkte (Deutschland) Gmbh Kaltfließverbesserer für Brennstofföle pflanzlichen oder tierischen Ursprungs
DE10349850C5 (de) 2003-10-25 2011-12-08 Clariant Produkte (Deutschland) Gmbh Kaltfließverbesserer für Brennstofföle pflanzlichen oder tierischen Ursprungs
DE10357877B4 (de) * 2003-12-11 2008-05-29 Clariant Produkte (Deutschland) Gmbh Brennstofföle aus Mitteldestillaten und Ölen pflanzlichen oder tierischen Ursprungs mit verbesserten Kälteeigenschaften
DE10357880B4 (de) 2003-12-11 2008-05-29 Clariant Produkte (Deutschland) Gmbh Brennstofföle aus Mitteldestillaten und Ölen pflanzlichen oder tierischen Ursprungs mit verbesserten Kälteeigenschaften
DE10357878C5 (de) * 2003-12-11 2013-07-25 Clariant Produkte (Deutschland) Gmbh Brennstofföle aus Mitteldestillaten und Ölen pflanzlichen oder tierischen Ursprungs mit verbesserten Kälteeigenschaften
US20050138859A1 (en) * 2003-12-16 2005-06-30 Graham Jackson Cold flow improver compositions for fuels
CN100460489C (zh) * 2006-01-10 2009-02-11 中国石油化工股份有限公司 一种低硫柴油多效添加剂组合物
CN100460488C (zh) * 2006-01-10 2009-02-11 中国石油化工股份有限公司 低硫柴油多效添加剂的制备方法
DE102006001381A1 (de) * 2006-01-11 2007-07-12 Clariant International Limited Additive für schwefelarme Mineralöldestillate, umfassend Pfropfcopolymere auf Basis von Ethylen-Vinylester-Copolymeren
CA2645486A1 (fr) * 2006-03-15 2007-08-23 Exxonmobil Upstream Research Company Procede de production d'une boue hydratee non obstruante
US8980804B2 (en) * 2006-07-28 2015-03-17 Afton Chemical Corporation Alkyl acrylate copolymer dispersants and uses thereof
BRPI0817188A2 (pt) * 2007-09-25 2015-03-17 Exxonmobil Upstream Res Co Método para controlar hidratos em um sistema de produção submarino
ATE547472T1 (de) 2009-09-25 2012-03-15 Evonik Rohmax Additives Gmbh Zusammensetzung zur verbesserung der kaltflusseigenschaften von brennstoffölen
CN102191093A (zh) * 2010-03-10 2011-09-21 中国石油天然气股份有限公司 一种柴油低温流动性能改进剂的制备方法
KR101394564B1 (ko) * 2011-01-07 2014-05-14 한국화학연구원 바이오디젤용 저온 유동성 향상제
KR101781672B1 (ko) * 2011-03-29 2017-09-25 니치유 가부시키가이샤 연료유용 유동성 향상제 및 연료유 조성물
US10465027B2 (en) 2014-12-18 2019-11-05 Evonik Oil Additives Gmbh Method for the preparation of copolymers of alkyl methacrylates and maleic anhydride
CN107108809B (zh) * 2014-12-18 2021-03-09 赢创运营有限公司 制备甲基丙烯酸烷基酯和马来酸酐的共聚物的方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE546263A (fr) * 1955-03-22
GB802589A (en) * 1955-03-22 1958-10-08 California Research Corp Compounded hydrocarbon fuels
US2892690A (en) * 1955-03-22 1959-06-30 California Research Corp Compounded hydrocarbon fuels
US4161452A (en) * 1977-01-28 1979-07-17 Rohm And Haas Company Polyolefinic copolymer additives for lubricants and fuels
NL187859C (nl) * 1979-12-13 1992-02-03 Inst Francais Du Petrole Terpolymeren en koolwaterstofoliesamenstellingen, die dergelijke terpolymeren bevatten.
FR2567536B1 (fr) * 1984-07-10 1986-12-26 Inst Francais Du Petrole Compositions d'additifs destinees notamment a ameliorer les proprietes de filtrabilite a froid des distillats moyens de petrole
FR2572410B1 (fr) * 1984-10-25 1987-09-04 Elf Aquitaine Copolymeres d'ethylene greffes utilisables notamment comme additifs pour l'inhibition du depot de paraffines dans les huiles brutes et compositions renfermant les huiles et lesdits additifs
IN184481B (fr) * 1986-09-24 2000-08-26 Exxon Chemical Patents Inc
GB8706369D0 (en) * 1987-03-18 1987-04-23 Exxon Chemical Patents Inc Crude oil
DE3905681A1 (de) * 1989-02-24 1990-08-30 Basf Ag Konzentrierte mischungen von pfropfcopolymerisaten aus estern von ungesaettigten saeuren und ethylen-vinylester-copolymerisaten

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018054892A1 (fr) 2016-09-21 2018-03-29 Basf Se Terpolymères d'anhydride de l'acide maléique, d'acrylates et d'alpha-oléfines, en particulier destinés à être utilisés comme agent d'amélioration de l'écoulement de pétrole

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US5178641A (en) 1993-01-12
CA2055416A1 (fr) 1992-05-15
DE59101024D1 (de) 1994-03-24
ATE101639T1 (de) 1994-03-15
DE4036225A1 (de) 1992-05-21
ES2049071T3 (es) 1994-04-01
FI915128A (fi) 1992-05-15
NO914445L (no) 1992-05-15
NO914445D0 (no) 1991-11-13
EP0485773A1 (fr) 1992-05-20
FI915128A0 (fi) 1991-10-30

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