EP0485774B1 - 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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EP0485774B1
EP0485774B1 EP91118117A EP91118117A EP0485774B1 EP 0485774 B1 EP0485774 B1 EP 0485774B1 EP 91118117 A EP91118117 A EP 91118117A EP 91118117 A EP91118117 A EP 91118117A EP 0485774 B1 EP0485774 B1 EP 0485774B1
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Prior art keywords
copolymers
alkyl
mol
added
vinyl
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EP0485774A1 (fr
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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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10L1/1966—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 poly-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
    • 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 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 with long-chain alkyl vinyl ethers and ethylenically unsaturated dicarboxylic acid derivatives 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 levels of paraffins depending on the origin of the crude oil and depending on 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 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 accompanied by 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 reduce the pour point of heating oil containing wax.
  • These are e.g. Homopolymers or copolymers of alkyl esters of unsaturated mono- or dicarboxylic acids and homopolymers or copolymers of various alkyl vinyl ethers. Also mentioned are: "Reaction products of copolymers of acid anhydrides of unsaturated dicarboxylic acids and monoolefins or other olefinically unsaturated compounds with an aliphatic amine containing a long hydrocarbon chain". Copolymers with monoolefins are preferred.
  • 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 give 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-A-2 592 658 describes mixtures of an ethylene polymer and a reaction product of a primary amine with a copolymer of e.g. Acrylic acid alkyl esters and / or alkyl vinyl ethers, diisobutene and maleic anhydride and their use as an additive to middle distillates.
  • EP-A-360 419 describes middle distillates which contain polymers of vinyl ethers with hydrocarbon radicals of 1 to 17 carbon atoms. Alkyl acrylates or methacrylates are mentioned as comonomers. In the examples, however, only polymers from alkyl vinyl ethers with up to 4 carbon atoms in the side chain are described. These C 1 to C 4 vinyl ethers are copolymerized with maleic or fumaric acid derivatives. Examples of copolymers with acrylic acid derivatives are not given. The claimed additives can be used together with other flow improvers.
  • 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 90 mol%, preferably 40 to 90 mol% and particularly preferably 60 to 90 mol% of alkyl (meth) acrylates, 5 to 60 mol%, preferably 5 to 40 mol % and particularly preferably 10 to 30 mol% of olefinically unsaturated dicarboxylic acids or their anhydrides, 5 to 60 mol%, preferably 5 to 40 mol% and particularly preferably 10 to 30 mol% of alkyl vinyl ethers.
  • 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 30, 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) acrylate, 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 or itaconic acid or their anhydrides, fumaric acid and mixtures thereof.
  • Maleic anhydride is preferred.
  • alkyl vinyl ethers examples include octadecyl vinyl ether, eicosyl vinyl ether, docosyl vinyl ether, tetracosyl vinyl ether, hexacosyl vinyl ether and octacosyl vinyl ether and mixtures thereof.
  • copolymers B together with flow improvers, have synergistic effects. Although the copolymers B alone show little or no flow-improving effect, the combination of A and B far exceeds the individual efficacies.
  • the carboxylic acid (anhydride) groupings on the copolymer B can be completely or partially reacted with compounds containing amino or hydroxyl groups. This is not necessary to get the desired effectiveness. However, in some cases the effectiveness can be increased by the reaction and the solubility in the middle distillate or the compatibility with other components can be influenced favorably.
  • Alkylamines are compounds containing amino groups preferably in which R 1 is a straight-chain or branched alkyl radical having 1 to 30, preferably 8 to 26 and particularly preferably 12 to 24 carbon atoms and R 2 is hydrogen, methyl or R 1 .
  • R 1 is a straight-chain or branched alkyl radical having 1 to 30, preferably 8 to 26 and particularly preferably 12 to 24 carbon atoms
  • R 2 is hydrogen, methyl or R 1 .
  • ethylhexylamine, octadecylamine, oleylamine, tallow fatty amine, N-methyloctadecylamine and preferably behenylamine, dibehenylamine and hydrogenated ditallow fatty amine may be mentioned.
  • alkylarylamines or arylamines and cyclic amines, which may have a heteroatom can also be used.
  • R 1 - (OR 2 ) n -OH Compounds of the formula R 1 - (OR 2 ) n -OH, in which R 1 is C 1 - to C ao- alkyl, C s - to C 12 -aryl, or C 1 - to C 30 -alkylaryl, are especially hydroxyl-containing compounds and R 2 represents C 1 to C 4 alkyl and n is an integer from 0 to 30 is preferred.
  • Examples of compounds containing hydroxyl groups include: alcohols such as 2-ethylhexanol, n-hexadecanol and n-octadecanol, alkylphenols such as iso-octylphenol, iso-nonylphenol and their reaction products with alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide.
  • Examples of the flow improvers A are the already mentioned polymers 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 are 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-A-261 957, additive D) and those in DE-A-36 24 are also suitable 147 specified mixtures of 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 usual polymerization inhibitors e.g. Hydroquinone derivatives and esterification catalysts such as sulfuric acid, p-toluenesulfonic acid or acidic ion exchangers
  • alkyl (meth) acrylates Further possibilities for the production of the 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. In these production processes, too, the ester should be worked up to such an extent that no acid is present.
  • the vinyl ethers can be obtained by known processes by reacting alkanols with acetaldehyde and subsequent elimination of water or by catalytic addition of acetylene to alkanols. Particularly pure monomers can also be obtained here by distillation. With vinyl ethers with more than 20 to 22 carbon atoms in the alkyl part, the undecomposed distillation is technically difficult to carry out. In these cases, cleaning by filtration, extraction or recrystallization to remove the catalysts is recommended.
  • the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, e.g. 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 compounds containing amino or hydroxyl groups.
  • the reaction of the polymers with amines takes place at temperatures of 50 to 250 ° 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.
  • the use of 2 moles of amine per mole of anhydride leads to the amide / ammonium salt. This can be converted into the diamide by heating to 150 to 200 ° C with elimination of water. When using 1 mole of a primary amine per mole of anhydride, the resulting monoamide can be converted into the imide by heating to 150 to 250 ° C.
  • the reaction of the polymers with alcohols, alkylphenols or their alkoxylates also takes place at temperatures of 50 to 250 ° C.
  • the alcohol or the phenol are used in amounts of 1 to 2 moles per mole of anhydride. If 1 mole of alcohol is used, the half-ester is formed, with 2 moles of alcohol an esterification catalyst has to be added and the water of reaction has to be removed so that the diester can be formed completely.
  • the copolymers B can also be reacted both with an amino group-containing compound and with a hydroxyl group-containing compound. If the reaction is first carried out with an alcohol, then with an amine, an ester / ammonium salt is obtained, depending on the conditions, or an ester / amide at a higher temperature and removal of the water of reaction. If the reaction is first with the amine, then with the alcohol, an ester / amide is obtained at the same time with removal of the water of reaction at a higher temperature.
  • 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, di-cumyl 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., the use of solvents with boiling temperatures below the polymerization temperature advantageously being 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 the use of 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 1-buten-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 .-%.
  • 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 into the flow improver according to the invention directly in the melt or after absorption in a suitable solvent.
  • a continuous high-pressure process which permits space-time yields of 1 to 10 kg of polymer per liter of reactor and hour is also suitable for producing the desired copolymers.
  • the polymerization apparatus e.g. 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 are preferably polymerized from (meth) acrylic esters, unsaturated dicarboxylic acids or their anhydrides and vinyl ethers 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, maleic anhydride and octadecyl vinyl ether 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 2 to 60 preferably from 5 to 30 minutes, at temperatures between 200 and 400 ° C. continuously discharged from the reaction zone.
  • 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%.
  • 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 which fulfill this requirement and which 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 n-hexane, cyclohexane, methylcyclohexane, n-octane, iso-octane, paraffin oils, Shellsol® TD , T and Ksie and tetrahydrofuran and Dioxane, tetrahydrofuran and dioxane being particularly suitable for achieving low molecular weight copolymers.
  • the solution polymerization it is expedient to initially introduce solvent and part of the monomer mixture (for example about 5 to 20%) and to meter in the rest of the monomer mixture with the initiator and, if appropriate, coinitiator, regulator and solvent.
  • the monomers can also be metered in individually at different rates. This is recommended for monomers with very different reactivity and if a particularly uniform distribution of the less reactive monomer in the polymer is desired. The less reactive monomer is metered in faster and the more reactive monomer more slowly. It is also possible to introduce the entire amount of a monomer, preferably the less reactive anhydride or vinyl ether, and to meter in only the (meth) acrylate.
  • 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, alkylphenols and their adducts with ethylene oxide, propylene oxide and / or butylene oxide and sharks of the best or diesters of dicarboxylic acids with alkanols or (Oligo) alkylene oxide half ethers such as motto 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.
  • 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 a ratio of A: B of 40:60, however, to 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, Cellulosechemie, Volume 13, pages 58 to 64 and 71 to 74 (1932)), determined in a 2% (w / v) xylene solution of the copolymers B, are between 10 and 50 , preferably between 10 and 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.
  • a clear, light yellow, viscous, approximately 50% by weight polymer solution was obtained.
  • the K value of the polymer was 30.6; the molar ratio of acrylate to maleic anhydride to vinyl ether is approximately 80:10:10.
  • a clear, light yellow, viscous, approximately 50% by weight polymer solution was obtained.
  • the K value of the polymer was 18.5; the molar ratio of acrylate to maleic anhydride to vinyl ether is about 70:15:15.
  • Example 5 As in Example 5, but 94 g of n-octadecyl vinyl ether were used instead of the C 18 to C 22 vinyl ether. A clear, light yellow, viscous, approximately 50% by weight polymer solution was obtained. The K value of the polymer was 20.3; the molar ratio of acrylate to maleic anhydride to vinyl ether is about 70:15:15.
  • 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.
  • the reaction with alcohols and their alkoxylates took place at 150 ° C. in 3 to 6 hours and was catalyzed with 1 mol% methanesulfonic acid.
  • the flow improvers FI (A) and FI (B) are commercially available products, e.g. the Keroflux® brands from BASF.
  • Middle distillate I, II, III and IV Heating oils and diesel fuels in commercial West German refinery quality were used as middle distillates. They are referred to as middle distillate I, II, III and IV.

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Claims (8)

1. Distillat moyen de pétrole brut ayant des propriétés d'écoulement améliorées à froid, contenant de faibles quantités
A) d'un agent d'amélioration de l'écoulement traditionnel à base d'éthylène et
B) d'un copolymère qui se compose
a) de 10 à 90% en moles d'un ou plusieurs acrylates d'alkyle ou méthacrylates d'alkyle avec des chaînes alkyle en C1-Cao et
b) de 5 à 60% en moles d'un ou plusieurs acides dicarboxyliques à insaturation éthylénique ou de leurs anhydrides et
c) de 5 à 60% en moles d'un ou plusieurs oxydes d'alkyle et de vinyle avec des chaînes latérales en C18-C28,
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 90% en moles des monomères indiqués sous a) et jusqu'à, à chaque fois, 5 à 40% en moles des monomères indiqués sous b) et c).
3. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce que les copolymères se composent de (méth)acrylates d'alkyle en C4-C22, d'anhydride maléique ou d'anhydride itaconique et d'oxydes d'alkyle et de vinyle en C18-C28-4. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce que les substituants alkyle dans les copolymères sont linéaires et non ramifiés.
5. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce que les acides dicarboxyliques ou leurs anhydrides dans les copolymères B ont réagi avec des composés contenant des groupements amino et/ou contenant des groupements hydroxy.
6. Distillat moyen de pétrole brut selon la revendication 1, caractérisé en ce que les agents d'amélioration de l'écoulement traditionnels sont des 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 de l'écoulement A et les copolymères B dans des quantités représentant ensemble de 50 à 5000 ppm.
EP91118117A 1990-11-14 1991-10-24 Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées Expired - Lifetime EP0485774B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT91118117T ATE101640T1 (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
DE4036226 1990-11-14
DE4036226A DE4036226A1 (de) 1990-11-14 1990-11-14 Erdoelmitteldestillate mit verbesserten fliesseigenschaften in der kaelte

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EP0485774A1 EP0485774A1 (fr) 1992-05-20
EP0485774B1 true EP0485774B1 (fr) 1994-02-16

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EP (1) EP0485774B1 (fr)
AT (1) ATE101640T1 (fr)
CA (1) CA2055417A1 (fr)
DE (2) DE4036226A1 (fr)
ES (1) ES2049072T3 (fr)
FI (1) FI915127A (fr)
NO (1) NO914444L (fr)

Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
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
DE19739271A1 (de) * 1997-09-08 1999-03-11 Clariant Gmbh Additiv zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten
PL1675881T3 (pl) 2003-10-22 2011-05-31 Innospec Leuna Gmbh Dodatek stosowany jako składnik kompozycji mineralnych
DE10349858B4 (de) * 2003-10-22 2006-11-16 Leuna Polymer Gmbh Additiv als Bestandteil von additivierten Mineralölen
DE10349862B4 (de) * 2003-10-22 2006-11-16 Leuna Polymer Gmbh Additiv als Bestandteil von Mineralölzusammensetzungen
DE10349850C5 (de) 2003-10-25 2011-12-08 Clariant Produkte (Deutschland) Gmbh Kaltfließverbesserer für Brennstofföle pflanzlichen oder tierischen Ursprungs
DE10357878C5 (de) 2003-12-11 2013-07-25 Clariant Produkte (Deutschland) Gmbh Brennstofföle aus Mitteldestillaten und Ölen pflanzlichen oder tierischen Ursprungs mit verbesserten Kälteeigenschaften
DE102004028495B4 (de) * 2004-06-11 2007-08-30 Clariant Produkte (Deutschland) Gmbh Kaltfließverbessererzusammensetzungen in naphthalinarmem Solvent Naphtha
EP1674554A1 (fr) * 2004-12-24 2006-06-28 Clariant Produkte (Deutschland) GmbH Additifs pour distillats d'huiles minérales, à faible contenu en soufre, comprenant un copolymère greffé à base de copolymères d'éthylène-acétate de vinyle.

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FR1147212A (fr) * 1955-03-22 1957-11-20 California Research Corp Composition combustible à base d'hydrocarbure
NL148099B (nl) * 1966-03-17 1975-12-15 Shell Int Research Werkwijze voor het verlagen van het vloeipunt van een brandstofmengsel.
NL6709453A (fr) * 1967-07-07 1969-01-09
US4161452A (en) * 1977-01-28 1979-07-17 Rohm And Haas Company Polyolefinic copolymer additives for lubricants and fuels
FR2566288B1 (fr) * 1984-06-21 1991-10-18 Elf Aquitaine Additifs polymeriques utilisables pour l'inhibition du depot de paraffines dans les huiles brutes
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
FR2592658B1 (fr) * 1986-01-09 1988-11-04 Inst Francais Du Petrole Compositions d'additifs destinees notamment a ameliorer les proprietes de filtrabilite a froid des distillats moyens de petrole.
ES2032318T3 (es) * 1987-09-15 1993-02-01 Basf Aktiengesellschaft Carburantes para motores otto.
GB8820071D0 (en) * 1988-08-24 1988-09-28 Exxon Chemical Patents Inc Fuel compositions

Also Published As

Publication number Publication date
EP0485774A1 (fr) 1992-05-20
DE59101025D1 (de) 1994-03-24
NO914444L (no) 1992-05-15
DE4036226A1 (de) 1992-05-21
CA2055417A1 (fr) 1992-05-15
FI915127A (fi) 1992-05-15
ATE101640T1 (de) 1994-03-15
NO914444D0 (no) 1991-11-13
ES2049072T3 (es) 1994-04-01
FI915127A0 (fi) 1991-10-30

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