EP0486836B1 - 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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EP0486836B1
EP0486836B1 EP91118118A EP91118118A EP0486836B1 EP 0486836 B1 EP0486836 B1 EP 0486836B1 EP 91118118 A EP91118118 A EP 91118118A EP 91118118 A EP91118118 A EP 91118118A EP 0486836 B1 EP0486836 B1 EP 0486836B1
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copolymers
monomers
middle distillate
weight
mineral oil
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EP0486836A1 (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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    • 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
    • C10L1/1963—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
    • 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
    • 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
    • C10L1/22—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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring

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 are distinguished 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. Homo- or copolymers of alkyl esters of unsaturated mono- or dicarboxylic acids as well as homo- or copolymers of various alkyl vinyl ethers.
  • DE-A-20 47 448 describes the addition of a mixture consisting of polyvinyl ethers and ethylene-vinyl acetate copolymers to paraffin-based crude oils.
  • EP-A-360 419 describes middle distillates which contain polymers of vinyl ethers with hydrocarbon radicals of 1 to 17 carbon atoms.
  • the following are among the comonomers: Called alkyl acrylates or methacrylates. In the examples, however, only polymers from alkyl vinyl ethers with up to 4 carbon atoms in the side chain are described.
  • These C1 to C4 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.
  • the weight ratio of monomers according to formula I to monomers according to formula II is between 10:90 and 95: 5, preferably between 40:60 and 95: 5 and particularly preferably between 60:40 and 90:10 and the 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.
  • the alkyl radicals R2 and R3 are preferably straight-chain and unbranched. However, up to 20% by weight of cyclic and / or branched portions can also be present.
  • Examples of monomers according to formula I are 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.
  • Examples of monomers according to formula II are n-octadecyl vinyl ether, n-eicosyl vinyl ether, n-docosyl vinyl ether, n-tetracosyl vinyl ether, n-hexacosyl vinyl ether and n-octacosyl vinyl ether and mixtures thereof.
  • the copolymers B consist of at least 70% by weight of monomers of the formulas I and II.
  • other ethylenically unsaturated monomers can be present, such as, for example, styrene, alkylstyrenes, straight-chain or branched olefins with 2 to 16 Carbon atoms, vinyl esters of C1- to C5-carboxylic acids, acrylonitrile, N-alkyl-substituted acrylamides, N-containing, ethylenically unsaturated heterocycles such as vinylpyrrolidone, vinylimidazole or vinylpyridine, hydroxyl- or amino group-containing monomers such as butanediol monoacrylate, hexanediol monoacrylate, dimethylethylaminoethylamate, and ) acrylic acid esters from C1 to C8 alkanols such as methyl methacrylate, ethyl acrylate
  • 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 are derived from alkanols with 1 to 12 carbon atoms.
  • 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 monomers according to formula I 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
  • vinyl ethers can polymerize cationically under acidic conditions or decompose in the presence of water and acid to form acetaldehyde, which interferes with the radical polymerization, the neutralization of the catalyst acid and excess (meth) acrylic acid with e.g. Amines or their removal indicated by washing the ester solution with alkaline agents and water to prepare the copolymers B.
  • Particularly pure esters can be obtained by distillation of the pre-cleaned ester solution.
  • the vinyl ethers of the formula II 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 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, dicyclohexylproxidicarbonate, di-2-ethylhexyl peroxidate carbonate, tert.
  • customary radical donors such as acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexylproxidicarbonate, di-2-ethylhexyl peroxidate carbonate, 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., the use of solvents with boiling temperatures below the polymerization temperature advantageously being carried out under pressure.
  • the polymerization is expediently carried out in the absence of air, ie if it is not possible to work under boiling conditions, for example 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 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 added directly to the middle distillate as a solidified melt or after being taken up in a suitable solvent together with the flow improver.
  • a copolymer of (meth) acrylic acid esters and vinyl ethers 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 of 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% and can be added to the middle distillate without further treatment.
  • 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 K, as well as 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 advisable for monomers with very different reactivities, as is the case with (meth) acrylates and vinyl ethers and when a particularly uniform distribution of the less reactive vinyl ether 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 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 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 as well as half esters or diesters of dicarboxylic acids with alkanols or (Oligo) alkylene oxide half 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.
  • 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 together in amounts of 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.
  • Examples 4 to 18 were prepared by a procedure analogous to that in Example 3.
  • Examples 17 to 20 are comparative examples and do not form part of the present invention.
  • the flow improvers FI (A), FI (B) and FI (C) are commercially available products, e.g. the Keroflux® brands from BASF.
  • Middle distillate I 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. Middle distillate I. II III IV Cloud point (° C) + 6 + 4th + 4th + 5 CFPP (° C) 0 - 2nd - 1 - 2nd Initial boiling point (° C) 155 131 169 174 20% boiling point (° C) 232 216 222 219 50% boiling point (° C) 280 262 262 272 90% boiling point (° C) 352 346 351 365 End of boiling point (° C) 382 375 381 385

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Claims (7)

  1. Distillats moyens du pétrole à propriétés d'écoulement au froid améliorées, qui contiennent de faibles quantités
    A) d'agents d'amélioration de l'écoulement habituels à base d'éthylène, et
    B) des copolymères qui se composent pour au moins 70% en poids d'un ou plusieurs monomères aussi bien de la formule I que de la formule II :
    Figure imgb0013
    dans lesquelles
       R¹ représente un atome d'hydrogène ou le radical méthyle, R² représente un radical alkyle en c₈ à C₁₈ et R³ représente un radical alkyle en C₁₈ à C₂₈ et le rapport pondéral de A à B varie de 40 à 60 à 95 à 5.
  2. Distillats moyens du pétrole suivant la revendication 1, caractérisés en ce que le rapport quantitatif des monomères de la formule I aux monomères de la formule II dans les copolymères B varie de 10 à 90 à 95 à 5.
  3. Distillats moyens du pétrole suivant la revendication 1, caractérisés en ce que les substituants du type alkyle dans les copolymères B sont linéaires et non ramifiés.
  4. Distillats moyens du pétrole suivant la revendication 1, caractérisés en ce que les copolymères peuvent contenir jusqu'à 30% en poids d'autres monomères éthyléniquement insaturés.
  5. Distillats moyens du pétrole suivant la revendication 1, caractérisés en ce que l'on utilise, à titre d'agents d'amélioration de l'écoulement habituels, des copolymères de l'éthylène avec l'acétate de vinyle, le propionate de vinyle ou l'acrylate d'éthylhexyle.
  6. Distillats moyens du pétrole suivant la revendication 1, caractérisés en ce que les copolymères sont greffés jusqu'à raison de 0 à 100% sur les agents d'amélioration de l'écoulement habituels.
  7. Distillats moyens du pétrole suivant la revendication 1, caractérisés en ce que les distillats moyens du pétrole contiennent les agents d'amélioration de l'écoulement A et les copolymères B ensemble en proportions allant de 50 à 5000 ppm.
EP91118118A 1990-11-14 1991-10-24 Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées Expired - Lifetime EP0486836B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4036227 1990-11-14
DE4036227A DE4036227A1 (de) 1990-11-14 1990-11-14 Erdoelmitteldestillate mit verbesserten fliesseigenschaften in der kaelte

Publications (2)

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EP0486836A1 EP0486836A1 (fr) 1992-05-27
EP0486836B1 true EP0486836B1 (fr) 1995-02-15

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EP91118118A Expired - Lifetime EP0486836B1 (fr) 1990-11-14 1991-10-24 Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées

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EP (1) EP0486836B1 (fr)
AT (1) ATE118529T1 (fr)
CA (1) CA2055418A1 (fr)
DE (2) DE4036227A1 (fr)
ES (1) ES2068464T3 (fr)
FI (1) FI105824B (fr)
NO (1) NO304077B1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2710652B1 (fr) * 1993-09-30 1995-12-01 Elf Antar France Composition d'additifs d'opérabilité à froid des distillats moyens.
KR100749220B1 (ko) * 2003-10-22 2007-08-13 로이나 폴리머 게엠베하 미네랄 오일 조성물의 성분으로서의 첨가제 혼합물
ATE547472T1 (de) 2009-09-25 2012-03-15 Evonik Rohmax Additives Gmbh Zusammensetzung zur verbesserung der kaltflusseigenschaften von brennstoffölen
CN104837872B (zh) 2012-12-18 2017-08-08 巴斯夫欧洲公司 乙烯‑乙烯基酯共聚物和(甲基)丙烯酸烷基酯构成的聚合物组合物，其制备方法及其作为原油、矿物油或矿物油产品的倾点下降剂的用途
US9574146B2 (en) 2012-12-18 2017-02-21 Basf Se Polymeric compositions composed of ethylene-vinyl ester copolymers alkyl (meth)acrylates, processes for production thereof and use thereof as pour point depressants for crude oils, mineral oils or mineral oil products
MX2015007942A (es) 2012-12-18 2015-10-09 Basf Se Formulaciones polimericas en solventes con alto punto de inflamacion, procedimiento para su preparacion y su uso como depresores del punto de fluidez para crudos petroleros, aceites minerales y productos a base de aceites minerales.
AR100387A1 (es) 2014-02-18 2016-10-05 Basf Se Copolímeros que comprenden etileno, ésteres de vinilo y ésteres de ácido (met)acrílico, sus formulaciones y usos como depresor del punto de fluidez, inhibidor de cera y potenciador de flujo para petróleos crudos
CA2964455A1 (fr) 2014-10-13 2016-04-21 Avery Dennison Corporation Emulsions polymeres d'acetate de vinyle-ethylene/acrylique, produits et procedes associes
DE102015226635A1 (de) 2015-12-23 2017-06-29 Clariant International Ltd Polymerzusammensetzungen mit verbesserter Handhabbarkeit
WO2019185490A1 (fr) 2018-03-26 2019-10-03 Basf Se Polyéthers hyper-ramifiés et leur utilisation, en particulier comme abaisseurs de point d'écoulement et inhibiteurs de cire
EP3798261A1 (fr) 2019-09-26 2021-03-31 Clariant International Ltd Compositions polymères et leur utilisation en tant que point d'écoulement dans des huiles hydrocarbonées contenant de la paraffine

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Publication number Priority date Publication date Assignee Title
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
US3961915A (en) * 1974-12-27 1976-06-08 Exxon Research And Engineering Company Synergistic additive in petroleum middle distillate fuel
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.
GB8820071D0 (en) * 1988-08-24 1988-09-28 Exxon Chemical Patents Inc Fuel compositions
DE3905681A1 (de) * 1989-02-24 1990-08-30 Basf Ag Konzentrierte mischungen von pfropfcopolymerisaten aus estern von ungesaettigten saeuren und ethylen-vinylester-copolymerisaten

Also Published As

Publication number Publication date
DE4036227A1 (de) 1992-05-21
NO914443D0 (no) 1991-11-13
CA2055418A1 (fr) 1992-05-15
FI105824B (fi) 2000-10-13
EP0486836A1 (fr) 1992-05-27
ATE118529T1 (de) 1995-03-15
NO304077B1 (no) 1998-10-19
FI915126A (fi) 1992-05-15
ES2068464T3 (es) 1995-04-16
NO914443L (no) 1992-05-15
FI915126A0 (fi) 1991-10-30
DE59104601D1 (de) 1995-03-23

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