EP0890633B1 - Use of copolymers of ethylene and unsaturated carboxylic esters in middle distillates to improve cold flow properties - Google Patents

Use of copolymers of ethylene and unsaturated carboxylic esters in middle distillates to improve cold flow properties Download PDF

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EP0890633B1
EP0890633B1 EP98111799A EP98111799A EP0890633B1 EP 0890633 B1 EP0890633 B1 EP 0890633B1 EP 98111799 A EP98111799 A EP 98111799A EP 98111799 A EP98111799 A EP 98111799A EP 0890633 B1 EP0890633 B1 EP 0890633B1
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mol
copolymers
structural units
carbon atoms
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French (fr)
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EP0890633A1 (en
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Matthias Dr. Krull
Werner Dr. Reimann
Markus Kupetz
Waltraud Nagel
Raimund Wildfang
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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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
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds 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 an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • 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
    • 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 fuel oils, the middle distillates and copolymers of ethylene and Contain esters of unsaturated carboxylic acids, and which show improved cold flow behavior.
  • Crude oils and middle distillates obtained by distilling crude oils such as gas oil, diesel oil or heating oil contain different amounts of n-paraffins depending on the origin of the crude oils, crystallize the temperature as platelet-shaped crystals and partially with the inclusion of oil agglomerate. This leads to a deterioration in the flow properties of these oils or Distillates, which, for example, during the extraction, transport, storage and / or use of Mineral oils and mineral oil distillates can occur. With mineral oils this can Crystallization phenomenon during transport through pipelines, especially in winter, leads to deposits the pipe walls, in individual cases, e.g. if a pipeline is at a standstill, even to completely block it to lead.
  • the flow and cold behavior of mineral oils and mineral oil distillates is determined by specifying the pour point (determined according to ISO 3016) and the cold filter plugging point (CFPP; determined according to EN 116) described. Both parameters are measured in ° C.
  • Typical flow improvers for crude oils and middle distillates are copolymers of ethylene with Carboxylic acid ester of vinyl alcohol. So according to DE-A-11 47 799 petroleum distillate propellant or fuels with a boiling point between about 120 and 400 ° C oil-soluble copolymers from ethylene and vinyl acetate with a molecular weight between about 1,000 and 3,000. Copolymers containing about 60 to 99% by weight of ethylene and about 1 to 40% by weight are preferred. Contain vinyl acetate. They are particularly effective when used in radical polymerization an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2,100 were manufactured (DE-A-1914 756).
  • copolymers based on ⁇ , ⁇ -unsaturated compounds and Maleic anhydride used as a flow improver.
  • DE-196 45 603 describes copolymers of 60 to 99 mol% derived from ethylene Structural units and 1 to 40 mol% of structural units that differ from maleic acid, its Derive anhydride or its imides.
  • DE-1 162 630 discloses copolymers of ethylene and vinyl esters of straight-chain fatty acids 4 to 18 carbon atoms as a pour point reducing additive for distillate fuels of medium size Siedelage such as Hiezöl or diesel oil.
  • EP-A-0 217 602 discloses ethylene copolymers with vinyl esters bearing C 1 to C 18 alkyl radicals as flow improvers for mineral oil distillates with boiling ranges (90-20)% below 100 ° C.
  • EP-A-0 493 769 discloses terpolymers which consist of ethylene, vinyl acetate and neononane or Neodecanoic acid vinyl esters are produced, and their use as additives for Mineratöldestillate.
  • EP-A-0 746 598 discloses copolymers of ethylene and di-alkyl fumarates mixed with Mineral oils with a cloud point below -10 ° C.
  • the main problems are those for use under arctic conditions produced winter qualities of diesel fuels with their extreme Katte properties, such as a cloud point below -8 ° C and especially below -15 ° C, very much narrow distillation cuts with boiling ranges from 20 to 90 vol .-% less than 120 ° C, in particular less than 100 ° C and sometimes also less than 80 ° C, and a distillation volume of 95% by volume Temperatures below 360 ° C, especially below 350 ° C and especially below 330 ° C.
  • the Cold properties of such distillates can currently only be achieved by adding low-boiling, low-paraffin components, e.g. Kerosene, can be improved satisfactorily.
  • composition caused by narrow distillation cuts and low boiling ends is problematic for the response behavior of flow improvers to these oils:
  • These oils have a paraffin distribution with a maximum at around C 12 to C 14 and contain only insignificant amounts of the n-paraffins with hydrocarbon chains that crystallize from conventional grades longer as C 18 .
  • the cloud points and CFPP values are so low, especially in terms of winter qualities, that conventional flow improvers do not respond and the properties of the liquid have to be adjusted by diluting with kerosene.
  • the cloud point of the mineral oils mentioned under A) is preferably below -15 ° C.
  • the boiling ranges (90-20%) of the distillation cuts are preferably less than 100 ° C., in particular less than 80 ° C. It is preferred to use mineral oils with a 95% distillation point below 360 ° C, especially below 350 ° C, especially below 330 ° C.
  • R 1 is preferably hydrogen.
  • R 3 preferably represents a linear or branched C 8 -C 18 alkyl radical.
  • R denotes a neoalkyl radical with 7 to 11 carbon atoms, in particular a neoalkyl radical with 8, 9 or 10 carbon atoms.
  • the neoalkyl acids from which the above-mentioned neoalkyl radicals can be derived are described by the formula (3):
  • R 'and R are linear alkyl radicals with a total of preferably 5 to 9, in particular 6, 7 or 8, carbon atoms.
  • the vinyl ester used for the copolymerization accordingly has the formula (4):
  • Suitable comonomers are those which can be derived from acrylic acid:
  • Preferred radicals R 3 are, for example, butyl, tert-butyl, pentyl, neopentyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and behenyl.
  • the fuel oil compositions according to the invention preferably contain copolymers in which the comonomers B1) with 90 to 96 mol% and the comonomers B2) with 4 to 10 mol% are included.
  • the copolymers mentioned under B) are as usual by the usual copolymerization for example suspension polymerization, solvent polymerization, gas phase polymerization or high-pressure mass polymerization.
  • The is preferred High pressure bulk polymerization at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 300, in particular 100 to 250 ° C.
  • the reaction of the Monomers are initiated by radical initiators (radical chain initiators).
  • radical initiators radical chain initiators
  • Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-Butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances Amounts of 0.001 to 20 wt .-%, preferably 0.01 to 10 wt .-%, based on the Monomer mixture used.
  • the copolymers mentioned under B) preferably have melt viscosities at 140 ° C. of 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
  • the desired Melt viscosity of these copolymers is given the given composition of Monomer mixture by varying the reaction parameters pressure and temperature and possibly by adding moderators.
  • the moderators are hydrogen, saturated or unsaturated hydrocarbon, e.g. Propane, aldehydes, e.g. Propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g.
  • the moderators are used in amounts of up to 20% by weight, preferably 0.05 to 10% by weight the mixture of monomers applied.
  • the copolymers mentioned under B) can contain up to 3 mol% of vinyl acetate or up to 5 mol% of more Comonomers included.
  • Such comonomers can, for example, vinyl esters, vinyl ethers, Acrylic acid alkyl esters, methacrylic acid alkyl esters or higher olefins with at least 5 Be carbon atoms. Hexene, 4-methylpentene, octene or are preferred as higher olefins Diisobutylene.
  • monomer mixtures which in addition to ethylene and optionally a moderator 1 to 50% by weight, preferably 3 to 40% by weight Comonomer included.
  • a moderator 1 to 50% by weight preferably 3 to 40% by weight Comonomer included.
  • the composition of the monomer mixture is carried by the different ones Polymerization rate of the monomers calculation.
  • the polymers fall as colorless Melt, which solidify to waxy solids at room temperature.
  • High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or Tube reactors, carried out batchwise or continuously, have proven particularly useful Tubular reactors.
  • Solvents such as aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, benzene or toluene can be contained in the reaction mixture.
  • the solvent-free mode of operation is preferred.
  • the Polymerization is the mixture of the monomers, the initiator and, if used, the Moderator, a tubular reactor via the reactor inlet and one or more side branches fed.
  • the monomer streams can have different compositions here (EP-A-0 271 738).
  • the copolymers mentioned under B) are the mineral oils mentioned under A) or Mineral oil distillates added in the form of solutions or dispersions. These solutions or Dispersions preferably contain 1 to 90, in particular 10 to 80,% by weight of the copolymers.
  • Suitable solvents or dispersing agents are aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, Pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures such as solvents Naphtha, "" Shellsol AB, "Solvesso 150," Solvesso 200, “Exxsol,” ISOPAR and "Shellsol D types.
  • the Fuel oils according to the invention preferably contain 0.001 to 2, in particular 0.005 to 0.5 % By weight of copolymer, based on the distillate.
  • the fuel oils of the invention may contain other oil-soluble co-additives that are already for only the flow properties of crude oils, lubricating oils or fuel oils improve.
  • co-additives are copolymers containing vinyl acetate or terpolymers of ethylene, polar compounds which effect paraffin dispersion (paraffin dispersants), and Comb polymers.
  • Oil-soluble polar compounds with ionic or polar have been found as paraffin dispersants Groups, e.g. Amine salts and / or amides proven by the reaction aliphatic or aromatic Amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, Tri- or tetracarboxylic acids or their anhydrides are obtained (cf. US-4 211 534).
  • paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated Compounds optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (cf.
  • EP-A-0 154 177 the reaction products of alkenylspirobislactones with amines (cf. EP-A-0 413 279) and according to EP-A-0 606 055, reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated Compounds and polyoxyalkenyl ethers of lower unsaturated alcohols.
  • Comb polymers are polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers - Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Examples of suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf.
  • EP-A-0 153 176 copolymers of a C 6 -C 24 - ⁇ -olefin and an NC 6 - to C 22 -alkylmaleimide (cf. EP- A-0 320 766), furthermore esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
  • the new fuel oils can contain other additives, for example Dewaxing agents, corrosion inhibitors, antioxidants, lubricity additives or Sludge inhibitors.
  • Table 3 shows the effectiveness of the additives as flow improvers for mineral oil distillates using the CFPP test (Cold Filter Plugging Test according to EN 116) in various distillates from Scandinavian refineries.
  • the additives are used as 50% solutions in solvent naphtha.
  • EVA copolymer ethylene-vinyl acetate copolymer
  • V1 melt viscosity V 140 of 125 mPas
  • V2 melt viscosity
  • Test oil 1 Test oil 4
  • Test oil 5 Test oil 6
  • the CFPP is determined according to EN116, the PP according to ISO 3016 with an automatic device (Herzog MC 852).

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  • Engineering & Computer Science (AREA)
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Abstract

Fuel oil contains: (A) a mineral oil having a cloud point of less than -8 degrees C, a boiling point of less than 120 degrees C and a difference between CFPP and PP of less than 10 degrees C; and (B) one or more copolymers contg. bivalent structural units of formula: CH2CH2 (1) and one or more bivalent structural units for formula: CH2CR1CR2 (2) (where, R1 = H or CH3; R2 = COOR3, OR3 or OCOR3; and R3 = 4-30C alkyl); or a unit derived from maleic acid of formula (2a).

Description

Die vorliegende Erfindung betrifft Brennstofföle, die Mitteldestillate und Copolymere aus Ethylen und Estern ungesättigter Carbonsäuren enthalten, und die ein verbessertes Kaltfließverhalten zeigen.The present invention relates to fuel oils, the middle distillates and copolymers of ethylene and Contain esters of unsaturated carboxylic acids, and which show improved cold flow behavior.

Rohöle und durch Destillation von Rohölen gewonnene Mitteldestillate wie Gasöl, Dieselöl oder Heizöl, enthalten je nach Herkunft der Rohöle unterschiedliche Mengen an n-Paraffinen, die bei Emiedrigung der Temperatur als plättchenförmige Kristalle auskristallisieren und teilweise unter Einschluß von Öl agglomerieren. Dadurch kommt es zu einer Verschlechterung der Fließeigenschaften dieser Öle bzw. Destillate, wodurch beispielsweise bei Gewinnung, Transport, Lagerung und/oder Einsatz der Mineralöle und Mineralöldestillate Störungen auftreten können. Bei Mineralölen kann dieses Kristallisationsphänomen beim Transport durch Rohrleitungen vor allem im Winter zu Ablagerungen an den Rohrwänden, in Einzelfällen, z.B. bei Stillstand einer Pipeline, sogar zu deren völliger Verstopfung führen. Auch bei der Lagerung und Weiterverarbeitung der Mineralöle kann die Ausfällung von Paraffinen Schwierigkeiten verursachen. So kann es im Winter unter Umständen erforderlich sein, die Mineralöle in beheizten Tanks zu lagem. Bei Mineralöldestillaten können als Folge der Kristallisation Verstopfung der Filter in Dieselmotoren und Feuerungsanlagen auftreten, wodurch eine sichere Dosierung der Brennstoffe verhindert wird und gegebenenfalls eine völlige Unterbrechung der Kraftstoff- bzw. Heizmittelzufuhr eintritt.Crude oils and middle distillates obtained by distilling crude oils such as gas oil, diesel oil or heating oil, contain different amounts of n-paraffins depending on the origin of the crude oils, crystallize the temperature as platelet-shaped crystals and partially with the inclusion of oil agglomerate. This leads to a deterioration in the flow properties of these oils or Distillates, which, for example, during the extraction, transport, storage and / or use of Mineral oils and mineral oil distillates can occur. With mineral oils this can Crystallization phenomenon during transport through pipelines, especially in winter, leads to deposits the pipe walls, in individual cases, e.g. if a pipeline is at a standstill, even to completely block it to lead. Precipitation of can also occur during the storage and processing of mineral oils Paraffins cause difficulties. So it may be necessary in winter, the Store mineral oils in heated tanks. Mineral oil distillates can result from crystallization Clogging of the filters in diesel engines and combustion plants occur, making them safe Dosing of the fuel is prevented and, if necessary, a complete interruption of the Fuel or heating medium supply occurs.

Neben den klassischen Methoden zur Beseitigung der auskristallisierten Paraffine (thermisch, mechanisch oder mit Lösungsmitteln), die sich lediglich auf die Entfernung der bereits gebildeten Ausfällungen beziehen, wurden in den letzten Jahren chemische Additive (sogenannten Fließverbesserer oder Paraffin-Inhibitoren) entwickelt, die durch physikalisches Zusammenwirken mit den ausfallenden Paraffinkristallen dazu führen, daß deren Form, Größe und Adhäsionseigenschaften modifiziert werden. Die Additive wirken dabei als zusätzliche Kristallkeime und kristallisieren teilweise mit den Paraffinen aus, wodurch eine größere Anzahl von kleineren Paraffinkristallen mit veränderter Kristallform resultiert. Ein Teil der Wirkung der Additive wird auch durch eine Dispergierung der Paraffinkristalle erklärt. Die modifizierten Paraffinkristalle neigen weniger zur Agglomeration, so daß sich die mit diesen Additiven versetzten Öle noch bei Temperaturen pumpen bzw. verarbeiten lassen, die oft mehr als 20°C tiefer liegen als bei nichtadditivierten Ölen.In addition to the classic methods for removing the crystallized paraffins (thermal, mechanically or with solvents) that only affect the removal of those already formed Related precipitates, chemical additives (so-called Flow improvers or paraffin inhibitors) developed by physical interaction with The failing paraffin crystals cause their shape, size and adhesive properties be modified. The additives act as additional crystal nuclei and partially crystallize with the paraffins, resulting in a larger number of smaller paraffin crystals with altered Crystal form results. Part of the effect of the additives is also by dispersing the Paraffin crystals explained. The modified paraffin crystals are less prone to agglomeration, so that the oils mixed with these additives can still be pumped or processed at temperatures, which are often more than 20 ° C lower than with non-additive oils.

Das Fließ- und Kälteverhalten von Mineralölen und Mineralöldestillaten wird durch Angabe des Pour-Points (bestimmt nach ISO 3016) und des Cold-Filter-Plugging-Points (CFPP; bestimmt nach EN 116) beschrieben. Beide Kenngrößen werden in °C gemessen.The flow and cold behavior of mineral oils and mineral oil distillates is determined by specifying the pour point (determined according to ISO 3016) and the cold filter plugging point (CFPP; determined according to EN 116) described. Both parameters are measured in ° C.

Typische Fließverbesserer für Rohöle und Mitteldestillate sind Copolymerisate des Ethylens mit Carbonsäureestem des Vinylalkohols. So setzt man nach der DE-A-11 47 799 Erdöldestillat-Treib- bzw. -Brennstoffen mit einem Siedepunkt zwischen etwa 120 und 400°C öllösliche Mischpolymerisate aus Ethylen und Vinylacetat mit einem Molekulargewicht zwischen etwa 1.000 und 3.000 zu. Bevorzugt werden Mischpolymerisate, die etwa 60 bis 99 Gew.-% Ethylen und etwa 1 bis 40 Gew.-% Vinylacetat enthalten. Sie sind besonders wirksam, wenn sie durch radikalische Polymerisation in einem inerten Lösungsmittel bei Temperaturen von etwa 70 bis 130°C und Drücken von 35 bis 2.100 atü hergestellt wurden (DE-A-1914 756).Typical flow improvers for crude oils and middle distillates are copolymers of ethylene with Carboxylic acid ester of vinyl alcohol. So according to DE-A-11 47 799 petroleum distillate propellant or fuels with a boiling point between about 120 and 400 ° C oil-soluble copolymers from ethylene and vinyl acetate with a molecular weight between about 1,000 and 3,000. Copolymers containing about 60 to 99% by weight of ethylene and about 1 to 40% by weight are preferred. Contain vinyl acetate. They are particularly effective when used in radical polymerization an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2,100 were manufactured (DE-A-1914 756).

Andere als Fließverbesserer eingesetzte Polymerisate enthalten neben Ethylen und Vinylacetat z.B. Hexen-1 (vgl. EP-A-0184 083), Diisobutylen (vgl. EP-A-0 203 554) oder ein Isoolefin der Formel

Figure 00020001
wobei R und R' gleich oder verschieden sind und Wasserstoff oder C1-C4-Alkylreste bedeuten (EP-A-0 099 646). Auch Mischpolymerisate aus Ethylen, Alkencarbonsäureester und/oder Vinylester und Vinylketon werden als Stockpunktemiedriger und zur Verbesserung des Fließverhaltens von Rohölen und Mitteldestillaten der Rohöle verwendet (EP-A-0 111 888).In addition to ethylene and vinyl acetate, other polymers used as flow improvers contain, for example, hexene-1 (cf. EP-A-0184 083), diisobutylene (cf. EP-A-0 203 554) or an isoolefin of the formula
Figure 00020001
wherein R and R 'are the same or different and are hydrogen or C 1 -C 4 alkyl radicals (EP-A-0 099 646). Copolymers of ethylene, alkenecarboxylic acid ester and / or vinyl ester and vinyl ketone are also used as pour point depressants and to improve the flow behavior of crude oils and middle distillates of the crude oils (EP-A-0 111 888).

Daneben werden auch Copolymere auf der Basis von α,β-ungesättigten Verbindungen und Maleinsäureanhydrid als Fließverbesserer verwendet. In addition, copolymers based on α, β-unsaturated compounds and Maleic anhydride used as a flow improver.

DE-196 45 603 beschreibt Copolymere aus 60 bis 99 mol -% von Ethylen abgeleiteten Struktureinheiten und 1 bis 40 mol-% aus Struktureinheiten, die sich von der Maleinsäure, ihrem Anhydrid oder dessen Imiden ableiten.DE-196 45 603 describes copolymers of 60 to 99 mol% derived from ethylene Structural units and 1 to 40 mol% of structural units that differ from maleic acid, its Derive anhydride or its imides.

DE-1 162 630 offenbart Copolymerisate aus Ethylen und Vinylestem von geradkettigen Fettsäuren mit 4 bis 18 Kohlenstoffatomen als stockpunktemiedrigendes Additiv für Destillatbrennstoffe mittlerer Siedelage wie Hiezöl oder Dieselöl.DE-1 162 630 discloses copolymers of ethylene and vinyl esters of straight-chain fatty acids 4 to 18 carbon atoms as a pour point reducing additive for distillate fuels of medium size Siedelage such as Hiezöl or diesel oil.

EP-A-0 217 602 offenbart Ethylen-Copolymere mit C1- bis C18-Alkylresten tragenden Vinylestem als Fließverbesserer für Mineralöldestillate mit Siedebereichen (90 - 20) % von unter 100°C.EP-A-0 217 602 discloses ethylene copolymers with vinyl esters bearing C 1 to C 18 alkyl radicals as flow improvers for mineral oil distillates with boiling ranges (90-20)% below 100 ° C.

EP-A-0 493 769 offenbart Terpolymere, die aus Ethylen, Vinylacetat und Neononan- bzw. Neodecansäurevinylester hergestellt werden, sowie ihre Verwendung als Additive für Mineratöldestillate.EP-A-0 493 769 discloses terpolymers which consist of ethylene, vinyl acetate and neononane or Neodecanoic acid vinyl esters are produced, and their use as additives for Mineratöldestillate.

EP-A-0 746 598 offenbart Copolymerisate von Ethylen und Di-Alkylfumaraten in Mischung mit Mineralölen, die einen Cloud Point von unterhalb -10°C aufweisen.EP-A-0 746 598 discloses copolymers of ethylene and di-alkyl fumarates mixed with Mineral oils with a cloud point below -10 ° C.

Die Wirksamkeit der bekannten Zusatzstoffe zur Verbesserung der Eigenschaften von Mineralölfraktionen ist u.a. abhängig von der Herkunft des Mineralöls, aus dem sie gewonnen wurden und damit insbesondere von dessen Zusammensetzung. Additive, die zur Einstellung bestimmter Eigenschaftswerte von Fraktionen eines Rohöls hervorragend geeignet sind, können daher bei Destillaten von Rohölen anderen Ursprungs zu völlig unbefriedigenden Ergebnissen führen.The effectiveness of known additives to improve the properties of Mineral oil fractions include depending on the origin of the mineral oil from which they were obtained and in particular its composition. Additives used to adjust certain Property values of fractions of a crude oil are therefore extremely suitable Distillates of crude oils of other origin lead to completely unsatisfactory results.

Im Zuge des gestiegenen Umweltbewußtseins werden neuerdings Kraftstoffe hergestellt, die bei ihrer Verbrennung geringere Umweltbelastungen verursachen. Entsprechende Dieselkraftstoffe zeichnen sich durch einen sehr geringen Schwefelgehalt von weniger als 500 ppm und insbesondere weniger als 100 ppm, einen niedrigen Aromatengehalt und eine niedrige Dichte von weniger als 0,86, insbesondere weniger als 0,84 g/ml aus. Sie lassen sich mit herkömmlichen Fließverbesserem nicht oder nur ungenügend additivieren. Probleme bereiten dabei vor allem die für den Einsatz unter arktischen Bedingungen hergestellten Winterqualitäten von Dieselkraftstoffen mit ihren extremen Kätteeigenschaften, wie z.B. einem Cloud Point kleiner -8°C und insbesondere kleiner -15°C, sehr engen Destillationsschnitten mit Siedebereichen von 20 bis 90 Vol.-% kleiner 120°C, insbesondere kleiner 100°C und teilweise auch kleiner 80°C, und einem Destillationsvolumen von 95 Vol-% bei Temperaturen unter 360°C, insbesondere unter 350°C und speziell unter 330°C. Die Kälteeigenschaften solcher Destillate können derzeit nur über die Zugabe von leichter siedenden, paraffinarmen Komponenten, wie z.B. Kerosin, zufriedenstellend verbessert werden.In the course of increasing environmental awareness, fuels are now being produced that are used in their Burn cause less environmental pollution. Draw appropriate diesel fuels a very low sulfur content of less than 500 ppm and in particular less than 100 ppm, a low aromatic content and a low density of less than 0.86, in particular less than 0.84 g / ml. They cannot be done with conventional flow improvers or insufficiently additive. The main problems are those for use under arctic conditions produced winter qualities of diesel fuels with their extreme Katte properties, such as a cloud point below -8 ° C and especially below -15 ° C, very much narrow distillation cuts with boiling ranges from 20 to 90 vol .-% less than 120 ° C, in particular less than 100 ° C and sometimes also less than 80 ° C, and a distillation volume of 95% by volume Temperatures below 360 ° C, especially below 350 ° C and especially below 330 ° C. The Cold properties of such distillates can currently only be achieved by adding low-boiling, low-paraffin components, e.g. Kerosene, can be improved satisfactorily.

Problematisch für das Ansprechverhalten von Fließverbesserem an diesen Ölen ist die durch enge Destillationsschnitte und niedrige Siedeenden verursachte Zusammensetzung: Diese Öle haben eine Paraffinverteilung mit Maximum bei etwa C12 bis C14 und enthalten nur unwesentliche Mengen der aus herkömmlichen Qualitäten auskristallisierenden n-Paraffine mit Kohlenwasserstoffketten länger als C18. Die Cloud-Points und CFPP-Werte liegen speziell bei den Winterqualitäten so niedrig, daß herkömmliche Fließverbesserer nicht ansprechen und die Kätteeigenschaften durch Verdünnen mit Kerosin eingestellt werden müssen.The composition caused by narrow distillation cuts and low boiling ends is problematic for the response behavior of flow improvers to these oils: These oils have a paraffin distribution with a maximum at around C 12 to C 14 and contain only insignificant amounts of the n-paraffins with hydrocarbon chains that crystallize from conventional grades longer as C 18 . The cloud points and CFPP values are so low, especially in terms of winter qualities, that conventional flow improvers do not respond and the properties of the liquid have to be adjusted by diluting with kerosene.

Es bestand daher die Aufgabe, neue Brennstofföle mit einer gegenüber dem Stand der Technik verbesserten Fließfähigkeit in der Kälte zu entwickeln.It was therefore the task of new fuel oils with a compared to the prior art to develop improved flowability in the cold.

Überraschenderweise wurde gefunden, daß Hauptkettenpolymere aus Ethylen, die Seitenketten mit mehr als 5 Kohlenstoffatomen tragen, geeignet sind, den CFPP auch in den oben beschriebenen Mitteldestillaten abzusenken. Ethylen/Vinylacetat-Copolymere mit entsprechenden Comonomergehalten sind dagegen in Kohlenwasserstoffen praktisch unlöslich.Surprisingly, it was found that main chain polymers made of ethylene, the side chains with carry more than 5 carbon atoms, are suitable, the CFPP also in those described above Lower middle distillates. Ethylene / vinyl acetate copolymers with corresponding In contrast, comonomer contents are practically insoluble in hydrocarbons.

Gegenstand der Erfindung sind Brennstofföle, bestehend aus

  • A) einem Mineralöl mit einem Schwefelgehalt von weniger als 100 ppm, einem Cloud Point von weniger als -8°C, einem Siedebereich (90-20 %) von weniger als 120°C und einer Differenz zwischen cold filter plugging point (CFPP) und pour point (PP) von weniger als 10°C, und
  • B) einem Copolymer, enthaltend 85 bis 97 mol-% bivalente Struktureinheiten der Formel
  • B1) -CH2-CH2- und 3 bis 15 mol-% einer oder mehrerer der bivalenten Struktureinheiten B2)
  • B2) -CH2-CR1R2-
    • worin R1 Wasserstoff oder Methyl und R2 COOR3, OR3 oder OCOR3 bedeuten, wobei R3 für einen Alkylrest mit mindestens 8 und höchstens 24 Kohlenstoffatomen steht, und bis zu 3 mol-% vom Vinylacetat abgeleitete Struktureinheiten oder bis zu 5 mol-% von weiteren Comonomeren abgeleitete Struktureinheiten.The invention relates to fuel oils consisting of
  • A) a mineral oil with a sulfur content of less than 100 ppm, a cloud point of less than -8 ° C, a boiling range (90-20%) of less than 120 ° C and a difference between cold filter plugging point (CFPP) and pour point (PP) of less than 10 ° C, and
  • B) a copolymer containing 85 to 97 mol% of bivalent structural units of the formula
  • B1) -CH 2 -CH 2 - and 3 to 15 mol% of one or more of the bivalent structural units B2)
  • B2) -CH 2 -CR 1 R 2 -
    • where R 1 is hydrogen or methyl and R 2 is COOR 3 , OR 3 or OCOR 3 , where R 3 is an alkyl radical having at least 8 and at most 24 carbon atoms, and up to 3 mol% of structural units derived from vinyl acetate or up to 5 mol % of structural units derived from further comonomers.

    Der Cloud Point der unter A) genannten Mineralöle liegt vorzugsweise unter -15°C. Die Siedebereiche (90-20 %) der Destillationsschnitte betragen vorzugsweise weniger als 100°C, insbesondere weniger als 80°C. Bevorzugt ist die Verwendung von Mineralölen mit einem 95 %-Destillationspunkt von unter 360°C, insbesondere unter 350°C, speziell unter 330°C.The cloud point of the mineral oils mentioned under A) is preferably below -15 ° C. The boiling ranges (90-20%) of the distillation cuts are preferably less than 100 ° C., in particular less than 80 ° C. It is preferred to use mineral oils with a 95% distillation point below 360 ° C, especially below 350 ° C, especially below 330 ° C.

    Vorzugsweise bedeutet R1 Wasserstoff. R3 steht vorzugsweise für einen linearen oder verzweigten C8-C18-Alkylrest. In einer weiteren, besonders bevorzugten Ausführungsform der Erfindung bedeutet R einen Neoalkylrest mit 7 bis 11 Kohlenstoffatomen, insbesondere einen Neoalkylrest mit 8, 9 oder 10 Kohlenstoffatomen. Die Neoalkylsäuren, von denen sich die oben genannten Neoalkylreste ableiten lassen, werden durch die Formel (3) beschrieben:

    Figure 00050001
    R' und R" sind lineare Alkylreste mit zusammen vorzugsweise 5 bis 9, insbesondere 6, 7 oder 8 Kohlenstoffatomen. Der zur Copolymerisation verwendete Vinylester hat demzufolge die Formel (4):
    Figure 00060001
    R 1 is preferably hydrogen. R 3 preferably represents a linear or branched C 8 -C 18 alkyl radical. In a further, particularly preferred embodiment of the invention, R denotes a neoalkyl radical with 7 to 11 carbon atoms, in particular a neoalkyl radical with 8, 9 or 10 carbon atoms. The neoalkyl acids from which the above-mentioned neoalkyl radicals can be derived are described by the formula (3):
    Figure 00050001
    R 'and R "are linear alkyl radicals with a total of preferably 5 to 9, in particular 6, 7 or 8, carbon atoms. The vinyl ester used for the copolymerization accordingly has the formula (4):
    Figure 00060001

    Weitere geeignete Comonomere sind solche, die sich von der Acrylsäure ableiten lassen:

    Figure 00060002
    Other suitable comonomers are those which can be derived from acrylic acid:
    Figure 00060002

    Bevorzugte Reste R3 sind beispielsweise Butyl, tert.-Butyl, Pentyl, neo-Pentyl, Octyl, 2-Ethylhexyl, Decyl, Dodecyl, Tetradecyl, Hexadecyl, Octadecyl und Behenyl.Preferred radicals R 3 are, for example, butyl, tert-butyl, pentyl, neopentyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and behenyl.

    Die erfindungsgemäßen Brennstoffölzusammensetzungen enthalten vorzugsweise Copolymere, in denen die Comonomere B1) mit 90 bis 96 mol-% und die Comonomere B2) mit 4 bis 10 mol-% enthalten sind.The fuel oil compositions according to the invention preferably contain copolymers in which the comonomers B1) with 90 to 96 mol% and the comonomers B2) with 4 to 10 mol% are included.

    Die unter B) genannten Copolymere sind durch die üblichen Copolymerisationsverfahren wie beispielsweise Suspensionspolymerisation, Lösungsmittelpolymerisation, Gasphasenpolymerisation oder Hochdruckmasse-polymerisation herstellbar. Bevorzugt ist dabei die Hochdruckmassepolymerisation bei Drucken von vorzugsweise 50 bis 400, insbesondere 100 bis 300 MPa und Temperaturen von vorzugsweise 50 bis 300, insbesondere 100 bis 250°C. Die Reaktion der Monomeren wird durch Radikale bildende Initiatoren (Radikalkettenstarter) eingeleitet. Zu dieser Substanzklasse gehören z.B. Sauerstoff, Hydroperoxide, Peroxide und Azoverbindungen wie Cumolhydroperoxid, t-Butylhydroperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis(2-ethylhexyl)peroxidcarbonat, t-Butylperpivalat, t-Butylpermaleinat, t-Butylperbenzoat, Dicumylperoxid, t-Butylcumylperoxid, Di-(t-butyl)peroxid, 2,2'-Azo-bis(2-methylpropanonitril), 2,2'-Azo-bis(2-methylbutyronitril). Die Initiatoren werden einzeln oder als Gemisch aus zwei oder mehr Substanzen in Mengen von 0,001 bis 20 Gew.-%, vorzugsweise 0,01 bis 10 Gew.-%, bezogen auf das Monomerengemisch, eingesetzt. The copolymers mentioned under B) are as usual by the usual copolymerization for example suspension polymerization, solvent polymerization, gas phase polymerization or high-pressure mass polymerization. The is preferred High pressure bulk polymerization at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 300, in particular 100 to 250 ° C. The reaction of the Monomers are initiated by radical initiators (radical chain initiators). To this Substance classes belong e.g. Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-Butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile). The initiators are used individually or as a mixture of two or more substances Amounts of 0.001 to 20 wt .-%, preferably 0.01 to 10 wt .-%, based on the Monomer mixture used.

    Vorzugsweise haben die unter B) genannten Copolymere Schmelzviskositäten bei 140°C von 20 bis 10.000 mPas, insbesondere von 30 bis 5000 mPas, speziell von 50 bis 2000 mPas. Die gewünschte Schmelzviskosität dieser Copolymerisate wird bei gegebener Zusammensetzung des Monomerengemisches durch Variation der Reaktionsparameter Druck und Temperatur und gegebenenfalls durch Zusatz von Moderatoren eingestellt. Als Moderatoren haben sich Wasserstoff, gesättigte oder ungesättigte Kohlenwasserstoff, z.B. Propan, Aldehyde, z.B. Propionaldehyd, n-Butyraldehyd oder Isobutyraldehyd, Ketone, z.B. Aceton, Methylethylketon, Methylisobutylketon, Cyclohexanon oder Alkohole, z.B. Butanol, bewährt. In Abhängigkeit von der angestrebten Viskosität werden die Moderatoren in Mengen bis zu 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-%, bezogen auf das Monomerengemisch, angewandt.The copolymers mentioned under B) preferably have melt viscosities at 140 ° C. of 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas. The desired Melt viscosity of these copolymers is given the given composition of Monomer mixture by varying the reaction parameters pressure and temperature and possibly by adding moderators. The moderators are hydrogen, saturated or unsaturated hydrocarbon, e.g. Propane, aldehydes, e.g. Propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone or alcohols, e.g. Butanol, proven. Depending on the desired viscosity the moderators are used in amounts of up to 20% by weight, preferably 0.05 to 10% by weight the mixture of monomers applied.

    Die unter B) genannten Copolymere können bis zu 3 mol-% Vinylacetat oder bis zu 5 mol-% weiterer Comonomere enthalten. Solche Comonomere können beispielsweise Vinylester, Vinylether, Acrylsäurealkylester, Methacrylsäurealkylester oder höhere Olefine mit mindestens 5 Kohlenstoffatomen sein. Bevorzugt als höhere Olefine sind Hexen, 4-Methylpenten, Octen oder Diisobutylen.The copolymers mentioned under B) can contain up to 3 mol% of vinyl acetate or up to 5 mol% of more Comonomers included. Such comonomers can, for example, vinyl esters, vinyl ethers, Acrylic acid alkyl esters, methacrylic acid alkyl esters or higher olefins with at least 5 Be carbon atoms. Hexene, 4-methylpentene, octene or are preferred as higher olefins Diisobutylene.

    Um die unter B) genannten Copolymerisate zu erhalten verwendet man Monomerengemische, die außer Ethylen und gegebenenfalls einem Moderator 1 bis 50 Gew.-%, vorzugsweise 3 bis 40 Gew.-% Comonomer enthalten. Mit der von der Zusammensetzung des Copolymerisats abweichenden Zusammensetzung des Monomerengemisches trägt man der unterschiedlichen Polymerisationsgeschwindigkeit der Monomeren Rechnung. Die Polymerisate fallen als farblose Schmelzen an, die bei Raumtemperatur zu wachsartigen Feststoffen erstarren.In order to obtain the copolymers mentioned under B), monomer mixtures are used which in addition to ethylene and optionally a moderator 1 to 50% by weight, preferably 3 to 40% by weight Comonomer included. With that deviating from the composition of the copolymer The composition of the monomer mixture is carried by the different ones Polymerization rate of the monomers calculation. The polymers fall as colorless Melt, which solidify to waxy solids at room temperature.

    Die Hochdruckmassepolymerisation wird in bekannten Hochdruckreaktoren, z.B. Autoklaven oder Rohrreaktoren, diskontinuierlich oder kontinuierlich durchgeführt, besonders bewährt haben sich Rohrreaktoren. Lösungsmittel wie aliphatische und/oder aromatische Kohlenwasserstoffe oder Kohlenwasserstoffgemische, Benzol oder Toluol, können im Reaktionsgemisch enthalten sein. Bevorzugt ist die lösungsmittelfreie Arbeitsweise. In einer bevorzugten Ausführungsform der Polymerisation wird das Gemisch aus den Monomeren, dem Initiator und, sofem eingesetzt, dem Moderator, einem Rohrreaktor über den Reaktoreingang sowie über einen oder mehrere Seitenäste zugeführt. Hierbei können die Monomerenströme unterschiedlich zusammengesetzt sein (EP-A-0 271 738).High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or Tube reactors, carried out batchwise or continuously, have proven particularly useful Tubular reactors. Solvents such as aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, benzene or toluene can be contained in the reaction mixture. The solvent-free mode of operation is preferred. In a preferred embodiment of the Polymerization is the mixture of the monomers, the initiator and, if used, the Moderator, a tubular reactor via the reactor inlet and one or more side branches fed. The monomer streams can have different compositions here (EP-A-0 271 738).

    Die unter B) genannten Copolymerisate werden den unter A) genannten Mineralölen oder Mineralöldestillaten in Form von Lösungen oder Dispersionen zugesetzt. Diese Lösungen oder Dispersionen enthalten vorzugsweise 1 bis 90, insbesondere 10 bis 80 Gew.-% der Copolymerisate. Geeignete Lösungs- oder Dispersionsmittel sind aliphatische und/oder aromatische Kohlenwasserstoffe oder Kohlenwasserstoffgemische, z.B. Benzinfraktionen, Kerosin, Decan, Pentadecan, Toluol, Xylol, Ethylbenzol oder kommerzielle Lösungsmittelgemische wie Solvent Naphtha, ""Shellsol AB, "Solvesso 150, "Solvesso 200, "Exxsol, "ISOPAR- und "Shellsol D-Typen. Die erfindungsgemäßen Brennstofföle enthalten vorzugsweise 0,001 bis 2, insbesondere 0,005 bis 0,5 Gew.-% Copolymerisat, bezogen auf das Destillat.The copolymers mentioned under B) are the mineral oils mentioned under A) or Mineral oil distillates added in the form of solutions or dispersions. These solutions or Dispersions preferably contain 1 to 90, in particular 10 to 80,% by weight of the copolymers. Suitable solvents or dispersing agents are aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, Pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures such as solvents Naphtha, "" Shellsol AB, "Solvesso 150," Solvesso 200, "Exxsol," ISOPAR and "Shellsol D types. The Fuel oils according to the invention preferably contain 0.001 to 2, in particular 0.005 to 0.5 % By weight of copolymer, based on the distillate.

    Die erfindungsgemäßen Brennstofföle können weitere öllösliche Co-Additive enthalten, die bereits für sich allein die Kaftfließeigenschaften von Rohölen, Schmierölen oder Brennölen verbessem. Beispiele solcher Co-Additive sind Vinylacetat enthaltende Copolymerisate oder Terpolymerisate des Ethylens, polare Verbindungen, die eine Paraffindispergierung bewirken (Paraffindispergatoren), sowie Kammpolymere.The fuel oils of the invention may contain other oil-soluble co-additives that are already for only the flow properties of crude oils, lubricating oils or fuel oils improve. Examples such co-additives are copolymers containing vinyl acetate or terpolymers of ethylene, polar compounds which effect paraffin dispersion (paraffin dispersants), and Comb polymers.

    Als Paraffindispergatoren haben sich öllösliche polare Verbindungen mit ionischen oder polaren Gruppen, z.B. Aminsalze und/oder Amide bewährt, die durch Reaktion aliphatischer oder aromatischer Amine, vorzugsweise langkettiger aliphatischer Amine, mit aliphatischen oder aromatischen Mono-, Di-, Tri- oder Tetracarbonsäuren oder deren Anhydriden erhalten werden (vgl. US-4 211 534). Andere Paraffindispergatoren sind Copolymere des Maleinsäureanhydrids und α,β-ungesättigten Verbindungen, die gegebenenfalls mit primären Monoalkylaminen und/oder aliphatischen Alkoholen umgesetzt werden können (vgl. EP-A-0 154 177), die Umsetzungsprodukte von Alkenylspirobislactonen mit Aminen (vgl. EP-A-0 413 279) und nach EP-A-0 606 055, Umsetzungsprodukte von Terpolymerisaten auf Basis α,β-ungesättigter Dicarbonsäureanhydride, α,β-ungesättigter Verbindungen und Polyoxyalkenylether niederer ungesättigter Alkohole.Oil-soluble polar compounds with ionic or polar have been found as paraffin dispersants Groups, e.g. Amine salts and / or amides proven by the reaction aliphatic or aromatic Amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, Tri- or tetracarboxylic acids or their anhydrides are obtained (cf. US-4 211 534). Other Paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated Compounds optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (cf. EP-A-0 154 177), the reaction products of alkenylspirobislactones with amines (cf. EP-A-0 413 279) and according to EP-A-0 606 055, reaction products of terpolymers based on α, β-unsaturated dicarboxylic anhydrides, α, β-unsaturated Compounds and polyoxyalkenyl ethers of lower unsaturated alcohols.

    Kammpolymere sind Polymere, bei denen Kohlenwasserstoffreste mit mindestens 8, insbesondere mindestens 10 Kohlenstoffatomen an einem Polymemickgrat gebunden sind. Vorzugsweise handelt es sich um Homopolymeren, deren Alkylseitenketten mindestens 8 und insbesondere mindestens 10 Kohlenstoffatome enthalten. Bei Copolymeren weisen mindestens 20 %, bevorzugt mindestens 30 % der Monomeren Seitenketten auf (vgl. Comb-like Polymers - Structure and Properties; N.A. Platé and V.P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Beispiele für geeignete Kammpolymere sind z.B. Fumarat/Vinylacetat-Copolymere (vgl. EP-A-0 153 176), Copolymere aus einem C6-C24-α-Olefin und einem N-C6- bis C22-Alkylmaleinsäureimid (vgl. EP-A-0 320 766), femer veresterte Olefin/Maleinsäureanhydrid-Copolymere, Polymere und Copolymere von α-Olefinen und veresterte Copolymere von Styrol und Maleinsäureanhydrid.Comb polymers are polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers - Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Examples of suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP-A-0 153 176), copolymers of a C 6 -C 24 -α-olefin and an NC 6 - to C 22 -alkylmaleimide (cf. EP- A-0 320 766), furthermore esterified olefin / maleic anhydride copolymers, polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride.

    Die neuen Brennstofföle können andere Zusatzstoffe enthalten, beispielsweise Entwachsungshilfsmittel, Korrosionsinhibitoren, Antioxidantien, Lubricity-Additive oder Schlamminhibitoren.The new fuel oils can contain other additives, for example Dewaxing agents, corrosion inhibitors, antioxidants, lubricity additives or Sludge inhibitors.

    BeispieleExamples

    Es wurden folgende Additive A1 bis A5 hergestellt:

  • A1: Mit Cocosfettalkylamin imidiertes Ethylen-MSA-Copolymer mit 30 Gew.-% (8 mol-%) MSA.
  • A2: Ethylen-VeoVa-Copolymer mit 7 mol-% VeoVa 10 und einer V140 von 200 mPas.
  • A3: Ethylen-VeoVa-Copolymer mit 14 mol-% VeoVa 10 und einer V140 von 270 mPas.
  • A4: Ethylen-VeoVa-Copolymer mit 7 mol-% VeoVa 11 und einer V140 von 84 mPas.
  • A5: Copolymerisat aus Ethylen und 8 mol-% Stearylacrylat mit einer V140 = 65 mPas.
    • MSA =
    Maleinsäureanhydrid
    VeoVa 10/11 =
    Neodecan-/Neoundecansäurevinylester
    V140 =
    gemäß ISO 3219 mit Platte-Kegel-Meßsystem bei 140°C bestimmte Schmelzviskosität des Copolymers
    The following additives A1 to A5 were produced:
  • A1: Ethylene-MSA copolymer imidized with coconut fatty alkylamine with 30% by weight (8 mol%) of MSA.
  • A2: Ethylene VeoVa copolymer with 7 mol% VeoVa 10 and a V 140 of 200 mPas.
  • A3: Ethylene VeoVa copolymer with 14 mol% VeoVa 10 and a V 140 of 270 mPas.
  • A4: Ethylene VeoVa copolymer with 7 mol% VeoVa 11 and a V 140 of 84 mPas.
  • A5: Copolymer of ethylene and 8 mol% stearyl acrylate with a V 140 = 65 mPas.
    • MSA =
    maleic anhydride
    VeoVa 10/11 =
    Neodecanoic / Neoundecansäurevinylester
    V 140 =
    according to ISO 3219 with plate-cone measuring system at 140 ° C determined melt viscosity of the copolymer

    Wirksamkeit der AdditiveEffectiveness of the additives

    Tabelle 3 gibt die Wirksamkeit der Additive als Fließverbesserer für Mineralöldestillate an Hand des CFPP-Tests (Cold Filter Plugging Test nach EN 116) in verschiedenen Destillaten skandinavischer Raffinerien wieder. Die Additive werden als 50 %ige Lösungen in Solvent Naphtha eingesetzt. Als Vergleich werden die Wirksamkeit eines handelsüblichen Ethylen-Vinylacetat-Copolymers (EVA-Copolymer) mit 13,3 mol-% Vinylacetat und einer Schmelzviskosität V140 von 125 mPas (V1) und eines handelsüblichen Eihylen-Vinylacetat-Neodecansäurevinylester-Terpolymers mit 16 mol-% Vinylacetat, 1,2 mol-% Neodecansäurevinylester und einer Schmelzviskosität V140 von 140 mPas (V2) wiedergegeben. Charakterisierung der Testöle: Testöl 1 Testöl 4 Testöl 5 Testöl 6 Siedebeginn 195°C 190°C 192°C 183°C 20 % 226°C 219°C 218°C 226°C 90 % 280°C 291°C 288°C 330°C 95 % 300°C 311°C 306°C 347°C Cloud Point -30°C -24°C -27°C -9°C CFPP -31°C -29°C -34°C -12°C Pour Point -30°C -27°C -27°C -21°C CFPP-PP -1°C -2°C -7°C 9°C Dichte (15°C) 0,821 0,817 0,819 0,835 Table 3 shows the effectiveness of the additives as flow improvers for mineral oil distillates using the CFPP test (Cold Filter Plugging Test according to EN 116) in various distillates from Scandinavian refineries. The additives are used as 50% solutions in solvent naphtha. As a comparison, the effectiveness of a commercially available ethylene-vinyl acetate copolymer (EVA copolymer) with 13.3 mol% of vinyl acetate and a melt viscosity V 140 of 125 mPas (V1) and of a commercially available ethylene-vinyl acetate-neodecanoic acid vinyl ester terpolymer with 16 mol% % Vinyl acetate, 1.2 mol% neodecanoic acid vinyl ester and a melt viscosity V 140 of 140 mPas (V2). Characterization of the test oils: Test oil 1 Test oil 4 Test oil 5 Test oil 6 Initial boiling point 195 ° C 190 ° C 192 ° C 183 ° C 20% 226 ° C 219 ° C 218 ° C 226 ° C 90% 280 ° C 291 ° C 288 ° C 330 ° C 95% 300 ° C 311 ° C 306 ° C 347 ° C Cloud point -30 ° C -24 ° C -27 ° C -9 ° C CFPP -31 ° C -29 ° C -34 ° C -12 ° C Pour point -30 ° C -27 ° C -27 ° C -21 ° C CFPP PP -1 ° C -2 ° C -7 ° C 9 ° C Density (15 ° C) 0,821 0,817 0.819 0.835

    Der CFPP wird nach EN116 bestimmt, der PP nach ISO 3016 mit einem automatischen Gerät (Herzog MC 852).

    Figure 00110001
    The CFPP is determined according to EN116, the PP according to ISO 3016 with an automatic device (Herzog MC 852).
    Figure 00110001

    Liste der verwendeten HandelsbezeichnungenList of trade names used

    Solvent Naphtha ®Shellsol AB ®Solvesso 150Solvent Naphtha ®Shellsol AB ®Solvesso 150 aromatische Lösemittelgemische mit Siedebereich 180 bis 210°Caromatic solvent mixtures with boiling range 180 to 210 ° C ®Solvesso 200®Solvesso 200 aromatisches Lösemittelgemisch mit Siedebereich 230 bis 287°Caromatic solvent mixture with boiling range 230 to 287 ° C ®Exxsol®Exxsol dearomatisierte Lösemittel in verschiedenen Siedebereichen, beispielsweise "Exxsol D60:187 bis 215°Cdearomatized solvents in various boiling ranges, for example "Exxsol D60: 187 to 215 ° C ®ISOPAR (Exxon)®ISOPAR (Exxon) isoparaffinische Lösemittelgemische in verschiedenen Siedebereichen, beispielsweise "ISOPAR L: 190 bis 210°Cisoparaffinic solvent mixtures in various boiling ranges, for example "ISOPAR L: 190 to 210 ° C ®Shellsol D®Shellsol D hauptsächlich aliphatische Lösemittelgemische in verschiedenen Siedebereichenmainly aliphatic solvent mixtures in different boiling ranges

    Claims (11)

    1. The use of one or more copolymers containing from 85 to 97 mol% of bivalent structural units of the formula
      B1) -CH2-CH2- and from 3 to 15 mol% of one or more of the bivalent structural units B2)
      B2) -CH2-CR1R2-
      in which R1 is hydrogen or methyl and R2 is COOR3, OR3 or OCOR3, R3 being an alkyl radical having at least 8 and at most 24 carbon atoms, and which may contain up to 3 mol% of structural units derived from vinyl acetate or up to 5 mol% of structural units derived from further comonomers, for improving the cold flow properties of mineral oils having a sulphur content of less than 100 ppm, a cloud point of less than -8°C, a boiling range (90-20%) of less than 120°C and a difference between cold filter plugging point (CFPP) and pour point (PP) of less than 10°C.
    2. The use as claimed in claim 1, wherein R1 is hydrogen.
    3. The use as claimed in claim 1 and/or 2, wherein R3 is a neoalkyl radical having 7 to 11 carbon atoms.
    4. The use as claimed in claim 1 and/or 2, wherein R3 is C8-C18-alkyl or a neoalkyl radical having 8, 9 or 10 carbon atoms.
    5. The use as claimed in one or more of claims 1 to 4, wherein the copolymers stated under B) have melt viscosities at 140°C of from 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
    6. The use as claimed in one or more of claims 1 to 5, wherein the copolymers stated under B) contain vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates or higher olefins having at least 5 carbon atoms, preferably hexene, 4-methylpentene, octene or diisobutylene.
    7. The use as claimed in one or more of claims 1 to 6, wherein the mineral oils have cloud points below -15°C.
    8. The use as claimed in one or more of claims 1 to 7, wherein the mineral oils have boiling ranges (90-20%) of less than 100°C, in particular less than 80°C.
    9. The use as claimed in one or more of claims 1 to 8, wherein the mineral oils have a 95% distillation point of less than 360°C.
    10. The use as claimed in one or more of claims 1 to 9, wherein the copolymers stated under B) contain from 4 to 10 mol% of comonomers B2).
    11. The use as claimed in one or more of claims 1 to 10, wherein the coadditives used are polar compounds which disperse paraffin (paraffin dispersants), comblike polymers, dewaxing assistants, corrosion inhibitors, antioxidants, lubricity additives or sludge inhibitors.
    EP98111799A 1997-07-08 1998-06-26 Use of copolymers of ethylene and unsaturated carboxylic esters in middle distillates to improve cold flow properties Expired - Lifetime EP0890633B1 (en)

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    DE19729055A DE19729055C2 (en) 1997-07-08 1997-07-08 Fuel oils based on middle distillates and copolymers of ethylene and unsaturated carboxylic acid esters

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    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE19802690C2 (en) * 1998-01-24 2003-02-20 Clariant Gmbh Additive for improving the cold flow properties of fuel oils
    DE10012267B4 (en) * 2000-03-14 2005-12-15 Clariant Gmbh Copolymer blends and their use as an additive to improve the cold flow properties of middle distillates
    DE10012269C2 (en) 2000-03-14 2003-05-15 Clariant Gmbh Use of copolymer mixtures as an additive to improve the cold flow properties of middle distillates
    DE10349851B4 (en) * 2003-10-25 2008-06-19 Clariant Produkte (Deutschland) Gmbh Cold flow improver for fuel oils of vegetable or animal origin
    JP4520160B2 (en) * 2004-01-08 2010-08-04 東邦化学工業株式会社 Fluidity improver for fuel oil
    US8152869B2 (en) 2007-12-20 2012-04-10 Shell Oil Company Fuel compositions
    WO2009080679A1 (en) * 2007-12-20 2009-07-02 Shell Internationale Research Maatschappij B.V. Process to prepare a gas oil and a base oil
    US8152868B2 (en) 2007-12-20 2012-04-10 Shell Oil Company Fuel compositions

    Family Cites Families (22)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB1165084A (en) * 1966-07-26 1969-09-24 Exxon Research Engineering Co Ethylene-Vinyl Ester Copolymers as Pour Depressants for Distillate Fuels
    US3792983A (en) * 1968-04-01 1974-02-19 Exxon Research Engineering Co Ethylene and acrylate esters, their preparation and their use as wax crystal modifiers
    US3762888A (en) * 1970-11-16 1973-10-02 Exxon Research Engineering Co Fuel oil composition containing oil soluble pour depressant polymer and auxiliary flow improving compound
    JPS5661488A (en) * 1979-10-25 1981-05-26 Nippon Synthetic Chem Ind Co Ltd:The Hydrocarbon oil composition
    JPS59126496A (en) * 1983-01-11 1984-07-21 Nippon Zeon Co Ltd Fuel oil composition
    CA1339640C (en) * 1987-07-28 1998-01-27 Tadayuki Ohmae Flow-improved fuel oil composition
    GB8820071D0 (en) * 1988-08-24 1988-09-28 Exxon Chemical Patents Inc Fuel compositions
    DE4020640A1 (en) * 1990-06-29 1992-01-02 Hoechst Ag TERPOLYMERISATES OF ETHYLENE, THEIR PRODUCTION AND THEIR USE AS ADDITIVES FOR MINERAL OIL DISTILLATES
    DE4042206A1 (en) * 1990-12-29 1992-07-02 Hoechst Ag ETHYLENE TERPOLYMERISES, THEIR PREPARATION AND THEIR USE AS ADDITIVES FOR MINERALOLE DISTILLATES
    GB9213904D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
    GB9213870D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
    DE4227905A1 (en) * 1992-08-22 1994-02-24 Hoechst Ag Copolymers of ethylene
    DE4241948A1 (en) * 1992-12-12 1994-06-16 Hoechst Ag Graft polymers, their preparation and use as pour point depressants and flow improvers for crude oils, residual oils and middle distillates
    DK0606055T3 (en) * 1993-01-06 1998-04-14 Clariant Gmbh Terpolymers on the basis of alpha, beta-unsaturated dicarboxylic acid anhydrides, alpha-beta-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols
    GB9403660D0 (en) * 1994-02-25 1994-04-13 Exxon Chemical Patents Inc Oil compositions
    GB9424565D0 (en) * 1994-12-06 1995-01-25 Exxon Chemical Patents Inc Fuel oil compositions
    JPH08165480A (en) * 1994-12-13 1996-06-25 Nippon Oil & Fats Co Ltd Fluidity improver for fuel oil
    JPH09208973A (en) * 1996-02-01 1997-08-12 Nof Corp Fuel oil composition
    DE19620118C1 (en) * 1996-05-18 1997-10-23 Hoechst Ag Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates
    DE19645603A1 (en) * 1996-11-06 1998-05-07 Clariant Gmbh Copolymers and terpolymers based on alpha, beta-unsaturated compounds and alpha, beta-unsaturated dicarboxylic acid anhydrides
    DE19700159A1 (en) * 1997-01-07 1998-07-09 Clariant Gmbh Increasing flow of mineral oil or distillate containing paraffin, especially at low temperature
    JP3790518B2 (en) * 2002-02-21 2006-06-28 三洋化成工業株式会社 Fluidity improver and fuel oil composition

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    DE59810973D1 (en) 2004-04-22
    DE19729055A1 (en) 1999-01-14
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