EP0890633A1 - Middle distillates and ethylene and unsaturated carboxylic esters copolymers containing fuel oils - Google Patents
Middle distillates and ethylene and unsaturated carboxylic esters copolymers containing fuel oils Download PDFInfo
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- EP0890633A1 EP0890633A1 EP98111799A EP98111799A EP0890633A1 EP 0890633 A1 EP0890633 A1 EP 0890633A1 EP 98111799 A EP98111799 A EP 98111799A EP 98111799 A EP98111799 A EP 98111799A EP 0890633 A1 EP0890633 A1 EP 0890633A1
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- fuel oils
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Classifications
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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
- 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
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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
- 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
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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
- 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
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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
- C10L1/22—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, middle distillates and copolymers contain from ethylene and esters of unsaturated carboxylic acids, and the one 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 ones depending on the origin of the crude oils Amounts of n-paraffins which, when the temperature is lowered, are platelet-shaped Crystallize crystals and partially agglomerate with the inclusion of oil. This leads to a deterioration in the flow properties of these oils or distillates, which means, for example, during extraction, transport, storage and / or use of mineral oils and mineral oil distillates can occur. With mineral oils, this crystallization phenomenon can occur during transport Pipelines, especially in winter, to build up deposits on the pipe walls 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 Specification of the pour point (determined according to ISO 3016) and the cold filter plugging point (CFPP; determined according to EN 116). Both parameters are in ° C measured.
- Typical flow improvers for crude oils and middle distillates are copolymers of Ethylene with carboxylic acid esters of vinyl alcohol. So you bet after the DE-A-11 47 799 petroleum distillate fuels with a boiling point between about 120 and 400 ° C oil-soluble copolymers of ethylene and Vinyl acetate with a molecular weight between about 1,000 and 3,000. Copolymers which contain about 60 to 99% by weight of ethylene and about are preferred Contain 1 to 40 wt .-% vinyl acetate. They are particularly effective when passed through radical polymerization in an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2,100 atü (DE-A-19 14 756).
- polymers used as flow improvers contain, in addition to ethylene and vinyl acetate, for example hexene-1 (cf. EP-A-0 184 083), diisobutylene (cf. EP-A-0 203 554) or an isoolefin of the formula 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).
- copolymers based on ⁇ , ⁇ -unsaturated Compounds and maleic anhydride used as flow improvers.
- DE-196 45 603 describes copolymers of 60 to 99 mol% of ethylene derived structural units and 1 to 40 mol% of structural units that are derived from maleic acid, its anhydride or its imides.
- DE-1 162 630 discloses copolymers of ethylene and vinyl esters of straight chain fatty acids with 4 to 18 carbon atoms as Pour point lowering additive for distillate fuels of medium boiling point such as Hot oil 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 mineral oil distillates.
- EP-A-0 746 598 discloses copolymers of ethylene and di-alkyl fumarates in Mix with mineral oils that have a cloud point below -10 ° C.
- the effectiveness of the known additives to improve the properties of mineral oil fractions includes depending on the origin of the mineral oil from which they were obtained and, in particular, from its composition. Additives that are used to set certain property values of fractions of a Crude oils are ideally suited for distillates of crude oils of other origin lead to completely unsatisfactory results.
- Corresponding diesel fuels are characterized by 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 can be used with conventional Do not add or only insufficiently add flow improvers. Problems arise especially those made for use under arctic conditions Winter qualities of diesel fuels with their extreme cold properties, such as e.g.
- a cloud point below -8 ° C and especially below -15 ° C very narrow Distillation cuts with boiling ranges from 20 to 90 vol .-% below 120 ° C, in particular less than 100 ° C and sometimes also less than 80 ° C, and one Distillation volume of 95 vol% at temperatures below 360 ° C, in particular below 350 ° C and especially below 330 ° C.
- the cold properties of such distillates can currently only by adding low-boiling, low paraffin Components such as Kerosene, can be improved satisfactorily.
- composition caused by narrow distillation cuts and low boiling points 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 for the winter qualities, that conventional flow improvers do not respond and the cold properties have to be adjusted by diluting with kerosene.
- the task was therefore to create new fuel oils with one compared to the stand the technology to develop improved flowability in the cold.
- the sulfur content of the mineral oils mentioned under A) is preferably less than 500, especially less than 300 ppm, especially less than 100 ppm.
- Your cloud point is preferably below -15 ° C.
- the boiling ranges (90-20%) of the Distillation cuts are preferably less than 100 ° C, especially less than 80 ° C.
- the use of mineral oils with a 95% distillation point is preferred 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 5 -C 24 alkyl radical, particularly preferably 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 therefore has the formula (4):
- Other 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 85 to 97 mol% and the Comonomers B2) with 3 to 15 mol% are contained. 4 to are particularly preferred 10 mol% B2) and 90 to 96 mol% B1).
- the copolymers mentioned under B) are by the usual copolymerization processes such as suspension polymerization, Solvent polymerization, gas phase polymerization or high pressure bulk polymerization producible.
- High-pressure bulk polymerization is preferred 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 is caused by free radical initiators (Radical chain starter) initiated.
- This class of substances includes 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 made individually or as a mixture two or more substances in amounts of 0.001 to 20% by weight, preferably 0.01 to 10 wt .-%, based on the monomer mixture, used.
- the copolymers mentioned under B) preferably have melt viscosities 140 ° C from 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 composition of the monomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired.
- Hydrogen, saturated or unsaturated hydrocarbon e.g. Propane, aldehydes, e.g. Propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g.
- the moderators become dependent on the desired viscosity in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture, applied.
- the copolymers mentioned under B) can contain up to 4% by weight of vinyl acetate or up to Contain 5 wt .-% of other comonomers.
- Such comonomers can for example vinyl esters, vinyl ethers, acrylic acid alkyl esters, methacrylic acid alkyl esters or higher olefins with at least 5 carbon atoms.
- Preferred as higher Olefins are hexene, 4-methylpentene, octene or diisobutylene.
- the high pressure mass polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tubular reactors, carried out batchwise or continuously, Tube reactors have proven particularly useful. Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, Benzene or toluene can be contained in the reaction mixture. The is preferred solvent-free mode of operation.
- the Polymerization is the mixture of the monomers, the initiator and, if provided used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches fed.
- the monomer streams be composed differently (EP-A-0 271 738).
- the copolymers mentioned under B) become the mineral oils mentioned under A) or mineral oil distillates in the form of solutions or dispersions.
- This Solutions or dispersions preferably contain 1 to 90, in particular 10 to 80% by weight of the copolymers.
- Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g.
- the fuel oils according to the invention preferably contain 0.001 to 2, in particular 0.005 to 0.5 wt .-% copolymer, based on the Distillate.
- the fuel oils according to the invention can contain further oil-soluble co-additives contain the cold flow properties of crude oils, Improve lubricating oils or fuel oils.
- co-additives are Copolymers containing vinyl acetate or terpolymers of ethylene, polar Compounds that cause paraffin dispersion (paraffin dispersants), as well as comb polymers.
- Oil-soluble polar compounds with ionic ones have been found as paraffin dispersants or polar groups, e.g. Amine salts and / or amides proven by 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 Pat. No. 4,211,534).
- Other Paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be reacted (cf.
- EP-A-0 154 177 the reaction products of alkenyl spirobislactones with amines (cf. EP-A-0 413 279) and according to EP-A-0 606 055, reaction products of Terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid 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), also 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 3
- Test oil 4 Test oil 5
- Test oil 6 Start of boiling 195 ° C 127 ° C 190 ° C 192 ° C 183 ° C 20% 226 ° C 193 ° C 219 ° C 218 ° C 226 ° C 90% 280 ° C 318 ° C 291 ° C 288 ° C 330 ° C 95% 300 ° C 330 ° C 311 ° C 306 ° C 347 ° C Cloud point -30 ° C -23 ° C -24 ° C -27 ° C -9 ° C CFPP -31 ° C -23 ° C -29 ° C -34 ° C -12 ° C Pour point -30 ° C -42 ° C -27 ° C -27 ° C -21 ° C CFPP-PP -1 ° C 19 ° C -2 ° C -7 ° C 9 ° C Density (15 °)
- the CFPP is determined according to EN116, the PP according to ISO 3016 with an automatic device (Herzog MC 852).
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Abstract
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, middle distillates and copolymers contain from ethylene and esters of unsaturated carboxylic acids, and the one 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 Erniedrigung 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 lagern. 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 ones depending on the origin of the crude oils Amounts of n-paraffins which, when the temperature is lowered, are platelet-shaped Crystallize crystals and partially agglomerate with the inclusion of oil. This leads to a deterioration in the flow properties of these oils or distillates, which means, for example, during extraction, transport, storage and / or use of mineral oils and mineral oil distillates can occur. With mineral oils, this crystallization phenomenon can occur during transport Pipelines, especially in winter, to build up deposits on the pipe walls Individual cases, e.g. if a pipeline is at a standstill, even to completely block it to lead. The can also be used for the storage and processing of mineral oils Precipitation of paraffins cause difficulties. So it can be in winter It may be necessary to store the mineral oils in heated tanks. At Mineral oil distillates can clog the filter as a result of crystallization Diesel engines and firing systems occur, creating safe metering 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° tiefer liegen als bei nichtadditivierten Ölen.In addition to the classic methods for removing the crystallized paraffins (thermal, mechanical or with solvents) that only affect the Removal of the already formed precipitates have been made in the last Years of chemical additives (so-called flow improvers or paraffin inhibitors) developed through 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, causing a larger number of results in smaller wax crystals with a changed crystal shape. A part of The effect of the additives is also explained by the dispersion of the wax crystals. The modified paraffin crystals are less prone to agglomeration, so that the pump oils mixed with these additives at temperatures or can be processed, which are often more than 20 ° 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 Specification of the pour point (determined according to ISO 3016) and the cold filter plugging point (CFPP; determined according to EN 116). Both parameters are in ° C measured.
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-19 14 756).Typical flow improvers for crude oils and middle distillates are copolymers of Ethylene with carboxylic acid esters of vinyl alcohol. So you bet after the DE-A-11 47 799 petroleum distillate fuels with a boiling point between about 120 and 400 ° C oil-soluble copolymers of ethylene and Vinyl acetate with a molecular weight between about 1,000 and 3,000. Copolymers which contain about 60 to 99% by weight of ethylene and about are preferred Contain 1 to 40 wt .-% vinyl acetate. They are particularly effective when passed through radical polymerization in an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2,100 atü (DE-A-19 14 756).
Andere als Fließverbesserer eingesetzte Polymerisate enthalten neben Ethylen und Vinylacetat z.B. Hexen-1 (vgl. EP-A-0 184 083), Diisobutylen (vgl. EP-A-0 203 554) oder ein Isoolefin der Formel 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 Stockpunkterniedriger und zur Verbesserung des Fließverhaltens von Rohölen und Mitteldestillaten der Rohöle verwendet (EP-A-0 111 888).Other polymers used as flow improvers contain, in addition to ethylene and vinyl acetate, for example hexene-1 (cf. EP-A-0 184 083), diisobutylene (cf. EP-A-0 203 554) or an isoolefin of the formula 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. 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.In addition, copolymers based on α, β-unsaturated Compounds and maleic anhydride used as flow improvers. DE-196 45 603 describes copolymers of 60 to 99 mol% of ethylene derived structural units and 1 to 40 mol% of structural units that are derived from maleic acid, its anhydride or its imides.
DE-1 162 630 offenbart Copolymerisate aus Ethylen und Vinylestern von geradkettigen Fettsäuren mit 4 bis 18 Kohlenstoffatomen als stockpunkterniedrigendes 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 with 4 to 18 carbon atoms as Pour point lowering additive for distillate fuels of medium boiling point such as Hot oil or diesel oil.
EP-A-0 217 602 offenbart Ethylen-Copolymere mit C1- bis C18-Alkylresten tragenden Vinylestern 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 Mineralöldestillate.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 mineral oil distillates.
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 in Mix with mineral oils that have 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 the known additives to improve the properties of mineral oil fractions includes depending on the origin of the mineral oil from which they were obtained and, in particular, from its composition. Additives that are used to set certain property values of fractions of a Crude oils are ideally suited for 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 Fließverbesserern nicht oder nur ungenügend additivieren. Probleme bereiten dabei vor allem die für den Einsatz unter arktischen Bedingungen hergestellten Winterqualitäten von Dieselkraftstoffen mit ihren extremen Kälteeigenschaften, 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 increased environmental awareness, fuels are becoming more and more popular manufactured that cause less environmental pollution when burned. Corresponding diesel fuels are characterized by 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 can be used with conventional Do not add or only insufficiently add flow improvers. Problems arise especially those made for use under arctic conditions Winter qualities of diesel fuels with their extreme cold properties, such as e.g. a cloud point below -8 ° C and especially below -15 ° C, very narrow Distillation cuts with boiling ranges from 20 to 90 vol .-% below 120 ° C, in particular less than 100 ° C and sometimes also less than 80 ° C, and one Distillation volume of 95 vol% at temperatures below 360 ° C, in particular below 350 ° C and especially below 330 ° C. The cold properties of such distillates can currently only by adding low-boiling, low paraffin Components such as Kerosene, can be improved satisfactorily.
Problematisch für das Ansprechverhalten von Fließverbesserern 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 Kälteeigenschaften durch Verdünnen mit Kerosin eingestellt werden müssen.The composition caused by narrow distillation cuts and low boiling points 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 for the winter qualities, that conventional flow improvers do not respond and the cold properties 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.The task was therefore to create new fuel oils with one compared to the stand the technology 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 of ethylene, the Side chains with more than 5 carbon atoms are suitable, the CFPP also lower in the middle distillates described above. Ethylene / vinyl acetate copolymers with corresponding comonomer contents, however, are in Hydrocarbons practically insoluble.
Gegenstand der Erfindung sind Brennstofföle, enthaltend
Der Schwefelgehalt der unter A) genannten Mineralöle beträgt vorzugsweise weniger als 500, insbesondere weniger als 300 ppm, speziell weniger als 100 ppm. Ihr Cloud Point 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 sulfur content of the mineral oils mentioned under A) is preferably less than 500, especially less than 300 ppm, especially less than 100 ppm. Your cloud point is preferably below -15 ° C. The boiling ranges (90-20%) of the Distillation cuts are preferably less than 100 ° C, especially less than 80 ° C. The use of mineral oils with a 95% distillation point is preferred below 360 ° C, especially below 350 ° C, especially below 330 ° C.
Vorzugsweise bedeutet R1 Wasserstoff. R3 steht vorzugsweise für einen linearen
oder verzweigten C5-C24-Alkylrest, besonders bevorzugt 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:
R und R
Die erfindungsgemäßen Brennstoffölzusammensetzungen enthalten vorzugsweise Copolymere, in denen die Comonomere B1) mit 85 bis 97 mol-% und die Comonomere B2) mit 3 bis 15 mol-% enthalten sind. Besonders bevorzugt sind 4 bis 10 mol-% B2) und 90 bis 96 mol-% B1).The fuel oil compositions according to the invention preferably contain Copolymers in which the comonomers B1) with 85 to 97 mol% and the Comonomers B2) with 3 to 15 mol% are contained. 4 to are particularly preferred 10 mol% B2) and 90 to 96 mol% B1).
Die unter B) genannten Copolymere sind durch die üblichen Copolymerisationsverfahren wie beispielsweise Suspensionspolymerisation, Lösungsmittelpolymerisation, Gasphasenpolymerisation oder Hochdruckmassepolymerisation 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 by the usual copolymerization processes such as suspension polymerization, Solvent polymerization, gas phase polymerization or high pressure bulk polymerization producible. High-pressure bulk polymerization is preferred 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 is caused by free radical initiators (Radical chain starter) initiated. This class of substances includes 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 made individually or as a mixture two or more substances in amounts of 0.001 to 20% by weight, 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 140 ° C from 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 composition of the monomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired. 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. In The moderators become dependent on the desired viscosity in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture, applied.
Die unter B) genannten Copolymere können bis zu 4 Gew.-% Vinylacetat oder bis zu 5 Gew.-% 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 4% by weight of vinyl acetate or up to Contain 5 wt .-% of other comonomers. Such comonomers can for example vinyl esters, vinyl ethers, acrylic acid alkyl esters, methacrylic acid alkyl esters or higher olefins with at least 5 carbon atoms. Preferred as higher Olefins are hexene, 4-methylpentene, octene or 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), use is made Monomer mixtures which, in addition to ethylene and optionally a moderator 1 to Contain 50 wt .-%, preferably 3 to 40 wt .-% comonomer. With that of the Composition of the copolymer different composition of the Monomer mixture one carries the different Polymerization rate of the monomers calculation. The polymers fall as colorless melts that turn into wax-like solids at room temperature freeze.
Die Hochdruckmassepolymensation 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, sofern 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).The high pressure mass polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tubular reactors, carried out batchwise or continuously, Tube reactors have proven particularly useful. Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, Benzene or toluene can be contained in the reaction mixture. The is preferred solvent-free mode of operation. In a preferred embodiment of the Polymerization is the mixture of the monomers, the initiator and, if provided used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches fed. Here the monomer streams be composed differently (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) become the mineral oils mentioned under A) or mineral oil distillates in the form of solutions or dispersions. This Solutions or dispersions preferably contain 1 to 90, in particular 10 to 80% by weight of the copolymers. Suitable solvents or dispersants 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 wt .-% copolymer, based on the Distillate.
Die erfindungsgemäßen Brennstofföle können weitere öllösliche Co-Additive enthalten, die bereits für sich allein die Kaltfließeigenschaften von Rohölen, Schmierölen oder Brennölen verbessern. Beispiele solcher Co-Additive sind Vinylacetat enthaltende Copolymerisate oder Terpolymerisate des Ethylens, polare Verbindungen, die eine Paraffindispergierung bewirken (Paraffindispergatoren), sowie Kammpolymere.The fuel oils according to the invention can contain further oil-soluble co-additives contain the cold flow properties of crude oils, Improve lubricating oils or fuel oils. Examples of such co-additives are Copolymers containing vinyl acetate or terpolymers of ethylene, polar Compounds that cause paraffin dispersion (paraffin dispersants), as well as 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 Alkenyl-spirobislactonen 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 ones have been found as paraffin dispersants or polar groups, e.g. Amine salts and / or amides proven by 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 Pat. No. 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 reacted (cf. EP-A-0 154 177), the reaction products of alkenyl spirobislactones 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 acid 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 Polymerrückgrat 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), ferner 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), also 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.
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
- 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 / neoundecanoic acid vinyl ester
- V 140 =
- according to ISO 3219 with plate-cone measuring system at 140 ° C determined melt viscosity of the copolymer
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 Ethylen-Vinylacetat-Neodecansäurevinylester-Terpolymers
mit 16 mol-% Vinylacetat, 1,2 mol-%
Neodecansäurevinylester und einer Schmelzviskosität V140 von 140 mPas (V2)
wiedergegeben.
Der CFPP wird nach EN116 bestimmt, der PP nach ISO 3016 mit einem automatischen Gerät (Herzog MC 852). The CFPP is determined according to EN116, the PP according to ISO 3016 with an automatic device (Herzog MC 852).
Claims (12)
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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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EP0931824A2 (en) * | 1998-01-24 | 1999-07-28 | Clariant GmbH | Process to improve the cold flow properties of fuel oils |
EP1134275A2 (en) * | 2000-03-14 | 2001-09-19 | Clariant GmbH | Copolymer blends and their use as additive to improve the cold flow properties of middle distillates |
EP1146108A2 (en) * | 2000-03-14 | 2001-10-17 | Clariant GmbH | Copolymer blends and their use as additive to improve the cold flow properties of middle distillates |
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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 |
EP2231833A2 (en) | 2007-12-20 | 2010-09-29 | Shell Internationale Research Maatschappij B.V. | Fuel compositions |
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- 1997-07-08 DE DE19729055A patent/DE19729055C2/en not_active Expired - Fee Related
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1998
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- 1998-06-26 EP EP98111799A patent/EP0890633B1/en not_active Expired - Lifetime
- 1998-06-26 AT AT98111799T patent/ATE262021T1/en active
- 1998-07-07 JP JP19192098A patent/JP4754664B2/en not_active Expired - Fee Related
- 1998-07-07 CA CA002242517A patent/CA2242517C/en not_active Expired - Fee Related
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0931824A2 (en) * | 1998-01-24 | 1999-07-28 | Clariant GmbH | Process to improve the cold flow properties of fuel oils |
EP0931824A3 (en) * | 1998-01-24 | 1999-09-15 | Clariant GmbH | Process to improve the cold flow properties of fuel oils |
US6110238A (en) * | 1998-01-24 | 2000-08-29 | Clariant Gmbh | Process for improving the cold-flow properties of fuel oils |
EP1134275A2 (en) * | 2000-03-14 | 2001-09-19 | Clariant GmbH | Copolymer blends and their use as additive to improve the cold flow properties of middle distillates |
EP1146108A2 (en) * | 2000-03-14 | 2001-10-17 | Clariant GmbH | Copolymer blends and their use as additive to improve the cold flow properties of middle distillates |
EP1146108A3 (en) * | 2000-03-14 | 2002-08-07 | Clariant GmbH | Copolymer blends and their use as additive to improve the cold flow properties of middle distillates |
EP1134275A3 (en) * | 2000-03-14 | 2002-08-07 | Clariant GmbH | Copolymer blends and their use as additive to improve the cold flow properties of middle distillates |
US6565616B1 (en) | 2000-03-14 | 2003-05-20 | Clariant Gmbh | Copolymer blends and their use as additives for improving the cold flow properties of middle distillates |
US6593426B2 (en) | 2000-03-14 | 2003-07-15 | Clariant Gmbh | Copolymer blends and their use as additives for improving the cold flow properties of middle distillates |
Also Published As
Publication number | Publication date |
---|---|
DE59810973D1 (en) | 2004-04-22 |
JP4754664B2 (en) | 2011-08-24 |
CA2242517A1 (en) | 1999-01-08 |
DE19729055A1 (en) | 1999-01-14 |
EP0890633B1 (en) | 2004-03-17 |
DE19729055C2 (en) | 2000-07-27 |
JPH1171587A (en) | 1999-03-16 |
ATE262021T1 (en) | 2004-04-15 |
CA2242517C (en) | 2007-05-29 |
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