EP0007590A1 - Middle distillates of petroleum, suitable as diesel fuel or as light heating oil, and with improved filtration properties - Google Patents

Middle distillates of petroleum, suitable as diesel fuel or as light heating oil, and with improved filtration properties Download PDF

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Publication number
EP0007590A1
EP0007590A1 EP79102558A EP79102558A EP0007590A1 EP 0007590 A1 EP0007590 A1 EP 0007590A1 EP 79102558 A EP79102558 A EP 79102558A EP 79102558 A EP79102558 A EP 79102558A EP 0007590 A1 EP0007590 A1 EP 0007590A1
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EP
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Prior art keywords
copolymers
ethylene
middle distillates
monomeric
esters
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EP79102558A
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German (de)
French (fr)
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EP0007590B1 (en
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Hans-Henning Dr. Chem. Vogel
Manfred Schramm
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BASF SE
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BASF SE
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Priority claimed from DE19782832738 external-priority patent/DE2832738A1/en
Priority claimed from DE19792908564 external-priority patent/DE2908564A1/en
Application filed by BASF SE filed Critical BASF SE
Priority to AT79102558T priority Critical patent/ATE17T1/en
Publication of EP0007590A1 publication Critical patent/EP0007590A1/en
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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
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the invention relates to middle distillates of petroleum which are suitable as diesel fuels or light heating oil with improved filterability at temperatures above and below the cloud point and improved flow behavior.
  • monomers are added as solubilizers.
  • middle distillates such as gas oils, diesel oils or egg oils, such as those obtained from petroleum by distillation
  • paraffin wax is excreted in the form of platelet-shaped crystals, some of which also contain oil.
  • the fluidity of the petroleum distillate - fuels is significantly impaired.
  • this leads to the clogging of filters and thus to the interruption or non-uniform supply of the fuel to the combustion units such as engines or jet engines.
  • Malfunctions in heating oils can also occur in winter if such precipitations, due to low temperatures, occur.
  • the pumping of middle distillates through pipelines over long distances can also be affected in winter by the precipitation of wax crystals.
  • Such additives change the size and shape of the wax crystals so that the oil remains fluid even at low temperatures.
  • Such additives are known as "pour point improvers" or “flow improvers” or “pour point improvers”.
  • condensation products from chlorinated paraffins and naphthalene used. In order to be sufficiently successful, however, such condensation products must be used in relatively large amounts.
  • efforts have recently been made to switch off chlorinated hydrocarbons for this purpose as far as possible in order to avoid corrosive gases which are produced during combustion.
  • the polymers previously proposed as pour point and flow improvers now have the described properties in practical use at low temperatures, i.e. temperatures below the cloud point, as modifiers or growth inhibitors for paraffin crystals, but in many cases they show up to about above the cloud point plus 30 ° C considerable disadvantage le.
  • diesel engines used in practice are equipped with filter materials of different pore sizes depending on the application. An unimpeded fuel supply must be guaranteed at all times, even under extreme conditions.
  • diesel engines have very narrow-pore fuel filters with pore sizes of 2 to 40 ⁇ . Multi-layer filters made of materials with very different pore sizes for coarse and fine filtration are also frequently used.
  • the invention consists in middle distillates of petroleum, which are suitable as diesel fuels or light heating oil, with improved fileability and improved flow behavior with a content of small amounts of modifiers in the form of copolymers, selected from the group of binary copolymers of ethylene and a vinyl ester of a C 2 - or C 3 -alkane carboxylic acid and binary copolymers of a C 1 to C 8 alkyl ester of a C 3 or C 4 alkene monocarboxylic acid, the copolymers copolymerizing 60 to 95% by weight of ethylene and 5 to 40% by weight of the olefinically unsaturated ester contain and have a viscosity in the melt, measured according to DIN 51 562 (ASTM D 445) at 120 ° C from 100 to 5000 mm 2 / sec, which are characterized in that the middle distillates in addition to the copolymers 0.1 to 10 vol .%, based on the copolymer, the monomeric vinyl esters of a C
  • the monomers are preferably present in amounts of 0.5 to 5% by volume, based on the copolymer.
  • binary copolymers which are obtained by polymerizing ethylene and vinyl acetate or alkyl acrylates without solvents at pressures from 500 to 2,000 bar and temperatures from 100 to 350 ° C., preferably 200 to 300 ° C., and the molecular weights from 500 to 10,000, preferably 1,000 to 5,000.
  • the radical copolymerization can be started simply with air, but also by means of suitable proxidic initiators or by adding L suitable controllers (e.g. aliphatic aldehydes) can be controlled.
  • the unreacted ethylene and the vinyl acetate and low-boiling oligomers are preferably separated off by decompression of the reactor and the solvent-imparting monomers are subsequently added to the ethylene-free copolymer.
  • the monomers are preferably subsequently added to the copolymer.
  • the monomers contained in the copolymers are, in particular, vinyl esters of carboxylic acids with 1 to 4 carbon atoms, preferably vinyl acetate with vinyl propionate, and acrylic and methacrylic esters of C 1 to C 8 alkanols, in particular butyl, isobutyl, 2-ethylhexyl and Lauryl acrylate into consideration.
  • esters of maleic acid are dimethyl maleate or dibutyl maleate.
  • the monomers serving as solubilizers are generally added, alone or in combination with one another, to the copolymers prepared by the known processes, which are generally of very tough consistency and, for example, have viscosities in the range from 100 to 5000 mm 2 / s at 120 ° C.
  • the copolymers are usually dispersed in suitable solvents which have little or no solubility-improving effect. They are used e.g. higher-boiling, highly aromatic products, e.g. contain multiple alkylated benzenes, toluenes, xylenes, ethylbenzenes and optionally also higher alkylated naphthalenes. Another frequently used method is the dispersion of the copolymeric waxes in suitable petroleum distillates. Heavy gasoline, petroleum, diesel oil or gas oil fractions are used here in particular.
  • the monomers serving as solubility improvers can therefore be added to the copolymer waxes themselves, but also to the dispersions of these waxes in suitable dispersants; elevated temperatures e.g. 30 to 90 ° C and thorough mixing by stirring or pumping are advisable.
  • polymerization-sensitive unsaturated esters such as vinyl acetate or acrylic acid esters or unsaturated oligomers
  • polymerization inhibitors are e.g. polyalkylated phenols, nitrogen-containing aromatic heterocycles or alkylated aromatic aminophenols or substituted or unsubstituted phenylenediamines.
  • the minimal discoloration of the petroleum distillates caused by the inhibitors is insignificant.
  • the polymeric waxes settle in the dispersions.
  • the dispersions with a low proportion (eg 1 to 50% by weight) of copolymeric ethylene / vinyl fatty acid ester ⁇ or. Ethylene / acrylic acid esters, the dispersions obtained are not as stable as with higher proportions (for example over 50% by weight) of copolymer wax. It has now additionally been found that the additions of monomers to copolymeric waxes described above also have a thickening effect for the dispersions of the copolymeric waxes in the stated concentrations.
  • the stability of the dispersions is also increased considerably in many cases.
  • the copolymeric waxes do not settle or only to a very small extent.
  • a certain amount of the petroleum distillate to be examined (e.g. kerosene, gas oil, diesel fuel, heating oil EL according to DIN 51 601) is filtered in a water jet vacuum in portions of 100 ml each through a membrane filter. The flow times are measured per 100 ml.
  • Sartorius membrane filter attachment type SM 16307 Sartorius membrane filter type SM 11301 pore size 8 / u, n-Pentar
  • the selected petroleum distillate is filtered through a paper pleated filter to remove coarse suspended matter and dirt.
  • the sample which has been pre-cleaned in this way, is filtered in a water jet vacuum through a bluing belt filter.
  • a certain amount of flow improver dispersion or cow axis is mixed into 3,000 ml of the petroleum distillate pretreated in this way at room temperature.
  • the petroleum distillate modified in this way is filtered through a membrane filter in portions of 100 ml.
  • the throughput time for 100 ml of liquid is measured and graphically plotted against the filtered volume.
  • the time axis is divided logarithmically.
  • Method B Quantitative determination of the high molecular weight proportions of copolymer wax which are insoluble in petroleum distillate.
  • the membrane filter Before filtration, the membrane filter is washed with 100 ml of n-pentane, dried and weighed. After filtration of the petroleum distillate to be examined, the membrane filter is washed again oil-free with 100 ml and n-pentane, dried and weighed out. The amount of higher molecular weight residue which is insoluble in petroleum distillate is given in% by weight based on copolymer wax.
  • method A ensures that the filtration curves of petroleum distillate fuels and fuels, which do not contain copolymeric waxes, do not show an increase in the filtration time as the volume of the filtration increases.
  • the filtration time per 100 ml of filtered product depends only on the viscosity or density of the petroleum distillate. According to method A, petroleum distillates not modified with copolymer waxes do not indicate filter clogging.
  • the above filtration test can be varied by filtering smaller volumes (e.g. portions of 20 ml each). In this way it is possible to distinguish more clearly between very similar cow axes, which all result in a very bad filtration curve according to method A.
  • the membrane filter In the case of copolymer waxes with extremely low proportions of higher molecular weight compounds, the membrane filter only clogs at higher throughputs of modified petroleum distillate. (e.g. 10 to 1001.) In this case, larger sample volumes of 500 or 1,000 ml are recommended for the filtration test.
  • the temperature is essential for the filtering behavior of petroleum distillates modified with flow improvers. It could be shown that the solubility of the small amounts of higher molecular weight compounds contained in the copolymer waxes is a function of the temperature.
  • the solubilizing effect of the monomers extends to temperatures from well above the natural cloud point of the petroleum distillates (eg 30 ° C) to far below the cloud point (eg -40 ° C). At or below the cloud point in petroleum distillates, the precipitation of paraffin crystals begins with a further decrease in temperature.
  • ethylene / fatty acid vinyl esters or ethylene / acrylic acid esters as flow improvers, these paraffin crystals are modified and their growth is disturbed, the oil is cloudy due to excreted paraffins, but remains flowable and pumpable.
  • Table 1 shows the physical data of various copolymer waxes based on ethylene / vinyl acetate. The table also shows the proportions of monomeric vinyl acetate still present in the copolymer washes.
  • the cowaxes listed in Table 1 were adjusted as 50% dispersions in various dispersing agents and the filtering behavior of various gas oils after addition of 500 ppm by volume of the dispersions which act as flow improvers was investigated using Method A.
  • the higher molecular weight components present in the 50% dispersions and determined by Method 3 are summarized in Table 2.
  • 1 and 2 show the filtration curves of the cow axis from Table 2 determined according to Method A. A, where here and in the following t means the filtration time in seconds and v the filtration volume in ml.
  • Table 2 and FIGS. 1 and 2 show, all of the cow axes investigated in the dispersants used have poor filterability (according to method A) and correspondingly large proportions of higher molecular weight products according to method B.
  • the following examples show the mode of action of the solubilizers claimed.
  • the Cowachs No. 1 already mentioned in Table 1 and FIG. 1 was mixed with the solubilizers according to the invention as a 50% dispersion in C 4 -oxoalkahol residue as a dispersing agent.
  • the dispersions thus improved were added to a diesel fuel in an amount of 500 ppm by volume and investigated according to methods A and 3.
  • Cowachs No. 3 mentioned in Table 1 was adjusted as a 50% dispersion in C 4 oxo alcohol residue. As Table 2 shows, an amount of 5.6% higher molecular weight components was found in the method B filtration test. Curve 5 in Fig. 1 and A in Fig. 4 shows correspondingly poor filtering behavior (according to method A). When 1% by weight of vinyl acetate is added to the 50% dispersion of Cowachs No. 3 in the C 4 -oxoalcohol residue, after adding 500 vol Method B found only 0.34% higher molecular weight. Curve B in Fig. 4 shows the filtration curves according to method A.
  • the filtration test according to method A was carried out extra easily (according to DIN 51 601) after adding 500 ppm by volume of the 50% dispersion of the copolymer wax in C 4 oxo alcohol residue to a commercially available heating oil. Filtration curve No. 1 shown in FIG. 5 was obtained.
  • a filtration test according to methods A and B with the addition of 800 vol.ppm of the 40% dispersion to a commercially available heating oil is carried out extra easily (in accordance with DIN 51 601).
  • the filter test is carried out immediately, as well as after 8 days and 30 days of the additive heating oil.
  • the associated filtration curves 1, 2 and 3 in FIG. 6 and, according to Method B a proportion of higher molecular weight compounds of 9.5 (curve 1), 9, 7 (curve 2) and 10.1% by weight (based on cowachs) are obtained. .
  • Further filtration tests according to methods A and B are carried out after an amount of 0.5% by weight of monomeric vinyl acetate had previously been added to the dispersion. From this improved flow improver dispersion, 800 vol.ppm were also added to the same heating oil.
  • the filter test of the additive heating oil is also carried out here immediately or after 8 days and 30 days.
  • a copolyner wax prepared by continuous polymerization without solvent at a temperature of 245 ° C and a pressure of 1,500 bar from ethylene and 2-ethylhexyl acrylate with a content of 46.2% by weight 2-ethylhexyl acrylate, a viscosity at (120 ° C) of 252 mm 2 / s and an average molecular weight of 2,440 was adjusted as a 58% dispersion in petroleum, heated to 80 ° C. with stirring for one hour, cooled to room temperature and subjected to a filtration test according to methods A and B.
  • a commercial heating oil (extra light) was mixed with 500 ppm of the 58% dispersion.
  • the filtration test was repeated after 24, 48, 108 and 240 hours at room temperature.
  • the amount of polymeric residues and the associated filtration curves are shown in Tables 4 and 7.
  • t means filtration time in seconds
  • v filtration volume in ml curves 1, 2, 3, 4 according to, (a) after 24, 48, 108 and 240 hours, curves 5, 6, 7, 8 according to (b) after 24, 48 , 108 and 240 hours.
  • the copolymer wax No. 1 described in Table 1 is adjusted as a 50% dispersion in an oxo alcohol residue from the butanol synthesis.
  • the dispersion is heated to 80 ° C. with stirring, allowed to cool to room temperature and after a standing time of 36 days at room temperature for the filter test A and 3 used.
  • a commercial heating oil (extra light) from the cloud point -2 ° C is mixed with 500 ppm by weight of the dispersion and cooled to 0 ° C in the course of 35 minutes.
  • diesel oil is pumped through a commercially available fuel filter.
  • the apparatus consists of an insulated storage vessel (B 1) with a volume of 110 1 for the diesel oil, in which there is a cooling coil operated with cooling brine (s), a Bosch fuel pump (P-1) for 0-1.5 bar , a Kraftstaffiltar (F), Bosch no. 1457434052, with differential pressure gauge (PI-2) and a continuous fuel flow meter (FI).
  • the PI-1 and PI-3 pressure measuring points and the TI-1, TI-2 and TI-3 temperature displays are also installed.
  • the quantity of diesel oil pumped through the filter F is collected in the receptacle B-2 (volume 110 1).
  • the pump and filter are located in a cool box operated with dry ice in order to avoid temperature increases due to heat conduction and pump work.
  • the criterion for covering the fuel filter with high molecular weight components from the copolymeric flow improver is the pressure increase of the differential pressure sonoceter PI-2.
  • Curve 1 Cowaehs from ethylene-vinyl acetate with 28.1% by weight vinyl acetate, average molecular weight 2,160, melt viscosity (120 ° C.) 230 mm 2 / s, content of monomeric vinyl acetate 0.07% by weight, as 50% Dispersion in oxo oil residue from butanol synthesis. Dosage of the dispersion in diesel oil: 500 vol ppm - without further addition of solubilizers - temperature: + 0 ° C.
  • Curve 2 same as 1, but after adding 0.5% by weight of monomeric vinyl acetate (stabilized), based on cowachs.
  • Curve 3 as 2, but with 1.0% by weight of monomeric vinyl acetate.
  • Curve 4 as 2, but with 3.0% by weight of mononer vinyl acetate.
  • the Cowachs No. 1 mentioned in Table 1 and FIG. 1 was added as a 50% dispersion in C 4 -oxoalcohol residue as a dispersant with the solubilizers according to the invention.
  • the dispersions thus improved were added to a diesel fuel in an amount of 500 ppm by volume and investigated according to methods A and B.
  • the following table shows the effect of the solubilizers on the amount of the higher molecular residue contained in Cowachs No. 1.
  • the residues were determined according to method B. 11 shows the filtration curves belonging to table 5.

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Abstract

1. Middle distillates of petroleum suitable for use as diesel fuels or light fuel oil, having improved filterability and improved flow behaviour and containing small amounts of modifiers in the form of copolymers selected from the group consisting of binary copolymers of ethylene and a vinyl ester of a C2 - or C3 -alkanecarboxylic acid and binary copolymers of ethylene and a C1 - to C8 -alkyl ester of a C3 - or C4 -alkenemonocarboxylic acid, the copolymers containing 60 to 95 % by weight of ethylene units and 5 to 40 % by weight of units of the olefinically unsaturated ester and having a melt viscosity, measured according to DIN 51 562 (ASTM D 445) at 120 degrees C, of from 100 to 5000 mm**2/sec, characterized in that they contain, in addition to the copolymers, from 0.1 to 10 % by volume, based on the copolymer, of the monomeric vinyl ester of a C2 - to C3 -alkanecarboxylic acid or a C1 - to C8 -alkyl ester of a C3 - to C4 -alkenecarboxylic acid.

Description

Gegenstand der Erfindung sind Mitteldestillat\e des Erdöls, die als Dieseltreibstoffe oder leichtes Heizöl geeignet sind mit verbesserter Filtrierbarkeit bei Temperaturen oberhalb und unterhalb des Trübungspunktes und verbessertem Fließverhalten. Neben den an sich bekanrten Copolymeren werden Monomere als Lösungsvermittler zugesetzt.The invention relates to middle distillates of petroleum which are suitable as diesel fuels or light heating oil with improved filterability at temperatures above and below the cloud point and improved flow behavior. In addition to the copolymers known per se, monomers are added as solubilizers.

Sogenannte Mitteldestillate, wie Gasöle, Dieselöle oder Eeizöle, wie sie durch Destillation aus Erdölen gewonnen werden, haben je nach Herkunft des Rohöls unterschiedliche Gehalte an Paraffinen. Bei tiefen Temperaturen kommt es zur Ausscheidung von Paraffinwachs in Form plättchenförmiger Kristalle, die teilweise auch noch öl eingeschlossen enthalten. Hierdurch wird die Fließfähigkeit der Erdöldestillat - Brenn- bzw. Treibstoffe erheblich beeinträchtigt. Dies führt z.B. im Fall von Dieselkraftstoff zur Verstopfung von Filtern und damit zur Unterbrechung bzw. nicht gleichmäßigen Zufuhr des Kraftstoffs zu den Verbrennungsaggregaten wie Motoren oder Düsentriebwerken. Ebenso können Störungen bei Heizölen im Winter auftreten, wenn derartige Ausscheidungen, bedingt durch tiefe Temperaturen, auftreten. Aber auch das Fördern von Mitteldestillaten durch Rohrleitungen über größere Entfernungen kann im Winter durch das Ausfallen von Paraffinkristallen beeinträchtigt werden.So-called middle distillates, such as gas oils, diesel oils or egg oils, such as those obtained from petroleum by distillation, have different paraffin contents depending on the origin of the crude oil. At low temperatures, paraffin wax is excreted in the form of platelet-shaped crystals, some of which also contain oil. As a result, the fluidity of the petroleum distillate - fuels is significantly impaired. In the case of diesel fuel, for example, this leads to the clogging of filters and thus to the interruption or non-uniform supply of the fuel to the combustion units such as engines or jet engines. Malfunctions in heating oils can also occur in winter if such precipitations, due to low temperatures, occur. However, the pumping of middle distillates through pipelines over long distances can also be affected in winter by the precipitation of wax crystals.

Es ist seit langem bekannt, verschiedene Zusätze als Modifikatoren für das Kristallwachstum den Erdöldestillat-Brenn- und Treibstoffen, insbesondere den Mitteldestillaten, zuzusetzen.It has long been known to add various additives as modifiers for crystal growth to petroleum distillate fuels, in particular middle distillates.

Derartige Zusätze verändern Größe und Form der Wachskristalle, so daß das öl auch bei tiefen Temperaturen fließfähig bleibt. Solche Zusätze sind unter der Bezeichnung "Stockpunktverbesserer" bzw. "Fließverbesserer" oder "Fließpunktverbesserer" bekannt. Für diesen Zweck wurden z.B. gemäß US-Patentschrift 21 89 924 Kondensationsprodukte aus chlorierten Paraffinen und Naphthalin verwendet. Um einen ausreichenden Erfolg zu haben, müssen solche Kondensationsprodukte jedoch in relativ großen Mengen angewandt werden. Darüber hinaus ist man in neuerer Zeit bestrebt, chlorierte Kohlenwasserstoffe für diesen Einsatzzweck möglichst auszuschalten, um korrosive Gase, die bei der Verbrennung entstehen, zu vermeiden.Such additives change the size and shape of the wax crystals so that the oil remains fluid even at low temperatures. Such additives are known as "pour point improvers" or "flow improvers" or "pour point improvers". For this purpose e.g. according to US Pat. No. 2,189,924 condensation products from chlorinated paraffins and naphthalene used. In order to be sufficiently successful, however, such condensation products must be used in relatively large amounts. In addition, efforts have recently been made to switch off chlorinated hydrocarbons for this purpose as far as possible in order to avoid corrosive gases which are produced during combustion.

Auch die Verwendung öllöslicher bzw. in Erdöldestillaten dispergierbarer Copolymerisate als Stockpunkt und/oder Fließverbesserer ist wohl bekannt (vgl. z.B. US-Patentschrift 38 32 150).The use of oil-soluble or petroleum distillate-dispersible copolymers as pour point and / or flow improver is also well known (see e.g. U.S. Patent 38 32 150).

Die bisher als Stockpunkt- und Fließverbesserer vorgeschlagenen Polymeren weisen nun in der praktischen Anwendung bei tiefen Temperaturen, d.h. Temperaturen unterhalb des Trübungspunktes zwar die beschriebenen Eigenschaften als Modifikatoren bzw. Wachstumshemner für Paraffinkristalle auf, doch zeigen sie in vielen Fällen bei Temperaturen oberhalb des Trübungspunktes bis etwa plus 30°C erhebliche Nachtei- \ le. Dies gilt insbesondere z.B. für Copolymere aus Äthylen und Fettsäurevinylestern bzw. Äthylen und Acrylsäureestern, die nach bekannten großtechnischen Verfahren durch lösungsmittelfreie Polymerisation hergestellt werden.The polymers previously proposed as pour point and flow improvers now have the described properties in practical use at low temperatures, i.e. temperatures below the cloud point, as modifiers or growth inhibitors for paraffin crystals, but in many cases they show up to about above the cloud point plus 30 ° C considerable disadvantage le. This applies in particular, for example, to copolymers of ethylene and fatty acid vinyl esters or ethylene and acrylic acid esters, which are prepared by known large-scale processes by solvent-free polymerization.

Insbesondere die in der Praxis verwendeten Dieselmotoren sind je nach Einsatzzweck mit Filtermaterialien von unterschiedlicher Porenweite ausgestattet. Eine ungehinderte Kraftstoffzufuhr muß auch unter extremen Bedingungen jederzeit gewährleistet sein. Besonders im militärischen Bereich verfügen Dieselmotoren über sehr engporige Kraftstoffilter mit Porenweiten von 2 bis 40 µ. Mehrschichtenfilter aus Materialien stark unterschiedlicher Porenweite für Grob- und Feinfiltration werden ebenfalls häufig verwendet.In particular, the diesel engines used in practice are equipped with filter materials of different pore sizes depending on the application. An unimpeded fuel supply must be guaranteed at all times, even under extreme conditions. In the military sector in particular, diesel engines have very narrow-pore fuel filters with pore sizes of 2 to 40 µ. Multi-layer filters made of materials with very different pore sizes for coarse and fine filtration are also frequently used.

Umfangreiche Versuche haben gezeigt, daß Copolymere aus z.B. Äthylen und Fettsäurevinylestern sowie Äthylen und Acrylsäureestern, die nach den bekannten großtechnischen Verfahren hergestellt werden, stets noch geringe Anteile höhermolekularer in Erdöldestillat-Brenn- und Treibstoffen teilweise unlöslicher Polymerisationsprodukte enthalten.Extensive tests have shown that copolymers of e.g. Ethylene and fatty acid vinyl esters as well as ethylene and acrylic acid esters, which are produced by the known industrial processes, always contain small amounts of higher molecular weight polymerization products which are partly insoluble in petroleum distillate fuels and fuels.

Diese höhermolekularen Polymerisationsprodukte entstehen als Nebenprodukte bei der radikalischen Polymerisation von Äthylen und z.B. Fettsäurevinylestern bzw. Acrylsäureestern. In Abhängigkeit von Art und Menge der höhermolekularen Polymerisationsprodukte kann es deshalb in den. Erdöldestillat-Brenn- und Treibstoffen auch schon bei Temperaturen oberhalb des eigentlichen Trübungspunktes (d.h. dem Beginn der Ausscheidung von Paraffinwachs) zu unlöslichen Absetzungen kommen, die bei den engporigen Filtermaterialien bereits zu Verstopfungen führen können.These higher molecular weight polymerization products arise as by-products in the radical polymerization of ethylene and e.g. Fatty acid vinyl esters or acrylic acid esters. Depending on the type and amount of the higher molecular weight polymerization products, it can therefore be used in the. Petroleum distillate fuels, even at temperatures above the actual cloud point (i.e. the start of the separation of paraffin wax), lead to insoluble deposits that can lead to blockages in the narrow-pored filter materials.

Es bestand daher die Aufgabe, die bekannten Herstellverfahren für Copolymere zu verändern bzw. geeignete Maßnahmen vorzuschlagen, um Filterverstopfungen durch geringe Anteile höhermolekularer Polymerisationsprodukte zu verringern bzw. gänzlich auszuschalten.It was therefore the task of the known manufacturers drive for copolymers to change or propose suitable measures to reduce filter clogging by small proportions of higher molecular weight polymerization products or to completely eliminate them.

Bei den bekannten Eerstellverfahren für Copolymere aus Äthylen und z.B. Fettsäurevinylestern bzw. Acrylsäureestern arbeitet man z.B. nach dem Prinzip der Lösungs- bzw. Suspensionspolymerisation unter Druck bei erhöhten Temperaturen. Bei diesen Verfahren wird nach beendeter Reaktion das Lösungsmittel und die nicht umgesetzten Monomeren durch Destillation abgetrennt, wie dies z.B. in der deutschen Patentschrift 25 15 805 beschrieben ist.In the known production processes for copolymers from ethylene and e.g. Fatty acid vinyl esters or acrylic acid esters are e.g. according to the principle of solution or suspension polymerization under pressure at elevated temperatures. In these processes, after the reaction has ended, the solvent and the unreacted monomers are separated off by distillation, as is e.g. is described in German Patent 25 15 805.

Bei anderen Verfahren zur Herstellung der Copolymeren arbeitet man z.B. vollkommen ohne Lösungsmittel bei Drücken von 500 bis 2 000 bar und Temperaturen von z.B. 100 bis 350°C, wobei gegen Ende der Reaktion das nicht umgesetzte Äthylen und die nicht umgesetzten Fettsäurevinylester bzw. Acrylsäurester durch Entspannen des Reaktors abgetrennt werden. Insbesondere bei den lösungsmittlfreien Polymerisationsverfahren kann es zur Bildung der in Erdöldestillat-Brenn- und Treibstoffen unlöslichen Anteile kommen.Other processes for the preparation of the copolymers e.g. completely without solvents at pressures of 500 to 2,000 bar and temperatures of e.g. 100 to 350 ° C, the unreacted ethylene and the unreacted fatty acid vinyl esters or acrylic acid esters being separated off by letting down the reactor towards the end of the reaction. In the case of the solvent-free polymerization processes in particular, fractions which are insoluble in petroleum distillate fuels can be formed.

Es wurde nun gefunden, daß man die Löslichkeit der nach an sich bekannten Verfahren hergestellten Copolymeren aus Äthylen und Fettsäurevinylestern bzw. Äthylen und Acrylsäureestern in den Erdöldestillat-Brenn- und Treibstoffen durch geringe Mengen der entsprechenden Monomere beträchtlich verbessern kann. Die als Lösungsvermittler wirkenden Monomere verursachen im wesentlichen eine Quellung der wachsartigen höhermolekularen Copolymeren, wodurch bei der praktischen Anwendung, d.h. der Zugabe dieser Copolymeren zu Erdöldestillat, Brenn- und Treibstoffen eine starke Verbesserung der Löslichkeit für das Copolymere und damit eine beträchtliche Verbesserung der Filtrier- ' barkeit für das Erdöldestillat bei Temneraturen oberhalb des Trübungspunktes erreicht wird.It has now been found that the solubility of the copolymers of ethylene and fatty acid vinyl esters or ethylene and acrylic acid esters produced by known processes in petroleum distillate fuels and fuels can be considerably improved by small amounts of the corresponding monomers. The monomers acting as solubilizers essentially cause the wax-like higher molecular weight copolymers to swell, which in practical use, ie the addition of these copolymers to petroleum distillate, fuels and fuels, greatly improves the solubility for the copolymer and thus a considerable improvement in the filterability for the petroleum distillate at temperatures above the cloud point is achieved.

Demgemäß besteht die Erfindung in Mitteldestillaten des Erdöls, die als Dieseltreibstoffe oder leichtes Heizöl geeignet sind, mit verbesserter Filtriebarkeit und verbessertem Fließverhalten mit einem Gehalt geringer Mengen an Modifikatoren in Form von Copolymeren, ausgewählt aus der Gruppe binärer Copolymerisate aus Äthylen und einem Vinylester einer C2- oder C3-Alkancarbonsäure und binärer Copolymerisate eines C1- bis C8-Alkylesters einer C3- oder C4-Alkenmonocarbonsäure, wobei die Copolymerisate 60 bis 95 Gew.% Äthylen und 5 bis 40 Gew.% des olefinisch ungesättigten Esters einpolymerisiert enthalten und eine Viskosität in der Schmelze, gemessen nach DIN 51 562 (ASTM D 445) bei 120°C von 100 bis 5 000 mm2/sec aufweisen, die dadurch gekennzeichnet sind, daß die Mitteldestillate neben den Copolymeren 0,1 bis 10 Vol.%, bezogen auf das Copolymere, der monomeren Vinylester einer C2- bis C3-Alkancarbonsäure oder der monomeren C1- bis C8-Alkylester einer C3- oder C4-Alkencarbonsäure enthalten.Accordingly, the invention consists in middle distillates of petroleum, which are suitable as diesel fuels or light heating oil, with improved fileability and improved flow behavior with a content of small amounts of modifiers in the form of copolymers, selected from the group of binary copolymers of ethylene and a vinyl ester of a C 2 - or C 3 -alkane carboxylic acid and binary copolymers of a C 1 to C 8 alkyl ester of a C 3 or C 4 alkene monocarboxylic acid, the copolymers copolymerizing 60 to 95% by weight of ethylene and 5 to 40% by weight of the olefinically unsaturated ester contain and have a viscosity in the melt, measured according to DIN 51 562 (ASTM D 445) at 120 ° C from 100 to 5000 mm 2 / sec, which are characterized in that the middle distillates in addition to the copolymers 0.1 to 10 vol .%, based on the copolymer, the monomeric vinyl esters of a C 2 - to C 3 -alkane carboxylic acid or the monomeric C 1 - to C 8 -alkyl esters of a C 3 - or C 4 -Alken carboxylic acid included.

Die Monomeren sind vorzugsweise in Mengen von 0,5 bis 5 Vol.%, bezogen auf das Copolymerisat, enthalten.The monomers are preferably present in amounts of 0.5 to 5% by volume, based on the copolymer.

Gemäß der Erfindung verwendet man bevorzugt solche binären Copolymere, die durch Polymerisation von Äthylen und Vinylacetat bzw. Alkylacrylaten ohne Lösungsmittel bei Drücken von 500 bis 2 000 bar und Temperaturen von 100 bis 350°C, vorzugsweise 200 bis 300°C erhalten werden und die Molgewichte von 500 bis 10 000, vorzugsweise 1 000 bis 5 000, aufweisen. Dabei kann die radikalische Copolymerisation einfach mit Luft, aber auch durch geeignete proxidische Initiatoren gestartet bzw. durch Zugabe L geeigneter Regler (z. B. aliphatische Aldehyde) gesteuert werden.According to the invention, preference is given to using such binary copolymers which are obtained by polymerizing ethylene and vinyl acetate or alkyl acrylates without solvents at pressures from 500 to 2,000 bar and temperatures from 100 to 350 ° C., preferably 200 to 300 ° C., and the molecular weights from 500 to 10,000, preferably 1,000 to 5,000. The radical copolymerization can be started simply with air, but also by means of suitable proxidic initiators or by adding L suitable controllers (e.g. aliphatic aldehydes) can be controlled.

Nach beendeter Polymerisation werden vorzugsweise das nicht umgesetzte Äthylen und das Vinylacetat sowie niedrigsiedende Oligomere durch Entspannen des Reaktors abgetrennt und dem äthylenfreien Copolymeren die lösungsvermittelnden Monomeren nachträglich zugesetzt.After the polymerization has ended, the unreacted ethylene and the vinyl acetate and low-boiling oligomers are preferably separated off by decompression of the reactor and the solvent-imparting monomers are subsequently added to the ethylene-free copolymer.

Zwar setzt man vorzugsweise die Monomere nachträglich dem Copolymerisat zu. Es ist jedoch auch möglich, die Polymerisationsmischung vor der Entspannung auf Temperaturen unterhalb des Siedepunktes der Monomere abzukühlen, so daß außer Äthylen die nicht umgesetzten Monomere bei der Entspannung nicht oder nur teilweise verdampfen. Auch eine Kombination beider Maßnahmen ist möglich.The monomers are preferably subsequently added to the copolymer. However, it is also possible to cool the polymerization mixture to temperatures below the boiling point of the monomers before the expansion, so that, apart from ethylene, the unreacted monomers do not or only partially evaporate during the expansion. A combination of both measures is also possible.

Als in den Copolymerisaten enthaltene Monomere kommen insbesondere Vinylester von Carbonsäuren mit 1 bis 4 Kohlenstoffatomen, vorzugsweise Vinylacetat mit Vinylpropionat sowie Acrylsäure- und Methacrylsäureester von Cl- bis C8-Alkanolen, insbesondere Butyl-, Isobutyl-, 2-Äthyl-hexyl- und Laurylacrylat in Betracht.The monomers contained in the copolymers are, in particular, vinyl esters of carboxylic acids with 1 to 4 carbon atoms, preferably vinyl acetate with vinyl propionate, and acrylic and methacrylic esters of C 1 to C 8 alkanols, in particular butyl, isobutyl, 2-ethylhexyl and Lauryl acrylate into consideration.

Als Ester der Maleinsäure kommen insbesondere Maleinsäuredimethylester oder -dibutylester in Betracht.Particularly suitable esters of maleic acid are dimethyl maleate or dibutyl maleate.

Wie bereits erwähnt, werden im allgemeinen die als Löslichkeitsvermittler dienenden Monomeren allein oder in Kombination miteinander den nach den bekannten Verfahren hergestell ten Copolymeren nachträglich zugesetzt, die in der Regel von sehr zäher Konsistenz sind und z.B. Viskositäten im Bereich von 100 bis 5 000 mm2/s bei 120°C haben.As already mentioned, the monomers serving as solubilizers are generally added, alone or in combination with one another, to the copolymers prepared by the known processes, which are generally of very tough consistency and, for example, have viscosities in the range from 100 to 5000 mm 2 / s at 120 ° C.

Zur Viskositätserniedrigung und einfacheren Anwendung werden die Copolymeren meist in geeigneten Lösungsmitteln, die keine oder nur geringe löslichkeitsverbessernde Wirkung haben, dispergiert. Verwendung finden dabei z.B. höhersiedende hocharomatische Produkte, die z.B. mehrfach alkylierte Benzole, Toluole, Xylole, Äthylbenzole und gegebenenfalls auch höheralkylierte Naphthaline enthalten. Eine andere häufig angewendete Methode ist die Dispersion der copolymeren Wachse in geeigneten Erdöldestillaten. Hier werden insbesondere Schwerbenzin, Petroleum, Dieselöl bzw. Gasöl-Fraktionen verwendet.To lower the viscosity and make it easier to use, the copolymers are usually dispersed in suitable solvents which have little or no solubility-improving effect. They are used e.g. higher-boiling, highly aromatic products, e.g. contain multiple alkylated benzenes, toluenes, xylenes, ethylbenzenes and optionally also higher alkylated naphthalenes. Another frequently used method is the dispersion of the copolymeric waxes in suitable petroleum distillates. Heavy gasoline, petroleum, diesel oil or gas oil fractions are used here in particular.

Die als Löslichkeitsverbesserer dienenden Monomeren können deshalb sowohl den copolymeren Wachsen selbst, aber auch den Dispersionen dieser Wachse in geeigneten Dispergiermitteln zugesetzt werden; erhöhte Temperaturen von z.B. 30 bis 90°C und eine gute Durchmischung durch Rühren oder Umpumpen sind zweckmäßig.The monomers serving as solubility improvers can therefore be added to the copolymer waxes themselves, but also to the dispersions of these waxes in suitable dispersants; elevated temperatures e.g. 30 to 90 ° C and thorough mixing by stirring or pumping are advisable.

Bei Verwendung polymerisationsenpfindlicher ungesättigter Ester, wie Vinylacetat oder Acrylsäureester oder ungesättigter Oligomerer ist es empfehlenswert, diese durch Zugabe von technisch üblichen Polymerisationsinhibitoren zu stabilisieren, um eine nachträgliche Polymerisation dieser Komponenten nach deren Zugabe als Lösungsvermittler zu vermeiden. Übliche Polymerisationsinhibitoren sind z.B. mehrfach alkylierte Phenole, stickstoffhaltige aromatische Heterocyclen bzw. alkylierte aromatische Aminophenole bzw. substituierte oder unsubstituierte Phenylendiamine. Die durch die Inhibitoren verursachte minimale Verfärbung der Erdöldestillate ist unbedeutend.When using polymerization-sensitive unsaturated esters, such as vinyl acetate or acrylic acid esters or unsaturated oligomers, it is advisable to stabilize them by adding commercially available polymerization inhibitors in order to avoid subsequent polymerization of these components after they have been added as solubilizers. Common polymerization inhibitors are e.g. polyalkylated phenols, nitrogen-containing aromatic heterocycles or alkylated aromatic aminophenols or substituted or unsubstituted phenylenediamines. The minimal discoloration of the petroleum distillates caused by the inhibitors is insignificant.

Je nach Molgewicht der verwendeten copolvmeren Wachse bzw. der Dichte und Zusammensetzung der Dispergiermittel sowie des Anteils der zu dispergierenden copolymeren Wachse kann es zu Absetzungen der polymeren Wachse in den Dispersionen kommen. Vor allem bei der Herstellung von Dispersionen mit einem niedrigen Anteil (z.B. 1 bis 50 Gew.%) an copolymeren Äthylen/Fettsäurevinylester \bzw. Äthylen/Acrylsäureester, sind die erhaltenen Dispersionen nicht so stabil wie bei höheren Anteilen (z.B. über 50 Gew.%) an copolymerem Wachs. Es wurde nun zusätzlich gefunden, daß die oben beschriebenen Zusätze von Monomeren zu copolymeren Wachsen in den angegebenen Konzentrationen auch noch über eine verdickende Wirkung für die Dispersionen der copolymeren Wachse verfügen.Depending on the molecular weight of the copolymer waxes used or the density and composition of the dispersants and the proportion of the copolymeric waxes to be dispersed the polymeric waxes settle in the dispersions. Especially in the production of dispersions with a low proportion (eg 1 to 50% by weight) of copolymeric ethylene / vinyl fatty acid ester \ or. Ethylene / acrylic acid esters, the dispersions obtained are not as stable as with higher proportions (for example over 50% by weight) of copolymer wax. It has now additionally been found that the additions of monomers to copolymeric waxes described above also have a thickening effect for the dispersions of the copolymeric waxes in the stated concentrations.

Durch Zugabe der Monomeren zu den Dispersionen der copolymeren Wachse wird in vielen Fällen auch die Stabilität der Dispersionen beträchtlich erhöht. Eine Absetzung der copolymeren Wachse findet nicht oder lediglich in sehr geringem Ausmaß statt.By adding the monomers to the dispersions of the copolymeric waxes, the stability of the dispersions is also increased considerably in many cases. The copolymeric waxes do not settle or only to a very small extent.

Aus der US-PS 36 27 838 ist bekannt, daß man eine besonders gute Fließpunktverbesserung erhält, wenn man die Polymerisation so führt, daß stets, selbst am Ende der Reaktion freies Vinylacetat vorliegt. Aus Spalte 2, Zeilen 2Q und 30 geht jedoch hervor, daß die Monomeren bei der Aufarbeitung entfernt werden ("The product is stripped free of solvent a.nd unreacted vinyl acetate under vacuum"). Demnach wird gemäß dieser Patentschrift ein von Monomeren befreites Produkt verwendet, während gemäß der Lehre der vorliegenden Erfindung die Monomeren in den Produkten belassen oder zugesetzt werden.From US-PS 36 27 838 it is known that a particularly good pour point improvement is obtained if the polymerization is carried out so that free vinyl acetate is always present, even at the end of the reaction. However, column 2, lines 2Q and 30 show that the monomers are removed during the workup ("The product is stripped free of solvent and unreacted vinyl acetate under vacuum"). Accordingly, according to this patent specification, a product freed from monomers is used, while according to the teaching of the present invention, the monomers are left in or added to the products.

Zur Erläuterung der Erfindung sind im folgenden zahlreiche Filtrationsversuche angegeben, wobei die Viskositäten einer Vielzahl von Dispergiermitteln unter Zugabe der Monomeren gemessen werden.To explain the invention, numerous filtration tests are given below, the viscosities of a large number of dispersants being measured with the addition of the monomers.

Ein geeigneter Filtrationstest für Erdöldestillat-Treib-' und Brennstoffe, die copolymere Fließverbesserer enthalten, wird wie folgt durchgeführt :A suitable filtration test for petroleum distillate fuels and fuels which contain copolymeric flow improvers is carried out as follows:

Zweck der Bestimmung:Purpose of the determination:

Prüfung der Filtrierbarkit von Erdöldestillaten, die copolymere Fließverbesserer enthalten, bei Temneraturen oberhalb des Cloud-points.Testing the filterability of petroleum distillates containing copolymeric flow improvers at temperatures above the cloud point.

Kurzbeschreibung des VerfahrensBrief description of the procedure

Eine bestimmte Menge des zu untersuchenden Erdöldestillates (z.B. Kerosin, Gasöl, Dieselkraftstoff, Heizöl EL nach DIN 51 601) wird im Wasserstrahlvakuum in Portionen von je 100 ml über ein Membranfilter, filtriert. Die Durchflußzeiten werden je 100 ml gemessen.A certain amount of the petroleum distillate to be examined (e.g. kerosene, gas oil, diesel fuel, heating oil EL according to DIN 51 601) is filtered in a water jet vacuum in portions of 100 ml each through a membrane filter. The flow times are measured per 100 ml.

Geräte und ChemikalienEquipment and chemicals

5 000 ml Saugflasche Wasserstrahlpumpe Panierfaltenfilter Blaubandfilter Nr. 5893 0 15 cm 5 000 ml. Glasflasche 100 ml Meßzylinder5 000 ml water bottle pump Breadfold filter Blue band filter No. 589 3 0 15 cm 5 000 ml. Glass bottle 100 ml measuring cylinder

Sartorius-Memhranfilteraufsatz Typ SM 16307 Sartorius-Membranfilter Typ SM 11301 Porengröße 8/u, n-PentarSartorius membrane filter attachment type SM 16307 Sartorius membrane filter type SM 11301 pore size 8 / u, n-Pentar

Durchführung der FiltrationFiltration

Das ausgewählte Erdöldestillat wird vor dem Versuch über ein Papierfaltenfilter filtriert, um grobe Schwebstoffe und Schmutzteile zu entfernen. Zur Feinreinigung wird die so vorgereinigte Probe im Wasserstrahlvakuum über ein Blzubandfilter filtriert.The selected petroleum distillate is filtered through a paper pleated filter to remove coarse suspended matter and dirt. For fine cleaning, the sample, which has been pre-cleaned in this way, is filtered in a water jet vacuum through a bluing belt filter.

In 3 000 ml des auf diese Weise vorbehandelten Erdöldestillats werden eine bestimmte Menge Fließverbessererdispersion oder Cowachse bei Raumtemperatur zugemischt. Die Filtration des so modifizierten Erdöldestillats über ein Membranfilter erfolgt in Portionen von je 100 ml. Es wird jeweils die Durchlaufzeit für 100 ml Flüssigkeit gemessen und graphisch gegen das filtrierte Volumen aufgetragen. Die Zeitachse ist logarithmisch geteilt.A certain amount of flow improver dispersion or cow axis is mixed into 3,000 ml of the petroleum distillate pretreated in this way at room temperature. The petroleum distillate modified in this way is filtered through a membrane filter in portions of 100 ml. The throughput time for 100 ml of liquid is measured and graphically plotted against the filtered volume. The time axis is divided logarithmically.

Auswertung der BestimmungEvaluation of the determination

Methode A: Vergleich der so erhaltenen Filtrationskurven.Method A: Comparison of the filtration curves obtained in this way.

Methode B: Quantitative Bestimmung der höhermolekularren, im Erdöldestillat unlöslichen Anteile an Copolymerwachs.Method B: Quantitative determination of the high molecular weight proportions of copolymer wax which are insoluble in petroleum distillate.

Vor der Filtration wird das Membranfilter mit 100 ml n-Pentan gewaschen, getrocknet und gewogen. Nach erfolgter Filtration des zu untersuchenden Erdöldestillats wird das Membranfilter erneut mit 100 ml und n-Pentan ölfrei gewaschen, getrocknet und zurückgewogen. Die Menge an höhermolekularem, im Erdöldestillat, unlöslicher Rückstand wird angegeben in Gew.% bezogen auf Copolymerwachs.Before filtration, the membrane filter is washed with 100 ml of n-pentane, dried and weighed. After filtration of the petroleum distillate to be examined, the membrane filter is washed again oil-free with 100 ml and n-pentane, dried and weighed out. The amount of higher molecular weight residue which is insoluble in petroleum distillate is given in% by weight based on copolymer wax.

Die-vorstehend beschriebene Methode erlaubt die Untersuchung sowohl von nicht modifizierten Erdöldestillaten, als auch von Erdöldestillaten, die copolymere Wachse oder Dispersionen bzw. Lösungen dieser Wachse enthalten. Durch Vorversuche gemäß Methode A mit Filtern verschiedener Porenweiten wird sichergestellt, daß bei Verwendung eines Membranfilters mit einer Porenweite von 8 µ zwischen Copolymerwachsen mit unterschiedlichen Gehalten an höhermolekularen Anteilen unterschieden werden kann.The method described above allows the investigation of both unmodified petroleum distillates and petroleum distillates containing copolymeric waxes or dispersions or solutions of these waxes. Preliminary tests according to Method A with filters with different pore sizes ensure that when using a membrane filter with a pore size of 8 .mu.m a distinction can be made between copolymer waxes with different contents of higher molecular weight.

Außerdem wird mit der Methode A sichergestellt, daß die Filtrationskurven von Erdöldestillat-Treib- und Brennstoffen, die keine copolymeren Wachse enthalten, keine Zunahme der Filtrationsdauer mit zunehmendem Piltrationsvolumen zeigen. Die Filtrationsdauer je 100 ml filtrierten Produkt ist nur von der Viskosität bzw. Dichte des Erdöldestillats abhängig. Nicht mit copolymeren Wachsen modifizierte Erdöldestillate geben nach Methode A keinen Hinweis auf Filterverstopfungen.In addition, method A ensures that the filtration curves of petroleum distillate fuels and fuels, which do not contain copolymeric waxes, do not show an increase in the filtration time as the volume of the filtration increases. The filtration time per 100 ml of filtered product depends only on the viscosity or density of the petroleum distillate. According to method A, petroleum distillates not modified with copolymer waxes do not indicate filter clogging.

Die nachfolgenden Beispiele erläutern die Erfindung unter Verwendung des vorstehend beschriebenen Filtrationstestes (Methode A und B).The following examples illustrate the invention using the filtration test described above (methods A and B).

Bei Copolymerwachsen mit extrem hohen Anteilen an höhermclekularen Verbindungen, die üblicherweise stärkere Filterverstopfungen verursachen können, kann der vorstehende Filtrationstest variiert werden, indem kleinere Volumina (z.B. Portionen zu je 20 ml) filtriert werden. Auf diese Weise kann zwischen sehr ähnlichen Cowachsen, die alle eine sehr schlechte Filtrationskurve nach Methode A ergeben, deutlicher unterschieden werden.In the case of copolymer waxes with extremely high proportions of higher-molecular compounds, which can usually cause severe filter blockages, the above filtration test can be varied by filtering smaller volumes (e.g. portions of 20 ml each). In this way it is possible to distinguish more clearly between very similar cow axes, which all result in a very bad filtration curve according to method A.

Bei Copolymerwachsen mit extrem geringen Anteilen an höhermolekularen Verbindungen verstopft das Membranfilter erst bei-größeren Durchsätzen an modifiziertem Erdöldestillat. (z.B. 10 bis 1001.) In diesem Fall sind auch größere Probevolumina von 500 bzw. 1 000 ml für den Filtrationstest empfehlenswert.In the case of copolymer waxes with extremely low proportions of higher molecular weight compounds, the membrane filter only clogs at higher throughputs of modified petroleum distillate. (e.g. 10 to 1001.) In this case, larger sample volumes of 500 or 1,000 ml are recommended for the filtration test.

Die Wirksamkeit des Monomeren-Zusatzes bleibt bei konstanter Temperatur auch nach längerer Lagerzeit der Dispersionen copolymerer Wachse erhalten.The effectiveness of the addition of monomers is retained at constant temperature even after the dispersions of copolymeric waxes have been stored for a long time.

Wesentlich für das Filtrierverhalten von mit Fließverbesserern modifizierten Erdöldestillaten ist jedoch die Temperatur. Es konnte gezeigt werden, daß die Löslichkeit der in den copolymeren Wachsen enthaltenen geringen Anteile höhermolekularer Verbindungen eine Funktion der Temperatur ist.However, the temperature is essential for the filtering behavior of petroleum distillates modified with flow improvers. It could be shown that the solubility of the small amounts of higher molecular weight compounds contained in the copolymer waxes is a function of the temperature.

So erhält man bei Filtrationstesten nach Methode A mit abnehmenden Filtrationstenperaturen des modifizierten Erdöldestillats für dasselbe Copolymerwachs einen steileren Verlauf der Filtrationskurven und nach Methode 3 eine entsprechend größere Menge an unter diesen Bedingungen unlöslichen höhermolekularen Verbindungen im Copolymerwachs.In filtration tests according to method A, with decreasing filtration temperatures of the modified petroleum distillate for the same copolymer wax, the filtration curves are steeper and, according to method 3, a correspondingly larger amount of higher molecular weight compounds in the copolymer wax which are insoluble under these conditions.

Gleichwohl bleibt die stark lösungsvermittelnde Wirkung der erfindunggemäß zu verwendenden Monomeren auch bei tieferen Temperaturen erhalten, ggfs. sind lediglich die Zugabemengen der Lösungsvermittler zum Copolymerwachs zu erhöhen.Nevertheless, the strong solubilizing effect of the monomers to be used according to the invention is retained even at lower temperatures; if necessary, only the amounts of the solubilizers added to the copolymer wax need to be increased.

Die lösungsvermittelnde Wirkung der Monomeren erstreckt sich auf Temperaturen von weit oberhalb des natürlichen Trübungspunktes der Erdöldestillate (z.B. 30°C) bis weit unterhalb des Trübungspunktes (z.B. -40°C). Beim bzw. unterhalb des Trübungspunktes beginnt bei Erdöldestillaten mit weiter abnehmenden Temperatur die Ausscheidung von Paraffinkristallen. Durch Zugabe von Äthylen/Fettsäurevinylestern bzw. Äthylen/Acrylsäureestern als Fließverbesserer werden diese Paraffinkristalle modifiziert und in ihrem Wachstum gestört, das Öl ist zwar trübe durch ausgeschiedene Paraffine, bleibt aber fließ- und pumpfähig. Bei Verwendung der copolymeren Fließverbesserern, die noch bestimmte Mengen an höhermolekularen Anteile mit abnehmenden Temperaturen zunehmend unlöslicher, so daß sie entweder bereits oberhalb oder auch erst unterhalb des natürlichen Trübungspunkts der Erdöldestillate zusammen mit den Paraf- finen ausfallen können und zu Störungen im Kälteverhalten der Erdöldestillate führen. Filter- und Ventilverstopfungen werden in diesen Fällen demnach nicht durch die in ihrer Kristallform modifizierten Paraffinkristalle unterhalb des Trübungspunktes hervorgerufen, sondern bereits oberhalb des Trübungspunktes durch das Ausfallen unlöslicher höhermolekularer Anteile im copolymeren Fließverbesserer. Für die einwandfreie Wirksamkeit der copolymeren Fließverbesserer ist es deshalb erforderlich, die Anteile der aufgrund des Polymerisationsprozesses stets vorhandenen höhermolekularen Verbindungen so gut wie möglich in Lösung zu halten. Dies geschieht durch Zugabe der erfindungsgemäßen Lösungsvermittler.The solubilizing effect of the monomers extends to temperatures from well above the natural cloud point of the petroleum distillates (eg 30 ° C) to far below the cloud point (eg -40 ° C). At or below the cloud point in petroleum distillates, the precipitation of paraffin crystals begins with a further decrease in temperature. By adding ethylene / fatty acid vinyl esters or ethylene / acrylic acid esters as flow improvers, these paraffin crystals are modified and their growth is disturbed, the oil is cloudy due to excreted paraffins, but remains flowable and pumpable. When using the copolymeric flow improvers, the still certain amounts of higher molecular weight components become increasingly insoluble with decreasing temperatures, so that they either already above or only below the natural cloud point of the petroleum distillates together with the paraf- finen can fail and lead to disturbances in the cold behavior of the petroleum distillates. In these cases, filter and valve blockages are therefore not caused by the wax crystals modified in their crystal form below the cloud point, but rather above the cloud point by the precipitation of insoluble, higher molecular weight fractions in the copolymeric flow improver. For the effective effectiveness of the copolymeric flow improvers, it is therefore necessary to keep the proportions of the higher molecular compounds which are always present due to the polymerization process as good as possible in solution. This is done by adding the solubilizers according to the invention.

Beispiel 1example 1

In Tabelle 1 sind die physikalischen Daten verschiedener Copolymerwachse auf Basis Äthylen/Vinylacetat zusammengestellt. Die Tabelle zeigt außerdem die in den Copolymerwashsen noch vorhandenen Anteile an monomerem Vinylacetat.Table 1 shows the physical data of various copolymer waxes based on ethylene / vinyl acetate. The table also shows the proportions of monomeric vinyl acetate still present in the copolymer washes.

Die in Tabelle 1 aufgeführten Cowachse wurden in verschiedenen Dispergiermitteln als 50 %ige Dispersionen eingestellt und das Filtrierverhalten verschiedener Gasöle nach Zugabe von 500 Vol.-ppm der als Fließverbesserer wirksamen Dispersionen nach Methode A untersucht. Die in den 50 %igen Dispersionen vorhandenen und nach Methode 3 ermittelten höhermolekularen Anteile sind in der Tabelle 2 zusammengestellt. Fig. 1 und 2 zeigt die nach Methode.A bestimmten Filtrationskurven der Cowachse aus Tabelle 2, wobei hier und im folgenden t die Filtrationszeit in Sekunden und v das Filtrationsvolumen in ml bedeutet.

Figure imgb0001
Figure imgb0002
Wie Tabelle 2 und Fig. 1 und 2 zeigen, weisen alle untersuchten Cowachse in den verwendeten Dispergiermitteln eine schlechte Filtrierbarkeit (nach Methode A) und entsprechend große Anteile höhermolekularer Produkte nach Methode B auf. Die nachfolgenden Beispiele zeigen die Wirkungsweise der beanspruchten Lösungsvermittler.The cowaxes listed in Table 1 were adjusted as 50% dispersions in various dispersing agents and the filtering behavior of various gas oils after addition of 500 ppm by volume of the dispersions which act as flow improvers was investigated using Method A. The higher molecular weight components present in the 50% dispersions and determined by Method 3 are summarized in Table 2. 1 and 2 show the filtration curves of the cow axis from Table 2 determined according to Method A. A, where here and in the following t means the filtration time in seconds and v the filtration volume in ml.
Figure imgb0001
Figure imgb0002
 As Table 2 and FIGS. 1 and 2 show, all of the cow axes investigated in the dispersants used have poor filterability (according to method A) and correspondingly large proportions of higher molecular weight products according to method B. The following examples show the mode of action of the solubilizers claimed.

Beispiel 2Example 2

Das in Tabelle 1 und Fig. 1 bereits erwähnte Cowachs Nr. 1 wurde als 50 %ige Dispersion in C4-Oxoalkaholrückstand als Dispergiernittal mit den erfindungsgemäßen Lösungsvermittlern versatzt. Die so verbesserten Dispesionen wurden in einer Menge von 500 Vol.-ppm einem Dieselkraftstoff zugemischt und nach Methode A und 3 untersucht.The Cowachs No. 1 already mentioned in Table 1 and FIG. 1 was mixed with the solubilizers according to the invention as a 50% dispersion in C 4 -oxoalkahol residue as a dispersing agent. The dispersions thus improved were added to a diesel fuel in an amount of 500 ppm by volume and investigated according to methods A and 3.

Die Wirkung der Lösungsvermittler auf die Menge des im Cowachs Nr. 1 enthaltenen höhermolekularen Rückstandes zeigt die Tabelle 3. Die Rückstände wurden nach Methode B bestimmt. In der Fig. 3 sind die zu Tabelle 3 gehörenden Filtrationskurven dargestellt.

Figure imgb0003
The effect of the solubilizers on the amount of the higher molecular weight residue contained in Cowachs No. 1 is shown in Table 3. The residues were determined by Method B. 3 shows the filtration curves belonging to table 3.
Figure imgb0003

Beispiel 3Example 3

Das in Tabelle 1 erwähnte Cowachs Nr. 3 wurde als 50 %ige Dispersion in C4-Oxoalkoholrückstand eingestellt. Wie Tabelle 2 zeigt wird beim Filtrationstest nach Methode B eine Menge von 5,6 % höhermolekularer Anteile gefunden. Kurve 5 in Fig. 1 und A in Fig. 4 zeigt entsprechend schlechtes Filtrierverhalten (nach Methode A). Bei Zugabe von 1 Gew. % Vinylacetat zu der 50 %igen Dispersion von Cowachs Nr. 3 im C4-Oxoalkoholrückstand werden nach Zugabe von 500 Vol.- ppm der so verbesserten Dispersion zu einen Heizöl EL (nach DIN 51601) und dem Filtertest nach Methode B nur noch 0,34 % höhermolekulare Anteile gefunden. Die Kurve B in Fig. 4 zeigt die Filtrationskurven nach Methode A.Cowachs No. 3 mentioned in Table 1 was adjusted as a 50% dispersion in C 4 oxo alcohol residue. As Table 2 shows, an amount of 5.6% higher molecular weight components was found in the method B filtration test. Curve 5 in Fig. 1 and A in Fig. 4 shows correspondingly poor filtering behavior (according to method A). When 1% by weight of vinyl acetate is added to the 50% dispersion of Cowachs No. 3 in the C 4 -oxoalcohol residue, after adding 500 vol Method B found only 0.34% higher molecular weight. Curve B in Fig. 4 shows the filtration curves according to method A.

Beispiel 4Example 4

Ein durch Polymerisation ohne Lösungsmittel bei 220°C und 1 500 bar hergestelltes Copolymerwachs aus Äthylen und Vinylacetat mit einem Vinylacetatgehalt von 28,5 Gew.%, einer Viskosität (120°C) von 210 mm2/s; einem mittleren Molekulargewicht von 1 880 und einem Gehalt von 0, 75 Gew.% an monomerem Vinylacetat (bezogen auf Copolymer) wurde als 50 %ige Dispersion in einem C4-Oxoalkoholrückstand eingestellt.A copolymer wax made of ethylene and vinyl acetate with a vinyl acetate content of 28.5% by weight and a viscosity (120 ° C) of 210 mm 2 / s; an average molecular weight of 1,880 and a content of 0.75% by weight of monomeric vinyl acetate (based on the copolymer) was adjusted as a 50% dispersion in a C 4 -oxoalcohol residue.

.Der Filtrationstest nach Methode A wurde nach Zugabe von 500 Vol.-ppm der 50 %igen Dispersion des Copolymerwachses in C4-Oxoalkoholrückstand zu einem handelsüblichen Heizöl extra leicht (gemäß DIN 51 601) durchgeführt. Es wurde die in Fig. 5 dargestellte Filtrationskurve Nr. 1 erhalten.The filtration test according to method A was carried out extra easily (according to DIN 51 601) after adding 500 ppm by volume of the 50% dispersion of the copolymer wax in C 4 oxo alcohol residue to a commercially available heating oil. Filtration curve No. 1 shown in FIG. 5 was obtained.

Die Abhängigkeit der lösungsvermittelnden Wirkung vom Gehalt an moncmerem Vinylacetat wurde anschließend durch steigende Zugaben weiterer Mengen an monomerem Vinylacetat ebenfalls im Filtrationstast nach Methode A aufgezeigt.The dependence of the solubilizing effect on the content of monomeric vinyl acetate was subsequently increased by the addition of further amounts of monomeric vinyl acetate also shown in the filtration button according to method A.

Fig. 5 zeigt die Abhängigkeit der lösungsvermttelnden Wirkung vom Gehalt an monomerem Vinylacetats in der Dispersion im Filtrationstest nach Methode A. In den Filtrationskurven 2, 3 4 und 5 wurden der 50 %igen Dispersion des Copolymerwachses zusätzlich 0,25, 0,50, 1,0 und 3,0 Gew.% monomeres Vinylacetat zugesetzt.5 shows the dependency of the solution-mediating effect on the content of monomeric vinyl acetate in the dispersion in the filtration test according to method A. In filtration curves 2, 3 4 and 5, the 50% dispersion of the copolymer wax was additionally 0.25, 0.50, 1 , 0 and 3.0% by weight of monomeric vinyl acetate were added.

Beispiel 5Example 5

Ein durch kontinuierliche Polymerisation ohne Lösungsmittel bei 220°C und 1 500 bar aus Äthylen und Vinylacetat hergestelltes Copolymerwachs mit einen Gehalt von 27,2 Gew.% Vinylaeetat und einer Viskosität bei 120°C von 365 mm2/s und einem mittleren Molekulargewicht von 2 230 und einem Restgehalt an monomerem Vinylacetat von 0,55 Gew.% (bezogen auf Copclymer) wird als 40 %ige Dispersion in Petroleum eingestallt.A copolymer wax prepared from ethylene and vinyl acetate by continuous polymerization without solvent at 220 ° C and 1,500 bar with a content of 27.2% by weight of vinyl acetate and a viscosity at 120 ° C of 365 mm 2 / s and an average molecular weight of 2 230 and a residual monomeric vinyl acetate content of 0.55% by weight (based on copolymer) is stabled as a 40% dispersion in petroleum.

Es wird ein Filtrationstest nach Methode A und B unter Zugabe von 800 vol.-ppm der 40 %igen Dispersion zu einem handelsüblichen Heizöl extra leicht (gemäß DIN 51 601) durchgeführt. Der Filtertest erfolgt sofort, sowie nach 8 Tagen und 30 Tagen Standzeit des additivierten Heizöls. Man erhält die zugehörigen Filtrationskurven 1, 2 und 3 in Fig. 6 und nach Methode B einen Anteil höhermolekularer Verbindungen von 9,5 (Kurve 1), 9, 7 (Kurve 2) und 10,1 Gew.% (bezogen auf Cowachs). Weitere Filtrationsteste nach Methode A und B werden durchgeführt, nachdem zuvor der Dispersion eine Menge von 0,5 Gew.% monomeres Vinylacetat zugegeben worden war. Von dieser verbesserten Flieaverbesserer-Dispersion wurden dem gleichen Heizöl ebenfalls 800 Vol.- ppm zugesetzt.A filtration test according to methods A and B with the addition of 800 vol.ppm of the 40% dispersion to a commercially available heating oil is carried out extra easily (in accordance with DIN 51 601). The filter test is carried out immediately, as well as after 8 days and 30 days of the additive heating oil. The associated filtration curves 1, 2 and 3 in FIG. 6 and, according to Method B, a proportion of higher molecular weight compounds of 9.5 (curve 1), 9, 7 (curve 2) and 10.1% by weight (based on cowachs) are obtained. . Further filtration tests according to methods A and B are carried out after an amount of 0.5% by weight of monomeric vinyl acetate had previously been added to the dispersion. From this improved flow improver dispersion, 800 vol.ppm were also added to the same heating oil.

Der Filtertest des so additivienen Heizöls erfolgt auch hier sofort bzw. nach 8 Tagen und 30 Tagen.The filter test of the additive heating oil is also carried out here immediately or after 8 days and 30 days.

Man erhält die zugehörigen Filtrationskurven 4, 5 und 6 in Fig. 6 und nach Methode B Anteile höhermolskularer Verbindungen von 0,38 % (Kurve 4) und 0,45 % (Kurven 5 und 6).The associated filtration curves 4, 5 and 6 in FIG. 6 and, according to method B, proportions of higher molecular weight compounds of 0.38% (curve 4) and 0.45% (curves 5 and 6) are obtained.

Beispiel 6Example 6

a) Ein durch kontinuierliche Polymerisation ohne Lösungsmittel bei einer Temperatur von 245°C und einen Druck von 1 500 bar aus Äthylen und 2-Äthylhexylacrylat hergestelltes Copolynerwachs mit einem Gehalt von 46,2 Gew.% 2-Äthylhexylacrylat, einer Viskosität bei (120°C) von 252 mm2/s und einem mittleren Molekulargewicht von 2 440 wurde als 58 %ige Dispersion in Petroleum eingestellt, eine Stunde unter Rühren auf 80°C erwärmt, auf Raumtemperaur abgekühlt und einem Filtrationstest nach Methode A und B unterzogen. Dabei wurde ein handelsübliches Heizöl (extra leicht) mit 500 ppm der 58 %igen Dispersion versetzt. Der Filtrationstest wurde nach 24, 48, 108 und 240 Stunden bei Raumtemperatur wiederholt. Die Menge an polymeren Rückständen und die zugehörigen Filtrationskurven zeigen Tabelle 4 und Fig. 7.a) A copolyner wax prepared by continuous polymerization without solvent at a temperature of 245 ° C and a pressure of 1,500 bar from ethylene and 2-ethylhexyl acrylate with a content of 46.2% by weight 2-ethylhexyl acrylate, a viscosity at (120 ° C) of 252 mm 2 / s and an average molecular weight of 2,440 was adjusted as a 58% dispersion in petroleum, heated to 80 ° C. with stirring for one hour, cooled to room temperature and subjected to a filtration test according to methods A and B. A commercial heating oil (extra light) was mixed with 500 ppm of the 58% dispersion. The filtration test was repeated after 24, 48, 108 and 240 hours at room temperature. The amount of polymeric residues and the associated filtration curves are shown in Tables 4 and 7.

b) Der 58 %igen Dispersion wurden nun 1 Gew.% Vinylacetat (stabilisiert mit 0,1 % 2,6 Di-tert.-butyl-p-Kresol) zugegeben, die Mischung unter Rühren auf 30°C erwärmt, auf Raumtemperatur abgekühlt und der Filtrationstest A und B nach Zugabe von 500 ppm der mit Vinylacetat versetzten Dispersion nach 24, 48, 108 und 240 Stunden bei Rauntemperatur durchgeführt. Die Mengen an polymeren Rückständen und die zugehörigen Filtrationskurven enthält Tabelle 4 und Fig. 7. Darin bedeuten t Filtrations- zeit in Sekunden, v Filtrationsvolumen in ml, die Kurven 1, 2, 3, 4 gemäß, (a) nach 24, 48, 108 und 240 Stunden, die Kurven 5, 6, 7, 8 gemäß (b) nach 24, 48, 108 und 240 Stunden.

Figure imgb0004
b) 1% by weight of vinyl acetate (stabilized with 0.1% of 2,6 di-tert-butyl-p-cresol) was then added to the 58% dispersion, the mixture was heated to 30 ° C. with stirring and cooled to room temperature and the filtration test A and B after addition of 500 ppm of the dispersion mixed with vinyl acetate was carried out after 24, 48, 108 and 240 hours at room temperature. The amounts of polymeric residues and the associated filtration curves are shown in Table 4 and Fig. 7. Here, t means filtration time in seconds, v filtration volume in ml, curves 1, 2, 3, 4 according to, (a) after 24, 48, 108 and 240 hours, curves 5, 6, 7, 8 according to (b) after 24, 48 , 108 and 240 hours.
Figure imgb0004

Beispiel 7Example 7

Um die Wirkung des Monomerzusatzes bei Durchführung des Filtrationstestes in der Nähe des Trübungspunktes des modifizierten Erdöldestillats zu zeigen, wird das in Tabelle 1 beschriebene Copolymerwachs Nr. 1 als 50 %ige Dispersion in einem Oxoalkoholrückstand aus der Butanolsynthese eingestellt. Die Dispersion wird unter Rühren auf 80°C erwärmt, auf Raumtemperatur abkühlen lassen und nach einer Standzeit von 36 Tagen bei Raumtemperatur für den Filtertest A und 3 verwendet. Dazu wird ein handelsübliches Heizöl (extra leicht) vom Trübungspunkt -2°C mit 500 Gew.-ppm der Dispersion versetzt und in einem Kühlbad im Verlauf von 35 Minuten auf 0°C abgekühlt. Das so erhaltene öl wird nach Methode B filtriert. Es wird ein polymerer Rückstand von 130 mg (= 26,2 % bezogen auf Wachsanteil in der Dispersion) erhalten.In order to show the effect of the monomer addition when carrying out the filtration test in the vicinity of the cloud point of the modified petroleum distillate, the copolymer wax No. 1 described in Table 1 is adjusted as a 50% dispersion in an oxo alcohol residue from the butanol synthesis. The dispersion is heated to 80 ° C. with stirring, allowed to cool to room temperature and after a standing time of 36 days at room temperature for the filter test A and 3 used. For this purpose, a commercial heating oil (extra light) from the cloud point -2 ° C is mixed with 500 ppm by weight of the dispersion and cooled to 0 ° C in the course of 35 minutes. The oil thus obtained is filtered according to method B. There is obtained a polymeric residue of 13 0 mg (= 26.2% based on wax content in the dispersion).

Führt man den gleichen Test nach vorheriger Zugabe von 1 Gew.% Vinylacetat (bezogen auf Wachs und stabilisiert mit 0,1 % 2,6-Di-tert-butyl-p-Kresol) zu der Dispersion durch, so erhält man nach Methode B nur einen polymeren Rückstand von 44,2 mg (= 8,8 %).If the same test is carried out after the addition of 1% by weight of vinyl acetate (based on wax and stabilized with 0.1% of 2,6-di-tert-butyl-p-cresol) to the dispersion, method B is obtained only a polymeric residue of 44.2 mg (= 8.8%).

Erhöht man die Menge Vinylacetat auf insgesamt 3 Gew.% und verfährt in der gleichen Weise, so erhält man nur noch 5,5 mg (= 1,1 %) an polymerem RückstandIf the amount of vinyl acetate is increased to a total of 3% by weight and the same procedure is followed, only 5.5 mg (= 1.1%) of polymeric residue is obtained

Beispiel 8Example 8

In einem Großversuch werden in einer kontinuierlichen Polymerisationsanlage bei einer Temperatur von 240 bis 250°C und einem Druck von 1 500 bar 30.000 kg eines copolymeren Wachses aus Äthylen und Vinylacetat mit einem Gehalt von 29.,2 % Vinylacetat, einer Viskosität (bei 120°C) von 247 mm2/s und einem mittleren Molekulargewicht von 1 940 hergestellt.In a large-scale experiment, 30,000 kg of a copolymeric wax made of ethylene and vinyl acetate with a content of 29.2% vinyl acetate and a viscosity (at 120 °.) Are in a continuous polymerization plant at a temperature of 240 to 250 ° C and a pressure of 1,500 bar C) of 247 mm 2 / s and an average molecular weight of 1,940.

a) Eine Durchschnittsprobe des Wachses mit einem Gehalt an monomerem Vinylacetat von 0,6 % wird dann als 50 %ige Dispersion in einem Oxoölrückstand aus der Butanolsynthese eingestellt. Man versetzt einen handelsüblichen Dieselkraftstoff mit einem cloud-point von -2°C bei Raumtemperatur mit 500 Gew.-ppm dieser Dispersion, kühlt die Mischung im Verlauf von 35 Minuten in einem Kühlbzd auf 0°C ab und führt anschließend einen Filtrationstest nach Methode A und B durch. Es wird einpolynerer Rückstand von 37,2 mg (= 7,4 Gew.% bezogen auf den Wachsanteil in der Dispersion) erhalten.a) An average sample of the wax with a content of monomeric vinyl acetate of 0.6% is then set as a 50% dispersion in an oxo oil residue from the butanol synthesis. A commercially available diesel fuel with a cloud point of -2 ° C. at room temperature is mixed with 500 ppm by weight of this dispersion, and the mixture is cooled in a cooling cabinet over the course of 35 minutes to 0 ° C and then carries out a filtration test according to methods A and B. A polymeric residue of 37.2 mg (= 7.4% by weight based on the wax content in the dispersion) is obtained.

b) Werden der 50 %igen Dispersion 2 Gew.% Vinylacetat (bezogen auf Wachs und stabilisiert mit 0,1 % 2,6-Di-tert.-butyl-p-Kresol) zugesetzt und der oben beschriebene Filtrationstest bei 0°C wiederbolt, erhält man nur noch 4,1 mg polymeren Rückstand (= 0,83 Gew.% bezogen auf den Waehsanteil in der Dispersion). Die Filtrationskurven beider Filtrationsteste zeigt Fig. 8.b) 2% by weight of vinyl acetate (based on wax and stabilized with 0.1% of 2,6-di-tert-butyl-p-cresol) are added to the 50% dispersion and the filtration test described above is repeated at 0 ° C. , only 4.1 mg of polymeric residue are obtained (= 0.83% by weight, based on the proportion by weight in the dispersion). The filtration curves of both filtration tests are shown in Fig. 8.

Beispiel 9Example 9

In einer wie in Fig. 9 dargestellten kontinuierlich zu betreibenden Apparatur wird Dieselöl über ein handelsübliches Kraftstoffilter gepumpt. Die Apparatur besteht aus einem isolierten Vorratsgefäß (B 1) mit einem Volumen von 110 1 für das Dieselöl, in dem sich eine mit Kühlsole (s) betriebene Kühlschlange befindet, einer Bosch-Kraftstoffpumpe (P-1) für 0-1,5 bar, einem Kraftstaffiltar (F), Bosch-Nr. 1457434052, mit Differenzdruckmanometer (PI-2) und einer kontinuierlichen Kraftstoffdurchflußnessung (FI). Weiterhin aind installiert die Druckmeßstellen PI-1 und PI-3 sowie die Temperaturanzeigen TI-1, TI-2 und TI-3. Die über das Filter F gepumpte Menge Dieselöl wird im Sammelgefäß B-2 (Volumen 110 1) aufgefangen. Pumpe und Filter befinden sich in einer mit Trockeneis betriebenen Kühlbox, um Temperaturerhöhungen durch Wärmeleitung und Pumpenarbeit zu vermeiden.In an apparatus to be operated continuously as shown in FIG. 9, diesel oil is pumped through a commercially available fuel filter. The apparatus consists of an insulated storage vessel (B 1) with a volume of 110 1 for the diesel oil, in which there is a cooling coil operated with cooling brine (s), a Bosch fuel pump (P-1) for 0-1.5 bar , a Kraftstaffiltar (F), Bosch no. 1457434052, with differential pressure gauge (PI-2) and a continuous fuel flow meter (FI). The PI-1 and PI-3 pressure measuring points and the TI-1, TI-2 and TI-3 temperature displays are also installed. The quantity of diesel oil pumped through the filter F is collected in the receptacle B-2 (volume 110 1). The pump and filter are located in a cool box operated with dry ice in order to avoid temperature increases due to heat conduction and pump work.

In dieser Apparatur wurden vorher über ein Papierfilter vorgereinigte Gasöle bei Temperaturen unmittelbar oberhalb ihres Trübungspunktes mit einer Durchflußmenge von 10 1/h über das Filter F gepumpt.In this apparatus, gas oils which had previously been cleaned using a paper filter were pumped through the filter F at a temperature of just above their cloud point at a flow rate of 10 l / h.

Sin Kriterium für die Belegung des Kraftstoffilters mit höhemolekularen Anteilen aus den copolymeren Fließverbesserem ist der Druckanstieg des Differenzdrucksonoceters PI-2.The criterion for covering the fuel filter with high molecular weight components from the copolymeric flow improver is the pressure increase of the differential pressure sonoceter PI-2.

Die Kurven für den jeweiligen Druekverlauf (mm WS) werden gegen die Versuchsdauer grafisch aufgetragen. Die nachfolgende Fig.10 in der P den Druckabfall in mm Wassersäule und t die Versuchsdauer in Sekunden bedeuten, zeigt die Ergebnisse mit verschiedenen copolymeren Äthylen-Vinylacetat-Wachsen als Fließverbesserer mit und ohne Zugabe von momomerem Vinylacetat.The curves for the respective pressure curve (mm WS) are plotted against the test duration. The following Fig. 10 in which P is the pressure drop in mm of water and t is the test duration in seconds shows the results with various copolymeric ethylene-vinyl acetate waxes as flow improvers with and without the addition of monomeric vinyl acetate.

Kurve 1: Cowaehs aus Äthylen-Vinylacetat mit 28,1 Gew.-% Vinylaeetat, mittleres Molgewicht 2 160, Schmelzviskosität (120°C) 230 mm2/s, Gehalt an monomerem Vinylacetat 0,07 Gew.%, als 50 %ige Dispersion in Oxoölrückstand aus der Butanolsynthese.
Dosierung der Dispersion in Dieselöl: 500 Vol-ppm - ohne weitere Zugabe von Lösungsversittlern - Temperatur: + 0°C.Curve 1: Cowaehs from ethylene-vinyl acetate with 28.1% by weight vinyl acetate, average molecular weight 2,160, melt viscosity (120 ° C.) 230 mm 2 / s, content of monomeric vinyl acetate 0.07% by weight, as 50% Dispersion in oxo oil residue from butanol synthesis.
Dosage of the dispersion in diesel oil: 500 vol ppm - without further addition of solubilizers - temperature: + 0 ° C.

Kurve 2: wrie 1, jedoch nach Zugabe von 0,5 Gew.% an monomerem Vinylacetat (stabilisiert), bezogen auf Cowachs.Curve 2: same as 1, but after adding 0.5% by weight of monomeric vinyl acetate (stabilized), based on cowachs.

Kurve 3: wie 2, jedoch mit 1,0 Gew.% an monomerem Vinylacetat.Curve 3: as 2, but with 1.0% by weight of monomeric vinyl acetate.

Kurve 4: wie 2, jedoch mit 3,0 Gew.% an mononerem Vinylacetat.Curve 4: as 2, but with 3.0% by weight of mononer vinyl acetate.

Beispiel 10Example 10

Das in Tabelle 1 und Fig. erwähnte Cowachs Nr. 1 wurde als 50 %ige Dispersion in C4-Oxoalkoholrückstand als Dispergiermittel mit den erfindungsgemäßen Lösungsvermittlern versetzt. Die so verbesserten Dispersionen wurden in einer Menge von 500 Vol.-ppm einem Dieselkraftstoff zugemischt und nach Methode A und B untersucht.The Cowachs No. 1 mentioned in Table 1 and FIG. 1 was added as a 50% dispersion in C 4 -oxoalcohol residue as a dispersant with the solubilizers according to the invention. The dispersions thus improved were added to a diesel fuel in an amount of 500 ppm by volume and investigated according to methods A and B.

Die Wirkung der Lösungsversittler auf die Menge des im Cowachs Nr. 1 enthaltenen höhermolekularen Rückstandes zeigt die folgende Tabelle. Die Rückstände wurden nach Methode B bestimmt. In der Fig. 11 sind die zur Tabelle 5 gehörenden Filtrationskurven dargestellt.

Figure imgb0005
The following table shows the effect of the solubilizers on the amount of the higher molecular residue contained in Cowachs No. 1. The residues were determined according to method B. 11 shows the filtration curves belonging to table 5.
Figure imgb0005

Claims (6)

1. Mitteldestillate des Erdöls, die als Dieseltreibstoffe oder leichtes Heizöl geeignet sind, mit verbesserter Filtrierbarkeit und verbessertem Fließverhalten mit ei- nem Gehalt geringer Mengen an Modifikatoren in Form von Copolymeren, ausgewählt aus der Gruppe binärer Copoly- merisate aus Äthylen und einem Vinylester einer C2- oder C3-Alkancarbonsäure und binärer Copolymerisate eines C - bis C8-Alkylesters einer C3- oder C4-Alkenmonocarbon- säure, wobei die Copolymerisate 60 bis 95 Gew.% Äthylen und 5 bis 40 Gew.% des olefiniseh ungesättigten Esters einpolymerisiert enthalten und eine Viskosität in der Schmelze, gemessen nach DIN 51 562 (ASTH D 445) bei 120°C, von 100 bis 1 000 m2/sec aufweisen, dadurch gekennzeichnet, daß die Mittelcestillate neben den Copolymeren 0,1 bis 10 Vol.%, bezogen auf das Copolynere, der monomeren Vinylester einer C2- bis C3-Alkencarboneäure oder von monomeren C1- bis C8-Alkylester einer C3- oder C4-Alkencarbonsäure enthalten. 1st Middle distillates of petroleum suitable as diesel fuels or light fuel oil, low product having improved filterability and improved flow behavior with egg n em content amounts of modifiers in the form of copolymers selected from the group of binary copoly m erisate of ethylene and a Vinylester a C 2 - or C 3 -alkane carboxylic acid and binary copolymers of a C - to C 8 -alkyl ester of a C 3 - or C 4 -alkylene monocarboxylic acid, the copolymers containing 60 to 95% by weight of ethylene and 5 to 40% by weight of the olefinically unsaturated Polymerized esters contained and a viscosity in the melt, measured according to DIN 51 562 (ASTH D 445) at 120 ° C, from 100 to 1000 m2 / sec, characterized in that the middle distillates in addition to the copolymers 0.1 to 10 vol %, based on the copolymer, of the monomeric vinyl esters of a C 2 to C 3 alkenecarboxylic acid or of monomeric C 1 to C 8 alkyl esters of a C 3 or C 4 alkenecarboxylic acid. 2. Mitteldestillate gemäß Anspruch 1, dadurch gekennzeichnet, daß die binären Copolymerisate durch lösungsmittelfreie, radikalische Polymerisation bei Drücken von 500 bis 2000 bar und Temperaturen von 100 bis 350°C, vorzugsweise 200 bis 300°C, hergestellt werden und Molgewichte von 500 bis 10 000, vorzugsweise 1000 bis 5000, aufweisen.2. Middle distillates according to claim 1, characterized in that the binary copolymers are prepared by solvent-free, radical polymerization at pressures of 500 to 2000 bar and temperatures of 100 to 350 ° C, preferably 200 to 300 ° C, and molecular weights of 500 to 10 000, preferably 1000 to 5000, have. 3. Mitteldestillate gemäß Anspruch 2, dadurch gekennzeichnet, daß gegen Ende der Polymerisationsreaktion der zuzusetzenden Polymere das nicht umgesetzte Äthylen gemeinsam mit dem nicht umgesetzten monomeren Vinylester bzw. monomeren C1- bis C8-Alkylester von C3- oder C4-Alkenmonocarbon- säuren durch Entspannen des Reaktors zunächst abgetrennt und die genannten monomeren Vinylester bzw. monomeren C1- bis C8-Alkylester von C3- oder C4-Alkenmonocarbonsäuren nachträglich in Mengen von 0,1 bis 10 Vol.%, bezogen auf das Copolymere, dem nun äthylenfreien Copolymeren wieder zugesetzt werden.3. Middle distillates according to claim 2, characterized in that towards the end of the polymerization reaction of the polymers to be added, the unreacted ethylene together with the unreacted monomeric vinyl ester or monomeric C 1 - to C 8 -alkyl esters of C 3 - or C 4 -alkene monocarbon- acids are first separated off by decompressing the reactor and the monomeric vinyl esters or monomeric C 1 - to C 8 alkyl esters of C 3 or C 4 alkene monocarboxylic acids in amounts of 0.1 to 10% by volume, based on the copolymer, to which the ethylene-free copolymer is then added again. 4. Mitteldestillate gemäß Anspruch 1, dadurch gekennzeichnet, daß sie monomeres Vinylacetat enthalten.4. middle distillates according to claim 1, characterized in that they contain monomeric vinyl acetate. 5. Mitteldestillate gemäß Anspruch 1, dadurch gekennzeichnet, daß sie monomere Acrylsäureester von C1- bis C8-Alkanolen enthalten.5. middle distillates according to claim 1, characterized in that they contain monomeric acrylic acid esters of C 1 - to C 8 -alkanols. 6. Mitteldestillate gemäß Anspruch 1, dadurch gekennzeichnet, daß sie monomere C1-C8-Alkylester der Maleinsäure enthalten.
Zeichn.6. middle distillates according to claim 1, characterized in that they contain monomeric C 1 -C 8 alkyl esters of maleic acid.
Sign.
EP79102558A 1978-07-26 1979-07-20 Middle distillates of petroleum, suitable as diesel fuel or as light heating oil, and with improved filtration properties Expired EP0007590B1 (en)

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DE19782832738 DE2832738A1 (en) 1978-07-26 1978-07-26 Petroleum middle distillate fuels with improved filterability - contg. copolymer of ethylene! and unsatd. ester, and monomeric ester
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DE19792908564 DE2908564A1 (en) 1979-03-05 1979-03-05 Petroleum middle distillate fuels with improved filterability - contg. copolymer of ethylene! and unsatd. ester, and monomeric ester
DE2908564 1979-03-05

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Cited By (13)

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DE4311660C1 (en) * 1993-04-08 1994-01-13 Leuna Werke Ag Fuels with improved low-temp. flow - contg. copolymer of ethylene] and vinyl] acetate with asymmetric molecular wt. distribution
US5814110A (en) * 1986-09-24 1998-09-29 Exxon Chemical Patents Inc. Chemical compositions and use as fuel additives
WO1999029748A1 (en) * 1997-12-05 1999-06-17 Basf Aktiengesellschaft Method for producing ethylene copolymers in segmented tubular reactors and utilizing copolymers as a flow improver
US6495495B1 (en) 1999-08-20 2002-12-17 The Lubrizol Corporation Filterability improver
EP0900836B2 (en) † 1997-09-08 2008-06-11 Clariant Produkte (Deutschland) GmbH Additive for mineral oils and mineral oil distillates flowability improvement
WO2011001352A1 (en) 2009-07-03 2011-01-06 Total Raffinage Marketing Ethylene/vinyl acetate/unsaturated esters terpolymer as an additive for improving the resistance to cold of liquid hydrocarbons such as middle distillates and fuels
WO2011134923A1 (en) 2010-04-27 2011-11-03 Basf Se Quaternized terpolymer
WO2011138400A1 (en) 2010-05-07 2011-11-10 Basf Se Terpolymer and use thereof to improve the low-temperature flow properties of middle-distillate fuels
US8642521B2 (en) 2003-12-04 2014-02-04 Basf Se Fuel oil compositions with improved cold flow properties
US8790426B2 (en) 2010-04-27 2014-07-29 Basf Se Quaternized terpolymer
US9102767B2 (en) 2009-03-25 2015-08-11 Total Raffinage Marketing Low molecular weight (meth)acrylic polymers, free of sulphur-containing, metallic and halogenated compounds and with low residual monomer content, method for preparing the same and uses thereof
WO2016075070A1 (en) 2014-11-10 2016-05-19 Basf Se Ethylene-propylheptyl(meth-)acrylate copolymers
WO2021250115A1 (en) 2020-06-10 2021-12-16 Total Marketing Services Hydrocarbon fluid having improved cold temperature properties

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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
DE2515805A1 (en) * 1974-04-17 1975-10-30 Exxon Research Engineering Co ETHYLENE CO-POLYMERS, PROCESS FOR THEIR MANUFACTURING AND DISTILLED OILS CONTAINING THE SAME
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Publication number Priority date Publication date Assignee Title
US5814110A (en) * 1986-09-24 1998-09-29 Exxon Chemical Patents Inc. Chemical compositions and use as fuel additives
DE4311660C1 (en) * 1993-04-08 1994-01-13 Leuna Werke Ag Fuels with improved low-temp. flow - contg. copolymer of ethylene] and vinyl] acetate with asymmetric molecular wt. distribution
EP0620265A1 (en) * 1993-04-08 1994-10-19 Leuna-Werke Gmbh Fuel composition with improved low temperature flow behaviour
EP0900836B2 (en) † 1997-09-08 2008-06-11 Clariant Produkte (Deutschland) GmbH Additive for mineral oils and mineral oil distillates flowability improvement
WO1999029748A1 (en) * 1997-12-05 1999-06-17 Basf Aktiengesellschaft Method for producing ethylene copolymers in segmented tubular reactors and utilizing copolymers as a flow improver
DE19754039A1 (en) * 1997-12-05 1999-06-24 Basf Ag Process for the production of ethylene copolymers in segmented tubular reactors and use of the copolymers as flow improvers
US6495495B1 (en) 1999-08-20 2002-12-17 The Lubrizol Corporation Filterability improver
US10526558B2 (en) 2003-12-04 2020-01-07 Basf Se Fuel oil compositions with improved cold flow properties
US10047314B2 (en) 2003-12-04 2018-08-14 Basf Se Fuel oil compositions with improved cold flow properties
US9605227B2 (en) 2003-12-04 2017-03-28 Basf Se Fuel oil compositions with improved cold flow properties
US8642521B2 (en) 2003-12-04 2014-02-04 Basf Se Fuel oil compositions with improved cold flow properties
US9102767B2 (en) 2009-03-25 2015-08-11 Total Raffinage Marketing Low molecular weight (meth)acrylic polymers, free of sulphur-containing, metallic and halogenated compounds and with low residual monomer content, method for preparing the same and uses thereof
WO2011001352A1 (en) 2009-07-03 2011-01-06 Total Raffinage Marketing Ethylene/vinyl acetate/unsaturated esters terpolymer as an additive for improving the resistance to cold of liquid hydrocarbons such as middle distillates and fuels
US8790426B2 (en) 2010-04-27 2014-07-29 Basf Se Quaternized terpolymer
WO2011134923A1 (en) 2010-04-27 2011-11-03 Basf Se Quaternized terpolymer
WO2011138400A1 (en) 2010-05-07 2011-11-10 Basf Se Terpolymer and use thereof to improve the low-temperature flow properties of middle-distillate fuels
WO2016075070A1 (en) 2014-11-10 2016-05-19 Basf Se Ethylene-propylheptyl(meth-)acrylate copolymers
WO2021250115A1 (en) 2020-06-10 2021-12-16 Total Marketing Services Hydrocarbon fluid having improved cold temperature properties

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EP0007590B1 (en) 1981-02-18
NO145725B (en) 1982-02-08
NO792453L (en) 1980-01-29
DE2960183D1 (en) 1981-04-02
NO145725C (en) 1982-05-19

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