EP0084148A2 - Petrol middle distillate with modified flow properties - Google Patents
Petrol middle distillate with modified flow properties Download PDFInfo
- Publication number
- EP0084148A2 EP0084148A2 EP82111819A EP82111819A EP0084148A2 EP 0084148 A2 EP0084148 A2 EP 0084148A2 EP 82111819 A EP82111819 A EP 82111819A EP 82111819 A EP82111819 A EP 82111819A EP 0084148 A2 EP0084148 A2 EP 0084148A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- ethylene
- weight
- vinyl propionate
- copolymer
- petrol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003209 petroleum derivative Substances 0.000 claims abstract description 6
- 238000009835 boiling Methods 0.000 claims abstract description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
Definitions
- the invention relates to middle distillates, in particular light heating oil and diesel oil, containing a flow improver, which consists of a copolymer of ethylene with vinyl propionate.
- middle distillates such as gas oils, diesel oils or heating 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 e.g. in the case of diesel fuel, for clogging of filters and thus for interrupting or not evenly supplying the fuel to the combustion units, such as engines or jet engines.
- Malfunctions in heating oils can also occur in winter if such precipitations occur due to low temperatures.
- the pumping of middle distillates through pipelines over longer distances can also be affected in winter by the precipitation of paraffin 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 under the name "Pour point improver” or flow improver “or” pour point improver "known.
- ethylene-vinyl acetate copolymers which have a molecular weight of 1000 to 3000 and a vinyl acetate content of 1 to 40% by weight.
- This object is achieved according to the invention with a distillate preparation consisting of a petroleum distillate in the boiling range from 120 to 400 ° C. and 0.005 to 0.5% by weight of an ethylene-vinyl propionate copolymer with a molecular weight of 1000 to 3000 and a comonomer content of 5 to 29%. %, preferably 12 to 28.5% by weight, vinyl propionate.
- the ethylene-vinyl propionate copolymers are prepared in a manner known per se by any process for the radical polymerization of ethylene.
- the copolymers to be used according to the invention are advantageously prepared by high-pressure polymerization without addition of solvents, at temperatures between 100 and 350 ° C. and pressures between 500 and 3000 bar using oxygen or conventional initiators such as di-t-butyl peroxide, t-butyl perpivalate or t-butyl perisononanate.
- oxygen or conventional initiators such as di-t-butyl peroxide, t-butyl perpivalate or t-butyl perisononanate.
- Conventional compounds such as aldehydes, ketones, mercaptans and alkenes and alkanes with 3 or more carbon atoms are used as regulators. Examples include propionaldehyde, acetone, propylene, butene, isobutane and pentane.
- tubular reactors are tubular polymerization vessels whose length is 10,000 to 40,000 times the tube diameter.
- autoclave reactors the interior of which is usually in the ratio of the height to the diameter of the circular cross section from 1: 1 to 20: 1, the reaction material is moved with the aid of stirrers.
- a mixture of 12.6 kg / h of ethylene, 5.5 kg / h of vinyl propionate and 0.31 kg / h of propionaldehyde are passed continuously through a 1 l stirred autoclave kept at a pressure of 1500 bar.
- the temperature in the autoclave is maintained at 250 ° C. by the continuous addition of 2.2 g / h of tert-butyl perisononanate in a paraffin hydrocarbon mixture (bp. 63-80 ° C.).
- 4.9 kg of ethylene-vinyl propionate wax with a vinyl propionate content of 28.4% by weight and a melt viscosity (at 120 ° C.) of 250 mm 2 / s are obtained.
- the average molecular weight (number average M n ) is 1730 (Mechrolab vapor phase osmometer Model 301 A, solvent toluene).
- a mixture of 12.2 kg / h of ethylene, 5.6 kg / h of vinyl acetate and 0.55 kg / h of propionaldehyde are continuously passed through a 1 l stirred autoclave kept at a pressure of 1500 bar.
- a temperature of 250 ° C. is maintained in the autoclave by the continuous addition of 5.5 g / h of tert-butyl perisononanate in a paraffin-hydrocarbon mixture (bp. 175-210).
- 5.3 kg of ethylene-vinyl acetate wax were obtained with a vinyl acetate content of 28.3% by weight and a melt viscosity (at 120 ° C. ) of 250 mm 2 / s.
- the average molecular weight (number average M n) is 1760 (Mechrolab vapor phase osmometer model 301 A, solvent toluene).
- Table II shows the effectiveness of the copolymers described in Preparation Examples 1 to 6 with regard to their CFPP value.
- Examples 4 and 5 are listed for comparison with products with a higher vinyl propionate content,
- Example 6 is listed for comparison with ethylene-vinyl acetate copolymers.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
Description
Die Erfindung betrifft Mitteldestillate, insbesondere leichtes Heizöl und Dieselöl, mit einem Gehalt eines Fließverbesserers, der aus einem Copolymerisat des Ethylens mit Vinylpropionat besteht.The invention relates to middle distillates, in particular light heating oil and diesel oil, containing a flow improver, which consists of a copolymer of ethylene with vinyl propionate.
Sogenannte Mitteldestillate, wie Gasöle, Dieselöle oder Heizöle, 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 in Winter auftreten, wenn derartige Ausscheidungen, bedingt durch tiefe Teüperaturen, 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 heating 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. This leads e.g. in the case of diesel fuel, for clogging of filters and thus for interrupting or not evenly supplying the fuel to the combustion units, such as engines or jet engines. Malfunctions in heating oils can also occur in winter if such precipitations occur due to low temperatures. However, the pumping of middle distillates through pipelines over longer distances can also be affected in winter by the precipitation of paraffin 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.Such additives change the size and shape of the wax crystals so that the oil remains fluid even at low temperatures. Such additives are under the name "Pour point improver" or flow improver "or" pour point improver "known.
Insbesondere sind gemäß der deutschen Patentschrift 1 147 799 Ethylen-Vinylacetat-Copolymere bekannt, die ein Molekulargewicht von 1000 bis 3000 und einen Vinylacetatgehalt von 1 bis 40 Gew.% aufweisen.In particular, according to German Patent 1,147,799, ethylene-vinyl acetate copolymers are known which have a molecular weight of 1000 to 3000 and a vinyl acetate content of 1 to 40% by weight.
Gemäß der deutschen Auslegeschrift 19 14 756 sollen besonders solche Copolymerisate der genannten Art wirksam sein, die durch Lösungsmittelpolymerisation unterhalb 130°C hergestellt worden sind.According to German Auslegeschrift 19 14 756 copolymers of the type mentioned are particularly effective, which have been prepared by solvent polymerization below 130 ° C.
Des weiteren ist aus der DE-OS 21 02 469 bekannt, Copolymerisate von Ethylen mit 30 bis 75 Gew.% Vinylestern oder Acrylsäure- und Methacrylsäureestern, die sich von Alkoholen mit 1 bis 12 Kohlenstoffatomen ableiten, als Zusatz zu Erdölfraktionen zu verwenden.Furthermore, it is known from DE-OS 21 02 469 to use copolymers of ethylene with 30 to 75% by weight of vinyl esters or acrylic and methacrylic acid esters, which are derived from alcohols with 1 to 12 carbon atoms, as an additive to petroleum fractions.
Alle bisher bekannten Zusätze führen in einer Reihe von Erdölfraktionen nur zu einer unbefriedigenden Verbesserung der Fließfähigkeit.All of the additives known to date only lead to an unsatisfactory improvement in flowability in a number of petroleum fractions.
Es bestand daher die Aufgabe einen Zusatz zu Erdölfraktionen zu finden, der zu einer Verbesserung der Fließfähigkeit in Erdölfraktionen führt, bei der bisher bekannte Zusätze einen nur ungenügenden Effekt erbrachten.It was therefore the task of finding an additive to petroleum fractions, which leads to an improvement in the flowability in petroleum fractions, in which previously known additives had an insufficient effect.
Diese Aufgabe wird erfindungsgemäß gelöst mit einer Destillatclzubereitung, bestehend aus einem Erdöldestillat im Siedebereich von 120 bis 400°C und 0,005 bis 0,5 Gew.% eines Ethylen-Vinylpropionatcopolymerisats mit einem Molekulargewicht von 1000 bis 3000 und einem Comonomerengehalt von 5 bis 29 Gew.%, vorzugsweise 12 bis 28,5 Gew.%, Vinylpropionat.This object is achieved according to the invention with a distillate preparation consisting of a petroleum distillate in the boiling range from 120 to 400 ° C. and 0.005 to 0.5% by weight of an ethylene-vinyl propionate copolymer with a molecular weight of 1000 to 3000 and a comonomer content of 5 to 29%. %, preferably 12 to 28.5% by weight, vinyl propionate.
Die Herstellung der Ethylen-Vinylpropionat-Copolymeren ' erfolgt in an sich bekannter Weise nach jedem Verfahren zur radikalischen Polymerisation von Ethylen.The ethylene-vinyl propionate copolymers are prepared in a manner known per se by any process for the radical polymerization of ethylene.
Die Herstellungsmethode der Copolymerisate durch Lösungsmittelpolymerisation ist in den genannten deutschen Patentschriften eingehend beschrieben, so daß bezüglich der Polymerisationsmethode nur auf diese Vorliteratur Bezug genommen wird.The method of preparation of the copolymers by solvent polymerization is described in detail in the aforementioned German patents, so that reference is made only to this preliminary literature with regard to the polymerization method.
Vorteilhaft stellt man jedoch die erfindungsgemäß zu verwendenden Copolymerisate durch Hochdruckpolymerisation ohne Lösungsmittelzusätze her, bei Temperaturen zwischen 100 und 350oC und Drücken zwischen 500 bis 3000 bar unter Verwendung von Sauerstoff oder üblichen Initiatoren, wie Di-t.-butylperoxid, t-Butylperpivalat oder t-Butylperisononanat. Als Regler verwendet man übliche Verbindungen wie Aldehyde, Ketone, Mercaptane und Alkene und Alkane mit 3 oder mehr C-Atomen. Beispiele hierfür sind Propionaldehyd, Aceton, Propylen, Buten, Isobutan und Pentan.However, the copolymers to be used according to the invention are advantageously prepared by high-pressure polymerization without addition of solvents, at temperatures between 100 and 350 ° C. and pressures between 500 and 3000 bar using oxygen or conventional initiators such as di-t-butyl peroxide, t-butyl perpivalate or t-butyl perisononanate. Conventional compounds such as aldehydes, ketones, mercaptans and alkenes and alkanes with 3 or more carbon atoms are used as regulators. Examples include propionaldehyde, acetone, propylene, butene, isobutane and pentane.
Derartige Polymerisationsverfahren sind beispielsweise in Ullmanns Encyklopädie der technischen Chemie, 4. Auflage, 19. Band, S. 169-178 beschrieben. Die Anordnungen für die Polymerisationszone lassen sich zweckmäßig in Rohrreaktoren und/oder Autoklavenreaktoren einteilen. Unter Rohrreaktoren versteht man rohrförmige Polymerisationsgefäße, deren Längenausdehnung das 10 000- bis 40 000-fache des Rohrdurchmessers beträgt. In Autoklavenreaktoren, deren Innenraum meist im Verhältnis von Höhe zu Durchmesser des kreisförmigen Querschnitts von 1 : 1 bis ,20 : 1 hat, wird das Reaktionsgut mit Hilfe von Rührern bewegt.Polymerization processes of this type are described, for example, in Ullmann's Encyklopedia of Industrial Chemistry, 4th Edition, 19th Volume, pp. 169-178. The arrangements for the polymerization zone can advantageously be divided into tubular reactors and / or autoclave reactors. Tubular reactors are tubular polymerization vessels whose length is 10,000 to 40,000 times the tube diameter. In autoclave reactors, the interior of which is usually in the ratio of the height to the diameter of the circular cross section from 1: 1 to 20: 1, the reaction material is moved with the aid of stirrers.
Die folgenden Angaben beziehen sich sämtlich auf die Herstellung in einem kontinuierlich betriebenen Rührautoklaven mit einem Innenvolumen von 1 1.The following details all relate to the production in a continuously operated stirred autoclave with an internal volume of 1 1.
In den folgenden Beispielen ist die Herstellung der Ethylen-Vinylpropionat-Copolymerisate und die Wirkung als Mitteldestillatzusatz im einzelnen beschrieben.The preparation of the ethylene-vinyl propionate copolymers and the action as a middle distillate additive are described in detail in the following examples.
Herstellung der Ethylen-Vinylpropionat-CopolymerisateProduction of the ethylene-vinyl propionate copolymers
Eine Mischung von 12,6 kg/h Ethylen, 5,5 kg/h Vinylpropionat und 0,31 kg/h Propionaldehyd werden kontinuierlich durch einen auf einem Druck von 1500 bar gehaltenen 1 1-Rührautoklaven geleitet. Durch die kontinuierliche Zugabe von 2,2 g/h tert.-Butylperisononanat in einem Paraffinkohlenwasserstoffgemisch (Kp. 63-80°C) wird eine Temperatur im Autoklaven von 250°C aufrechterhalten. Nach Entspannung des Reaktionsgemisches fallen 4,9 kg Ethylen--Vinylpropionat-Wachs mit einem Vinylpropionat-Gehalt von 28,4 Gew.% und einer Schmelzviskosität (bei 120°C) von 250 mm2/s an. Das mittlere Molekulargewicht (Zahlenmittel
Eine Mischung von 12,2 kg/h Ethylen, 5,6 kg/h Vinylacetat und 0,55 kg/h Propionaldehyd werden kontinuierlich durch einen auf einem Druck von 1500 bar gehaltenen 1 1-Rührautoklaven geleitet. Durch die kontinuierliche Zugabe von 5,5 g/h tert.-Butylperisononanat in einem Paraffinkohlenwasserstoffgemisch (Kp. 175-210) wird eine Temperatur im Autoklaven von 250°C aufrechterhalten. Nach Entspannung des Reaktionsgemisches fallen 5,3 kg Ethylen-Vinylacetat--Wachs mit einem Vinylacetatgehalt von 28,3 Gew.% und einer Schmelzviskosität (bei 120o C) von 250 mm2/s an. Das mittlere Molekulargewicht (Zahlenmittel
Die folgende Tabelle II gibt die Wirksamkeit der in den Herstellungsbeispielen 1 bis 6 beschriebenen Copolymeren bezüglich ihres CFPP-Wertes wieder. Beispiele 4 und 5 sind zum Vergleich mit Produkten höherer Vinylpropionatanteile, Beispiel 6 ist zum Vergleich mit Ethylen-Vinylacetatcopolymeren aufgeführt.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3201541 | 1982-01-20 | ||
| DE19823201541 DE3201541A1 (en) | 1982-01-20 | 1982-01-20 | PETROLEUM DISTILLATES WITH IMPROVED FLOW PROPERTIES |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0084148A2 true EP0084148A2 (en) | 1983-07-27 |
| EP0084148A3 EP0084148A3 (en) | 1983-08-03 |
| EP0084148B1 EP0084148B1 (en) | 1985-08-14 |
Family
ID=6153428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82111819A Expired EP0084148B1 (en) | 1982-01-20 | 1982-12-20 | Petrol middle distillate with modified flow properties |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0084148B1 (en) |
| DE (2) | DE3201541A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0217602A1 (en) * | 1985-09-24 | 1987-04-08 | Mitsubishi Petrochemical Co., Ltd. | Fuel oil additive and fuel oil having improved flowability |
| JPS6295392A (en) * | 1985-10-19 | 1987-05-01 | Showa Shell Sekiyu Kk | Fuel oil composition |
| EP0309897A2 (en) * | 1987-09-29 | 1989-04-05 | Hoechst Aktiengesellschaft | Copolymers of ethylene and methoxy acetic acid vinyl ester and their use as additives for mineral oil distillates |
| WO1994000537A1 (en) * | 1992-06-30 | 1994-01-06 | Exxon Chemical Patents Inc. | Oil additives and compositions |
| US6071993A (en) * | 1996-05-31 | 2000-06-06 | Basf Aktiengesellschaft | Paraffin dispersants for crude oil middle distillates |
| WO2014095412A1 (en) | 2012-12-18 | 2014-06-26 | Basf Se | Polymer compositions of ethylene-vinyl ester copolymers and alkyl(meth)acrylates, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products |
| WO2014095408A1 (en) | 2012-12-18 | 2014-06-26 | Basf Se | Polymer formulations in solvents with a high flash point, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products |
| US9574146B2 (en) | 2012-12-18 | 2017-02-21 | Basf Se | Polymeric compositions composed of ethylene-vinyl ester copolymers alkyl (meth)acrylates, processes for production thereof and use thereof as pour point depressants for crude oils, mineral oils or mineral oil products |
| WO2017089212A1 (en) | 2015-11-27 | 2017-06-01 | Basf Se | Copolymers comprising α-olefins and olefin dicarboxylic acid esters, production thereof, and use thereof as pour point depressants for crude oils, mineral oils, or mineral oil products |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1147799B (en) * | 1959-08-03 | 1963-04-25 | Exxon Research Engineering Co | Petroleum distillate propellant or fuel |
-
1982
- 1982-01-20 DE DE19823201541 patent/DE3201541A1/en not_active Withdrawn
- 1982-12-20 DE DE8282111819T patent/DE3265469D1/en not_active Expired
- 1982-12-20 EP EP82111819A patent/EP0084148B1/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1147799B (en) * | 1959-08-03 | 1963-04-25 | Exxon Research Engineering Co | Petroleum distillate propellant or fuel |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0217602A1 (en) * | 1985-09-24 | 1987-04-08 | Mitsubishi Petrochemical Co., Ltd. | Fuel oil additive and fuel oil having improved flowability |
| US4802892A (en) * | 1985-09-24 | 1989-02-07 | Mitsubishi Petrochemical Co., Ltd. | Fuel oil additive and fuel oil having improved flowability |
| JPS6295392A (en) * | 1985-10-19 | 1987-05-01 | Showa Shell Sekiyu Kk | Fuel oil composition |
| JPH0678547B2 (en) * | 1985-10-19 | 1994-10-05 | 昭和シェル石油株式会社 | Fuel oil composition |
| EP0309897A2 (en) * | 1987-09-29 | 1989-04-05 | Hoechst Aktiengesellschaft | Copolymers of ethylene and methoxy acetic acid vinyl ester and their use as additives for mineral oil distillates |
| EP0309897A3 (en) * | 1987-09-29 | 1991-05-15 | Hoechst Aktiengesellschaft | Copolymers of ethylene and methoxy acetic acid vinyl ester and their use as additives for mineral oil distillates |
| WO1994000537A1 (en) * | 1992-06-30 | 1994-01-06 | Exxon Chemical Patents Inc. | Oil additives and compositions |
| US6071993A (en) * | 1996-05-31 | 2000-06-06 | Basf Aktiengesellschaft | Paraffin dispersants for crude oil middle distillates |
| WO2014095412A1 (en) | 2012-12-18 | 2014-06-26 | Basf Se | Polymer compositions of ethylene-vinyl ester copolymers and alkyl(meth)acrylates, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products |
| WO2014095408A1 (en) | 2012-12-18 | 2014-06-26 | Basf Se | Polymer formulations in solvents with a high flash point, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products |
| US9574146B2 (en) | 2012-12-18 | 2017-02-21 | Basf Se | Polymeric compositions composed of ethylene-vinyl ester copolymers alkyl (meth)acrylates, processes for production thereof and use thereof as pour point depressants for crude oils, mineral oils or mineral oil products |
| US10072115B2 (en) | 2012-12-18 | 2018-09-11 | Basf Se | Polymeric compositions as pour point depressants for crude oils |
| US10287384B2 (en) | 2012-12-18 | 2019-05-14 | Basf Se | Polymeric compositions as pour point depressants for crude oils |
| WO2017089212A1 (en) | 2015-11-27 | 2017-06-01 | Basf Se | Copolymers comprising α-olefins and olefin dicarboxylic acid esters, production thereof, and use thereof as pour point depressants for crude oils, mineral oils, or mineral oil products |
| US10781385B2 (en) | 2015-11-27 | 2020-09-22 | Basf Se | Copolymers comprising a-olefins and olefin dicarboxylic acid esters, production thereof, and use thereof as pour point depressants for crude oils, mineral oils, or mineral oil products |
| US11236282B2 (en) | 2015-11-27 | 2022-02-01 | Basf Se | Copolymers comprising a-olefins and olefin dicarboxylic acid esters, production thereof, and use thereof as pour point depressants for crude oils, mineral oils, or mineral oil products |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3201541A1 (en) | 1983-07-28 |
| DE3265469D1 (en) | 1985-09-19 |
| EP0084148A3 (en) | 1983-08-03 |
| EP0084148B1 (en) | 1985-08-14 |
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