EP2204434A1 - Process for making an oxygenate as an additive in fuels, particularly in diesel fuels, gasoline and rapeseed methyl ester - Google Patents
Process for making an oxygenate as an additive in fuels, particularly in diesel fuels, gasoline and rapeseed methyl ester Download PDFInfo
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- EP2204434A1 EP2204434A1 EP09173054A EP09173054A EP2204434A1 EP 2204434 A1 EP2204434 A1 EP 2204434A1 EP 09173054 A EP09173054 A EP 09173054A EP 09173054 A EP09173054 A EP 09173054A EP 2204434 A1 EP2204434 A1 EP 2204434A1
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- oxygenate
- fuel
- methyl ester
- gasoline
- additive
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- 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
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- 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
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- 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
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
- C10L1/1855—Cyclic ethers, e.g. epoxides, lactides, lactones
Definitions
- the present invention describes the use and production of an oxygenate in diesel fuels, gasoline fuels and rapeseed methyl esters, in which the ignitability is increased and the particle emission is reduced. These improvements are z. B. achieved by a) preparation of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane from glycerol and acetone and b) reaction of the 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane prepared in step a) with isobutene to etherify the remaining OH group.
- Glycerol ethers are obtained as a by-product in the separation of tertiary olefins from the C 4 fraction during crude oil distillation. This is in the patent US 1,968,601 treated.
- the in 'the US 5,308,365 described invention refers to a diesel grade with low sulfur content by the addition of dialkyl and trialkyl derivatives of glycerol.
- glycerol ethers are intended to eliminate the hydrophilicity, to bring the boiling point reduction in the range of the boiling point of the fuel component and to achieve the lowering of the density while maintaining the cetane number.
- glycerol esters The production of glycerol esters is described in the GDR patent 156 803 described ben. It is about the production of triacetin.
- glycerol acetates The production of glycerol acetates is described in the publications of RR Tink, EY Speneer, JM Roxburgh - Can. J. Techn. 29 243 (1951 ) and RR Tink; AC Neish - Approx. J. Techn. 29 243 (1951 ) using the example of the reaction of glycerol with butyraldehyde.
- Glycerine as an extremely hydrophilic substance is miscible neither with petrol (OK) nor with diesel fuel (DK) and rapeseed methyl ester (RME).
- the task is to derivatize glycerol so that the products can be used as fuel components in DK, OK and rapeseed methyl ester. For this purpose, it is necessary to make them compatible with fuels in order to meet the fuel standards.
- Compatibility with the'DK, OK and RME is achieved by complete reaction of the hydroxyl groups present on the molecule of glycerol. On the one hand by the reaction to the acetal and the etherification of the remaining hydroxyl group by a tertiary olefin.
- the derivatives shown are miscible in every ratio with DK, OK and RME.
- a first reaction stage e.g. Glycerol reacted with acetone to 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane. Subsequently, the 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane is etherified in an acid-catalyzed reaction with isobutene.
- 300 g of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolan be submitted in an autoclave with 2.5 g of p-toluenesulfonic acid and cooled to -30 ° C. Subsequently, 600 g of isobutene are added. This mixture is reacted to 90 ° C using a magnetic stirrer.
- reaction vessel is cooled to room temperature and after opening the inlet valve, the unreacted isobutene is withdrawn, where it is condensed for reuse by deep cooling in a cold trap.
- the remaining in the pressure vessel reaction mixture is treated with sodium tert-butylate (5.0 g) and stirred for 3 hours at room temperature. It is then filtered and the filtrate fractionated.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
Description
Die vorliegende Erfindung beschreibt den Einsatz und die Herstellung eines Oxygenates in Dieselkraftstoffen, Ottokraftstoffen und Rapsmethylester, bei denen die Zündwilligkeit erhöht wird und die Partikelemission verringert wird. Diese Verbesserungen werden z. B. erreicht durch a) Herstellung von 2,2 Dimethyl-4-hydroxymethyl-1,3 dioxolan aus Glycerin und Aceton und b) Umsetzung des in Stufe a) hergestellten 2,2 Dimethyl-4-hydroxymethyl-1,3 dioxolan mit Isobuten, um die restliche OH-Gruppe zu verethern.The present invention describes the use and production of an oxygenate in diesel fuels, gasoline fuels and rapeseed methyl esters, in which the ignitability is increased and the particle emission is reduced. These improvements are z. B. achieved by a) preparation of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane from glycerol and acetone and b) reaction of the 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane prepared in step a) with isobutene to etherify the remaining OH group.
Der Zusatz von Sauerstoffverbindungen zu Kraftstoffen in Form von Alkoholen und Ethern hat sich bewährt. Durch diesen Einsatz konnten die ökologisch bedenklichen Bleiverbindungen, die als Antiklopfmittel in Kraftstoffen dienten, abgelöst werden. Es bestand die Aufgabe, durch Derivatisierung des Glycerinmoleküls eine Verbindung herzustellen, die sich als Kraftstoffkomponente eignet.The addition of oxygen compounds to fuels in the form of alcohols and ethers has been proven. Through this use, the ecologically questionable lead compounds, which were used as anti-knock agents in fuels, to be replaced. The object was to produce by derivatization of the glycerol molecule, a compound which is suitable as a fuel component.
Als geeignete Verbindungsklassen, die auch teilweise schon publiziert und schutzrechtlich beschrieben worden sind, boten sich folgende Verbindungsklassen an:
- Glycerinether
- Glycerinester
- Glycerinacetale
- glycerol ether
- Glycerinester
- glycerol acetals
Die Herstellung von Glycerinethern ist in verschiedenen.Patentschriften geschützt worden. So wird in der Patentschrift
Neben dieser allgemeinen Beschreibung für die Herstellung von Glycerinethern sind spezielle Katalysatorsysteme für die Umsetzung zu dieser Produktklasse in verschiedenen Patentschriften untersucht worden. In der
Als Nebenprodukt fallen Glycerinether bei der Abtrennung von tertiären Olefinen aus der C4-Fraktion bei der Rohöldestillation an. Dies wird in der Patentschrift
In der Patentschrift
In der
Nicht nur die einzelnen Verfahrensschritte zur Herstellung von Glycerinethern sind schutzrechtlich bearbeitet worden, sondern auch ihr Einsatz als Kraftstoffkomponente in Dieselkraftstoffen und Benzin.Not only the individual process steps for the production of glycerol ethers have been processed under protective law, but also their use as a fuel component in diesel fuels and gasoline.
Es ist bekannt, dass die Zugabe von Oxygenaten in Kraftstoffen eine Qualitätsverbesserung ergibt.It is known that the addition of oxygenates in fuels gives a quality improvement.
In der
Der Zusatz von Ethern in Dieselkraftstoffen ist in der
Die Verbesserung der Dieselkraftstoffqualität durch den Zusatz von aliphatischen Polyethern konnte in der Patentschrift
Die in' der
Der Einsatz dieser Gylcerinether soll dazu dienen, die Hydrophilie zu beseitigen, die Erniedrigung der Siedetemperatur in den Bereich des Siedediagramms der Kraftstoffkomponente zu bringen und die Absenkung der Dichte unter Beibehaltung der Cetanzahl zu erreichen.The use of these glycerol ethers is intended to eliminate the hydrophilicity, to bring the boiling point reduction in the range of the boiling point of the fuel component and to achieve the lowering of the density while maintaining the cetane number.
Der Nachteil dieser Substanzen ist, dass ein Glycerinethergemisch anfällt mit maximal 11 % an Triether. Der Rest besteht aus Mono- und Diether, die auf Grund der noch vorhandenen Hydroxylgruppen teilweise nicht löslich sind in den einzelnen Kraftstoffkomponenten.The disadvantage of these substances is that a Glycerinethergemisch obtained with a maximum of 11% of triethers. The remainder consists of mono- and diether, which are partially insoluble in the individual fuel components due to the remaining hydroxyl groups.
Durch die sterische Hinderung ist eine 100 %ige Umsetzung zu Triethern nicht möglich. Die Umsetzungsreaktion zu Glycerinethern ist nahezu thermoneutral und stark entropisch. Das führt dazu, dass mit zunehmender Temperatur die Ausbeute vermindert wird und eine Oligomerisierung eintritt. Bei einer Absenkung der Reaktionstemperatur wird aber die Umsetzung soweit verlangsamt, dass kaum noch ein nennenswerter Umsatz stattfindet.Due to steric hindrance 100% conversion to triethers is not possible. The reaction to glycerol ethers is almost thermoneutral and strongly entropic. As a result, as the temperature increases, the yield is reduced and oligomerization occurs. When lowering the reaction temperature but the reaction is so far slows down that hardly any significant turnover takes place.
Die Herstellung von Glycerinestern wird in der DDR-Patentschrift
Die Veresterung zu niederen Glycerinestern führt zwar den Siedepunkt in den Bereich des Dieselkraftstoffes, aber ohne einen längeren Acylrest wird kein ausreichendes Zündverhalten erreicht. Andererseits ist das Siedeverhalten des Triacetins zu hoch und schließt daher einen Einsatz im Ottokraftstoff aus. Bei Glycerinestern, die im Siedebereich der herkömmlichen Kraftstoffkomponenten liegen, ist die Löslichkeit in den Kraftstoffen nicht mehr gewährleistet.Although the esterification to lower glycerol esters leads the boiling point in the range of the diesel fuel, but without a longer acyl radical is not achieved sufficient ignition behavior. On the other hand, the boiling behavior of triacetin is too high and therefore excludes use in gasoline. For glycerol esters, which are in the boiling range of conventional fuel components, the solubility in the fuels is no longer guaranteed.
Der Nachteil dieser Substanzklasse liegt in den unzureichenden physikalischen Eigenschaften, die einen Einsatz in Ottokraftstoffen ausschließt und der mangelnden Zündwilligkeit in Dieselkraftstoffen.The disadvantage of this substance class lies in the inadequate physical properties which preclude use in gasoline fuels and the lack of ignition in diesel fuels.
Die Herstellung von Glycerinacetaten wird in den Veröffentlichungen von
Dioxolane mit längeren Alkylresten, deren Herstellung von
Ausschlaggebend für eine Zumischung in Dieselkraftstoff, Ottokraftstoff und Rapsmethylester ist seine Löslichkeit in diesen Kraftstoffkomponenten. Dies ist durch die vorhandene Hydroxylgruppe jedoch sehr problematisch. Wenn auch die Siedelage des Glycerins in seinen Acetalen drastisch abgesenkt wird, die Dichte liegt in allen Fällen deutlich über 1,02 g/ml.The decisive factor for an admixture in diesel fuel, petrol and rapeseed methyl ester is its solubility in these fuel components. However, this is very problematic due to the hydroxyl group present. Even if the boiling point of glycerine in its acetals is drastically lowered, the density is clearly above 1.02 g / ml in all cases.
Der Einsatz dieser Acetale im Dieselkraftstoff war enttäuschend wegen seines schlechten Zündverhaltens.The use of these acetals in diesel fuel was disappointing because of its poor ignition performance.
Glycerin als extrem hydrophile Substanz ist weder mit Ottokraftstoff (OK) noch mit Dieselkraftstoff (DK) und Rapsmethylester (RME) mischbar. Die Aufgabe besteht darin, Glycerin so zu derivatisieren, dass die Produkte als Kraftstoffkomponenten in DK, OK und Rapsmethylester eingesetzt werden können. Dazu ist es notwendig, sie mit Kraftstoffen verträglich zu machen, um die Kraftstoffnormen zu erfüllen.Glycerine as an extremely hydrophilic substance is miscible neither with petrol (OK) nor with diesel fuel (DK) and rapeseed methyl ester (RME). The task is to derivatize glycerol so that the products can be used as fuel components in DK, OK and rapeseed methyl ester. For this purpose, it is necessary to make them compatible with fuels in order to meet the fuel standards.
Die Verträglichkeit zu den'DK, OK und RME wird erreicht durch eine vollständige Umsetzung der am Molekül des Glycerins vorhandenen Hydroxylgruppen. Einerseits durch die Umsetzung zum Acetal und der Veretherung der noch vorhandenen Hydroxylgruppe durch ein tertiäres Olefin.Compatibility with the'DK, OK and RME is achieved by complete reaction of the hydroxyl groups present on the molecule of glycerol. On the one hand by the reaction to the acetal and the etherification of the remaining hydroxyl group by a tertiary olefin.
Die so dargestellten Derivate sind in jedem Verhältnis mischbar mit DK, OK und RME.The derivatives shown are miscible in every ratio with DK, OK and RME.
Der Zusatz solcher Substanzen ergab eine geringere Partikelemission und eine bessere Zündwilligkeit als reiner DK, OK und RME.The addition of such substances resulted in a lower particulate emission and a better ignitability than pure DK, OK and RME.
In einer ersten Reaktionsstufe wird z.B. Glycerin mit Aceton zum 2,2-Dimethyl-4- hydroxymethyl-1,3 dioxolan umgesetzt. Anschließend wird das 2,2-Dimethyl-4- hydroxymethyl-1,3 dioxolan in einer säurekatalysierten Reaktion mit Isobuten verethert.In a first reaction stage, e.g. Glycerol reacted with acetone to 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane. Subsequently, the 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane is etherified in an acid-catalyzed reaction with isobutene.
In einem 5 Liter-Kolben werden 600 g Glycerin (wasserfrei), 3600 g Aceton und 2,5 g p-Toluolsulfonsäure unter kräftigem Rühren vermischt. Die Reaktionsmischung wird bei Raumtemperatur gerührt und anschließend mit 60 g Kaliumcarbonat (wasserfrei) vermischt. Nach weiterem Rühren von ca. 1 Stunde wird die Reaktionsmischung filtriert und das Filtrat fraktioniert destilliert.600 g of glycerol (anhydrous), 3600 g of acetone and 2.5 g of p-toluenesulfonic acid are mixed with vigorous stirring in a 5 liter flask. The reaction mixture is stirred at room temperature and then mixed with 60 g of potassium carbonate (anhydrous). After further stirring for about 1 hour, the reaction mixture is filtered and the filtrate is fractionally distilled.
Nach einem Vorlauf von Aceton, das in eine weitere Reaktion eingesetzt werden kann, destilliert man bei einem Druck von 15 Torr das 2,2-Dimethyl-4-hydroxymethyl-1,3 dioxolan in einem Siedebereich von 82 - 84° C ab.After a forerun of acetone, which can be used in a further reaction, distilled at a pressure of 15 Torr, the 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane in a boiling range of 82-84 ° C.
Die Ausbeuten lagen bei 550 - 600 g. Nach gaschromatischer Prüfung besaß die Substanz eine Reinheit von > 98 % und einen Brechungsindex von n = 1,432.The yields were 550-600 g. After gas chromatographic examination, the substance had a purity of> 98% and a refractive index of n = 1.432.
300 g des 2,2 Dimethyl-4-hydroxymethyl-1,3 dioxolans werden in einem Autoklaven mit 2,5 g p-Toluolsulfonsäure vorgelegt und auf -30°C abgekühlt. Anschließend werden 600 g Isobuten zugegeben. Diese Mischung wird unter Verwendung eines Magnetrührers auf 90°C zur Reaktion gebracht.300 g of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolan be submitted in an autoclave with 2.5 g of p-toluenesulfonic acid and cooled to -30 ° C. Subsequently, 600 g of isobutene are added. This mixture is reacted to 90 ° C using a magnetic stirrer.
Anschließend wird das Reaktionsgefäß auf Raumtemperatur gekühlt und nach Öffnen des Einlaßventiles das nicht umgesetzte Isobuten abgezogen, wobei es zwecks Wiederverwendung durch Tiefkühlung in einer Kühlfalle kondensiert wird. Die im Druckgefäß zürückbleibende Reaktionsmischung wird mit Natriumtertiärbutylat (5,0 g) versetzt und 3 Stunden bei Raumtemperatur gerührt. Anschließend wird filtriert und das Filtrat fraktioniert.Subsequently, the reaction vessel is cooled to room temperature and after opening the inlet valve, the unreacted isobutene is withdrawn, where it is condensed for reuse by deep cooling in a cold trap. The remaining in the pressure vessel reaction mixture is treated with sodium tert-butylate (5.0 g) and stirred for 3 hours at room temperature. It is then filtered and the filtrate fractionated.
Nach einem relativ geringen Vorlauf geht das Endprodukt bei 20 Torr in einen Siedeintervall von 82 - 85° C über.After a relatively low flow, the final product at 20 Torr in a boiling interval of 82 - 85 ° C over.
Die beschriebenen Umsetzungen wurden mehrfach wiederholt und ergaben durchschnittliche Ausbeuten von 300 g.The reactions described were repeated several times and gave average yields of 300 g.
Nach gaschromatografischer Prüfung wurde bei der beschriebenen Umsetzung eine Reinheit von > 95 % und einen von der Reinheit abhängigen Brechungsindex nD = 1.4190 - 1.4260 erhalten.After gas chromatographic examination, a purity of> 95% and a purity-dependent refractive index n D = 1.4190 - 1.4260 were obtained in the described reaction.
Um ein Produkt mit einer Reinheit von > 99 % zu erhalten, wurde das Destillat mit' Phenylisocyanat versetzt und unter Rückfluß erhitzt. Anschließend wurde erneut im Vakuum fraktioniert. Das gewünschte Produkt fiel hierbei in einer mittels Gaschromatographie überprüften Reinheit von > 99 % an.In order to obtain a product with a purity of> 99%, the distillate was treated with 'phenyl isocyanate and heated under reflux. It was then fractionated again in vacuo. The desired product was obtained in a purified by gas chromatography purity of> 99%.
Die oben beschrieben Substanz wurde als Additiv Dieselkraftstoffen, Ottokraftstoffen und Rapsmethylester beigemischt. Dabei konnten wir feststellen, dass die Partikelemission verringert wird in Form der Trübung und die Zündwilligkeit in Form von dp max. anstieg.
Claims (13)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10328159 | 2003-06-24 | ||
EP04732568A EP1639061B1 (en) | 2003-06-24 | 2004-05-13 | Use of an oxygenate as an additive for the reduction of particulate emissions in fuels, particularly in diesel fuels, gasoline and rapeseed methyl ester |
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WOPCT/DE2004/000999 Previously-Filed-Application | 2004-05-13 | ||
EP04732568A Division EP1639061B1 (en) | 2003-06-24 | 2004-05-13 | Use of an oxygenate as an additive for the reduction of particulate emissions in fuels, particularly in diesel fuels, gasoline and rapeseed methyl ester |
EP04732568.3 Division | 2004-05-13 |
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EP09173054A Withdrawn EP2204434A1 (en) | 2003-06-24 | 2004-05-13 | Process for making an oxygenate as an additive in fuels, particularly in diesel fuels, gasoline and rapeseed methyl ester |
EP04732568A Expired - Lifetime EP1639061B1 (en) | 2003-06-24 | 2004-05-13 | Use of an oxygenate as an additive for the reduction of particulate emissions in fuels, particularly in diesel fuels, gasoline and rapeseed methyl ester |
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EP04732568A Expired - Lifetime EP1639061B1 (en) | 2003-06-24 | 2004-05-13 | Use of an oxygenate as an additive for the reduction of particulate emissions in fuels, particularly in diesel fuels, gasoline and rapeseed methyl ester |
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US (1) | US20090270643A1 (en) |
EP (2) | EP2204434A1 (en) |
JP (1) | JP2007509189A (en) |
CN (1) | CN100494327C (en) |
AT (1) | ATE455834T1 (en) |
AU (1) | AU2004259809A1 (en) |
BR (1) | BRPI0411849A (en) |
CA (1) | CA2530219A1 (en) |
DE (2) | DE502004010677D1 (en) |
HK (1) | HK1095354A1 (en) |
IL (1) | IL172757A0 (en) |
NO (1) | NO20060300L (en) |
RU (1) | RU2387702C2 (en) |
UA (1) | UA85188C2 (en) |
WO (1) | WO2005010131A1 (en) |
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FR2921385B1 (en) * | 2007-09-21 | 2010-02-26 | Inst Francais Du Petrole | PROCESS FOR TRANSFORMING BIOMASS TO PRODUCTS COMPRISING ACETAL GROUPS AND THEIR USE AS BIOFUELS |
US20090107555A1 (en) * | 2007-10-31 | 2009-04-30 | Aradi Allen A | Dual Function Fuel Atomizing and Ignition Additives |
DE102008015756B4 (en) | 2008-03-26 | 2013-08-29 | Süd-Chemie Ip Gmbh & Co. Kg | Synthesis of solketal in the presence of solid catalysts |
EA018090B1 (en) | 2008-05-28 | 2013-05-30 | Федеральное Государственное Бюджетное Учреждение Науки Институт Биохимической Физики Им. Н.М. Эмануэля Российской Академии Наук (Ибхф Ран) | Agent for increasing the octane number of a gasoline automobile fuel |
RU2522764C2 (en) * | 2012-06-08 | 2014-07-20 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Method of obtaining oxygenates increasing exploitation properties of fuels for internal combustion engines (versions) |
WO2017006141A1 (en) * | 2015-07-06 | 2017-01-12 | Rhodia Poliamida E Especialidades Ltda | Diesel compositions with improved cetane number and lubricity performances |
WO2017006142A1 (en) * | 2015-07-06 | 2017-01-12 | Rodhia Poliamida E Especialidades Ltda | Gasoline compositions with improved octane number |
RU2609264C1 (en) | 2015-12-09 | 2017-01-31 | Акционерное Общество "Газпромнефть - Московский Нпз" (Ао "Газпромнефть - Мнпз") | Method for producing high-octane components from olefins of catalytic cracking |
ES2894347T3 (en) * | 2016-09-21 | 2022-02-14 | Cepsa S A U | Solketal ethers, production method and uses thereof |
CN110256396A (en) * | 2019-05-06 | 2019-09-20 | 深圳市前海博扬研究院有限公司 | Glycerine acetal (ketone) ether and its synthetic method |
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- 2004-05-13 UA UAA200600615A patent/UA85188C2/en unknown
- 2004-05-13 US US10/562,409 patent/US20090270643A1/en not_active Abandoned
- 2004-05-13 JP JP2006515660A patent/JP2007509189A/en active Pending
- 2004-05-13 EP EP09173054A patent/EP2204434A1/en not_active Withdrawn
- 2004-05-13 DE DE502004010677T patent/DE502004010677D1/en not_active Expired - Lifetime
- 2004-05-13 AT AT04732568T patent/ATE455834T1/en active
- 2004-05-13 BR BRPI0411849-9A patent/BRPI0411849A/en not_active IP Right Cessation
- 2004-05-13 AU AU2004259809A patent/AU2004259809A1/en not_active Abandoned
- 2004-05-13 WO PCT/DE2004/000999 patent/WO2005010131A1/en active Application Filing
- 2004-05-13 EP EP04732568A patent/EP1639061B1/en not_active Expired - Lifetime
- 2004-05-13 CN CNB2004800177966A patent/CN100494327C/en not_active Expired - Fee Related
- 2004-05-13 RU RU2006101723/04A patent/RU2387702C2/en not_active IP Right Cessation
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Also Published As
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NO20060300L (en) | 2006-03-15 |
CN1813045A (en) | 2006-08-02 |
DE112004001621D2 (en) | 2006-05-11 |
EP1639061B1 (en) | 2010-01-20 |
CN100494327C (en) | 2009-06-03 |
WO2005010131A1 (en) | 2005-02-03 |
HK1095354A1 (en) | 2007-05-04 |
RU2387702C2 (en) | 2010-04-27 |
EP1639061A1 (en) | 2006-03-29 |
DE502004010677D1 (en) | 2010-03-11 |
US20090270643A1 (en) | 2009-10-29 |
AU2004259809A1 (en) | 2005-02-03 |
ATE455834T1 (en) | 2010-02-15 |
RU2006101723A (en) | 2007-07-27 |
JP2007509189A (en) | 2007-04-12 |
UA85188C2 (en) | 2009-01-12 |
CA2530219A1 (en) | 2005-02-03 |
IL172757A0 (en) | 2006-04-10 |
BRPI0411849A (en) | 2006-08-08 |
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