EP0334248A1 - Method of operating a diesel engine - Google Patents

Method of operating a diesel engine Download PDF

Info

Publication number
EP0334248A1
EP0334248A1 EP89104891A EP89104891A EP0334248A1 EP 0334248 A1 EP0334248 A1 EP 0334248A1 EP 89104891 A EP89104891 A EP 89104891A EP 89104891 A EP89104891 A EP 89104891A EP 0334248 A1 EP0334248 A1 EP 0334248A1
Authority
EP
European Patent Office
Prior art keywords
engine
lubricating oil
exhaust gas
iron
diesel
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
Application number
EP89104891A
Other languages
German (de)
French (fr)
Other versions
EP0334248B1 (en
Inventor
August-Wilhelm Dr. Preuss
Dieter Dr. Höhr
Kurt-Peter Dr. Schug
Hans-Jürgen Dipl.-Ing. Guttmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Veba Oel AG
Original Assignee
Veba Oel AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Veba Oel AG filed Critical Veba Oel AG
Priority to AT89104891T priority Critical patent/ATE73169T1/en
Publication of EP0334248A1 publication Critical patent/EP0334248A1/en
Application granted granted Critical
Publication of EP0334248B1 publication Critical patent/EP0334248B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/56—Acids of unknown or incompletely defined constitution
    • C10M129/60—Tall oil acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/18—Complexes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/18—Tall oil acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/08—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having metal-to-carbon bonds
    • C10M2227/081—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having metal-to-carbon bonds with a metal carbon bond belonging to a ring, e.g. ferocene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/16—Groups 8, 9, or 10
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01M—LUBRICATING OF MACHINES OR ENGINES IN GENERAL; LUBRICATING INTERNAL COMBUSTION ENGINES; CRANKCASE VENTILATING
    • F01M11/00—Component parts, details or accessories, not provided for in, or of interest apart from, groups F01M1/00 - F01M9/00
    • F01M11/04—Filling or draining lubricant of or from machines or engines
    • F01M11/0458—Lubricant filling and draining
    • F01M2011/0466—Filling or draining during running
    • F01M2011/0475—Filling or draining during running with combustion of used lubricant in the engine
    • 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 an engine lubricating oil for diesel engines equipped with a particle filter in the exhaust gas flow and a method for operating a diesel engine with a particle filter system downstream of the engine in the exhaust gas line, in which the temperature for the combustion of soot particles deposited on the filter system is reduced due to the presence of catalytically active substances is.
  • EP-0 052 478-B1 is an operating method for a diesel engine, in which one consecutively carries out the combustion of a diesel fuel in the engine, passes the engine exhaust through a separator and thereby removes soot particles from it and heats the separator to a sufficiently high temperature to cause oxidation of the soot particles, wherein particles of a catalyst which lowers the oxidation temperature of the soot are introduced into the separator with the exhaust gases.
  • Suitable catalyst substances are lead or copper or manganese or their mixture in elemental form or preferably in the form of chemical compounds, the catalyst substances preferably being added to the diesel fuel.
  • Effective diesel particle filter systems have therefore been developed by technology, in particular so-called monolithic ceramic filters, with honeycomb-like ceramic bodies that contain a large number of channels that are mutually closed at the ends, or ceramic wound filters made of circularly arranged, perforated steel support tubes with several layers of a roughened yarn Filters made of ceramic fibers are used (cf. ATV 1 / 2-88, pages 14 to 17).
  • the exhaust gas from the diesel engines flows through the labyrinth passages of the monolithic ceramic filters, the ceramic walls forming the honeycomb passages, in turn, being porous and permitting the passage of the exhaust gas cleaned of particles, or the exhaust gas particles being retained by the filaments of the ceramic yarns when flowing through the so-called wound filters.
  • the object of the invention is to ensure economical operation of a diesel engine with a particle filter system downstream of the engine in the exhaust pipe by providing new engine lubricating oils for diesel engines and to specify a corresponding method for operating a diesel engine in which such engine lubricating oils are used.
  • the temperatures which are sufficient for the regeneration of the diesel particle filter by burning should be so low that regeneration occurs as often as possible.
  • the filter In the case of unfavorable operating conditions of the diesel engine, for example a power output that lead to only low exhaust gas temperatures, the filter is so far covered with particles that the exhaust gas back pressure reaches impermissibly high values.
  • there is a risk that a filter that is too heavily loaded will be thermally loaded too much during regeneration due to burning and will melt locally, which can lead to a deterioration in the function of the filter.
  • the present invention resides in the fact that an engine lubricating oil for diesel engines equipped with a particle filter system with a catalytically active content of an iron compound is proposed.
  • the invention is based on the knowledge that a certain proportion of the lubricating oil also participates in engine combustion.
  • the catalytically active substance is also supplied in sufficient quantity to the diesel particle filter system with the hot engine exhaust gas when the engine is operated as intended, where a further quantitative reaction of the particulate organic components initially retained by the filter is important.
  • the purpose of the invention is also promoted by the catalytically favored conversion of the particulate organic constituents with the residual oxygen present in the exhaust gas, which takes place before it is deposited on the filter.
  • the content of catalytically active iron compounds in the exhaust gas stream sufficient for the diesel particle filter regeneration with weight ratios of 5 to 20,000, preferably 50 to 10,000, ppm of the iron compound, in particular the organometallic iron compound, based on the proposed additization of the lubricating oil Lubricating oil quantity, find use.
  • Ferrocene bis ( ⁇ -cyclopentadienyl) iron
  • iron compounds with a complex salt of an organic acid in which the ratio of the number of equivalents of the organic acid to the number of iron atoms is 3 or less, for example iron tallate are particularly suitable.
  • the aforementioned compounds are because of their catalytic activity and their good solubility and lubricating oil compatibility are particularly suitable as additives.
  • the proposed additization of the lubricating oil offers an advantageous alternative to introducing the catalytically active substances by additizing the diesel fuel or to a separate additional metering device.
  • the effect according to the invention was verified in a comparative test program with a stationary vehicle diesel engine, manufactured by Ford 2.5 l direct injection.
  • the engine is equipped with a diesel particulate filter system made of a ceramic monolith catalyst, manufactured by Corning, installed in the exhaust line downstream of the engine.
  • the engine was operated with a commercially available diesel engine lubricating oil of viscosity class 15W-40. With a constant power output of 18 kW, an exhaust gas back pressure rising from 100 mbar to approximately 350 mbar built up over a running time of 2 1/2 hours.
  • the engine lubricating oils according to the invention are added by direct dissolution, for example up to concentrations of 10,000 ppm, or else preparation of concentrated solutions in a suitable lubricating oil component. Additives in concentrations of 5 to 20,000 ppm, preferably 50 to 10,000 ppm, based on the engine lubricating oil (weight ratio), are preferred.
  • FIG. 1 shows schematically the experimental arrangement used for the installation of the diesel particle filter in the exhaust pipe of the diesel engine and the pressure measuring point.

Abstract

To avoid an unacceptably high exhaust gas back pressure when operating diesel engines equipped with a particle filter in the exhaust gas stream, an engine lubricating oil is used that has a catalytically active content of an iron compound in an amount of 5 to 20,000 ppm. The use of the additive facilitates the regeneration of the diesel particle filters by burning, especially under operating conditions of the diesel engine that lead only to relatively low exhaust gas temperatures. Iron compounds proposed are ferrocene, ferrocene derivatives, and iron salts of organic acids.

Description

Die Erfindung betrifft ein Motorschmieröl für mit einem Partikelfilter im Abgasstrom ausgerüstete Dieselmotoren und ein Verfahren zum Betreiben eines Dieselmotors mit einem dem Motor nachgeschalteten Partikelfiltersystem in der Abgasleitung, in dem aufgrund der Anwesenheit katalytisch wirksamer Substanzen die Temperatur für den Abbrand von auf dem Filtersystem abgelagerten Rußpartikeln abgesenkt ist.The invention relates to an engine lubricating oil for diesel engines equipped with a particle filter in the exhaust gas flow and a method for operating a diesel engine with a particle filter system downstream of the engine in the exhaust gas line, in which the temperature for the combustion of soot particles deposited on the filter system is reduced due to the presence of catalytically active substances is.

Aus der europäischen Patentschrift EP-0 052 478-B1 ist eine Betriebsmethode für einen Dieselmotor, bei dem man nacheinander die Verbrennung eines Dieselkraftstoffes im Motor vornimmt, die Motorabgase durch einen Abscheider leitet und dadurch Rußteilchen daraus entfernt sowie den Abscheider auf eine genügend hohe Temperatur erhitzt, um Oxidation der Rußteilchen zu bewirken, wobei Teilchen eines die Oxidationstemperatur des Rußes erniedrigenden Katalysators mit den Abgasen in den Abscheider eingeleitet werden, bekannt. Als geeignete Katalysatorsubstanzen werden Blei oder Kupfer oder Mangan oder deren Mischung in elementarer Form oder bevorzugt in Form chemischer Verbindungen angegeben, wobei die Katalysatorsubstanzen vorzugsweise dem Dieselkraftstoff zugesetzt werden sollen.From the European patent EP-0 052 478-B1 is an operating method for a diesel engine, in which one consecutively carries out the combustion of a diesel fuel in the engine, passes the engine exhaust through a separator and thereby removes soot particles from it and heats the separator to a sufficiently high temperature to cause oxidation of the soot particles, wherein particles of a catalyst which lowers the oxidation temperature of the soot are introduced into the separator with the exhaust gases. Suitable catalyst substances are lead or copper or manganese or their mixture in elemental form or preferably in the form of chemical compounds, the catalyst substances preferably being added to the diesel fuel.

Die betriebsbedingte Emission von Rußteilchen, im Abgas von Dieselmotoren ist von den Verordnungsgebern in verschiedenen Ländern bereits mehr oder weniger weitgehenden Beschränkungen unterworfen worden. Ziel dieser Beschränkungen ist eine möglichst vollständige Vermeidung des Ausstoßes von u. a. Ruß und polyzyklische Verbindungen enthaltenden Partikeln aufgrund des Betriebes von Dieselmotoren in die Atmosphäre.The regulation-related emission of soot particles in the exhaust gas of diesel engines is already more or less in different countries extensive restrictions have been subjected. The aim of these restrictions is to avoid, as far as possible, the emission of, among other things, particles containing soot and polycyclic compounds due to the operation of diesel engines into the atmosphere.

Von der Technik sind daher wirksame Dieselpartikelfiltersysteme entwickelt worden, wobei insbesondere sogenannte monolithische Keramikfilter, mit wabenartig aufgebauten Keramikkörpern, die eine Vielzahl von an den Enden wechselseitig verschlossenen Kanälen enthalten oder Keramik-Wickelfilter aus kreisförmig angeordneten, gelochten Stahl-Stützrohren mit mehreren Lagen eines aufgerauhten Garns aus keramischen Fasern Filter Verwendung finden (vgl. ATV 1/2-88, Seiten 14 bis 17).Effective diesel particle filter systems have therefore been developed by technology, in particular so-called monolithic ceramic filters, with honeycomb-like ceramic bodies that contain a large number of channels that are mutually closed at the ends, or ceramic wound filters made of circularly arranged, perforated steel support tubes with several layers of a roughened yarn Filters made of ceramic fibers are used (cf. ATV 1 / 2-88, pages 14 to 17).

Das Abgas der Dieselmotoren durchströmt die Labyrinthgänge der Monolithkeramikfilter, wobei die die Wabengänge bildenden Keramikwände ihrerseits porös sind und den Durchtritt des von Partikeln gereinigten Abgases gestatten bzw. beim Durchströmen der sogenannten Wickelfilter die Abgaspartikel von den Filamenten der Keramikgarne zurückgehalten werden.The exhaust gas from the diesel engines flows through the labyrinth passages of the monolithic ceramic filters, the ceramic walls forming the honeycomb passages, in turn, being porous and permitting the passage of the exhaust gas cleaned of particles, or the exhaust gas particles being retained by the filaments of the ceramic yarns when flowing through the so-called wound filters.

Da mit zunehmendem Beladungsgrad dieser abstromseitig vom Motor in der Abgasleitung eingebauten Filtersysteme ein entsprechend steigender Druckabfall auftritt, der zu einer Leistungsminderung des Dieselmotors führt, muß durch eine kontinuierliche oder auch periodische Regeneration der Filtersysteme ein Druckaufbau in dem Abgassystem vermieden werden.Since, as the degree of loading of these filter systems installed on the downstream side of the engine in the exhaust pipe, a correspondingly increasing pressure drop occurs, which leads to a reduction in the performance of the diesel engine, a continuous or periodic regeneration of the filter systems to avoid pressure build-up in the exhaust system.

Aufgabe der Erfindung ist, durch Zurverfügungstellung neuer Motorschmieröle für Dieselmotoren einen wirtschaftlichen Betrieb eines Dieselmotors mit einem dem Motor nachgeschalteten Partikelfiltersystem in der Abgasleitung zu gewährleisten und ein entsprechendes Verfahren zum Betreiben eines Dieselmotors, bei dem solche Motorschmieröle Verwendung finden, anzugeben.The object of the invention is to ensure economical operation of a diesel engine with a particle filter system downstream of the engine in the exhaust pipe by providing new engine lubricating oils for diesel engines and to specify a corresponding method for operating a diesel engine in which such engine lubricating oils are used.

Die zur Regeneration der Dieselpartikelfilter durch Abbrand ausreichenden Temperaturen sollen so niedrig liegen, daß möglichst oft Regeneration eintritt. Bei ungünstigen Betriebszuständen des Dieselmotors, beispielsweise einer Leistungsabgabe, die zu nur niedrigen Abgastemperaturen führen, wird der Filter so weit mit Partikeln belegt, daß der Abgasgegendruck unzulässig hohe Werte erreicht. Zudem entsteht die Gefahr, daß ein zu stark belegter Filter bei einer Regeneration durch Abbrand thermisch zu stark belastet wird und örtlich schmilzt, was zu einer Verschlechterung der Funktion des Filters führen kann.The temperatures which are sufficient for the regeneration of the diesel particle filter by burning should be so low that regeneration occurs as often as possible. In the case of unfavorable operating conditions of the diesel engine, for example a power output that lead to only low exhaust gas temperatures, the filter is so far covered with particles that the exhaust gas back pressure reaches impermissibly high values. In addition, there is a risk that a filter that is too heavily loaded will be thermally loaded too much during regeneration due to burning and will melt locally, which can lead to a deterioration in the function of the filter.

Die vorliegende Erfindung liegt nun darin, daß ein Motorschmieröl für mit einem Partikelfiltersystem ausgerüstete Dieselmotoren mit einem katalytisch wirksamen Gehalt einer Eisenverbindung vorgeschlagen wird. Der Erfindung liegt die Erkenntnis zugrunde, daß auch ein gewisser Anteil des Schmieröls an der motorischen Verbrennung teilnimmt. Durch die erfindungsgemäße Additivierung des Schmieröls wird die katalytisch wirksame Substanz beim bestimmungsgemäßen Betrieb des Motors in ausreichender Menge auch dem Dieselpartikelfiltersystem mit dem heißen Motorabgas zugeführt, wo es auf eine möglichst quantitative Weiterreaktion der zunächst vom Filter zurückgehaltenen partikelförmigen organischen Bestandteile ankommt. Selbstverständlich wird der Erfindungszweck auch bereits durch die katalytisch begünstigte Umsetzung der partikelförmigen organischen Bestandteile mit dem im Abgas befindlichen Restsauerstoff gefördert, die abläuft, bevor es zu deren Ablagerung auf dem Filter kommt. Erfindungsgemäß gelingt es, durch die vorgeschlagene Additivierung des Schmieröls, den für die Dieselpartikelfilterregeneration ausreichenden Gehalt an katalytisch wirksamen Eisenverbindungen im Abgasstrom aufrechtzuerhalten, wobei Gewichtsverhältnisse von 5 bis 20 000, vorzugsweise 50 bis 10 000 ppm der Eisenverbindung, insbesondere der metallorganischen Eisenverbindung, bezogen auf die Schmierölmenge, Verwendung finden.The present invention resides in the fact that an engine lubricating oil for diesel engines equipped with a particle filter system with a catalytically active content of an iron compound is proposed. The invention is based on the knowledge that a certain proportion of the lubricating oil also participates in engine combustion. Through the Additization of the lubricating oil according to the invention, the catalytically active substance is also supplied in sufficient quantity to the diesel particle filter system with the hot engine exhaust gas when the engine is operated as intended, where a further quantitative reaction of the particulate organic components initially retained by the filter is important. Of course, the purpose of the invention is also promoted by the catalytically favored conversion of the particulate organic constituents with the residual oxygen present in the exhaust gas, which takes place before it is deposited on the filter. According to the invention, it is possible to maintain the content of catalytically active iron compounds in the exhaust gas stream sufficient for the diesel particle filter regeneration, with weight ratios of 5 to 20,000, preferably 50 to 10,000, ppm of the iron compound, in particular the organometallic iron compound, based on the proposed additization of the lubricating oil Lubricating oil quantity, find use.

Insbesondere sind Ferrocen (Bis(π­-cyclopentadienyl)eisen) oder Eisenverbindungen mit einem komplexen Salz einer organischen Säure, in dem das Verhältnis der Anzahl der Äquivalente der organischen Säure zur Anzahl der Eisenatome einen Wert von 3 oder weniger beträgt, beispielsweise Eisentallat, geeignet. Die vorgenannten Verbindungen sind wegen ihrer katalytischen Wirksamkeit und ihrer guten Löslichkeit und Schmierölverträglichkeit als Additive besonders geeignet.Ferrocene (bis (π-cyclopentadienyl) iron) or iron compounds with a complex salt of an organic acid in which the ratio of the number of equivalents of the organic acid to the number of iron atoms is 3 or less, for example iron tallate, are particularly suitable. The aforementioned compounds are because of their catalytic activity and their good solubility and lubricating oil compatibility are particularly suitable as additives.

Die vorgeschlagene Additivierung des Schmieröls bietet eine vorteilhafte Alternative zu einer Einbringung der katalytisch wirksamen Substanzen durch Additivierung des Dieselkraftstoffes oder zu einer separaten zusätzlichen Dosierungseinrichtung.The proposed additization of the lubricating oil offers an advantageous alternative to introducing the catalytically active substances by additizing the diesel fuel or to a separate additional metering device.

Es läßt sich zeigen, daß die durch die erfindungsgemäße Additivierung in den aufstromseitig vom Filter befindlichen Abgasstrom zusätzlich eingebrachten aschebildenden Partikel weitgehend vom Filter zurückgehalten werden und nur zu einer vernachlässigbaren Verschlechterung des Filterdurchgangswiderstandes führen.It can be shown that the ash-forming particles additionally introduced into the exhaust gas flow upstream of the filter by the inventive additives are largely retained by the filter and only lead to a negligible deterioration in the filter volume resistance.

Der erfindungsgemäße Effekt wurde in einem Vergleichsversuchsprogramm mit einem stationär betriebenen Fahrzeug-Dieselmotor, Fabrikat Ford 2,5 l Direkteinspritzer, verifiziert. Der Motor ist mit einem abstromseitig vom Motor in der Abgasleitung installierten Dieselpartikelfiltersystem aus einem keramischen Monolithkatalysator, Fabrikat Corning, ausgestattet. Der Motor wurde mit einem handelsüblichen Dieselmotorschmieröl der Viskositätsklasse 15W-40 betrieben. Bei einer konstanten Leistungsabgabe von 18 kW baute sich über eine Laufzeit von 2 1/2 Stunden ein von 100 mbar auf etwa 350 mbar ansteigender Abgasgegendruck auf. Bei Steigerung der Leistungsaufnahme von 18 auf 25 kW wurde der Abgasgegendruck aufgrund höherer Abgastemperatur durch teilweisen Abbrand der Keramikfilterbelegung auf einen Wert von etwas unterhalb 250 mbar abgebaut, der innerhalb eines Zeitraums von einer halben Stunde auf etwa 300 mbar anstieg, um für den weiteren Verlauf der Versuchsdauer bei dieser Leistungsaufnahme auf einem Plateau von etwas unterhalb 300 mbar zu verharren. Der Betriebszustand mit einer Leistungsaufnahme von 45 kW wurde eingeschoben, um den Filter freizubrennen. Durch den Abbrand wurde zwar ein Abbau des Abgasgegendruckes auf 100 mbar erreicht, bei Drosselung der Leistungsabgabe auf den vorherigen Betriebszustand von 25 kW war jedoch ein stetiger Anstieg des Abgasgegendruckes zu beobachten, der sich asymptotisch einem Wert von etwa 400 mbar nähert. Dieser Abgasgegendruck bewirkt eine drastische Verschlechterung des Motorwirkungsgrades.The effect according to the invention was verified in a comparative test program with a stationary vehicle diesel engine, manufactured by Ford 2.5 l direct injection. The engine is equipped with a diesel particulate filter system made of a ceramic monolith catalyst, manufactured by Corning, installed in the exhaust line downstream of the engine. The engine was operated with a commercially available diesel engine lubricating oil of viscosity class 15W-40. With a constant power output of 18 kW, an exhaust gas back pressure rising from 100 mbar to approximately 350 mbar built up over a running time of 2 1/2 hours. When increasing the power consumption from 18 to 25 kW the exhaust back pressure was reduced to a value of slightly below 250 mbar due to the higher exhaust gas temperature, which rose within a period of half an hour to about 300 mbar, in order to keep the power consumption on a plateau of something for the further course of the test to remain below 300 mbar. The operating state with a power consumption of 45 kW was inserted to burn the filter free. The combustion did reduce the exhaust gas back pressure to 100 mbar, but when the power output was reduced to the previous operating state of 25 kW, a steady increase in the exhaust gas back pressure was observed, which asymptotically approaches a value of about 400 mbar. This exhaust back pressure causes a drastic deterioration in engine efficiency.

Beim Betrieb unter sonst identischen Bedingungen und einem analogen Zeitprogramm wie bei dem vorstehenden Vergleichsversuch mit einem mit 8 400 ppm Ferrocen additivierten Motorschmieröl der Viskositätsklasse 15W-40 ist bei einer Leistungsaufnahme von 18 kW bei einem anfänglichen Abgasgegendruck von 100 mbar ein geringfügiger Aufbau bis auf einen Druck von etwa 150 mbar zu beobachten, der dann konstant auf einem Niveau von etwa 150 mbar verbleibt. Auch bei Erhöhung der Leistungsabgabe auf 25 kW ist keine wesentliche Veränderung dieses Plateaus zu beobachten. Um Zustände zu erreichen, bei denen sichergestellt ist, daß die auf dem Filter angelagerten kohlenstoffhaltigen Partikel weitgehend abgebrannt sind, wurde ein Vollast-Motorbetriebszustand mit einer Leistungsabgabe von 45 kW zwischengeschaltet. Bei einer solchen in der Praxis allenfalls nur kurzfristig auftretenden Erhöhung der Leistungsabgabe steigt der Abgasgegendruck auf 350 mbar und verharrt mit etwas fallender Tendenz auf diesem Niveau. Bei Reduzierung der Leistungsabgabe auf 25 kW stellt sich ein stabiles Niveau ein, das mit etwa 150 mbar noch unter dem Niveau des vorhergegangenen Betriebszustandes bei einer Leistungsabgabe von 18 kW liegt. Diese Werte liegen nur unwesentlich über denen eines unbeladenen Filters und gewährleisten akzeptable Motorbetriebszustände.When operating under otherwise identical conditions and an analog time program as in the previous comparison test with an engine lubricating oil of viscosity class 15W-40 additized with 8 400 ppm ferrocene, with a power consumption of 18 kW and an initial exhaust gas back pressure of 100 mbar, there is a slight build up to a pressure of approximately 150 mbar, which then remains constant at a level of approximately 150 mbar. Even when the power output is increased to 25 kW, no significant change in this plateau can be observed. To achieve conditions in which it is ensured that the carbon-containing particles deposited on the filter have largely burned off, a full-load engine operating state was interposed with a power output of 45 kW. With such an increase in power output, which in practice occurs only briefly, the exhaust gas back pressure rises to 350 mbar and remains at this level with a somewhat decreasing tendency. When the power output is reduced to 25 kW, a stable level is reached, which at around 150 mbar is still below the level of the previous operating state with a power output of 18 kW. These values are only marginally higher than those of an unloaded filter and ensure acceptable engine operating conditions.

Die Additivierung der erfindungsgemäßen Motorschmieröle erfolgt durch Direktauflösung beispielsweise bis zu Konzentrationen von 10 000 ppm oder auch Herstellung konzentrierter Lösungen in einer geeigneten Schmierölkomponente. Bevorzugt sind Additivierungen in Konzentrationen von 5 bis 20 000 ppm, vorzugsweise 50 bis 10 000 ppm, bezogen auf das Motorschmieröl (Gewichtsverhältnis).The engine lubricating oils according to the invention are added by direct dissolution, for example up to concentrations of 10,000 ppm, or else preparation of concentrated solutions in a suitable lubricating oil component. Additives in concentrations of 5 to 20,000 ppm, preferably 50 to 10,000 ppm, based on the engine lubricating oil (weight ratio), are preferred.

In der Figur 1 ist schematisch die benutzte Versuchsanordnung der Installation des Dieselpartikelfilters in der Abgasleitung des Dieselmotors und der Druckmeßstelle zu ersehen.FIG. 1 shows schematically the experimental arrangement used for the installation of the diesel particle filter in the exhaust pipe of the diesel engine and the pressure measuring point.

In der Figur 2 sind in einem Diagramm die oben erläuterten Versuchsergebnisse mit dem additivierten Schmieröl im Vergleich zur Verwendung mit dem nichtadditivierten Schmieröl grafisch veranschaulicht.The test results explained above with the additive lubricating oil compared to the use with the non-additive lubricating oil are graphically illustrated in a diagram in FIG.

Mit der Verwendung der erfindungsgemäß additivierten Schmieröle ist es möglich, mit einem Dieselpartikelfiltersystem ausgerüstete Dieselmotore, die die US-Norm FTP 75 erfüllen, unter Zugrundelegung einer vertretbaren Lebensdauer des Filtersystems wirtschaftlich zu betreiben.With the use of the lubricating oils additized according to the invention, it is possible to operate diesel engines equipped with a diesel particle filter system that meet the US standard FTP 75 economically, on the basis of an acceptable service life of the filter system.

Claims (6)

1. Motorschmieröl für mit einem Partikelfilter im Abgasstrom ausgerüstete Dieselmotoren mit einem katalytisch wirksamen Gehalt in einer Menge von 5 bis 20 000, vorzugsweise 50 bis 10 000 ppm, einer Eisenverbindung.1. Engine lubricating oil for diesel engines equipped with a particle filter in the exhaust gas stream with a catalytically active content in an amount of 5 to 20,000, preferably 50 to 10,000 ppm, of an iron compound. 2. Motorschmieröl nach Anspruch 1, dadurch gekennzeichnet, daß es mit einer metallorganischen Eisenverbindung additiviert ist.2. Engine lubricating oil according to claim 1, characterized in that it is additized with an organometallic iron compound. 3. Motorschmieröl nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es mit Ferrocen oder einem Ferrocenderivat additiviert ist.3. Engine lubricating oil according to claim 1 or 2, characterized in that it is additized with ferrocene or a ferrocene derivative. 4. Motorschmieröl nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es mit einer Verbindung aus einem komplexen Salz einer organischen Säure und Eisen, in dem das Verhältnis der Anzahl der Äquivalente der organischen Säure zur Anzahl der Eisenatome einen Wert von 3 oder weniger aufweist, additiviert ist.4. Motor lubricating oil according to claim 1 or 2, characterized in that it has a compound of a complex salt of an organic acid and iron, in which the ratio of the number of equivalents of the organic acid to the number of iron atoms has a value of 3 or less, is additive. 5. Motorschmieröl nach Anspruch 4, dadurch gekennzeichnet, daß es mit Eisentallat additiviert ist.5. Engine lubricating oil according to claim 4, characterized in that it is additized with iron tallate. 6. Verfahren zum Betreiben eines Dieselmotors mit einem dem Motor nachgeschalteten Partikelfiltersystem in der Abgasleitung, in dem aufgrund der Anwesenheit katalytisch wirksamer Substanzen die Temperatur für den Abbrand von auf dem Filtersystem abgelagerten Rußpartikeln abgesenkt ist, dadurch gekennzeichnet, daß die katalytisch wirksamen Substanzen mittels eines additivierten Motorschmieröls gemäß einem der vorhergehenden Ansprüche beim bestimmungsgemäßen Betrieb des Motors zugeführt werden.6. Method for operating a diesel engine with a particle filter system downstream of the engine in the exhaust pipe, in which, due to the presence, more catalytically effective Substances the temperature for the combustion of soot particles deposited on the filter system is lowered, characterized in that the catalytically active substances are supplied by means of an additive engine lubricating oil according to one of the preceding claims when the engine is operated as intended.
EP89104891A 1988-03-19 1989-03-18 Method of operating a diesel engine Expired - Lifetime EP0334248B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89104891T ATE73169T1 (en) 1988-03-19 1989-03-18 METHOD OF OPERATING A DIESEL ENGINE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3809307A DE3809307A1 (en) 1988-03-19 1988-03-19 ENGINE LUBRICANE FOR DIESEL ENGINES AND METHOD FOR OPERATING A DIESEL ENGINE
DE3809307 1988-03-19

Publications (2)

Publication Number Publication Date
EP0334248A1 true EP0334248A1 (en) 1989-09-27
EP0334248B1 EP0334248B1 (en) 1992-03-04

Family

ID=6350194

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89104891A Expired - Lifetime EP0334248B1 (en) 1988-03-19 1989-03-18 Method of operating a diesel engine

Country Status (9)

Country Link
US (1) US4946609A (en)
EP (1) EP0334248B1 (en)
AT (1) ATE73169T1 (en)
DE (2) DE3809307A1 (en)
DK (1) DK88189A (en)
ES (1) ES2029909T3 (en)
FI (1) FI91163C (en)
GR (1) GR3004532T3 (en)
NO (1) NO172900C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4129408C1 (en) * 1991-09-04 1992-10-22 Chemische Betriebe Pluto Gmbh, 4690 Herne, De
WO2008009346A1 (en) 2006-07-15 2008-01-24 Daimler Ag Particle separator and method for regenerating a particle separator

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4133137A1 (en) * 1991-10-07 1992-04-23 Bernd Fischer Assisting oxidn. of particles in diesel engine - by addn. of catalytically supportive to lubricating oil
DE4138216C2 (en) * 1991-11-21 1994-02-03 Veba Oel Ag Process for adding fuel or fuels to ferrocene
US5235936A (en) * 1992-12-04 1993-08-17 Kracklauer John J Ferrocene injection system
US5746784A (en) * 1993-03-20 1998-05-05 Chemische Betriebe Pluto Gmbh Use of ferrocene
CN1089629C (en) * 1996-05-20 2002-08-28 迪奈克斯公司 Method and reactor for electrochemical conversion of material e. g. soot particles being insoluble in fluid
DE10043144C1 (en) * 2000-08-31 2001-12-13 Octel Deutschland Gmbh Use of solutions of 2,2-bisferrocenylalkanes in an aromatic solvent as combustion-promoting diesel fuel additives
RU2271363C2 (en) * 2000-08-31 2006-03-10 Дзе Ассошиэйтед Октел Компани Лимитед Compositions comprising dimeric or oligomeric ferrocenes
US6629407B2 (en) 2000-12-12 2003-10-07 Ethyl Corporation Lean burn emissions system protectant composition and method
US7556657B2 (en) * 2001-08-30 2009-07-07 Innospec Deutschland Gmbh Composition
DE10208326B4 (en) * 2002-02-27 2008-06-19 Innospec Deutschland Gmbh Additives for liquid fuels
JP4081005B2 (en) * 2001-08-30 2008-04-23 ザ アソーシエーテッド オクテル カンパニー リミテッド Composition
EP1344811A1 (en) * 2002-03-13 2003-09-17 Infineum International Limited Iron salt diesel fuel additive composition for improvement of particulate traps
US20030226312A1 (en) * 2002-06-07 2003-12-11 Roos Joseph W. Aqueous additives in hydrocarbonaceous fuel combustion systems
US6971337B2 (en) * 2002-10-16 2005-12-06 Ethyl Corporation Emissions control system for diesel fuel combustion after treatment system
US20040074140A1 (en) * 2002-10-16 2004-04-22 Guinther Gregory H. Method of enhancing the operation of a diesel fuel combustion after treatment system
US6892531B2 (en) 2003-04-02 2005-05-17 Julius J. Rim System for and methods of operating diesel engines to reduce harmful exhaust emissions and to improve engine lubrication
WO2004101717A2 (en) * 2003-05-12 2004-11-25 Southwest Research Institute High octane lubricants for knock mitigation in flame propagation engines
US20050011413A1 (en) * 2003-07-18 2005-01-20 Roos Joseph W. Lowering the amount of carbon in fly ash from burning coal by a manganese additive to the coal
US20050016057A1 (en) * 2003-07-21 2005-01-27 Factor Stephen A. Simultaneous reduction in NOx and carbon in ash from using manganese in coal burners
US7101493B2 (en) * 2003-08-28 2006-09-05 Afton Chemical Corporation Method and composition for suppressing coal dust
US7332001B2 (en) * 2003-10-02 2008-02-19 Afton Chemical Corporation Method of enhancing the operation of diesel fuel combustion systems
US20050091913A1 (en) * 2003-10-29 2005-05-05 Aradi Allen A. Method for reducing combustion chamber deposit flaking
US7543445B2 (en) 2004-10-19 2009-06-09 The Lubrizol Corporation Methods for regeneration and performance of a particulate filter of an internal combustion engine
FR2896806B1 (en) * 2006-01-30 2008-03-14 Rhodia Recherches & Tech LUBRICATING COMPOSITION COMPRISING A COLLOIDAL DISPERSION OF IRON AND ITS USE IN AN ENGINE FOR THE TREATMENT OF EXHAUST GASES
FR2896824B1 (en) * 2006-01-30 2008-03-07 Rhodia Recherches & Tech METHOD OF OPERATING AN ENGINE USING A LUBRICATING COMPOSITION COMPRISING A COLLOIDAL DISPERSION OF A RARE EARTH FOR CATALYZING SOOT COMBUSTION
WO2007125587A1 (en) * 2006-04-27 2007-11-08 Ibiden Co., Ltd. Additive for engine oil, engine oil and method of exhaust gas purification
US20070277431A1 (en) * 2006-05-30 2007-12-06 Kazushige Ohno Additive for engine oil, engine oil, and exhaust gas purifying method
US9194272B2 (en) * 2008-12-02 2015-11-24 Caterpillar Inc. Power system
JP6988741B2 (en) * 2018-08-29 2022-01-05 トヨタ自動車株式会社 Internal combustion engine control device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB902610A (en) * 1959-07-28 1962-08-01 Shell Int Research Novel organometallic salts
CH599464A5 (en) * 1974-12-23 1978-05-31 Autol Ag Fuel additives contg. ferrocene as combustion catalyst
DE2826147A1 (en) * 1977-06-20 1978-12-21 Mooney Chemicals ORGANIC METAL COMPOSITIONS OR COMPOUNDS AND PROCEDURES FOR THEIR PRODUCTION
EP0052478A1 (en) * 1980-11-13 1982-05-26 Ford Motor Company Limited Method of operating a diesel engine, and a diesel fuel composition
US4501677A (en) * 1983-11-02 1985-02-26 Exxon Research & Engineering Co. Heterocyclic nitrogen compounds--organometallic salt complexes as corrosion inhibitors in lubricating oils
EP0211233A1 (en) * 1985-07-02 1987-02-25 Nippon Shokubai Kagaku Kogyo Co., Ltd Exhaust gas cleaning catalyst and process for production thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE334248C (en) * 1917-10-10 1921-03-10 Otto Priess Dr Process for the preparation of titanium tetrachloride
GB737092A (en) * 1952-11-10 1955-09-21 Shell Refining & Marketing Co Fuels and lubricants for internal combustion engines
BE527388A (en) * 1953-03-20
US2982730A (en) * 1957-05-03 1961-05-02 Socony Mobil Oil Co Inc Radiation resistant lubricating oil
US3178367A (en) * 1961-06-12 1965-04-13 Exxon Research Engineering Co Method of preparing finely divided solid metal salts
US3535155A (en) * 1967-06-22 1970-10-20 Exxon Research Engineering Co Oil impregnated papers
US4198305A (en) * 1978-06-14 1980-04-15 Mobil Oil Corporation Lubricant compositions
US4483777A (en) * 1982-09-20 1984-11-20 Mobil Oil Corporation Stability improvers for water-in-oil emulsion

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB902610A (en) * 1959-07-28 1962-08-01 Shell Int Research Novel organometallic salts
CH599464A5 (en) * 1974-12-23 1978-05-31 Autol Ag Fuel additives contg. ferrocene as combustion catalyst
DE2826147A1 (en) * 1977-06-20 1978-12-21 Mooney Chemicals ORGANIC METAL COMPOSITIONS OR COMPOUNDS AND PROCEDURES FOR THEIR PRODUCTION
EP0052478A1 (en) * 1980-11-13 1982-05-26 Ford Motor Company Limited Method of operating a diesel engine, and a diesel fuel composition
US4501677A (en) * 1983-11-02 1985-02-26 Exxon Research & Engineering Co. Heterocyclic nitrogen compounds--organometallic salt complexes as corrosion inhibitors in lubricating oils
EP0211233A1 (en) * 1985-07-02 1987-02-25 Nippon Shokubai Kagaku Kogyo Co., Ltd Exhaust gas cleaning catalyst and process for production thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 102, Nr. 6, Februar 1985, Seite 149, Zusammenfassung Nr. 48366a, Columbus, Ohio, US; M. DOMINIAK et al.: "Tribological properties of selected sulfur-containing ferrocene derivatives", & SCHMIERUNGSTECHNIK 1984, 15(6), 178-80 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4129408C1 (en) * 1991-09-04 1992-10-22 Chemische Betriebe Pluto Gmbh, 4690 Herne, De
WO2008009346A1 (en) 2006-07-15 2008-01-24 Daimler Ag Particle separator and method for regenerating a particle separator

Also Published As

Publication number Publication date
DK88189D0 (en) 1989-02-24
EP0334248B1 (en) 1992-03-04
DE3809307A1 (en) 1989-09-28
FI91163C (en) 1994-05-25
FI890774A0 (en) 1989-02-17
FI890774A (en) 1989-09-20
DE58900886D1 (en) 1992-04-09
NO172900B (en) 1993-06-14
NO890620D0 (en) 1989-02-14
NO890620L (en) 1989-09-20
NO172900C (en) 1993-09-22
DK88189A (en) 1989-09-20
GR3004532T3 (en) 1993-04-28
ES2029909T3 (en) 1992-10-01
ATE73169T1 (en) 1992-03-15
US4946609A (en) 1990-08-07
FI91163B (en) 1994-02-15

Similar Documents

Publication Publication Date Title
EP0334248B1 (en) Method of operating a diesel engine
DE69726540T2 (en) emission control
EP1600612B1 (en) Process for separating nitrogen oxides and soot particles from a lean exhaust gas from a combustion engine and exhaust gas cleaning system therefor
DE602004003354T2 (en) A PARTICLE FILTER AND NOX-ABSORBER EXHAUST SYSTEM FOR INTERNAL COMBUSTION ENGINE WITH LUBRICANTS
DE10214343A1 (en) Filter for removing particulates from diesel engine exhaust gas has a catalytic coating comprising barium and magnesium compounds and a platinum-group metal
DE69902446T3 (en) IMPROVEMENTS OF THE POLLUTION
DE112006003231T5 (en) Multi-stage system for selective catalytic reduction
DE3407172A1 (en) DEVICE FOR PURIFYING THE EXHAUST GAS FROM DIESEL ENGINES
DE102011015734B4 (en) Exhaust treatment system for an internal combustion engine
EP2115277A1 (en) Method for regenerating soot filters in the exhaust gas system of a lean mix engine, and exhaust gas system therefor
DE10308288A1 (en) Process for removing nitrogen oxides from the exhaust gas of a lean-burn internal combustion engine and exhaust gas purification system therefor
AT521448B1 (en) Process and arrangement of Otto engines with improved particle filtering II
EP2112339A1 (en) Method and device for cleaning exhaust gases of a combustion motor
DE102011113766A1 (en) EXHAUST GAS TREATMENT SYSTEM FOR A COMBUSTION ENGINE
EP0806553B1 (en) Method to purify the exhaust gas of Diesel engines
DE60130406T3 (en) Apparatus and method for exhaust gas purification
EP0492101A1 (en) Use of organometallic additives for improving soot burning in diesel fuels
DE10048511A1 (en) Reduction of carbon monoxide, hydrocarbons and soot particles in lean exhaust gas from internal combustion engine, by using particle filter having catalytic coating of oxygen storage component(s) and platinum group metal(s)
EP1702147B1 (en) Method for operating a particle filter in the exhaust gas train of an internal combustion engine in a motor vehicle
DE4138216A1 (en) PROCESS FOR ADDITIVATING COMBUSTION OR FUEL FERROCENE
EP1250952A1 (en) Catalyst, filter and process for eliminating soot particles from Diesel exhaust gases
DE602004002557T2 (en) SYSTEM FOR REGENERATING A PARTICLE FILTER IN AN EXHAUST SYSTEM
DE60205036T2 (en) EXHAUST GAS FOR INTERNAL COMBUSTION ENGINE
DE602004002347T2 (en) Method and device for purifying exhaust gases of an internal combustion engine
DE10204073A1 (en) Exhaust system and method for regeneration of a particle filter

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19891111

17Q First examination report despatched

Effective date: 19900611

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 73169

Country of ref document: AT

Date of ref document: 19920315

Kind code of ref document: T

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 58900886

Country of ref document: DE

Date of ref document: 19920409

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2029909

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3004532

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EPTA Lu: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 89104891.0

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19990208

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19990215

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19990226

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19990302

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19990308

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19990310

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19990311

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19990312

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19990330

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19990331

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19990531

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000318

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000318

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000319

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000320

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000331

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000331

BERE Be: lapsed

Owner name: VEBA OEL A.G.

Effective date: 20000331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001001

EUG Se: european patent has lapsed

Ref document number: 89104891.0

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20000318

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001130

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20001001

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010103

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20010910

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050318