EP0325769B1 - Use of an unleaded liquid fuel containing ferrocen for operating a spark ignition engine - Google Patents

Use of an unleaded liquid fuel containing ferrocen for operating a spark ignition engine Download PDF

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Publication number
EP0325769B1
EP0325769B1 EP88121294A EP88121294A EP0325769B1 EP 0325769 B1 EP0325769 B1 EP 0325769B1 EP 88121294 A EP88121294 A EP 88121294A EP 88121294 A EP88121294 A EP 88121294A EP 0325769 B1 EP0325769 B1 EP 0325769B1
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EP
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Prior art keywords
ferrocene
fuel
operating
liquid fuel
exhaust gas
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Expired - Lifetime
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EP88121294A
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German (de)
French (fr)
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EP0325769A1 (en
Inventor
Dieter Dr. Höhr
August-Wilhelm Dr. Preuss
Kurt-Peter Dr. Schug
Helmut Riegel
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Octel Deutschland GmbH
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Veba Oel AG
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Priority to AT88121294T priority Critical patent/ATE79393T1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
    • 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
    • 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
    • F02B1/00—Engines characterised by fuel-air mixture compression
    • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
    • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

Definitions

  • the invention relates to the use of an unleaded liquid fuel containing 1 to 100 ppm by weight of ferrocene for operating an Otto engine.
  • the object of the present invention is to reduce the fuel consumption and the exhaust gas emissions when operating an Otto engine with an exhaust gas catalytic converter system for exhaust gas afterburning.
  • gasoline engines equipped with exhaust gas catalytic converter systems for exhaust gas afterburning can be operated with ferrocene-additive fuel with an improved effect of the catalytic converter system.
  • This is preferably a regulated catalyst system, built up on a bulk or monolithic carrier with a coating of a noble metal, an oxidic metal compound or a combination of both.
  • the positive effects of adding ferrocene are achieved by adding ferrocene to the fuel in amounts of 1 to 100, preferably 5 to 20, ppm by weight of ferrocene. Ferrocene is given to the fuel in the amounts required according to the recommended concentration due to its good Solubility added directly with mixing. It is expedient to prepare a concentrate of ferrocene dissolved in liquid fuel (petrol), an alcohol, an ether, an aromatic solvent or mixtures thereof or the like and then to mix the required volume with the fuel to adjust the desired ferrocene concentration.
  • liquid fuel petrol
  • an alcohol an alcohol
  • an ether an aromatic solvent or mixtures thereof or the like
  • Figure 1 documents the increase in OZ demand in the engines of the two test vehicles in comparison. The results are expressed as a pre-adjustment ° crank angle depending on the mileage in km and were measured with the same reference fuel. The results show no significant differences in both engines, but the increase in OZ demand from the 50,000 km mileage for the engine operated with ferrocene is slightly improved.
  • Figure 2 shows the fuel consumption values in the comparison of the two test vehicles, from which a significantly lower consumption of the vehicle operated with ferrocene can be demonstrated.
  • FIG. 8 and FIG. 9 show the pressure curve on a pressure-indicated 1-cylinder engine as a test engine, the family of curves shown in FIG. 8 representing approximately 30 combustion processes with ferrocene-additive fuel and the family of curves shown in FIG. 9 showing the corresponding courses without the addition of ferrocene under otherwise identical operating conditions. It can be seen that ferrocene brings about a clear equalization of the cycle variations and thus favorable conditions for engine running and fuel utilization.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Valve Device For Special Equipments (AREA)
  • Liquid Developers In Electrophotography (AREA)
  • Paper (AREA)
  • Coupling Device And Connection With Printed Circuit (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Catalysts (AREA)
  • Combustion Methods Of Internal-Combustion Engines (AREA)
  • Ignition Installations For Internal Combustion Engines (AREA)

Abstract

To reduce the fuel consumption and the exhaust gas emissions in a spark-ignition engine fitted with an exhaust catalyst system for post-combustion of the exhaust gas, a liquid fuel with an addition of 1 to 100 ppm by weight of ferrocene can be used.

Description

Die Erfindung betrifft die Verwendung eines 1 bis 100 Gew.-ppm Ferrocen enthaltenden unverbleiten flüssigen Kraftstoffs zum Betreiben eines Otto-Motors.The invention relates to the use of an unleaded liquid fuel containing 1 to 100 ppm by weight of ferrocene for operating an Otto engine.

Es ist das Ziel der Verordnungsgeber in den Industrieländern, die Emissionen aus Verbrennungskraftmotoren von insbesondere Kohlenmonoxid (CO), Stickstoffoxiden (NOx) und Kohlenwasserstoffen (CmHn) zu beschränken, um die mit diesen Emissionen verbundenen Umweltbelastungen zu begrenzen. Auch die als Klopfbremsen den Kraftstoffen für Otto-Motoren zugesetzten Bleiverbindungen sind hinsichtlich ihrer Anwendbarkeit zunehmenden Beschränkungen unterworfen. Durch Bleizusatz verbleiter Kraftstoff würde die zur Eliminierung der Schadstoffe CO, NOx und CmHn eingesetzten Abgaskatalysatoren durch Belegung der aktiven Zentren des Katalysators unwirksam machen (vergiften). Von den für die Reinigung von Autoabgasen entwickelten Lösungswegen haben katalytische Verfahren große Bedeutung erlangt (vgl. Chemiker-Zeitung, 97. Jahrgang 1973, Nr. 9, S. 469 ff.).It is the goal of regulators in industrialized countries to limit emissions from internal combustion engines, particularly carbon monoxide (CO), nitrogen oxides (NO x ) and hydrocarbons (C m H n ), in order to limit the environmental pollution associated with these emissions. The lead compounds added to the fuels for gasoline engines as knocking brakes are also subject to increasing restrictions with regard to their applicability. Adding leaded fuel would render the exhaust gas catalysts used to eliminate the pollutants CO, NO x and C m H n ineffective by poisoning the active centers of the catalyst. Catalytic processes have gained great importance from the approaches developed for the cleaning of car exhaust gases (cf. Chemiker-Zeitung, 97th year 1973, No. 9, p. 469 ff.).

Wegen der gesundheitsschädlichen Wirkung von in den Verbrennungsabgasen des Betriebes von Otto-Motoren enthaltenen Bleiverbindungen hat man nach Alternativen gesucht, die die günstige Wirkung des Zusatzes von Bleiverbindungen, nämlich insbesondere Verbesserung des Klopfverhaltens, aber auch eine gewisse günstige Wirkung in Bezug auf den Verschleiß der Auslaßventile von Viertakt-Otto-Motoren, ebenfalls aufweisen würden.Because of the health-damaging effect of lead compounds contained in the combustion exhaust gases from the operation of Otto engines, alternatives have been sought which have the beneficial effect of adding lead compounds, namely in particular improvement of the knocking behavior, but also a certain favorable effect Effect in terms of wear on the exhaust valves of four-stroke Otto engines, would also have.

So sind flüssige Kohlenwasserstoffmischungen, bestehend im wesentlichen aus Benzin und einer organometallischen Verbindung aus der Gruppe von Dicyclopentadienyleisen (Ferrocen) und benzinlöslichen Derivaten, zur Reduzierung des Kraftstoffverbrauchs und der Abgasverschmutzung sowie zur Entfernung oder Herabsetzung der Kohlenstoffabscheidungen vorgeschlagen worden, wobei derartige Mischungen auch noch die üblichen Zusätze eines Antiklopfmittels enthalten konnten (vgl. DE-OS 25 02 307).Liquid hydrocarbon mixtures, consisting essentially of gasoline and an organometallic compound from the group of dicyclopentadienyl iron (ferrocene) and gasoline-soluble derivatives, for reducing fuel consumption and exhaust gas pollution and for removing or reducing carbon deposits have been proposed, such mixtures also being the usual ones Could contain additives of an anti-knock agent (see. DE-OS 25 02 307).

Aufgabe der vorliegenden Erfindung ist dementsprechend die Verringerung des Kraftstoffverbrauches und der Abgasemissionen beim Betrieb eines Otto-Motors mit einem Abgaskatalysatorsystem zur Abgasnachverbrennung.Accordingly, the object of the present invention is to reduce the fuel consumption and the exhaust gas emissions when operating an Otto engine with an exhaust gas catalytic converter system for exhaust gas afterburning.

Es wurde gefunden, daß mit Abgaskatalysatorsystemen zur Abgasnachverbrennung ausgerüstete Otto-Motoren mit verbesserter Wirkung des Katalysatorsystems mit ferrocenadditiviertem Kraftstoff betrieben werden können. Vorzugsweise handelt es sich dabei um ein geregeltes Katalysatorsystem, aufgebaut auf einem Schüttgut- oder monolithischen Träger mit einer Beschichtung aus einem Edelmetall, einer oxidischen Metallverbindung oder einer Kombination aus beiden.It has been found that gasoline engines equipped with exhaust gas catalytic converter systems for exhaust gas afterburning can be operated with ferrocene-additive fuel with an improved effect of the catalytic converter system. This is preferably a regulated catalyst system, built up on a bulk or monolithic carrier with a coating of a noble metal, an oxidic metal compound or a combination of both.

Die positiven Wirkungen eines Ferrocen-Zusatzes werden bei Zusatzmengen von Ferrocen zu dem Kraftstoff in Mengen von 1 bis 100, vorzugsweise 5 bis 20 Gew.-ppm Ferrocen erreicht. Ferrocen wird dem Kraftstoff in den entsprechend der empfohlenen Konzentration erforderlichen Mengen aufgrund seiner guten Löslichkeit unter Vermischen direkt zugesetzt. Es ist zweckmäßig, ein Konzentrat von in flüssigem Kraftstoff (Benzin), einem Alkohol, einem Ether, einem aromatischen Lösungsmittel oder deren Gemischen o. dgl. gelöstem Ferrocen herzustellen und von diesem dann die erforderliche Volumenmenge dem Kraftstoff zur Einstellung der gewünschten Ferrocenkonzentration zuzumischen.The positive effects of adding ferrocene are achieved by adding ferrocene to the fuel in amounts of 1 to 100, preferably 5 to 20, ppm by weight of ferrocene. Ferrocene is given to the fuel in the amounts required according to the recommended concentration due to its good Solubility added directly with mixing. It is expedient to prepare a concentrate of ferrocene dissolved in liquid fuel (petrol), an alcohol, an ether, an aromatic solvent or mixtures thereof or the like and then to mix the required volume with the fuel to adjust the desired ferrocene concentration.

Der mit Ferrocen additivierte flüssige Kraftstoff ergab überraschend beim Betrieb eines mit einem geregelten Katalysatorsystem ausgerüsteten Otto-Motors unter Betriebsbedingungen im Feldtest die nachfolgend näher beschriebenen Vorteile. Die für die Feldtests eingesetzten serienmäßigen Fahrzeuge waren mit einem geregelten Katalysatorsystem, aufgebaut auf einem monolithischen Träger mit einer Beschichtung aus katalytisch wirksamen Metallen, ausgerüstet.The liquid fuel additized with ferrocene surprisingly gave the advantages described in more detail below when operating an Otto engine equipped with a regulated catalyst system under operating conditions in the field test. The standard vehicles used for the field tests were equipped with a regulated catalyst system, built on a monolithic carrier with a coating of catalytically active metals.

Ein Versuchsprogramm an einem druckindizierten 1-Zylinder-Motor zeigte eine Verminderung der sogenannten Zyklus-Variationen beim Betrieb mit ferrocenadditiviertem Kraftstoff. In Übertragung auf das Betriebsverhalten von Vollmotoren kann daraus auf einen gleichmäßigeren Motorlauf und bessere Kraftstoffausnutzung sowie bessere Möglichkeiten zu einem optimierten Verbrennungsablauf geschlossen werden.A test program on a pressure-indicated 1-cylinder engine showed a reduction in the so-called cycle variations when operating with ferrocene-additive fuel. In terms of the operating behavior of full engines, it can be concluded that the engine runs more smoothly and better, as well as better options for an optimized combustion process.

Die Erfindung wird weiter erläutert anhand der nachfolgend wiedergegebenen Figuren 1 bis 8, in denen Meßprogramme und die erzielten Ergebnisse an zwei serienmäßigen mit Abgaskatalysator und Lambdasonde ausgerüsteten Kraftfahrzeugen der oberen Mittelklasse über Laufleistungen im Feldtest unter typischen Straßenverkehrsbedingungen von 80 000 km dokumentiert sind, wobei beide Fahrzeuge mit dem gleichen Referenzkraftstoff betrieben wurden, mit dem einzigen Unterschied, daß das eine Fahrzeug mit dem mit Ferrocen additivierten Referenzkraftstoff betrieben wurde. Der mit Ferrocen additivierte Kraftstoff ist über das gesamte Versuchsprogramm mit einer Ferrocenkonzentration von 15 Gew.-ppm eingesetzt worden.The invention is further explained with reference to the figures 1 to 8 shown below, in which Measurement programs and the results obtained on two standard vehicles of the upper mid-range equipped with catalytic converter and lambda sensor are documented in field test mileage under typical road traffic conditions of 80,000 km, both vehicles being operated with the same reference fuel, with the only difference that one vehicle was operated with the reference fuel additized with ferrocene. The fuel additized with ferrocene was used throughout the entire test program with a ferrocene concentration of 15 ppm by weight.

Figur 1 dokumentiert den OZ-Bedarfsanstieg in den Motoren der beiden Testfahrzeuge im Vergleich. Die Ergebnisse sind ausgedrückt als Vorverstellung °-Kurbelwinkel in Abhängigkeit von der Laufleistung in km und wurden mit demselben Referenzkraftstoff gemessen. Die Ergebnisse zeigen keine signifikanten Unterschiede in beiden Motoren, jedoch ist der OZ-Bedarfsanstieg ab ca. 50 000 km Laufleistung für den mit Ferrocen betriebenen Motor geringfügig verbessert.Figure 1 documents the increase in OZ demand in the engines of the two test vehicles in comparison. The results are expressed as a pre-adjustment ° crank angle depending on the mileage in km and were measured with the same reference fuel. The results show no significant differences in both engines, but the increase in OZ demand from the 50,000 km mileage for the engine operated with ferrocene is slightly improved.

Figur 2 zeigt die Kraftstoffverbrauchswerte im Vergleich der beiden Testfahrzeuge, aus denen sich ein deutlich geringerer Verbrauch des mit Ferrocen betriebenen Fahrzeugs nachweisen läßt.Figure 2 shows the fuel consumption values in the comparison of the two test vehicles, from which a significantly lower consumption of the vehicle operated with ferrocene can be demonstrated.

Figur 3 weist die CO-Emissionen aus, gemessen nach der standardisierten Meßmethode im sog. FTP-Zyklus. Die Emission an Kohlenmonoxid des mit Ferrocen betriebenen Fahrzeugs sind deutlich geringer.Figure 3 shows the CO emissions, measured according to the standardized measurement method in the so-called FTP cycle. The emissions of carbon monoxide from the vehicle operated with ferrocene are significantly lower.

Aus Figur 4 ist ersichtlich, daß die CxHy Emissionen (Kohlenwasserstoffe) ab ca. 40 000 km Laufleistung bei ferrocenadditiviertem Krafftstoffbetrieb geringer werden.It can be seen from FIG. 4 that the C x H y emissions (hydrocarbons) decrease from approximately 40,000 km mileage with ferrocene-additive fuel operation.

Figur 5 dokumentiert eine deutliche Verringerung der NOx-Emissionen.Figure 5 documents a significant reduction in NO x emissions.

Figur 6 zeigt Ergebnisse der Analyse der in beiden Fahrzeugen verwendeten Schmieröle auf Abriebelemente. Die Meßwerte wurden ermittelt aus sog. Nullproben (niedrige Werte) unmittelbar nach dem Ölwechsel und aus den Endproben (hohe Werte), welche am Ende des Ölwechselintervalls gezogen und analysiert wurden.FIG. 6 shows results of the analysis of the lubricating oils used in both vehicles for wear elements. The measured values were determined from so-called zero samples (low values) immediately after the oil change and from the final samples (high values), which were drawn and analyzed at the end of the oil change interval.

Es zeigt sich, daß das bei Ferrocenzusatz zum Kraftstoff besonders interessierende Element Eisen als Fe analysiert) beim Betrieb mit additiviertem Kraftstoff erwartungsgemäß höher ist, jedoch ist kein Anstieg über die Laufleistung zu beobachten.It can be seen that the element iron, which is of particular interest when ferrocene is added to the fuel, is expected to be higher when operating with additive fuel, but no increase in mileage can be observed.

Figur 7 zeigt als weiteres Beispiel der Abriebelemente analoge Meßergebnisse wie Figur 6 für das Element Kupfer Cu, wobei die Cu-Gehalte der Schmierölendproben des mit ferrocenadditiviertem Kraftstoff betriebenen Fahrzeugs über die gesamte Laufleistung niedrigere Werte ausweisen.FIG. 7 shows, as a further example of the abrasion elements, measurement results analogous to FIG. 6 for the element copper Cu, the Cu contents of the lubricating oil end samples of the vehicle operated with ferrocene-additive fuel showing lower values over the entire mileage.

Figur 8 und Figur 9 zeigen den Druckverlauf an einem druckindizierten 1-Zylindermotor als Prüfmotor, wobei die in Figur 8 wiedergegebene Kurvenschar ca. 30 Verbrennungsabläufe mit ferrocenadditiviertem Kraftstoff und die in Figur 9 wiedergegebene Kurvenschar die entsprechenden Verläufe ohne Ferrocenzusatz unter sonst identischen Betriebsbedingungen darstellt. Es ist zu erkennen, daß durch Ferrocen eine deutliche Vergleichmäßigung der Zyklusvariationen und damit günstige Bedingungen für Motorlauf und Kraftstoffausnutzung bewirkt wird.FIG. 8 and FIG. 9 show the pressure curve on a pressure-indicated 1-cylinder engine as a test engine, the family of curves shown in FIG. 8 representing approximately 30 combustion processes with ferrocene-additive fuel and the family of curves shown in FIG. 9 showing the corresponding courses without the addition of ferrocene under otherwise identical operating conditions. It can be seen that ferrocene brings about a clear equalization of the cycle variations and thus favorable conditions for engine running and fuel utilization.

Claims (3)

  1. Use of an unleaded liquid fuel containing 1 to 100 wt.-ppm ferrocene to operate an Otto engine with an exhaust-gas catalyst system for secondary combustion of the exhaust gas in order to reduce fuel consumption and exhaust gas emissions.
  2. Use according to claim 1, in which the fuel contains 5 to 20 wt.-ppm ferrocene.
  3. Use according to claim 1 or claim 2, in which the exhaustgas catalyst system is a regulated system built up on a loose-material or monolithic carrier with a coating made from a noble metal, an oxidic metal compound or a combination of both.
EP88121294A 1988-01-23 1988-12-20 Use of an unleaded liquid fuel containing ferrocen for operating a spark ignition engine Expired - Lifetime EP0325769B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88121294T ATE79393T1 (en) 1988-01-23 1988-12-20 USE OF A FERROCENE CONTAINING UNLEAD.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3801947A DE3801947A1 (en) 1988-01-23 1988-01-23 METHOD FOR OPERATING AN OTTO ENGINE
DE3801947 1988-01-23

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EP0325769A1 EP0325769A1 (en) 1989-08-02
EP0325769B1 true EP0325769B1 (en) 1992-08-12

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EP (1) EP0325769B1 (en)
AT (1) ATE79393T1 (en)
DE (2) DE3801947A1 (en)
DK (1) DK170715B1 (en)
ES (1) ES2034143T3 (en)
FI (1) FI103361B (en)
GR (1) GR3005483T3 (en)
NO (1) NO171415C (en)

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DK25789A (en) 1989-07-24
EP0325769A1 (en) 1989-08-02
NO885410D0 (en) 1988-12-06
US4955331A (en) 1990-09-11
FI885763A (en) 1989-07-24
DE3801947C2 (en) 1990-06-21
NO171415B (en) 1992-11-30
ATE79393T1 (en) 1992-08-15
FI103361B1 (en) 1999-06-15
DE3801947A1 (en) 1989-08-03
DK170715B1 (en) 1995-12-18
FI103361B (en) 1999-06-15
ES2034143T3 (en) 1993-04-01
DK25789D0 (en) 1989-01-20
FI885763A0 (en) 1988-12-13
NO885410L (en) 1989-07-24
DE3873732D1 (en) 1992-09-17
GR3005483T3 (en) 1993-05-24
NO171415C (en) 1993-03-10

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