EP0689577A1 - Use of ferrocene - Google Patents

Use of ferrocene

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Publication number
EP0689577A1
EP0689577A1 EP94911173A EP94911173A EP0689577A1 EP 0689577 A1 EP0689577 A1 EP 0689577A1 EP 94911173 A EP94911173 A EP 94911173A EP 94911173 A EP94911173 A EP 94911173A EP 0689577 A1 EP0689577 A1 EP 0689577A1
Authority
EP
European Patent Office
Prior art keywords
ferrocene
fuels
deposits
additive
engines
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
EP94911173A
Other languages
German (de)
French (fr)
Other versions
EP0689577B1 (en
Inventor
Walter Thuenker
Gabriele Lohmann
Arnim Marschewski
Tage Ib Nielsen
Christian Luetzen
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.)
Innospec Deutschland GmbH
Octel Manufacturing Europe GmbH
Dampskibsselskabet AF 1912 AS
Dampskibsselskabet Svendborg AS
Original Assignee
Chemische Betriebe Pluto GmbH
Dampskibsselskabet AF 1912 AS
Dampskibsselskabet Svendborg AS
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Publication date
Application filed by Chemische Betriebe Pluto GmbH, Dampskibsselskabet AF 1912 AS, Dampskibsselskabet Svendborg AS filed Critical Chemische Betriebe Pluto GmbH
Publication of EP0689577A1 publication Critical patent/EP0689577A1/en
Application granted granted Critical
Publication of EP0689577B1 publication Critical patent/EP0689577B1/en
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Classifications

    • 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
    • F02B77/00—Component parts, details or accessories, not otherwise provided for
    • F02B77/04—Cleaning of, preventing corrosion or erosion in, or preventing unwanted deposits in, combustion engines
    • 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)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • 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
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture

Definitions

  • the invention relates to the use of ferrocene and / or ferrocene derivatives as an additive to heavy-quality internal combustion engine fuels for high-compression, self-igniting engines.
  • Ferrocene and its derivatives are known from the literature. Ferrocene and its production were first described in Nature 168 (1951), page 1039. Since then, ferrocene and its derivatives as well as corresponding manufacturing processes have been the subject of numerous patents, e.g. B. US 2,650,756, US 2,769,828, US 2,834,796, US 2,898,360, US 3,035,968, US 3,238,158 and US 3,437,634.
  • ferrocene can promote combustion processes.
  • DE 34 18 648 also names ferrocene (dicyclopentadienyl iron) as a possible additive in order to optimize the combustion of heating oil, i. H. to facilitate the conveyance of the heating oil by the burner and to favor the complete combustion of the heating oil.
  • Diesel fuel is understood here to mean a fuel which is known as "No. 2 fuel oil” according to ASTM. Such a fuel is a middle distillate from the petroleum refining process and is available under the name "Diesel” at petrol stations. This means that the 4-stroke diesel engines of road vehicles are usually operated, eg cars, buses, trucks.
  • the named fuel corresponds to DIN 51601 and is similar in quality to the heating oil EL. It is therefore a light to medium quality fuel. For large engines with low speed, such as those used in ships or power generation plants, fuels of heavier quality are used.
  • the problem here is that downstream units are impaired in their function by carbon-containing deposits. Such units are in particular turbochargers and heat exchangers.
  • deposits on valves, piston rings and in the combustion chamber are also undesirable since they can lead to a reduction in engine performance and / or to increased wear on the parts concerned.
  • the object of the invention is to facilitate said deposits to minimize or remove them.
  • this object was achieved by using ferrocene and / or ferrocene derivatives as an additive to heavy-quality internal combustion engine fuels for high-compression, self-igniting engines.
  • a ferrocene additive has surprisingly proven to be particularly cheap. This applies above all to relatively large engines, ie those with a total output of 400 to 100,000, preferably 15,000 to 50,000, in particular more than 30,000 kW.
  • the fuels in question can, for example, be residues from atmospheric crude oil distillation, from vacuum distillation or from a catalytic cracker.
  • the density of these fuels is in particular in the range between 0.9 and 1.0 kg / dm 3 .
  • These fuels can be classified more precisely on the basis of ISO 82 17.
  • the fuels are divided into two classes, so-called distilled marine fuels (marine distillate fuels) and so-called heavy residual fuels.
  • the former are given a DM type designation and the latter an RM type designation.
  • 2-stroke engines Many marine engines of large ships suitable for high seas are 2-stroke engines.
  • the invention is particularly suitable for these. This is particularly true when it comes to slow-running motors that have a speed of 900 to 50, preferably 200 to 50 revolutions / min, in particular a maximum speed of 100 revolutions / min. and have less.
  • good results can also be achieved with the additives according to the invention, even in the case of faster running engines and also in the case of 4-stroke engines.
  • Good results have been achieved with a ferrocene additive of 1 to 100 ppm. When the additives are below 1 ppm, the effects are not so clear that one could speak of a significant improvement over a non-additive fuel.
  • the additives can e.g. B. done in that the additive is dissolved in part of the fuel and then this solution z. B. is fed back via a metering pump the main flow of fuel.
  • ferrocene derivatives can also be used, at least in part.
  • Ferrocene derivatives are compounds in which, starting from ferrocenes, there are further substituents on one or both cyclopentadienyl rings. Examples include ethylferrocene, butylferrocene, acetylferrocene and 2,2-bis-ethylferrocenylpropane.
  • the heavy quality from the fuel used but also the deposits originating from the lubricating oil are effectively reduced.
  • a number of problems can arise if the turbochargers are affected by deposits.
  • the effectiveness of the turbocharger and ultimately also of the entire machine is reduced, so that higher fuel consumption results.
  • the deposits can cause the speed to drop, in extreme cases, to the standstill of one or more blade wheels of the turbocharger.
  • the paddle wheels are supplied with exhaust gas from a common exhaust gas "receiver" which brings the exhaust gases from several cylinders together ... If the gas is distributed unevenly, due to the different flow resistance, which in turn is due to the deposit is dependent, a decrease in the speed, a fluctuation in the speed or a considerable speed difference between the coupled turbochargers or even a standstill can take place.
  • Such water washes of the heat exchanger or of the boiler are generally carried out at least every two years when the ship is in the dry dock for prescribed maintenance and inspection work. Between two dry dock stays, however, five to six additional washes are usually necessary. These can be dispensed with when using the present invention.
  • FIG. 1 schematically shows the exhaust gas path of a ship engine of the size mentioned.
  • the exhaust gases from 3 or 4 cylinders are brought together in a so-called exhaust gas receiver (3, 4, 5) and fed to the turbochargers (6, 7, 8).
  • the exhaust gas flows emerging from the turbochargers are brought together in an exhaust pipe (9) and then flow through a so-called exhaust gas "boiler” (10), in which heat exchangers (11, 12, 13) are generated by means of their high, medium and low pressure steam can be.
  • the exhaust gases leave the system via the chimney (14).
  • the invention was successfully tested on a container ship with the results reported below.
  • Displacement 10 cylinders a 1, 6m 3 speed: max. 90 rpm.
  • Turbocharger speed approx. 10,000 rpm.
  • Consumption approx. 6 t / h at full load

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Supercharger (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Output Control And Ontrol Of Special Type Engine (AREA)
  • Lubrication Of Internal Combustion Engines (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

Described is the use of ferrocene and/or ferrocene derivatives as an additive to heavy-grade fuels for high-compression, auto-ignition internal combustion engines. This measure reduces functional impairment resulting from sedimentation in downstream units.

Description

Patentanmeldung Patent application
Verwendung von FerrocenUse of ferrocene
Die Erfindung betrifft die Verwendung von Ferrocen und/oder Ferrocenderivaten als Zusatz (Additiv) zu Verbrennungsmotor-Kraftstoffen schwerer Qualität für hochver¬ dichtende, selbstzündende Motoren.The invention relates to the use of ferrocene and / or ferrocene derivatives as an additive to heavy-quality internal combustion engine fuels for high-compression, self-igniting engines.
Ferrocen und seine Derivate sind aus der Literatur bekannt. Ferrocen und seine Herstellung wurden erstmals in Nature 168 (1951 ), Seite 1039 beschrieben. Seitdem sind Ferrocen und seine Derivate sowie entsprechende Herstellungsverfahren Ge¬ genstand zahlreicher Patente gewesen, z. B. US 2 650 756, US 2 769 828, US 2 834 796, US 2 898 360, US 3 035 968, US 3 238 158 und US 3 437 634.Ferrocene and its derivatives are known from the literature. Ferrocene and its production were first described in Nature 168 (1951), page 1039. Since then, ferrocene and its derivatives as well as corresponding manufacturing processes have been the subject of numerous patents, e.g. B. US 2,650,756, US 2,769,828, US 2,834,796, US 2,898,360, US 3,035,968, US 3,238,158 and US 3,437,634.
Es ist ebenfalls aus der Patentliteratur bekannt, daß Ferrocen Verbrennungspro¬ zesse begünstigen kann. Die DE 34 18 648 nennt neben vielen anderen Verbindun¬ gen auch Ferrocen (Dicyclopentadienyleisen) als ein mögliches Additiv, um die Ver¬ brennung von Heizöl zu optimieren, d. h. die Förderung des Heizöls durch den Brenner zu erleichtern und die vollständige Verbrennung des Heizöls zu begünsti¬ gen.It is also known from the patent literature that ferrocene can promote combustion processes. In addition to many other compounds, DE 34 18 648 also names ferrocene (dicyclopentadienyl iron) as a possible additive in order to optimize the combustion of heating oil, i. H. to facilitate the conveyance of the heating oil by the burner and to favor the complete combustion of the heating oil.
In der US 4 389 220 ist ein Verfahren zur Konditionierung eines Dieselmotors be¬ schrieben. Hierzu werden dem Dieselkraftstoff 20 bis 30 ppm Ferrocen zugefügt. Dadurch sollen kohlenstoffhaltige Ablagerungen im Verbrennungsraum entfernt und deren Neubildung vermieden werden. Gleichzeitig wurde gefunden, daß durch diese Maßnahmen der Kraftstoffverbrauch pro gefahrene Strecke bis zu 5 % geringer ist. Unter Dieselkraftstoff wird hier ein Kraftstoff verstanden, der nach ASTM als "No. 2 fuel oil" bekannt ist. Ein derartiger Kraftstoff ist ein Mitteldestillat des Erdölraffinerie- prozesses und ist unter der Bezeichnung "Diesel" an Tankstellen erhältlich. Damit werden üblicherweise die 4-Takt-Dieselmotoren von Straßenfahrzeugen betrieben z.B. PKW, Busse, LKW. Der genannte Kraftstoff entspricht der DIN 51601 und ist in seiner Qualität ähnlich dem Heizöl EL. Er ist somit ein Kraftstoff leichter bis mittlerer Qualität. Für große Motoren mit niedriger Drehzahl, wie sie z.B. in Schiffen oder Stromerzeu¬ gungsanlagen verwendet werden, werden Kraftstoffe schwererer Qualität verwendet. Hier besteht das Problem, daß nachgeschaltete Aggregate in ihrer Funktion durch kohlenstoffhaltige Ablagerungen beeinträchtigt werden. Derartige Aggregate sind insbesondere Turbolader sowie Wärmeaustauscher. Aber auch Ablagerungen an Ventilen, Kolbenringen sowie im Verbrennungsraum sind unerwünscht, da sie zu ei¬ ner Minderung der Motorleistung und/oder zu einem erhöhten Verschleiß der betrof¬ fenen Teile führen können.A method for conditioning a diesel engine is described in US Pat. No. 4,389,220. For this purpose, 20 to 30 ppm ferrocene are added to the diesel fuel. This is intended to remove carbon-containing deposits in the combustion chamber and to prevent them from forming again. At the same time, it was found that these measures reduce fuel consumption by up to 5% per route traveled. Diesel fuel is understood here to mean a fuel which is known as "No. 2 fuel oil" according to ASTM. Such a fuel is a middle distillate from the petroleum refining process and is available under the name "Diesel" at petrol stations. This means that the 4-stroke diesel engines of road vehicles are usually operated, eg cars, buses, trucks. The named fuel corresponds to DIN 51601 and is similar in quality to the heating oil EL. It is therefore a light to medium quality fuel. For large engines with low speed, such as those used in ships or power generation plants, fuels of heavier quality are used. The problem here is that downstream units are impaired in their function by carbon-containing deposits. Such units are in particular turbochargers and heat exchangers. However, deposits on valves, piston rings and in the combustion chamber are also undesirable since they can lead to a reduction in engine performance and / or to increased wear on the parts concerned.
Aufgabe der Erfindung ist es, die genannten Ablagerungen zu minimierem bzw. de¬ ren Entfernung zu erleichtern.The object of the invention is to facilitate said deposits to minimize or remove them.
Erfindungsgemäß wurde diese Aufgabe gelöst durch die Verwendung von Ferrocen und/oder Ferrocenderivaten als Zusatz (Additiv) zu Verbrennungsmotor-Kraftstoffen schwerer Qualität für hochverdichtende, selbstzündende Motoren.According to the invention, this object was achieved by using ferrocene and / or ferrocene derivatives as an additive to heavy-quality internal combustion engine fuels for high-compression, self-igniting engines.
Gerade beim Betreiben solcher großen Motoren mit schwerenTreibstoffen hat sich eine Ferrocen-Additivierung überraschenderweise als besonders günstig erwiesen. Dies gilt vor allen Dingen für relativ große Motoren, also solche mit einer Gesamt- leistung von 400 bis 100 000, vorzugsweise 15 000 bis 50 000, insbesondere mehr als 30.000 kW.Especially when operating such large engines with heavy fuels, a ferrocene additive has surprisingly proven to be particularly cheap. This applies above all to relatively large engines, ie those with a total output of 400 to 100,000, preferably 15,000 to 50,000, in particular more than 30,000 kW.
Je schwerer der Kraftstoff, desto eher ergeben sich in der Regel Probleme mit den genannten Ablagerungen. Bei diesen Kraftstoffen hat sich überraschend eine Addi- tivierung mit Ferrocen als besonders wirksam heraus gestellt. Dies war umso weni¬ ger zu erwarten gewesen als bekannt war, daß Ferrocen sehr wirksam bei der Ver¬ brennungsverbesserung von leichtem Heizöl aber weniger wirksam bei schwerem Heizöl ist.The heavier the fuel, the more likely there are problems with the deposits mentioned. Additization with ferrocene has surprisingly been found to be particularly effective with these fuels. This was all the less to be expected since it was known that ferrocene is very effective in improving the combustion of light heating oil but less effective in the case of heavy heating oil.
Insbesondere für Qualitäten, die üblicherweise als Marine-Heizöl, "Bunker C"-Quali- tät, Marine-Dieselkraftstoff bzw. dest. Marine-Dieselkraftstoff bezeichnet werden, ist die erfindungsgemäße Verwendung vorteilhaft. Wie anhand der Namen der Treib¬ stoffqualitäten unschwer erkennbar, werden diese hauptsächlich zum Betreiben von -mahnen Motoren verwendet. Die in Frage kommenden Kraftstoffe können beispielsweise Rückstände aus der at¬ mosphärischen Rohöldestillation, aus der Vakuumdestillation oder aus einem kata- lytischen Cracker sein. Die Dichte dieser Kraftstoffe liegt insbesondere im Bereich zwischen 0,9 und 1 ,0 kg/dm3. Genauer klassifizieren lassen sich diese Kraftstoffe anhand der ISO 82 17. Die Kraftstoffe werden dort in zwei Klassen, sogenannte destillierte Marine-Kraftstoffe (Marine Destillate Fuels) und sogenannte schwere Rückstandskraftstoffe (Heavy Residual Fuels) unterschieden. Erstere erhalten eine DM-Typenbezeichnung und letztere eine RM-Typenbezeichnung. Einige Typen sind nachstehend exemplarisch mit ihren wichtigsten Eigenschaften wie Dichte, Viskosi¬ tät, Schwefelgehalt und Kohlenstoffrückstand aufgeführt.In particular for qualities that are usually used as marine heating oil, "bunker C" quality, marine diesel fuel or dest. Are referred to marine diesel fuel, the use according to the invention is advantageous. As can easily be seen from the names of the fuel qualities, these are mainly used to operate dunning engines. The fuels in question can, for example, be residues from atmospheric crude oil distillation, from vacuum distillation or from a catalytic cracker. The density of these fuels is in particular in the range between 0.9 and 1.0 kg / dm 3 . These fuels can be classified more precisely on the basis of ISO 82 17. The fuels are divided into two classes, so-called distilled marine fuels (marine distillate fuels) and so-called heavy residual fuels. The former are given a DM type designation and the latter an RM type designation. Some types are listed below by way of example with their most important properties such as density, viscosity, sulfur content and carbon residue.
DMB DMC RMA RMG RMH 10 35 45DMB DMC RMA RMG RMH 10 35 45
Dichte kg/dm3 0,90 0,92 0,95 0,991 1 ,010 max. kinematische Viskosität cSt bei 40 °C 11 ,0 14,0 bei 100 °C 10 35 45Density kg / dm3 0.90 0.92 0.95 0.991 1, 010 max. kinematic viscosity cSt at 40 ° C 11, 0 14.0 at 100 ° C 10 35 45
max. Kohlenstoffrückstand Gew.-% 0,25 2,5 12 18 22Max. Carbon residue wt% 0.25 2.5 12 18 22
max. Schwefel-Gehalt Gew.-% 2,0 2,0 3,5 5,0 5,0Max. Sulfur content wt% 2.0 2.0 3.5 5.0 5.0
Alle DM- und RM-Typen sind im Sinne der vorliegenden Erfindung als Kraftstoffe einsetzbar.All DM and RM types can be used as fuels in the sense of the present invention.
Viele Schiffsmotoren von hochseetauglichen Großschiffen sind 2-Takt-Motoren. Für diese ist die Erfindung in besonderem Maß geeignet. Dies trifft insbesondere dann zu, wenn es sich um langsam laufende Motoren handelt, die eine Drehzahl von 900 bis 50, vorzugsweise 200 bis 50 Umdrehungen/min, insbesondere eine maximale Drehzahl von 100 Umdrehungen/min. und weniger aufweisen. Allerdings lassen sich auch bei schneller laufenden Motoren wie auch bei 4-Takt-Motoren gute Ergebnisse durch die erfindungsgemäße Additivierung erzielen. Gute Ergebnisse wurden mit einer Ferrocenadditivierung von 1 bis 100 ppm erzielt. Bei einer Additivierung unter 1 ppm sind die Effekte nicht so deutlich, daß man von einer wesentlichen Verbesserung gegenüber einem nicht additivierten Kraftstoff sprechen könnte. Bei einem Additivgehalt über 100 ppm ist eine Grenze erreicht, bei der eine zusätzliche Additivierung keine nennenswerten zusätzlichen Effekte be¬ wirkt. In der Regel wird ein Bereich von 5 bis 50 ppm bevorzugt. Ein optimaler Be¬ reich liegt zwischen 10 bis 30 ppm. Die Additivierung kann z. B. dadurch erfolgen, daß das Additiv in einem Teil des Kraftstoffes gelöst wird und diese Lösung dann z. B. über eine Dosierpumpe dem Hauptstrom des Kraftstoffes wieder zugeführt wird.Many marine engines of large ships suitable for high seas are 2-stroke engines. The invention is particularly suitable for these. This is particularly true when it comes to slow-running motors that have a speed of 900 to 50, preferably 200 to 50 revolutions / min, in particular a maximum speed of 100 revolutions / min. and have less. However, good results can also be achieved with the additives according to the invention, even in the case of faster running engines and also in the case of 4-stroke engines. Good results have been achieved with a ferrocene additive of 1 to 100 ppm. When the additives are below 1 ppm, the effects are not so clear that one could speak of a significant improvement over a non-additive fuel. With an additive content of more than 100 ppm, a limit is reached at which an additional additive has no significant additional effects. Typically a range of 5 to 50 ppm is preferred. An optimal range is between 10 to 30 ppm. The additives can e.g. B. done in that the additive is dissolved in part of the fuel and then this solution z. B. is fed back via a metering pump the main flow of fuel.
Anstelle von Ferrocen können zumindest teilweise auch Ferrocenderivate eingesetzt werden. Ferrocenderivate sind solche Verbindungen, bei denen ausgehend von Fer- rocengrundkörper sich an einem oder beiden Cyclopentadienyl-Ringen weitere Sub- stituenten befinden. Als Beispiele seien genannt Ethylferrocen, Butylferrocen, Ace- tylferrocen und 2,2-bis-Ethylferrocenylpropan.Instead of ferrocene, ferrocene derivatives can also be used, at least in part. Ferrocene derivatives are compounds in which, starting from ferrocenes, there are further substituents on one or both cyclopentadienyl rings. Examples include ethylferrocene, butylferrocene, acetylferrocene and 2,2-bis-ethylferrocenylpropane.
Erfindungsgemäß werden die aus dem eingesetzten Kraftstoff schwerer Qualität aber auch die aus dem Schmieröl stammenden Ablagerungen wirksam reduziert.According to the invention, the heavy quality from the fuel used but also the deposits originating from the lubricating oil are effectively reduced.
Durch die Ablagerungen werden die nachgeschalteten Aggregate wie Turbolader und Wärmetauscher als auch Motorteile wie Ventile und Kolbenringe teilweise in er¬ heblichem Umfang in ihrer Funktionsweise beeinträchtigt. Um die Ablagerungen zu entfernen, muß oftmals erheblicher Aufwand getrieben werden. So ist es z.B. bei hochseetüchtigen Großschiffen üblich, zur Reinigung der nachgeschalteten Turbo- lader zerkleinerte Nußschalen oder auch Reis in den Abgasstrom einzublasen. Durch dieses sogenannte "softblasting" werden die Schaufelräder als auch der vor¬ geschaltete Dύsenring von dem größten Teil der Ablagerungen befreit. Diese Pro¬ zedur wird üblicherweise täglich, bei Bedarf sogar zweimal am Tag durchgeführt und zwar bei voller Motorlast. Meistens ist jedoch diese Art der Reinigung nicht ausrei- chend. Deshalb wird zusätzlich etwa einmal pro Monat oder bei Bedarf auch öfter eine Wasserwäsche vorgenommen. Da diese Wäsche bei reduzierter Motorlast durchgeführt wird, ist damit auch immer ein Zeitverlust für das Schiff verbunden. Bei der Wäsche wird durch eine Düse Wasser vor dem Düsenring und den Schaufelrä¬ dern in den Abgasstrom eingeleitet. Diese Wasserwäsche bedeutet eine hohe Be- lastung für den Turbolader u. a. durch die thermische Schockwirkung. Deshalb wird versucht diese Wasserwäsche auf ein Minimum zu beschränken. Der normale Zeit¬ bedarf für eine solche Wäsche beträgt etwa 2 bis 3 Std.. Man orientiert sich dabei einfach an der Sauberkeit des Wassers nach den Spülvorgängen. Dabei ist übli¬ cherweise das Waschwasser 1 bis 2 Std. lang deutlich erkennbar stark verschmutzt. Durch die erfindungsgemäße Verwendung von Ferrocen-additiviertem Kraftstoff wird sowohl das "softblasting" als auch die Wasserwäsche im allgemeinen überflüssig. Das schont die betroffenen Aggregate ohne Funktionseinschränkung und spart Zeit und Arbeit.The function of the downstream units, such as turbochargers and heat exchangers, as well as engine parts, such as valves and piston rings, is impaired to a considerable extent by the deposits. In order to remove the deposits, considerable effort is often required. For example, in large ocean-going ships it is customary to blow crushed nut shells or rice into the exhaust gas stream to clean the downstream turbocharger. This so-called "softblasting" removes most of the deposits from the paddle wheels and the upstream nozzle ring. This procedure is usually carried out daily, if necessary even twice a day, with full engine load. In most cases, however, this type of cleaning is not sufficient. For this reason, water is washed in addition about once a month or more often if necessary. Since this washing is carried out with a reduced engine load, there is always a loss of time for the ship. During washing, water is introduced into the exhaust gas stream through a nozzle in front of the nozzle ring and the paddle wheels. This water wash means a high load for the turbocharger, among other things due to the thermal shock effect. That is why tries to keep this water wash to a minimum. The normal time required for such washing is about 2 to 3 hours. You simply orient yourself on the cleanliness of the water after the rinsing processes. The wash water is usually clearly soiled for 1 to 2 hours. The use of ferrocene-additized fuel according to the invention generally makes both "soft blasting" and water washing superfluous. This protects the affected units without functional restrictions and saves time and work.
Wenn die Turbolader durch Ablagerungen in ihrer Funktionsweise beinträchtigt sind, können eine Reihe von Problemen auftreten. Die Effektivität der Turbolader und damit letztendlich auch der gesamten Maschine verringert sich, so daß ein höherer Kraftstoffverbrauch resultiert. Durch die Ablagerungen kann es zu einem Absinken der Drehzahl, in Extremfällen bis zum Stillstand eines oder mehrerer Schaufelräder des Turboladers kommen. Bei Maschinen mit Mehrfachturboladern werden die Schaufelräder mit Abgas aus einem gemeinsamen Abgas-"receiver", der die Abgase aus mehreren Zylindern zusammenführt, versorgt... Wenn das Gas ungleichmäßig verteilt wird, bedingt durch den unterschiedlichen Strömungswiderstand, der wie¬ derum durch die Ablagerung bedingt ist, so kann ein Absinken in der Drehzahl, ein Schwanken der Drehzahl bzw. eine erhebliche Drehzahldifferenz zwischen den ge¬ koppelten Turboladern oder gar ein Stillstand erfolgen. Die vorgenannten auf Abla¬ gerungen zurückzuführenden Probleme können zu einer vorzeitigen Materialermü¬ dung bzw. im Extremfall zu Materialbruch führen. Bei besonders starken Ablagerun¬ gen kann dies ebenfalls bei kleineren Maschinen auftreten, die nicht mit Mehrfach- turbolader ausgestattet sind. Unregelmäßigkeiten in der Drehzahl, also unregelmä¬ ßiger Lauf, kann zu sehr starken Vibrationen führen, die bereits nach kurzer Zeit an Lagern und anderen Maschinenteilen zu Materialschäden führen können.A number of problems can arise if the turbochargers are affected by deposits. The effectiveness of the turbocharger and ultimately also of the entire machine is reduced, so that higher fuel consumption results. The deposits can cause the speed to drop, in extreme cases, to the standstill of one or more blade wheels of the turbocharger. In machines with multi-turbochargers, the paddle wheels are supplied with exhaust gas from a common exhaust gas "receiver" which brings the exhaust gases from several cylinders together ... If the gas is distributed unevenly, due to the different flow resistance, which in turn is due to the deposit is dependent, a decrease in the speed, a fluctuation in the speed or a considerable speed difference between the coupled turbochargers or even a standstill can take place. The aforementioned problems attributable to deposits can lead to premature material fatigue or, in extreme cases, to material breakage. In the case of particularly strong deposits, this can also occur in the case of smaller machines which are not equipped with multiple turbochargers. Irregularities in the rotational speed, that is to say irregular running, can lead to very strong vibrations which, after a short time, can lead to material damage to bearings and other machine parts.
Ungleichmäßige Ablagerungen an den Schaufelrädern führen zwar nicht unbedingt zu einem Absinken der Drehzahl bzw. zu Drehzahldifferenzen bei Mehrfachturbola¬ dern aber durch unrunden Lauf ebenfalls zu unerwünschten Vibrationen, die auch Ursache für einen erhöhten Verschleiß sein können.Uneven deposits on the paddle wheels do not necessarily lead to a drop in the speed or to speed differences in multiple turbochargers, but also to undesired vibrations due to non-circular running, which can also be the cause of increased wear.
Auch in den nachgeschalteten Wärmaustauschem ist ohne die erfindungsgemäße Additivierung festzustellen, daß sich an den Wärmeaustauscherflächen Ablagerun- gen bilden, die in Abhängigkeit von ihrer Stärke den Wärmeaustausch behindern. Auch diese überwiegend Ruß enthaltenen Ablagerungen müssen von Zeit zu Zeit durch eine Wasserwäsche, ggf. mit reinigenden Zusätzen, z. B. CuC.2-Lösung, ent¬ fernt werden. Durch die erfindungsgemäße Verwendung ferrocenadditivierter Kraft- Stoffe wird die Bildung von Ablagerungen sehr stark herabgesetzt. Wird nach einem, im Gegensatz zum bisherigen Stand der Technik, wesentlich längeren Zeitraum doch eine Wasserwäsche notwendig (z. B. im Trockendock), so wurde überraschen¬ derweise festgestellt, daß sich die Ablagerungen nach Betrieb mit erfindungsgemäß additiviertem Kraftstoff wesentlich leichter entfernen lassen. Dies ist möglicherweise auf eine geänderte Zusammensetzung der Ablagerungen zurückzuführen. Es wurde festgestellt, daß diese im Gegensatz zu einem Betrieb mit nicht additiviertem Kraft¬ stoff höhere Aschegehalte, niedrigere Heizwerte und einen niedrigeren Kohlen¬ stoffgehalt aufweisen. Es kann vermutet werden, daß diese Ablagerungen weniger hydrophob sind, da sie weniger ölige oder Öl-ähnliche Komponenten enthalten.Even in the downstream heat exchangers, it can be determined without the additives according to the invention that deposits form on the heat exchanger surfaces. form conditions that, depending on their strength, hinder heat exchange. These deposits, which mainly contain soot, must be washed from time to time with water, if necessary with cleaning additives, e.g. B. CuC.2 solution, be removed. The use of ferrocene-additive fuels according to the invention greatly reduces the formation of deposits. If, in contrast to the prior art, a considerably longer period of time does require water washing (e.g. in a dry dock), it was surprisingly found that the deposits can be removed much more easily after operation with fuel which has been additized according to the invention. This may be due to a change in the composition of the deposits. It was found that, in contrast to operation with non-additized fuel, these have higher ash contents, lower calorific values and a lower carbon content. It can be assumed that these deposits are less hydrophobic because they contain less oily or oil-like components.
Solche Wasserwäschen der Wärmeaustauscher bzw. des Boilers werden in der Re¬ gel spätestens alle zwei, Jahre durchgeführt, wenn sich das Schiff zu vorgeschrie- benen Wartungs- und Inspektionsarbeiten im Trockendock befindet. Zwischen zwei Trockendockaufenthalten sind jedoch normalerweise fünf bis sechs zusätzliche Wäschen notwendig. Diese können bei Anwendung der vorliegenden Erfindung entfallen.Such water washes of the heat exchanger or of the boiler are generally carried out at least every two years when the ship is in the dry dock for prescribed maintenance and inspection work. Between two dry dock stays, however, five to six additional washes are usually necessary. These can be dispensed with when using the present invention.
Beschreibung von Figur 1Description of Figure 1
Figur 1 zeigt schematisch den Abgasweg eines Schiffsmotors der genannten Grö¬ ßenordnung. Zu sehen ist der Motorblock (1) mit seinen insgesamt 10 Zylindern (2). Die Abgase aus jeweils 3 bzw. 4 Zylindern werden in einem sogenannten Abgas "Receiver" (3, 4, 5) zusammengeführt und den Turboladern (6, 7, 8) zugeführt. Die aus den Turboladern austretenden Abgasströme werden in einer Abgasleitung (9) zusammengeführt und strömen dann durch einen sogenannten Abgas-"Boiler" (10), in welchem sich Wärmeaustauscher befinden (11, 12, 13) mittels deren Hoch- Mittel- und Niederdruckdampf erzeugt werden kann. Die Abgase verlassen das System über den Schornstein (14). Die Erfindung wurde auf einem Containerschiff mit den nachfolgend mitgeteilten Er¬ gebnissen erfolgreich getestet.FIG. 1 schematically shows the exhaust gas path of a ship engine of the size mentioned. You can see the engine block (1) with its total of 10 cylinders (2). The exhaust gases from 3 or 4 cylinders are brought together in a so-called exhaust gas receiver (3, 4, 5) and fed to the turbochargers (6, 7, 8). The exhaust gas flows emerging from the turbochargers are brought together in an exhaust pipe (9) and then flow through a so-called exhaust gas "boiler" (10), in which heat exchangers (11, 12, 13) are generated by means of their high, medium and low pressure steam can be. The exhaust gases leave the system via the chimney (14). The invention was successfully tested on a container ship with the results reported below.
Technische Daten des Schiffes: 60.000 BRTTechnical data of the ship: 60,000 GRT
Technische Daten der Maschine Leistung: 33.000 kWTechnical data of the machine Power: 33,000 kW
Hubraum: 10 Zylinder a 1 ,6m3 Drehzahl: max. 90 U/min.Displacement: 10 cylinders a 1, 6m 3 speed: max. 90 rpm.
Drehzahl Turbolader: ca. 10 000 U/min. Verbrauch: ca. 6 t/h bei VollastTurbocharger speed: approx. 10,000 rpm. Consumption: approx. 6 t / h at full load
Nach erfolgreicher Anfahrphase wurden die Turbolader der Maschine dieses Schif- fes gründlich durch "softblasting" und Wasserwäsche gereinigt. Etwa 3 Monate später wurde, ohne daß zwischenzeitliche Reinigungen vorgenommen wurden, eine Wasserwäsche durchgeführt. Diese Wasserwäsche war zwar technisch nicht not¬ wendig, da die Turbolader zufriedenstellend arbeiteten, wurde aber durchgeführt, um Aufschluß über den Verschmutzungsgrad (Ablagerungen) zu gewinnen. Wäh- rend nach dem bisherigen Stand der Technik täglich ein "softblasting" und etwa einmal monatlich eine Wasserwäsche durchgeführt werden mußten und bei dieser das gebrauchte Waschwasser 1 bis 2 Std. lang stark verschmutzt war, wurde hier fast 3 Monate (85 Tage) auf jegliche Reinigungsmaßnahme verzichtet und trotzdem war das Waschwasser von Beginn an klar. Dieses läßt darauf schließen, daß sich in dem genannten Zeitraum praktisch keine Ablagerungen gebildet haben. Selbst Stellen, die mit den sonst üblichen Reinigungsmethoden nicht erreichbar sind, zeig¬ ten keine oder deutlich reduzierte Schmutzbeläge.After a successful start-up phase, the turbochargers of the machine of this ship were thoroughly cleaned by "softblasting" and water washing. About 3 months later, water was washed without any intermediate cleaning. This water washing was technically not necessary since the turbochargers worked satisfactorily, but was carried out in order to obtain information about the degree of contamination (deposits). Whereas according to the current state of the art a "softblasting" and a water wash had to be carried out daily and about once a month and the used wash water was heavily soiled for 1 to 2 hours, almost 3 months (85 days) was applied here to everyone Cleaning measures were dispensed with, and yet the wash water was clear from the start. This suggests that practically no deposits have formed in the period mentioned. Even spots that cannot be reached with the usual cleaning methods showed no or significantly reduced dirt deposits.
Bei den Wärmeausstauschern war schon visuell festzustellen, daß sich deutlich weniger Ablagerungen gebildet hatten. Die gebildeten Ablagerungen ließen sich we¬ sentlich einfacher und schneller als bisher durch Wasserwäsche entfernen.With the heat exchangers it was already possible to visually determine that significantly fewer deposits had formed. The deposits formed could be removed much more easily and quickly than before by water washing.
Auch an den Kolbenringen und Ventilen waren visuell keine Ablagerungen zu er¬ kennen. There were also no visible deposits on the piston rings and valves.

Claims

Patentansprüche Claims
1 . Verwendung von Ferrocen und/oder Ferrocenderivaten als Zusatz (Additiv) zu Verbrennungsmotor-Kraftstoffen schwerer Qualität, insbeson¬ dere mit einer Dichte von 0,9 bis 1 ,01 kg/dm3 für hochverdichtende, selbstzündende Motoren.1 . Use of ferrocene and / or ferrocene derivatives as an additive to heavy-duty internal combustion engine fuels, in particular with a density of 0.9 to 1.01 kg / dm3 for high-compression, self-igniting engines.
2. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, daß die additi- vierten Kraftstoffe zum Betreiben von Motoren mit einer Gesamtleistung von 400 bis 100 000, vorzugsweise 15.000 bis 50 000 kW eingesetzt , werden.2. Use according to claim 1, characterized in that the additive fuels are used to operate engines with a total output of 400 to 100,000, preferably 15,000 to 50,000 kW.
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die additivierten Kraftstoffe zum Betreiben von 2-Takt- Motoren eingesetzt werden.3. Use according to claim 1 or 2, characterized in that the additized fuels are used to operate 2-stroke engines.
4. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die additivierten Kraftstoffe zum Betreiben von 4-Takt- Motoren eingesetzt werden.4. Use according to claim 1 or 2, characterized in that the additive fuels are used to operate 4-stroke engines.
5. Verwendung nach mindestens einem der vorstehenden Ansprüche, da¬ durch gekennzeichnet, daß die additivierten Kraftstoffe zum Betreiben von langsam laufenden Motoren mit einer Drehzahl von 900 bis 50, vorzugs- weise 200 bis 50 U/min eingesetzt werden.5. Use according to at least one of the preceding claims, characterized in that the additive fuels are used to operate slow-running engines at a speed of 900 to 50, preferably 200 to 50 rpm.
6. Verwendung nach mindestens einem der vorstehenden Ansprüche da¬ durch gekennzeichnet, daß der Additivgehalt der Kraftstoffe 1 bis 100 ppm, insbesondere 5 bis 50 ppm, vorzugsweise 10 bis 30 ppm beträgt. 6. Use according to at least one of the preceding claims, characterized in that the additive content of the fuels is 1 to 100 ppm, in particular 5 to 50 ppm, preferably 10 to 30 ppm.
EP94911173A 1993-03-20 1994-03-15 Use of ferrocene Expired - Lifetime EP0689577B1 (en)

Applications Claiming Priority (3)

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DE4309066 1993-03-20
PCT/EP1994/000803 WO1994021755A2 (en) 1993-03-20 1994-03-15 Use of ferrocene

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JPH08508763A (en) 1996-09-17
WO1994021755A2 (en) 1994-09-29
NO953659L (en) 1995-09-15
JP3599337B2 (en) 2004-12-08
KR100274093B1 (en) 2000-12-15
PL310675A1 (en) 1995-12-27
DE4309066C2 (en) 1995-07-20
NO309777B1 (en) 2001-03-26
ES2099600T3 (en) 1997-05-16
NZ263179A (en) 1996-11-26
AU677388B2 (en) 1997-04-24
GR3023491T3 (en) 1997-08-29
DK0689577T3 (en) 1997-03-17
BR9405903A (en) 1995-12-26
PL177895B1 (en) 2000-01-31
DE4309066A1 (en) 1994-09-22
AU6377294A (en) 1994-10-11
FI954422A (en) 1995-09-19
WO1994021755A3 (en) 1994-12-08
CN1052034C (en) 2000-05-03
IS4140A (en) 1994-09-21
ZA941941B (en) 1995-01-16
CA2156747A1 (en) 1994-09-29
FI954422A0 (en) 1995-09-19
NO953659D0 (en) 1995-09-15
SG48900A1 (en) 1998-05-18
FI119551B (en) 2008-12-31
EP0689577B1 (en) 1997-02-26
IS1813B (en) 2002-07-08
CA2156747C (en) 2005-06-07
DE59401861D1 (en) 1997-04-03

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