JPH08508763A - Use of ferrocene - Google Patents

Abstract

(57) Summary The use of ferrocene and / or ferrocene derivatives as additives to heavy fuels for high compression, self-igniting internal combustion engines is described. This approach reduces depositional dysfunction in downstream units.

Description

FIELD OF THE INVENTION The present invention relates to the use of ferrocene and / or ferrocene derivatives as additives in heavy quality fuels for high compression, autoignition internal combustion engines. Ferrocene and its derivatives are well known in the literature. Ferrocene and its manufacture were first described in Nature 168 (1951), page 1039. Since then, ferrocene and its derivatives and the corresponding production processes have been the subject of numerous patents. For example, U.S. Pat.No. 2 650 756, U.S. Pat.No. 2 769 828, U.S. Pat.No. 2 834 769, U.S. Pat.No. 2 898 360, U.S. Pat.No. 3 035 968 , U.S. Pat. No. 3,238,158 and U.S. Pat. No. 3,437,634. It is likewise known from patent publications that ferrocene makes the combustion process desirable. German patent 34 18 648, in addition to many other compounds, is for optimizing the combustion of fuel oil, that is, facilitating the supply of fuel oil through the burner and ensuring complete combustion of the fuel oil. To make it desirable, ferrocene (dicyclopentadienyl iron) is mentioned as one possible additive. U.S. Pat. No. 4,389,220 discloses a method for conditioning a diesel engine. To do this, add 20-30 ppm of ferrocene to the diesel fuel. As a result, the carbon-containing deposit in the combustion chamber is removed, and formation of a new deposit is prevented. At the same time, it has been found that this measure reduces the fuel consumption per run by about 5%. Dezel fuel is a fuel known by AS ™ as "second fuel oil". This type of fuel is a middle distillate from the refining process of mineral oil and is available at gas stations under the name "diesel". This drives a four-cycle diesel engine on ordinary road vehicles, such as passenger cars, buses and trucks. The fuel corresponds to German Industrial Standard DIN 51601 and is similar in quality to fuel oil EL. Therefore, it is a light to medium quality fuel. Heavy fuel is used in low speed, large engines such as those used in ships or power generation equipment. Here, there is the problem that subsequent functional units are adversely affected by their carbon-containing deposits. Functional units of this kind are, in particular, turbochargers and heat exchangers. Deposits on valves, piston rings and in the combustion chamber are also undesirable. This is because the engine output decreases and / or the parts wear more. An object of the present invention is to minimize the above-mentioned deposits and facilitate their removal. The above problems have been solved by the present invention by the use of ferrocene and / or ferrocene derivatives as additives to the fuel of heavy-duty internal combustion engines for high compression, auto-ignition engines. The addition of ferrocene is surprisingly effective when driving such large engines that use heavy fuel. This applies above all to relatively large engines, that is to say engines with a total power output of 400 to 100 000, preferably 15 000 to 50 000, in particular 30,000 kW or more. The heavier the fuel, the more pronounced the problems with deposits described above will be. With these fuels, the addition of ferrocene unexpectedly becomes particularly effective. It is known that ferrocene is very effective at improving the combustion of light fuel oils, but less effective at heavier fuel oils. In particular, the use according to the invention is advantageous for marine fuel oil, "Bunker C" quality, quality commonly referred to as marine diesel fuel or distilled marine diesel fuel. It is mainly used to drive marine engines, as it is difficult to identify by the name of fuel quality. The fuel in question may be, for example, atmospheric crude oil distillation, vacuum distillation or residues from catalytic cracking. The density of this fuel lies especially in the range 0.9 to 1.0 kg / dm ³ . This fuel can be classified more accurately according to ISO 8217. Fuels are divided therein into two classes: so-called distilled desiccant fuels (Marine Desidual Fuels) and so-called heavy residual fuels. The former is called DM type and the latter is called RM type. Some types are illustratively described below along with important properties such as density, viscosity, sulfur content and carbon residue. All DM and RM types can be used as fuels within the meaning of this invention. Many large ship engines used for ocean voyages are two-stroke engines. The invention is particularly suitable for the above. This is especially true when dealing with slow engine speeds of 900 to 50 revolutions per minute, mainly 200 to 50 revolutions per minute, and especially less than 100 revolutions per minute. However, good results are obtained with the additive according to the invention even on fast engines such as in the case of 4-cycle engines. Good results are obtained with 1-100 ppm ferrocene. At 1 ppm or less of additive, this effect is not so remarkable that it is significantly improved as compared with the fuel without addition. Additives of 100 ppm or more have reached the limit of insignificant effects even if added further. Usually, the range of 5 to 50 ppm is desirable. The optimum range is between 10 and 30 ppm. The addition is carried out, for example, by dissolving the additive in a part of the fuel and introducing this solution into the main stream of the fuel by, for example, a metering pump. Instead of ferrocene, at least partly a ferrocene derivative can also be adopted. Ferrocene derivatives are compounds in which one or two cyclopentadienyl rings have other substitutions, starting from the ferrocene body. Examples are ethyl ferrocene, butyl ferrocene, acetyl ferrocene and ethyl ferrocenyl propane up to 2.2. According to the present invention, the deposits of the lubricating oil from the heavy fuel used can be effectively reduced. Due to the deposits, subsequent functional units such as turbochargers and heat exchangers and engine parts such as valves and piston rings are also affected in part on a large scale. The chopsticks must be expensive to remove the deposits. Thus, for example, on a large ocean-going vessel, finely-divided nut nuts or twigs are usually blown into the exhaust gas stream in order to wash the subsequent turbocharger. Due to this so-called "soft blasting", the impeller and the nozzle ring in front are also largely free of deposits. This procedure is usually performed daily and, if necessary, twice a day, at full engine power. However, this type of cleaning is at least not sufficient. Therefore, once a month, or when necessary, water washing is often performed. Since this cleaning is performed with the engine output reduced, it always causes a loss of time for the ship. In this cleaning, water is introduced through the nozzle into the exhaust gas week in front of the nozzle ring and impeller. This water washing means that the turbocharger becomes a heavy burden due to the heat shock effect. Therefore, attempts have been made to limit water washing to a minimum. The typical time required for such cleaning is about 2-3 hours. Strategy is easier by cleaning the water after the washing process. In that case, the washing water usually becomes significantly contaminated for 1 to 2 hours. Utilization of the ferrocene-loaded fuel according to the present invention generally results in excess of "soft blasting" and water washing. This cares for the functional unit in question, does not impose a restriction on the function and saves the action of time. When a turbocharger deposits and impairs its function, a series of problems arise. Fuel consumption is high because the efficiency of the turbocharger and ultimately the machine as a whole is reduced. The deposits reduce the number of revolutions, and in extreme cases even stop one or more impellers of the turbocharger. In the case of machines with multiple turbochargers, the impeller is supplied with exhaust gas from a common exhaust gas receiving location "reciever" which receives exhaust gas from many cylinders. If the gas is unevenly distributed due to the difference in the flow resistance caused by the deposits, the number of revolutions decreases, the number of revolutions fluctuates or there is a significant difference in the number of revolutions between the connected turbochargers, Driving stops. The above problems due to deposits accelerate material fatigue and, in extreme cases, cause material cracking. If the adhesion is particularly strong, this also occurs on small machines without multiple turbochargers. Irregular speeds, i.e. uneven operation, give rise to very large vibrations which, after a short time, lead to material damage to bearings and other machine parts. Non-uniform deposits on the impeller do not necessarily result in a lower rpm or, in the case of multiple turbochargers, a difference in rpm, which results in undesirable vibrations that cause increased wear due to uneven operation. It has been confirmed that, even in the subsequent heat exchanger, if the addition of the present invention is not performed, deposits are formed on the surface of the heat exchanger, and the deposits hinder the heat exchanger depending on its thickness. Predominantly soot deposits also need to be removed from time to time by washing with water and optionally with additives such as CuCl ₂ solution. The use of ferrocene-loaded fuels according to the invention leads to a very strong reduction in deposit formation. Surprisingly, if a water wash is required after a very long time (eg in a dry dock), unlike the prior art, operational deposits can be removed very easily with the added fuel according to the invention. Was confirmed. This is probably because the composition of the deposit has changed. It was confirmed that this shows a high ash content, a low heating value and a low carbon content, unlike the operation that does not use added fuel. It is presumed that these deposits are less hydrophobic. This is because these deposits do not contain oil components or oil-like components. Such water washing of heat exchangers or boilers is usually done every two years at the latest when the ship is in the dry dock for routine maintenance and inspection work. However, two moorings between dry docks usually require 5-6 additional cleanings. This can be omitted when using the present invention. Description of FIG. 1 FIG. 1 schematically shows the exhaust gas passage of a marine engine of the above degree. There is an engine block (1) with a total of 10 cylinders (2). The exhaust gas from each of the three or four cylinders is combined into a so-called exhaust gas "receiver" (3,4,5) and introduced into the turbocharger (6,7,8). The flow of exhaust gas discharged from the turbocharger collects in the exhaust gas conduit (9) and passes through the so-called exhaust gas "boiler" (10). Within this boiler are heat exchangers (11, 12, 13), which generate high, medium and low pressure steam. Exhaust gas leaves the system through the flue (14). This invention has been successfully tested with the results reported below for container ships. After the start period, the turbocharger of this machine on this ship is basically cleaned with a "soft blastlng" and a water wash. Without performing intermediate washing, water washing was performed once after about 3 months. This washing with water was not always necessary technically. This is because the turbocharger works satisfactorily. However, it was carried out in order to clarify the degree of contamination (adhesion). In the conventional technique, it is necessary to perform "softblasting" once a day and almost once a month for water cleaning. In this case, the cleaning water used was very dirty in 1 to 2 hours. (85 days) The wash procedure was omitted and the wash water was nevertheless initially clear. This makes it presumable that virtually no deposits were formed during the period. It did not show dirty coatings even in places that could not be achieved with conventional cleaning methods, or the coatings were significantly reduced. In the heat exchanger, it was visually confirmed that a significantly small amount of deposit was formed. The deposits formed could be removed by washing with water significantly easier and faster than before. No deposit could be visually confirmed even on the piston ring or the valve.

[Procedure of amendment] Patent Law Article 184-8 [Submission date] February 27, 1995 [Amendment content] Claims 1. Contains ferrocene and / or ferrocene derivatives in an amount of from 1 to 100 ppm, in particular from 5 to 50 ppm, mainly from 10 to 30 ppm, for operating a high compression, auto ignition engine having a rotation speed of 900 to 50, preferably 200 to 50 rpm, Use of internal combustion engine fuel with a density of 0.9-1.01 kg / dm ³ . 2. Use according to claim 1, characterized in that the engine of full power is 400-100,000, preferably 15,000-50,000kW. 3. Use according to claim 1 or 2, characterized in that the engine is a two-stroke engine. 4. Use according to claim 1 or 2, characterized in that the engine is a 4-cycle engine.

─────────────────────────────────────────────────── ─── Continued front page    (71) Applicant Dumpski Sselskavet Ahu             1912Actizel Scab             Däker-1098 Copenha, Denmark             Genker, Esplanade, 50 (72) Inventor Chunkel Walter             Germany, Day-46244 Bot             Rope, Leuvenkamp, 36 (72) Inventor Roman Gabrile             Federal Republic of Germany, Day-44532 Liu             Nen, Alfred-Seepe-Streller             2 (72) Inventor Marshewski Arnim             Germany, Day-45897 Gelze             Nkirchen, Becker Addsley,             110 (72) Inventor Nielsen Target Eve             Dakar-3060 Esper, Denmark             Gerde, Cogrevey, 4 (72) Inventor Rützen Christian             Dakar-2750 barrel barrel, Denmark             Puig, Viggo Bar Foods Array, 23

Claims (1)

[Claims] 1. Use of ferrocene and / or ferrocene derivatives as additives for internal combustion engine fuels of high compression, heavy quality for auto-ignition engines, in particular with a density of 0.9-1.01 kg / dm ³ . 2. Use according to claim 1, characterized in that the added fuel is used to operate an engine of full power of 400 to 100,000, preferably 15,000 to 50,000 kW. 3. Use according to claim 1 or 2, characterized in that the added fuel is used to operate a two-stroke engine. 4. Use according to claim 1 or 2, characterized in that the added fuel is used to operate a four-cycle engine. 5. 5. The fuel according to claim 1, characterized in that the added fuel is used to drive a slow-running engine with a speed of 900 to 50, preferably 200 to 50 rpm. Use of. 6. Use according to any one of claims 1 to 5, characterized in that the additive content of the fuel is 1 to 100 ppm, in particular 5 to 50 ppm, mainly 10 to 30 ppm.