FI119551B - Use of ferrous metal - Google Patents

Description

119551

Use of ferrocene

The invention relates to the use of ferrocene and / or ferrocene derivatives as 11-fuel (Additiv} high-crossings, for use in heavier-quality internal combustion engine fuels,

Ferrocene and its derivatives are known from the literature »Ferrocene and its preparation were first described in Nature 168 (1951), page 1039. 10 Thereafter, ferrocene and its derivatives, as well as the corresponding manufacturing processes, have been the subject of numerous U.S. Patent Nos. 2,650,756. , 2,769,828, 2,834,796, .2898,360, 3,035,968, 3,238,158, and 3,437,634.

It is also known from patent literature that ferrocene can contribute to the combustion process. DE 3 418 648 mentions, amongst many other associations, ferrocene (iron dicyclopentadienyl) as a possible additive for optimizing the combustion of fuel oil, i. to facilitate the transport of the fuel oil through the burner and thereby promote complete combustion of the fuel oil.

U.S. Patent No. 4,389,220 to U.S. Patent 4,389,220 discloses a method for controlling the air of a diesel engine (Conditioning). For this purpose, 20 to 30 ppm of ferrocene are added to ··· 25 diesel. This will remove the carbonaceous deposits from the fireplace and ··· ·. ···. avoiding their re-formation. At the same time, it was noticed that these measures reduce fuel consumption by up to 5% per trip. Die- • Φ * * * * ell * * sel sel sel sel sel sel 30 sel 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30. Of its type:] [*: Fuel is the middle distillate in the petroleum refining process and is available at gas stations under the designation "di-sei". It is normally used by 4-stroke diesel engines in road vehicles such as ♦ ·· * * 35 eg passenger cars, buses, trucks • 2 119551. This fuel conforms to DIN 51601 and corresponds to fuel oil EL. It is thus of light to medium fuel quality.

Larger engines with lower rpm, such as those used on ships or electric power plants, use heavier fuels. Thus, there is a problem that the carbonaceous deposits will interfere with the operation of the connected equipment. Such types of equipment include, in particular, turbochargers and heat exchangers. However, deposits in the valves, piston rings and combustion chamber are also undesirable as they may lead to reduced engine power and / or increased wear on the parts concerned.

An object of the invention is to minimize or facilitate the removal of said deposits.

This object is achieved, in accordance with the invention, by the use of ferrocene and / or ferrocene derivatives as an additive (additiv) in high-pressure internal combustion engines for high-pressure, self-igniting engines.

• ♦ ί, '· ϊ It is with such large engines: 4 * .j heavy fuels that use ferrocene additive ··· has proven to be particularly advantageous. This applies before ·· ** 25 for all large engines, that is to say, engines of size, ·. female power is 400-100,000, preferably 15,000-50,000, especially over 30,000 kW.

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The heavier the fuel, the earlier it turns out. normally have problems with said strata.

For these fuels, unexpectedly, the addition of ferrocene • t * ··· * has proved to be particularly effective. This was all the more unexpected than was known • that ferric roseene is very effective in improving light fuel oil *. 1, but less efficient heavy fuel oil • · · ** "35 burns.

• · · • · • 3 119551

Particularly for grades1 commonly referred to as marine fuel oil, "Bunker-C" grade, marine diesel or distilled marine diesel fuel, the use of the present invention is preferred. As is easy to see with reference to the names of fuels, they are mainly used for marine engines.

The fuels in question may be exemplified by a fraction of at least 10 atmospheric crude oil distillation, vacuum distillation, or catalytic cracking. These fuels have a density in particular in the range of 0.9 to 1.0 kg / dm3. These fuels can be further classified with reference to ISO 82 17. distilled marine fuels (Marine Destillate Fuels); Heavy Residual Fuels. The type designation of the former is DM and the type designation of the latter is HM. Some types are explained below empirically based on their most important properties such as density, viscosity, sulfur content and carbon residue.

• '.' • j DMB DMC RMA RMG RMH

1Ö 35 45 • · * ·· Density kg / mJ 0.90 0.92 0.95 0.991 1.010 ··· · · 25 Maximum kinematic t ·· ”: · viscosity • 1 at 40 ° C 11.0 14.0 - - - • · «at 100 ° C 10 35 45. . Max carbon residue

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30% by weight 0.25 2.5 12 18 22 • · * ··· 1 Sulfur content by weight% 2.0 2.0 3.5 5.0 5.0 • 1 1 ·; ··· All DM- and RM types are available on display .1. as a fuel in the sense of the present invention.

• 1 · • t · • · · • 1 · • · · • 4 119551

Many ocean-going large ship engines are powered by 2-stroke engines. For these purposes, the invention is particularly well suited. This is especially true for slow-running engines having a rotation speed of 900-50, preferably 200-50 rpm, and in particular a maximum speed of 100 rpm and less. Good results are also achieved with the fast-rotating motors, as with the 4-stroke engine, with the addition of the invention.

Good results were obtained with an addition of ferrocene of 1 to 100 ppm. With an addition of less than 1 ppm, the effects are not so obvious that one could talk of a substantial improvement in a fuel without 15 additives. At an additive content of more than 100 ppm, a limit is reached where the addition does not produce any appreciable additional effects. Normally, a range of 5 to 50 ppm is preferred. The optimum range is between 10 and 30 ppm. The addition may be effected, for example, by dissolving the additive in a portion of the fuel 20, and then passing this solution, for example by means of a metering pump, into the main fuel stream.

Ferrocene derivatives may also be used, at least in part, in place of ferrocene. Ferrocene derivatives * ·· are compounds in which one or both cyclopentanes are present in the ferrocene backbone. other substituents on the dienyl ring. Examples include * * · [···] size ethyl eroserosine, butyl errocene, acetyl ererocene and 2,2-bis-ethyl ererrocene propar.

. . According to the invention, heavy-duty fuels effectively reduce deposits of lubricant.

:] **: Deposits adversely affect rear-couplings- *: ** · dull devices such as turbochargers and heat exchangers. *. as well as engine parts such as valves and piston rings and, to a considerable extent, their operation. The removal of deposits often requires considerable costs. Thus, it is common for large craft suitable for wafers to purge 5 smaller nutshells or also rice to purge the rear-engined turbochargers. This so-called "Softblasting" cleans impellers as well as feedthrough nozzle ring for most of the deposition. This process is normally done daily, up to twice a day if necessary, with the engine at 10 full load, but in most cases this type of cleaning is not sufficient. Because this washing is done with the engine load reduced, there is always a waste of time on the ship as well, 15 water is discharged from the nozzle to the nozzle ring and into the exhaust stream in front of the wheels, this water washing implies a heavy load on the turboah therefore, it is intended to limit these water washings to a minimum, which normally requires about 2 to 3 hours, simply focusing on the purity of the water after the rinses. is normally 1-2 hours clearly visibly heavily soiled.

* · ··. Using according to the invention added with ferrocene

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25 fuels are "softblasting" as well as "ve" · * · *:, ·. Wiping is usually unnecessary. This protects such equipment battles without operating restrictions, and saves time and labor,. Because of the detrimental effect of the turbochargers on the operation of the turbochargers, a number of problems may occur *. · .. * mia The power of the turbochargers, and hence the power of the whole machine, '' **; decreases, resulting in increased fuel consumption. Deposits can lead to a reduction in rotation speed, in extreme cases one or more f · · '· of the turbocharger. "35 for the impeller to stop. On machines with multiple turbochargers, the exhaust gas is driven from a common "exhaust gas reservoir", which directs the exhaust gases from several cylinders together. If the gas is distributed unevenly, which may be due to different flow resistance, which, in turn, is due to sedimentation, this may result in a decrease in rotation speed, variation in rotation speed, or a significant difference in rotation speed between the connected turbochargers. The aforementioned problems due to stratification can lead to premature fatigue of the material or, in extreme cases, to material fracture. With extremely heavy deposits, this can also occur on smaller machines that are not equipped with multiple turbochargers. Irregularities in the speed of the wheels, i.e. uneven running, can lead to very strong vibrations which, even in a short period of time, can lead to material damage to bearings and other parts of the machine.

Although the uneven deposits on the impellers may not necessarily result in a decrease in rotation speed or differences in the rotation speed of multiple turbochargers, ♦ * due to the uneven running, there is also an undesirable increase in the vibration of the side.

M · * ··· 25 Also in the rear-mounted heat exchangers, the addition of the additive according to the invention can be observed,

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• deposits on the heat exchanger surfaces, which, depending on their strength, prevent heat exchange.

Also, these predominantly soot-containing deposits must be removed from time to time by washing with water, possibly with cleaning agents such as CuCl2 solution. By using, in accordance with the invention, fuels which have been added

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····· ferrocene, significantly reduces the formation of deposits. If, however, in contrast to the technology hitherto · • · «*; * | 35 119551 (e.g., dry dock), it was surprisingly found that the deposits are substantially easier to remove when the fuel added with the additive is used according to the invention. This is possibly due to the altered composition of the layers. It was then found that, as opposed to non-additive fuel, it has higher ash contents, lower calorific values and lower carbon content. It can then be assumed that these deposits are less hydrophobic because they contain fewer oily or oily components.

Such heat exchanger or boiler water washings shall be carried out, normally not later than every two years, when the ship has been inspected and maintained in accordance with regulations. However, five to six additional washes are usually required between the two dry yards. They may be dispensed with using the present invention. Description of Figure 1

Figure 1 schematically shows the exhaust gas flow of a marine engine of this magnitude. From this, a mpottor block 1 with a total of 10 \ * ·; Cylinders 2. The exhaust gases from each of the three or four cylinders are, respectively, • exhaust gases, MT "receiving" 3, 4, 5 and feeding the turbocharger in 6, ^ ί · 25 7, 8. Turbocharger outflows the exhaust gas streams to the conduit | · The exhaust gas in line 9 is assembled and then flows in a so-called.

··· · through the "exhaust boiler" 10, where the heat exchangers 11, 12, 13 are located and which can produce high, medium and low pressure steam. Exhaust gases are removed from the system through the chimney 14.

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The invention was successfully tested in the container with the following results.

• · X: • ·· • · ί • · B 119551

Vessel Specifications:

60,000 BHT

Machine specifications:

Power 33,000 kW

5 Capacity 10 cylinders 1.6 m3

Speed rotation. 90 rpm

Turbocharger rotation speed approx. 10,000 rpm

Consumption approx. 6 t / h at full load 10

After a successful start-up phase, the turbochargers of this ship's aircraft were thoroughly cleaned by "softblasting" and water washing. Approximately 3 months later, a water wash was performed and without any purification between 15 times. However, this water wash was not technically necessary as the turbochargers were operating satisfactorily but was carried out to obtain information on the degree of soiling (deposition). At the current state of the art, a daily 20 softblasing procedure and about once a month water wash, with 1 ~ • · *, * ·! 2 hours of heavily soiled water, was abandoned for almost 3 months (85 days). all the cleaning procedures, and, nevertheless, the washing water was clean from the start.

···· ··· 25 It can be inferred from this that virtually no deposits were formed during the said period. Up to ··· t.

those where otherwise conventional cleaning methods are not achievable, • had no or no., significantly reduced dirt coatings.

* Uaal 30 ista 30 uaal 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 selvästi selvästi selvästi selvästi selvästi selvästi selvästi selvästi selvästi selvästi selvästi selvästi which already had a significantly smaller number of layers. Deposits that were formed were substantially and simply removed faster and faster than before. *. water washing.

• · · *; '· 35 Neither piston rings nor valves could • i · * · *: visually detect any deposits.

Claims (4)

Use of the internal combustion engine fuel having a density of 0.9 - 1.01 kg / dm3 which contains ferrocene 5 and / or ferrocene derivatives in amounts of 1 - 100 ppm, especially 5 ~ 50 ppm, preferably 10 - 30 ppm, for the operation of highly compressive, self-igniting engines with a speed of 900 - 50, preferably 200 - 50 rpm. Use according to claim 1, characterized in that the motors have a rpm power of 400 - 100,000, preferably 15,000 - 50,000 kW. Use according to claim 1 or 2, characterized in that the motors are wash-cycle motors. Use according to claim 1 or 2, characterized in that the motors are four-stroke motors. • • φ t · ·· • • • · · · ♦ • • • ·· · ··· · ·· ♦ ··· • ···· t ♦ • · · · · «* ··· ··« · · · · · · · · 9 9 ··· • · ♦ 9 • · · • 99 9 9 9 9 9 9 9 9 99 9 9