EP0689577A1 - Use of ferrocene - Google Patents
Use of ferroceneInfo
- 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
Links
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
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4309066A DE4309066C2 (en) | 1993-03-20 | 1993-03-20 | Use of ferrocene |
DE4309066 | 1993-03-20 | ||
PCT/EP1994/000803 WO1994021755A2 (en) | 1993-03-20 | 1994-03-15 | Use of ferrocene |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0689577A1 true EP0689577A1 (en) | 1996-01-03 |
EP0689577B1 EP0689577B1 (en) | 1997-02-26 |
Family
ID=6483399
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94911173A Expired - Lifetime EP0689577B1 (en) | 1993-03-20 | 1994-03-15 | Use of ferrocene |
Country Status (19)
Country | Link |
---|---|
EP (1) | EP0689577B1 (en) |
JP (1) | JP3599337B2 (en) |
KR (1) | KR100274093B1 (en) |
CN (1) | CN1052034C (en) |
AU (1) | AU677388B2 (en) |
BR (1) | BR9405903A (en) |
CA (1) | CA2156747C (en) |
DE (2) | DE4309066C2 (en) |
DK (1) | DK0689577T3 (en) |
ES (1) | ES2099600T3 (en) |
FI (1) | FI119551B (en) |
GR (1) | GR3023491T3 (en) |
IS (1) | IS1813B (en) |
NO (1) | NO309777B1 (en) |
NZ (1) | NZ263179A (en) |
PL (1) | PL177895B1 (en) |
SG (1) | SG48900A1 (en) |
WO (1) | WO1994021755A2 (en) |
ZA (1) | ZA941941B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1752512A1 (en) | 2005-08-09 | 2007-02-14 | Infineum International Limited | A method of reducing piston deposits, smoke or wear in a diesel engine |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1056938B1 (en) * | 1998-02-20 | 2006-10-04 | John J. Kracklauer | Method for providing and maintaining catalytically active surface in internal combustion engine |
GB0011908D0 (en) * | 2000-05-16 | 2000-07-05 | Infineum Int Ltd | Process for operating diesel engines |
DE10043144C1 (en) * | 2000-08-31 | 2001-12-13 | Octel Deutschland Gmbh | Use of solutions of 2,2-bisferrocenylalkanes in an aromatic solvent as combustion-promoting diesel fuel additives |
JP4131748B1 (en) * | 2008-01-16 | 2008-08-13 | 株式会社タイホーコーザイ | Fuel additive |
ES2394922B1 (en) * | 2011-06-20 | 2014-01-14 | Juan Carlos PROCKIV CORZÓN | COMPOSITE LIQUID ECOLOGICAL ADDITIVE FOR FOSSIL FUELS DERIVED FROM OIL. |
WO2014165950A1 (en) * | 2013-04-10 | 2014-10-16 | Firmano Lino Junior | Non-deposit forming catalytic additive for additive oil cracking, and for fuel octane increase and combustion |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3341311A (en) * | 1953-07-27 | 1967-09-12 | Du Pont | Liquid hydrocarbon fuels |
US3265621A (en) * | 1961-05-22 | 1966-08-09 | Standard Oil Co | Lubricants containing a hydrocarbon diester of 1, 1'-di-alpha-hydroxy-ethyl ferrocene |
FR2273059B1 (en) * | 1974-01-21 | 1979-08-03 | Syntex Inc | |
DE2807419C2 (en) * | 1978-02-22 | 1979-07-05 | Kloeckner-Werke Ag, 4100 Duisburg | Process for operating blast furnaces |
US4389220A (en) * | 1980-06-04 | 1983-06-21 | Syntex (U.S.A.) Inc. | Method of conditioning diesel engines |
CA1322453C (en) * | 1988-08-15 | 1993-09-28 | Velino Ventures Inc. | Combustion of liquid hydrocarbons |
CN1034950A (en) * | 1988-11-23 | 1989-08-23 | 兰州燃料炉具实验厂 | The preparation of civilian heavy fuel oil (HFO) and special furnace set thereof |
US4908045A (en) * | 1988-12-23 | 1990-03-13 | Velino Ventures, Inc. | Engine cleaning additives for diesel fuel |
-
1993
- 1993-03-20 DE DE4309066A patent/DE4309066C2/en not_active Expired - Fee Related
-
1994
- 1994-03-15 DK DK94911173.6T patent/DK0689577T3/en active
- 1994-03-15 CN CN94191475A patent/CN1052034C/en not_active Expired - Fee Related
- 1994-03-15 PL PL94310675A patent/PL177895B1/en not_active IP Right Cessation
- 1994-03-15 ES ES94911173T patent/ES2099600T3/en not_active Expired - Lifetime
- 1994-03-15 DE DE59401861T patent/DE59401861D1/en not_active Expired - Lifetime
- 1994-03-15 NZ NZ263179A patent/NZ263179A/en not_active IP Right Cessation
- 1994-03-15 KR KR1019950703731A patent/KR100274093B1/en not_active IP Right Cessation
- 1994-03-15 BR BR9405903A patent/BR9405903A/en not_active IP Right Cessation
- 1994-03-15 CA CA002156747A patent/CA2156747C/en not_active Expired - Fee Related
- 1994-03-15 AU AU63772/94A patent/AU677388B2/en not_active Ceased
- 1994-03-15 SG SG1996003576A patent/SG48900A1/en unknown
- 1994-03-15 JP JP52063394A patent/JP3599337B2/en not_active Expired - Fee Related
- 1994-03-15 EP EP94911173A patent/EP0689577B1/en not_active Expired - Lifetime
- 1994-03-15 WO PCT/EP1994/000803 patent/WO1994021755A2/en active IP Right Grant
- 1994-03-16 IS IS4140A patent/IS1813B/en unknown
- 1994-03-18 ZA ZA941941A patent/ZA941941B/en unknown
-
1995
- 1995-09-15 NO NO953659A patent/NO309777B1/en not_active IP Right Cessation
- 1995-09-19 FI FI954422A patent/FI119551B/en not_active IP Right Cessation
-
1997
- 1997-05-19 GR GR970401140T patent/GR3023491T3/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9421755A2 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1752512A1 (en) | 2005-08-09 | 2007-02-14 | Infineum International Limited | A method of reducing piston deposits, smoke or wear in a diesel engine |
Also Published As
Publication number | Publication date |
---|---|
CN1119455A (en) | 1996-03-27 |
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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