EP0543477A2 - Procédé d'addition de ferrocène aux combustibles ou aux carburants - Google Patents

Procédé d'addition de ferrocène aux combustibles ou aux carburants Download PDF

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Publication number
EP0543477A2
EP0543477A2 EP92250345A EP92250345A EP0543477A2 EP 0543477 A2 EP0543477 A2 EP 0543477A2 EP 92250345 A EP92250345 A EP 92250345A EP 92250345 A EP92250345 A EP 92250345A EP 0543477 A2 EP0543477 A2 EP 0543477A2
Authority
EP
European Patent Office
Prior art keywords
ferrocene
combustion
carrier gas
gas stream
sublimator
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
EP92250345A
Other languages
German (de)
English (en)
Other versions
EP0543477A3 (en
EP0543477B1 (fr
Inventor
Hansjürgen Guttmann
Dieter Dr. Höhr
Heinz. Kuno Dr. Schädlich
Kurt-Peter Dr. Schug
Walter Dr. Thünker
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.)
Veba Oel AG
Original Assignee
Veba Oel AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Veba Oel AG filed Critical Veba Oel AG
Publication of EP0543477A2 publication Critical patent/EP0543477A2/fr
Publication of EP0543477A3 publication Critical patent/EP0543477A3/de
Application granted granted Critical
Publication of EP0543477B1 publication Critical patent/EP0543477B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • 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
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • 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
    • 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
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the invention relates to a method for additizing fuels with ferrocene for the improved combustion thereof with atmospheric oxygen or gases containing oxygen.
  • liquid hydrocarbon mixtures consisting essentially of gasoline and an organometallic compound from the Group of [bis ( l1 - cyclopentadienyl) iron], hereinafter referred to as ferrocene, and gasoline-soluble derivatives of ferrocene have been proposed, cf. DE - OS 25 02 307.
  • the task is derived from this to enable an improved metering of the additive ferrocene into the combustion chamber of an internal combustion engine or an oil heater without prior admixture as a solid or as a stock solution to the fuel, fuel or lubricant.
  • vaporous ferrocene is converted by sublimation into a stream of the combustion gas or a partial stream thereof and is fed to the chemical reaction by combustion with the fuel or fuel present in fine distribution as solid or liquid particles or in evaporated form.
  • the advantageous solution to the problem is based on the utilization of the sublimation properties of ferrocene.
  • This measure offers the advantage that the amount of ferrocene can be easily adapted to the optimally required amounts for the individual different operating states of the internal combustion engine by means of control measures.
  • the compacts or pellets produced from ferrocene crystals preferably have dimensions of 1 to 10 mm and are subjected to a carrier gas stream of the combustion gas or of parts of the combustion gas in a sublimator at values of pressure and temperature in the region of the boundary or coexistence line between solid and gaseous phase . From there, the carrier gas stream containing ferrocene is fed further into the combustion chamber.
  • Ferrocene is a substance that, depending on the manufacturing process, is obtained in the form of yellow-orange needles.
  • Moldings made of technically produced ferrocene such as pellets, pressed pieces or chips with dimensions of 1 to 10 mm can advantageously be placed in a suitable container of the sublimator.
  • the ferrocene compacts can be produced from solvent-moist ferrocene crystals, for example ethanol-moist (purity at least 98.5% by weight) from a crystallization solution, without the addition of binding agents or the like.
  • a preheating or preheating of the combustion air functioning as carrier gas stream to a temperature of 20 to 175, preferably 50 to 150 ° C. can be provided.
  • the operating states of the sublimator can vary from around minus 40 ° C at cold outside temperatures and an unprotected location to plus 150 ° C with appropriate heating by the burner or Result in engine operation.
  • additional heating for the sublimator, which helps to even out the operating behavior even when starting up.
  • the pressure prevailing in the sublimator due to the pressure of the carrier gas stream is preferably between 100 mbar and 3 bar.
  • the pressure and temperature conditions as well as the geometric dimensions of the sublimator and the amount of carrier gas can be specified so that an evaporated amount of ferrocene of 0.1 to 1,000, preferably 1 to 100 mg per kg of fuel or fuel is obtained.
  • a preferred mode of operation is that the carrier gas stream is preheated to a temperature of 20 to 175, preferably 50 to 150 ° C.
  • One application of the present method relates to the introduction of a carrier gas stream containing ferrocene into the combustion chamber of a diesel engine.
  • the diesel engine can be equipped on the exhaust side with a particle filter for retaining carbon-containing particles contained in the exhaust gas, referred to by the person skilled in the art as soot particles, which originate from an imperfect combustion of the diesel fuel with the combustion air in the engine.
  • FIG. 1 An arrangement in which the carrier gas stream is fed from the intake air line and is passed via the sublimator, which is fed with compacts from ferrocene and integrated in a motor vehicle engine, is shown in FIG.
  • the sublimator is arranged upstream of the air filter for the combustion air sucked in by the diesel engine.
  • the crankcase ventilation is, as usual, downstream of the air filter connected to the line of combustion air.
  • Points 1 and 2 designate the measuring point for the temperature in the sublimator or the temperature and the pressure upstream of the diesel particle filter.
  • FIG. 2 Another variant of the introduction of ferrocene is shown in FIG. 2.
  • Figures 1 and 2 are designed in more detail so that the carrier gas flow branches off from the intake air line provided in each motor vehicle engine or from the crankcase ventilation and from there into the sublimator charged with ferrocene pellets is introduced so that one at the selected Pressure and temperature conditions, the most complete possible transition of the ferrocene vapor into the carrier vapor stream is effected.
  • the ferrocene-laden carrier gas stream is combined with the necessary amount of intake air on the downstream side by an intake air filter, avoiding condensation, and supplied to the combustion chamber of the engine.
  • the exhaust gas from the fuel combustion is released into the atmosphere on the downstream side of the engine via the particle filter and a silencer.
  • Points 1 and 2 each designate measuring points for the temperature in the sublimator or for the temperature and the pressure before the combustion exhaust gases enter the particle filter.
  • test engine was a model of the make Opel 2.3 1 car diesel, naturally aspirated with a swirl chamber combustion process and a nominal output of 54 kw.
  • the engine was operated at 2,000 rpm and a load of 28 Nm torque (partial load).
  • the temperature in the sublimator was approximately 40 ° C.
  • the dotted curve denotes the measured values of the temperature at measuring point 2 in front of the diesel particle filter.
  • the solid sawtooth - like curve shows the course of the pressure on the upstream side of the diesel particulate filter.
  • the diesel particulate filter was regenerated by burning off the soot particles collected in the filter, reducing the pressure to approximately 50 mbar.
  • an exhaust gas counterpressure was built up again, which after values of approximately 200 to max. 350 mbar each followed by a spontaneous combustion after a cycle time of about 2 to 3 hours, so that overall an acceptable engine operating behavior resulted over the running time.
  • FIG. 4 shows a long-term test on the diesel particulate filter combustion behavior under comparable conditions as the diagram in FIG. 3, with the only difference that the combustion air was not additized by means of a carrier gas flow from the crankcase ventilation.
  • the arrangement also contained the sublimator as shown in FIG. 2, but the sublimator was not loaded with ferrocene pellets.
  • the dotted curve represents the temperature at measuring point 2 according to FIG. 2 in front of the diesel particle filter. It can be seen that a slow but steady increase from about 190 to about 280 ° C. was observed here.
  • the solid line shows an almost linear increase in the exhaust gas back pressure upstream of the diesel particle filter measured at measuring point 2 according to FIG. 2.
  • the proposed method achieves the object in an advantageous manner, since with a specialist selection reserved specification of the operating data of the sublimator, the form of use of the ferrocene substance as pellets, other molded parts such.
  • the introduction of the carrier gas stream additized with ferrocene into the combustion chamber significantly improves the combustion behavior in the engine, which is operated with commercially available fuels, in Otto or Wankel engines with and without a downstream catalyst for exhaust gas afterburning.
  • the occurrence of knocking in the engine is strongly suppressed.
  • the power output of the engine can be increased.
  • the influence of the active ingredient reduces fuel consumption.
  • the suppression of knocking processes by introducing the ferrocene active ingredient according to the invention is far stronger than if the active ingredient is contained in the fuel in a dissolved form.
  • ferrocene into the engine process according to the invention increases the combustion chamber cleanliness by reducing existing residues and prevents the build-up of new deposits on pistons, piston rings, in the cylinder and on the cylinder head.
  • gasoline engines without a downstream catalytic converter for exhaust gas afterburning or pollutant reduction, which are still equipped with exhaust valves that are susceptible to wear the ferrocene addition acts as a wear - reducing component on the exhaust valve seats.
  • ferrocene as an additive in the combustion of fuel in the combustion chamber reduces the particle emission and the proportion of polycyclic aromatic hydrocarbons that are attached to the carbon-containing particles.
  • the ferrocene addition according to the invention makes the regeneration capacity of a diesel particle filter connected downstream of a diesel engine without additional devices for increasing the temperature or for initiating processes for periodic combustion of the carbon-containing particles (diesel soot) accumulating on the filter in order to maintain lower acceptable values for the pressure drop on the downstream side improved or made possible by the filter.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Processes For Solid Components From Exhaust (AREA)
  • Catalysts (AREA)
  • Compounds Of Iron (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)
EP92250345A 1991-11-21 1992-11-23 Procédé d'addition de ferrocène aux combustibles ou aux carburants Expired - Lifetime EP0543477B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4138216A DE4138216C2 (de) 1991-11-21 1991-11-21 Verfahren zum Additivieren von Brenn- oder Kraftstoffen mit Ferrocen
DE4138216 1991-11-21

Publications (3)

Publication Number Publication Date
EP0543477A2 true EP0543477A2 (fr) 1993-05-26
EP0543477A3 EP0543477A3 (en) 1993-08-25
EP0543477B1 EP0543477B1 (fr) 1996-01-17

Family

ID=6445230

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92250345A Expired - Lifetime EP0543477B1 (fr) 1991-11-21 1992-11-23 Procédé d'addition de ferrocène aux combustibles ou aux carburants

Country Status (7)

Country Link
US (1) US5386804A (fr)
EP (1) EP0543477B1 (fr)
JP (1) JP3370707B2 (fr)
KR (1) KR100245839B1 (fr)
AT (1) ATE133194T1 (fr)
DE (2) DE4138216C2 (fr)
ES (1) ES2084271T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5386804A (en) * 1991-11-21 1995-02-07 Veba Oel Aktiengesellschaft Process for the addition of ferrocene to combustion or motor fuels
WO2007080070A1 (fr) * 2006-01-09 2007-07-19 Fraenkle Gerhard Juergen Procédé pour mélanger un additif avec un fluide et installation à cet effet

Families Citing this family (12)

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US5823148A (en) * 1996-05-29 1998-10-20 Housand, Sr.; Raymond W. Apparatus for introducing combustion supporting particles to an internal combustion engine
JP5064640B2 (ja) * 2000-08-31 2012-10-31 イノスペック リミテッド ２量体又はオリゴマーフェロセンを含有する組成物
US20060167184A1 (en) * 2000-10-18 2006-07-27 Waddell Walter H Innerliners for use in tires
DE60237323D1 (de) * 2001-08-30 2010-09-23 Innospec Ltd Zusammensetzung enthaltend Ferrocen-Derivate und Treibstoff diese enthaltend
KR100428749B1 (ko) * 2002-03-12 2004-04-28 한국화학연구원 연소분진 억제용 액상 조연소 촉매 조성물
US6892531B2 (en) 2003-04-02 2005-05-17 Julius J. Rim System for and methods of operating diesel engines to reduce harmful exhaust emissions and to improve engine lubrication
DE102004025327A1 (de) 2004-05-19 2005-12-08 Hjs Fahrzeugtechnik Gmbh & Co. Kg Verfahren zum Beladen eines Kraftstoff-Luft-Gemisches mit einem Additiv in Gasphase sowie Vorrichtung zum Bereitstellen eines Additivs in Gasphase
US8101014B2 (en) 2004-11-10 2012-01-24 Chemetall Gmbh Process for coating metallic surfaces with a multicomponent aqueous composition
CA2668181C (fr) * 2006-11-01 2012-01-24 Bharat Petroleum Corporation Limited Compositions de combustible hydrocarbone
BRPI0900653A2 (pt) * 2009-03-13 2010-11-09 Magneti Marelli Ltda sensor lógico para biodiesel
DE102010038143A1 (de) 2010-10-13 2012-04-19 Hjs Emission Technology Gmbh & Co. Kg Verfahren zum Absenken der Rußzündtemperatur von auf einem Partikelfilter akkumuliertem Ruß
CN104532182A (zh) * 2014-11-05 2015-04-22 汕头高新区腾力高分子材料科技有限公司 汽车节油减排器及节油方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5386804A (en) * 1991-11-21 1995-02-07 Veba Oel Aktiengesellschaft Process for the addition of ferrocene to combustion or motor fuels
WO2007080070A1 (fr) * 2006-01-09 2007-07-19 Fraenkle Gerhard Juergen Procédé pour mélanger un additif avec un fluide et installation à cet effet

Also Published As

Publication number Publication date
DE4138216A1 (de) 1993-05-27
DE59205100D1 (de) 1996-02-29
US5386804A (en) 1995-02-07
EP0543477A3 (en) 1993-08-25
EP0543477B1 (fr) 1996-01-17
DE4138216C2 (de) 1994-02-03
KR930010164A (ko) 1993-06-22
JPH05239478A (ja) 1993-09-17
KR100245839B1 (ko) 2000-03-02
ES2084271T3 (es) 1996-05-01
JP3370707B2 (ja) 2003-01-27
ATE133194T1 (de) 1996-02-15

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