EP0492101B1 - Verwendung von metallorganischen Additiven zur Verbesserung der Russverbrennung in Dieselkraftstoffen - Google Patents

Verwendung von metallorganischen Additiven zur Verbesserung der Russverbrennung in Dieselkraftstoffen Download PDF

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Publication number
EP0492101B1
EP0492101B1 EP91119110A EP91119110A EP0492101B1 EP 0492101 B1 EP0492101 B1 EP 0492101B1 EP 91119110 A EP91119110 A EP 91119110A EP 91119110 A EP91119110 A EP 91119110A EP 0492101 B1 EP0492101 B1 EP 0492101B1
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EP
European Patent Office
Prior art keywords
soot
filter
diesel fuel
acid
burning
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.)
Expired - Lifetime
Application number
EP91119110A
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German (de)
English (en)
French (fr)
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EP0492101A1 (de
Inventor
Bernd Dr. Krutzsch
Günter Chem.-Ing. Wenninger
Ekkehard Prof. Dr. Lindner
Michael Pabel
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Daimler Benz AG
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Daimler Benz AG
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Publication date
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Publication of EP0492101A1 publication Critical patent/EP0492101A1/de
Application granted granted Critical
Publication of EP0492101B1 publication Critical patent/EP0492101B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C10L1/1828—Salts thereof
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1886—Carboxylic acids; metal salts thereof naphthenic acid
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • 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
    • F02B51/00—Other methods of operating engines involving pretreating of, or adding substances to, combustion air, fuel, or fuel-air mixture of the engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2430/00—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics
    • F01N2430/04—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics by adding non-fuel substances to combustion air or fuel, e.g. additives
    • 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 the use of organometallic additives to improve the combustion of soot in diesel fuels.
  • diesel engines In addition to the pollutants that also occur in Otto engines, diesel engines emit soot particles, which have been assessed very critically for several years. Animal studies have shown that diesel exhaust has a carcinogenic potential. That is why diesel exhaust was included in the list for maximum workplace concentrations in 1987 as a carcinogenic agent.
  • the object of the invention is therefore to achieve regeneration of the particle filter, arranged in the exhaust pipe of a diesel engine, even at low temperatures.
  • the object is achieved according to the invention by using organometallic additives that are added to the diesel fuel.
  • alkali metal salts added according to the invention there are indications, especially for lithium compounds, that the combustion process is influenced favorably and the emission is already reduced within the engine. Above all, however, a soot is formed during the combustion process in the presence of the additives under investigation, which is much easier to oxidize after being deposited in a particle filter. This means that much lower exhaust gas temperatures are sufficient for particle filter regeneration and thus a critical soot mass occupancy in the filter is avoided.
  • lithium or sodium salts of tertiary butyl alcohol were added as additives to the diesel fuel in various concentrations. Concentrations were each based on the amount of alkali metal of the salt, expressed in millimoles of metal, added to one liter of diesel fuel.
  • the tests were carried out with a stationary prechamber diesel engine (DB OM 616 series). There was a honeycomb in the exhaust pipe Ceramic monolith arranged from cordierite. The additives were mixed directly into the diesel fuel before the combustion process.
  • the test was carried out with a stationary engine operating mode.
  • the particle filter was loaded at an engine speed of 4,000 rpm and an average pressure in the combustion chamber of approx. 1.0 bar.
  • the exhaust gas temperature upstream of the soot filter is approx. 350 ° C at this engine point.
  • the particle filter was loaded until the pressure in front of the filter had risen to 500 mbar.
  • Fig. 1 shows the very steep pressure rise within a short time (phase 1).
  • the temperature was increased by increasing the load (phase 2).
  • the equilibrium temperature (TGL) is reached at about 560 ° C in this experiment.
  • the proportion of the newly deposited soot corresponds to the proportion that is already oxidized at this exhaust gas temperature.
  • the filter is then slowly regenerated by increasing the temperature to 600 ° C (phase 3). However, the filter is only completely burned free at 700 ° C.
  • the following test was carried out with an engine operating mode as described in test 1.
  • the solution prepared was metered into the fuel in a ratio such that 1.2 millimoles of lithium were added with the metal salt per 1 liter of fuel.
  • the sooting time ie the time until a pressure of 550 mbar is built up in front of the particle filter, is significantly extended.
  • the equilibrium temperature is now reached at 450 ° C.
  • the temperature increase to 600 ° C leads to a very quick and complete regeneration of the particle filter.
  • test 2 The less steep pressure increase in test 2 compared to test 1 and the much lower blackening number could be an indication that the addition of the fuel additive has already reduced the particle emission within the engine.
  • soot already deposited in the filter it is also possible for soot already deposited in the filter to be oxidized continuously without complete regeneration occurring.
  • the metal salt added 1.2 mmol sodium per 1 liter of fuel.
  • the engine was operated transiently at different speeds and loads with exhaust gas temperatures between 200 ° C and 400 ° C. Numerous partly very strong regenerations take place.
  • the maximum pressure upstream of the filter is approximately 400 mbar (Fig. 5).
  • the lithium palmitate used 1.2 or 3.4 mmol lithium per 1 liter of fuel.
  • the equilibrium temperature for 1.2 mmol lithium is approx. 520 ° C, for 3.4 mmol Li approx. 500 ° C.
  • the filter regenerations carried out at 600 ° C are comparable to lithium tertiary butylate.
  • the lithium salt of phenylacetic acid was added to the diesel fuel. Since this compound has a much poorer solubility in diesel fuel than the other additives, only the lowest additive concentration of 0.24 mmol lithium / liter diesel fuel was tested; the experiment is again carried out as in experiment 1. The equilibrium temperature was approximately 520 ° C. There was no difference in the regeneration rate compared to the lithium tertiary butanolate, which had also been tested in the lowest concentration of 0.24 mmol lithium liter diesel fuel.
  • the advantages of the described method are, in particular, that with the metal salts of the specified organic compounds added according to the invention to the diesel fuel before combustion, the soot separated in the particle filter oxidizes at a temperature which is significantly lower than the normal ignition temperature and thus the particle filter can be regenerated more easily.
  • the additional emission which can occur as a result of the addition of the diesel fuel with the alkali metal compounds proposed here can be classified as harmless from an environmental and health point of view.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Processes For Solid Components From Exhaust (AREA)
  • Liquid Carbonaceous Fuels (AREA)
EP91119110A 1990-12-21 1991-11-09 Verwendung von metallorganischen Additiven zur Verbesserung der Russverbrennung in Dieselkraftstoffen Expired - Lifetime EP0492101B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4041127 1990-12-21
DE4041127A DE4041127A1 (de) 1990-12-21 1990-12-21 Verfahren zur verringerung der schadstoffemission der verbrennungsabgase von dieselmotoren

Publications (2)

Publication Number Publication Date
EP0492101A1 EP0492101A1 (de) 1992-07-01
EP0492101B1 true EP0492101B1 (de) 1995-09-06

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP91119110A Expired - Lifetime EP0492101B1 (de) 1990-12-21 1991-11-09 Verwendung von metallorganischen Additiven zur Verbesserung der Russverbrennung in Dieselkraftstoffen

Country Status (4)

Country Link
US (1) US5522905A (enrdf_load_stackoverflow)
EP (1) EP0492101B1 (enrdf_load_stackoverflow)
AT (1) ATE127510T1 (enrdf_load_stackoverflow)
DE (1) DE4041127A1 (enrdf_load_stackoverflow)

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JPH0674024A (ja) * 1992-08-24 1994-03-15 Toyota Motor Corp 燃料の燃焼方法
WO1995005665A1 (en) * 1993-08-12 1995-02-23 The Exzite Corporation Process for reducing pollution in energy production
FR2719081B1 (fr) * 1994-04-20 1996-07-05 Rhone Poulenc Chimie Un procédé de filtration et de combustion de matières carbonées.
FR2720441B1 (fr) * 1994-05-25 1996-09-06 Rhone Poulenc Chimie Un procédé de filtration et de combustion de matières carbonées issues de moteur à combustion interne.
CA2180181A1 (fr) * 1993-12-31 1995-07-06 Philippe Barthe Un procede de filtration et de combustion de matieres carbonees issues de moteur a combustion interne
JPH11504355A (ja) * 1995-04-24 1999-04-20 ジ アソシエーテッド オクテル カンパニー エルティーディー 改良された燃焼法
GB9622026D0 (en) * 1996-10-24 1996-12-18 Ass Octel Fuel additives
TW449617B (en) * 1996-07-05 2001-08-11 Shell Int Research Fuel oil compositions
FR2789910B1 (fr) * 1999-02-24 2004-07-09 Renault Procede de regeneration assistee de filtre a particules par apport de solution contenant des composes hydroxyles
ES2216953T3 (es) 1999-08-30 2004-11-01 MOSSI & GHISOLFI INTERNATIONAL S.A. Un proceso integrado para la produccion de acido 2,6-naftalen dicarboxilico.
US6102975A (en) * 1999-10-01 2000-08-15 Marr; Wesley D. Fuel conditioner and improver compositions
GB2355943B (en) * 1999-11-03 2004-03-03 Johnson Matthey Plc Improvements in pollution control
DE10205380A1 (de) * 2002-02-09 2003-08-21 Daimler Chrysler Ag Verfahren sowie Vorrichtung zur Behandlung von Dieselabgas
DE10323735A1 (de) 2003-05-24 2004-12-09 Daimlerchrysler Ag Verfahren zur Reinigung eines Partikelfilters
US7114336B2 (en) * 2004-01-30 2006-10-03 Woodward Governor Company Flow pulsing valve and fuel supply system for a turbine engine incorporating same
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US20100293841A1 (en) * 2009-05-20 2010-11-25 Zuckerman Mathew M Nitrated non-cyclic N-Alkane scaffolds with differentiated-mean combustive equivalencies as high energy density fuel improvers
US20110172474A1 (en) * 2010-01-07 2011-07-14 Lockheed Martin Corporation Aliphatic additives for soot reduction
SE541936C2 (en) 2017-02-03 2020-01-07 Scania Cv Ab Method of compacting ash deposited in a particulate filter by providing a low-temperature melting salt to said filter

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Also Published As

Publication number Publication date
ATE127510T1 (de) 1995-09-15
DE4041127C2 (enrdf_load_stackoverflow) 1992-07-16
US5522905A (en) 1996-06-04
EP0492101A1 (de) 1992-07-01
DE4041127A1 (de) 1992-02-20

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