EP1117751A1 - Method for desulphurizing engine fuel on board a motor vehicle - Google Patents
Method for desulphurizing engine fuel on board a motor vehicleInfo
- Publication number
- EP1117751A1 EP1117751A1 EP99970108A EP99970108A EP1117751A1 EP 1117751 A1 EP1117751 A1 EP 1117751A1 EP 99970108 A EP99970108 A EP 99970108A EP 99970108 A EP99970108 A EP 99970108A EP 1117751 A1 EP1117751 A1 EP 1117751A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fuel
- sulfur
- motor vehicle
- engine
- adsorption material
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
Definitions
- the invention relates to a method for desulfurizing a motor fuel on board a motor vehicle.
- Motor fuel is usually desulphurized using large chemical processes in refineries to produce the fuel.
- Known processes for this are extraction, adsorption (e.g. US 5,360,536), distillation or microbiological processes.
- the commercial motor fuels in Europe currently have a residual sulfur content of approx. 200 ppm. This is problematic with regard to the sulfur compatibility of modern exhaust gas aftertreatment systems that contain adsorbers and catalysts. Residual sulfur contents of less than 10 ppm should therefore be aimed for.
- the object of the invention is to provide a method for separating sulfur-containing components from an engine fuel that is suitable for use in mobile systems.
- only a small construction volume and a low weight should be required for its implementation.
- the fuel is desulfurized on board the motor vehicle by selective separation of the sulfur-containing fuel components by means of liquid phase adsorption.
- An adsorption material is used that selectively only adsorbs the sulfur-containing fuel components.
- solids with a high surface area are used as adsorbents, especially those substances which contain Al, Mg, Si or Ti in oxidic form. Examples include Al 2 0 3 , MgO, Si0 2 , Ti0 2 , zeolites, hydrotalcites or mixed oxides.
- a metal such as, for example, an alkali metal, an alkaline earth metal, a rare earth metal, or Ag, Cu, Co, Fe, Mn, Ni, V or Zn can also be used.
- Biogenic materials such as, for example, enzymes can also be used.
- the sulfur contained in the fuel can be converted into other sulfur compounds by microorganisms that are brought into contact with the fuel.
- the adsorption material has a temporary separation performance and must be replaced after some time within the maintenance intervals of the vehicle.
- the adsorption material can also be regenerated on board the motor vehicle, in particular by thermal treatment.
- the regeneration can advantageously be carried out by thermostatting using the coolant circuit in the vehicle (approx. 80 ° C) or the engine oil circuit (> 100 ° C).
- the adsorption device and fuel filter can be integrated in one structural unit.
- Adsorption material and the material for fuel filtering can, for example, be arranged or layered directly next to or on top of one another.
- the low-sulfur fuel is particularly suitable for adding to a lean-burn gasoline engine.
- the addition of low-sulfur diesel fuel can reduce the particle emissions in the exhaust gas.
- the low-sulfur fuel can also be used as a reducing agent for denitrification catalysts in lean exhaust gas.
- Another application of the low-sulfur fuel obtained with the method according to the invention is for the desulfation of a catalyst in an exhaust gas aftertreatment system of an engine.
- sulfur accumulates on the surface of the catalytic converter from time to time, which is removed by regeneration (desorption). This can only be done with low sulfur exhaust gas.
- the equipment required to carry out the method according to the invention is low. As a result, the construction volume and weight can also be kept small.
- the method according to the invention is therefore suitable for use in all mobile systems such as passenger or commercial vehicles or in rail-bound vehicles.
- Another advantage of the method according to the invention is that the low-sulfur fuel fraction is available on board immediately when the engine is started. An additional storage tank for low-sulfur fuel especially for the cold start phase can therefore be dispensed with.
- the low-sulfur fuel obtained can either be used directly or stored in a storage container.
- the method according to the invention can be used for all motor fuels, in particular petrol or diesel fuels, kerosene or methanol.
- Fig. 1 shows a first structure for performing the method according to the invention
- 2 shows a second structure for carrying out the method according to the invention
- Fig. 3 shows an adsorption device for performing the invention
- Fig. 4 shows an experimental setup for determining the adsorber properties and adsorber capacity
- Fig. 5 shows the effect of the fuel sulfur content on the NO x conversion
- the adsorption device can be connected in series (Fig. 1) or as a bypass to the normal fuel supply (Fig. 2) after the fuel pump.
- FIG. 1 An arrangement with a series connection of fuel pump and adsorption device is shown in FIG. 1.
- the fuel is removed from the fuel tank KT by means of an electric fuel pump KP, then passes through the adsorption device AD according to the invention before it is fed to the engine via the injection nozzle ED.
- the intake pipe of the engine is labeled AR.
- all fuel supplied to the engine is desulfurized.
- a valve V can be used to switch between the normal branch without an adsorption device and the branch with an adsorption device. This makes it possible to use desulfurization only in certain operating phases of the engine. For example, desulphurization can only be activated when the engine is lean and when the adsorber catalyst contained in the exhaust gas aftertreatment system is desulfated.
- the bypass circuit shown can increase the mileage of the adsorption device or make it smaller.
- FIG. 3 shows a schematic representation of an adsorption device in the form of a separation column, the interior of which is filled with the adsorption material.
- the sulfur-containing fuel mixture to be separated is added undiluted to the entrance of the separation column and to the adsorption material.
- the sulfur-containing fuel components are selectively adsorbed on the adsorption material.
- the non-adsorbed, sulfur-free, (generally low-boiling) fuel components leave the separation column as an eluate at the opposite end.
- the separation is surrounded by an annular channel through which a heat transfer medium flows to temper the separation column.
- the fuel is taken from a storage vessel and fed through the thermostated adsorption column via an HPLC pump (max. Throughput 10 ml / min).
- HPLC pump max. Throughput 10 ml / min.
- the eluate can be examined offline using a gas chromatograph and X-ray fluorescence analysis.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19845397A DE19845397C2 (en) | 1998-10-02 | 1998-10-02 | Method for desulfurizing a motor fuel on board a motor vehicle |
DE19845397 | 1998-10-02 | ||
PCT/EP1999/007267 WO2000020531A1 (en) | 1998-10-02 | 1999-10-01 | Method for desulphurizing engine fuel on board a motor vehicle |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1117751A1 true EP1117751A1 (en) | 2001-07-25 |
Family
ID=7883180
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99970108A Withdrawn EP1117751A1 (en) | 1998-10-02 | 1999-10-01 | Method for desulphurizing engine fuel on board a motor vehicle |
Country Status (5)
Country | Link |
---|---|
US (1) | US6749754B1 (en) |
EP (1) | EP1117751A1 (en) |
AU (1) | AU1151500A (en) |
DE (1) | DE19845397C2 (en) |
WO (1) | WO2000020531A1 (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3674553B2 (en) * | 2000-09-01 | 2005-07-20 | トヨタ自動車株式会社 | Equipment for removing sulfur-containing components in fuel |
DE10045939B4 (en) | 2000-09-16 | 2016-05-04 | Caterpillar Inc. | Sensor for determining the concentration of sulfur compounds in a liquid |
US7575688B2 (en) | 2004-03-15 | 2009-08-18 | Honeywell International Inc. | Apparatus and method for removing sulfur containing compounds from a post-refinery fuel stream |
US20090255875A1 (en) * | 2008-04-11 | 2009-10-15 | Unger Peter D | Improvements in regeneration of sulfur sorbents |
EP1725764A1 (en) * | 2004-03-15 | 2006-11-29 | Honeywell International, Inc. | Apparatus and method for storing and releasing sulfur containing aromatic compounds from a fuel stream of an internal combustion engine |
US8323603B2 (en) * | 2004-09-01 | 2012-12-04 | Sud-Chemie Inc. | Desulfurization system and method for desulfurizing a fuel stream |
US20060283780A1 (en) * | 2004-09-01 | 2006-12-21 | Sud-Chemie Inc., | Desulfurization system and method for desulfurizing a fuel stream |
US20060156620A1 (en) * | 2004-12-23 | 2006-07-20 | Clayton Christopher W | Fuels for compression-ignition engines |
US20060163113A1 (en) * | 2004-12-23 | 2006-07-27 | Clayton Christopher W | Fuel Compositions |
EP1984476A2 (en) * | 2006-02-15 | 2008-10-29 | Honeywell International Inc. | Apparatus and method for removing sulfur containing compounds from a post-refinery fuel stream |
JP2010505973A (en) * | 2006-09-29 | 2010-02-25 | ハネウェル・インターナショナル・インコーポレーテッド | Fuel filter |
US20100133193A1 (en) * | 2007-02-14 | 2010-06-03 | Honeywell International, Inc. | Diesel sulfur filter-nanoadsorber and method of filtering a liquid fuel |
US7704383B2 (en) | 2007-10-16 | 2010-04-27 | Honeywell Interational Inc. | Portable fuel desulfurization unit |
DE102008044306A1 (en) * | 2008-12-03 | 2010-06-10 | Robert Bosch Gmbh | Device for stabilizing an operating fluid for motor vehicles |
CN102428257B (en) * | 2009-05-18 | 2014-04-09 | 丰田自动车株式会社 | Exhaust gas purifying device for internal combustion engine |
US8742775B2 (en) * | 2009-07-17 | 2014-06-03 | Caterpillar Inc. | Zinc oxide sulfur sensor |
US9097661B2 (en) | 2011-01-27 | 2015-08-04 | Caterpillar, Inc. | Electrochemical sulfur sensor and the method of making the same |
US9427684B2 (en) | 2014-07-31 | 2016-08-30 | Ford Global Technologies, Llc | Portable pre-filtering fuel filler device |
CN112221505B (en) * | 2020-11-16 | 2022-11-29 | 榆林学院 | Ni 2+ -Fe 3+ -TiO 2 Preparation of-LDHs and application of LDHs in photocatalytic oxidation desulfurization |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3616375A (en) * | 1966-03-03 | 1971-10-26 | Inoue K | Method employing wave energy for the extraction of sulfur from petroleum and the like |
US3971712A (en) * | 1970-01-20 | 1976-07-27 | Pyromet, Inc. | Process for removing sulfur impurities from a fluid by contact with silver articles |
US4039130A (en) * | 1974-05-06 | 1977-08-02 | Val Verde Corporation | Mobile refinery |
US4259213A (en) * | 1979-07-23 | 1981-03-31 | Chevron Research Company | High copper level comulled and impregnated sulfur sorbent |
US4419968A (en) * | 1980-02-28 | 1983-12-13 | Phillips Petroleum Company | Method and apparatus for removing hydrogen sulfide from fuel for an internal combustion engine |
US4419273A (en) * | 1981-11-04 | 1983-12-06 | Chevron Research Company | Clay-based sulfur sorbent |
US4738771A (en) * | 1984-12-11 | 1988-04-19 | Union Oil Company Of California | Hydrocarbon upgrading process |
DE3733321A1 (en) * | 1987-10-02 | 1989-04-20 | Artur Richard Greul | Method and device for making refineries mobile |
DE3825169A1 (en) * | 1988-07-23 | 1990-02-01 | Huels Chemische Werke Ag | METHOD FOR FINE DESULFURATION OF HYDROCARBONS |
US5146036A (en) * | 1990-01-12 | 1992-09-08 | Phillips Petroleum Company | Transfer of catalyst |
US5057473A (en) * | 1990-04-12 | 1991-10-15 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Regenerative Cu La zeolite supported desulfurizing sorbents |
US5360536A (en) * | 1993-08-09 | 1994-11-01 | Uop | Removal of sulfur compounds from liquid organic feedstreams |
JPH1036859A (en) * | 1996-07-30 | 1998-02-10 | Sekiyu Sangyo Kasseika Center | High temperature desulfurization by microorganism |
DE19652681C1 (en) * | 1996-12-18 | 1998-04-02 | Dornier Gmbh | Removing components from motor fuel |
US6118037A (en) * | 1997-04-22 | 2000-09-12 | Snamprogetti S.P.A. | Process for the removal of contaminant compounds containing one or more heteroatoms of sulfur, nitrogen and/or oxygen from hydrocarbon streams |
US6235519B1 (en) * | 1998-02-26 | 2001-05-22 | Energy Biosystems Corporation | Gene involved in thiophene biotransformation from nocardia asteroides KGB1 |
DE19827195A1 (en) * | 1998-06-18 | 1999-12-23 | Volkswagen Ag | Process for the de-sulfation of a NOx storage catalytic converter |
US6156084A (en) * | 1998-06-24 | 2000-12-05 | International Fuel Cells, Llc | System for desulfurizing a fuel for use in a fuel cell power plant |
DE19842625C2 (en) * | 1998-09-17 | 2003-03-27 | Daimler Chrysler Ag | Method for operating an internal combustion engine system with sulfur enriching emission control component and thus operable internal combustion engine system |
US6129835A (en) * | 1998-12-28 | 2000-10-10 | International Fuel Cells, Llc | System and method for desulfurizing gasoline or diesel fuel to produce a low sulfur-content fuel for use in an internal combustion engine |
US6461859B1 (en) * | 1999-09-09 | 2002-10-08 | Instituto Mexicano Del Petroleo | Enzymatic oxidation process for desulfurization of fossil fuels |
US6271173B1 (en) * | 1999-11-01 | 2001-08-07 | Phillips Petroleum Company | Process for producing a desulfurization sorbent |
US6338794B1 (en) * | 1999-11-01 | 2002-01-15 | Phillips Petroleum Company | Desulfurization with zinc titanate sorbents |
-
1998
- 1998-10-02 DE DE19845397A patent/DE19845397C2/en not_active Expired - Fee Related
-
1999
- 1999-10-01 AU AU11515/00A patent/AU1151500A/en not_active Abandoned
- 1999-10-01 EP EP99970108A patent/EP1117751A1/en not_active Withdrawn
- 1999-10-01 WO PCT/EP1999/007267 patent/WO2000020531A1/en not_active Application Discontinuation
- 1999-10-01 US US09/806,465 patent/US6749754B1/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO0020531A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE19845397A1 (en) | 2000-04-13 |
US6749754B1 (en) | 2004-06-15 |
AU1151500A (en) | 2000-04-26 |
WO2000020531A1 (en) | 2000-04-13 |
DE19845397C2 (en) | 2000-09-14 |
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Legal Events
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STAA | Information on the status of an ep patent application or granted ep patent |
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18W | Application withdrawn |
Effective date: 20040731 |