WO2014072718A1 - Système de diagnostic à bord - Google Patents

Système de diagnostic à bord Download PDF

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Publication number
WO2014072718A1
WO2014072718A1 PCT/GB2013/052922 GB2013052922W WO2014072718A1 WO 2014072718 A1 WO2014072718 A1 WO 2014072718A1 GB 2013052922 W GB2013052922 W GB 2013052922W WO 2014072718 A1 WO2014072718 A1 WO 2014072718A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst component
ferromagnetic material
catalyst
magnetic field
field strength
Prior art date
Application number
PCT/GB2013/052922
Other languages
English (en)
Inventor
Andrew Francis Chiffey
Original Assignee
Johnson Matthey Public Limited Company
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 Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Publication of WO2014072718A1 publication Critical patent/WO2014072718A1/fr

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Classifications

    • 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
    • F01N11/00—Monitoring or diagnostic devices for exhaust-gas treatment apparatus, e.g. for catalytic activity
    • F01N11/002—Monitoring or diagnostic devices for exhaust-gas treatment apparatus, e.g. for catalytic activity the diagnostic devices measuring or estimating temperature or pressure in, or downstream of the exhaust apparatus
    • 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
    • F01N11/00—Monitoring or diagnostic devices for exhaust-gas treatment apparatus, e.g. for catalytic activity
    • 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
    • F01N2550/00—Monitoring or diagnosing the deterioration of exhaust systems
    • F01N2550/02—Catalytic activity of catalytic converters
    • 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
    • F01N2560/00—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics
    • F01N2560/12—Other sensor principles, e.g. using electro conductivity of substrate or radio frequency
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/72—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating magnetic variables
    • G01N27/82—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating magnetic variables for investigating the presence of flaws
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/40—Engine management systems

Definitions

  • the invention relates to an on-board diagnostics system for an exhaust system of an internal combustion engine, and a method for on-board diagnostics of a catalyst component in the exhaust system.
  • On-board diagnostics in the context of a motor vehicle is a generic term to describe the self-diagnostic and reporting capability of the vehicle's systems provided by a network of sensors linked to a suitable electronic management system.
  • OBD On-board diagnostics
  • Early examples of OBD systems would simply illuminate a malfunction indicator light if a problem were detected, but it provided no information on the nature of the problem.
  • More modern OBD systems use a standardized digital connection port and are capable of providing information on standardized diagnostic trouble codes and a selection of real-time data, which enable rapid problem identification and resolution of a vehicle's systems.
  • the invention is an on-board diagnostics system for an exhaust system of an internal combustion engine.
  • the on-board diagnostics system comprises one or more ferromagnetic materials and a means for measuring magnetic field strength.
  • the invention also includes a method for on-board diagnostics of a catalyst component in the exhaust system. The method comprises measuring the magnetic field strength of a ferromagnetic material located in close proximity to the catalyst component and determining whether the ferromagnetic material has been exposed to a temperature above the Curie temperature of the ferromagnetic material, as measured by a decrease in the measured magnetic field strength.
  • the on-board diagnostics system of the invention comprises one or more ferromagnetic materials and a means for measuring magnetic field strength.
  • Ferromagnetic materials include any material that has a large, positive susceptibility to an external magnetic field. Ferromagnetic materials become magnetized when the electron spins become aligned to an external magnetic field. They typically exhibit a strong attraction to magnetic fields and are able to retain their magnetic properties after the external field has been removed. In the scope of this invention, materials that have a net magnetization shall be considered ferromagnetic even if some electron spins are anti-aligned and reduce the overall net magnetization (sometimes referred to as ferrimagnetic materials). Therefore, the term "ferromagnetic material" as used in the scope of the invention also includes a ferrimagnetic material.
  • the magnetic effects of ferromagnetic materials are sensitive to temperature. At higher temperatures, the atoms of the ferromagnetic materials will move around more, throwing the spins out of alignment. Above a critical temperature known as the Curie temperature, ferromagnets lose their ferromagnetic properties. That is, the Curie temperature is the temperature above which a ferromagnetic material loses all of its ferromagnetic properties.
  • the ferromagnetic materials useful in the invention include Fe, Fe 2 0 3 , Co, NiFe 2 0 3 , and AINiCo (an aluminum-nickel-cobalt alloy).
  • the Curie temperature of Fe is 770°C; Fe 2 0 3 is 675°C; Co is 1 1 15°C; NiOFe 2 0 3 is 585°C; and AINiCo is about 800°C.
  • the on-board diagnostics system of the invention also includes a means for measuring magnetic field strength.
  • Means for measuring magnetic field strength are well known in the art.
  • the means for measuring magnetic field strength include magnetometers (such as a rotating coil, Hall-Effect (Gauss Tesla) magnetometers, NMR magnetometers, SQUID magnetometers, and fluxgate magnetometers), Hall-Effect semi-conductor sensors, and Gradiometers (including axial and planar gradiometers).
  • These means for measuring magnetic field strength are preferably portable devices that can easily be installed on a vehicle.
  • One particular advantage of using magnetic field strength for OBD purposes is that it can be monitored continuously, without changes to the combustion mode, and under a wide range of engine operating conditions including engine idling or when the engine is stopped.
  • the on-board diagnostics system of the invention is preferably used to detect the potential thermal deterioration of a catalyst component located in the exhaust system.
  • the catalyst component is preferably a three-way catalyst (TWC), a diesel oxidation catalyst (DOC), a lean NO x trap, a catalyzed soot filter (CSF), a selective catalytic reduction (SCR) catalyst, or an SCR coated filter (SCRF).
  • the catalyst components typically comprise a catalyst coating coated on a substrate.
  • the substrate is preferably a ceramic substrate or a metallic substrate.
  • the ceramic substrate may be made of any suitable refractory material, e.g., alumina, silica, titania, ceria, zirconia, magnesia, zeolites, silicon nitride, silicon carbide, zirconium silicates, magnesium silicates, aluminosilicates and metallo aluminosilicates (such as cordierite and spudomene), or a mixture or mixed oxide of any two or more thereof. Cordierite, a magnesium aluminosilicate, and silicon carbide are particularly preferred.
  • the metallic substrate may be made of any suitable metal, and in particular heat-resistant metals and metal alloys such as titanium and stainless steel as well as ferritic alloys containing iron, nickel, chromium, and/or aluminum in addition to other trace metals.
  • the substrate may be a filter substrate or a flow-through substrate, depending on the application. If the substrate is a flow-through substrate, it is preferably a honeycomb monolith.
  • the substrate is typically designed to provide a number of channels through which vehicle exhaust passes. The surface of the channels is loaded with the catalyst coating.
  • TWCs Three-way catalyst systems
  • the TWC preferably comprises a combination of two or more platinum group metals (PGMs), generally Pt/Rh, Pd/Rh or Pt/Pd/Rh.
  • PGMs platinum group metals
  • the PGMs and any catalyst promoters used, e.g. a barium-based compound, are typically supported by one or both of an oxygen storage component (OSC), e.g. a Ce-Zr mixed or composite oxide, and a high surface area inorganic oxide, e.g. alumina.
  • OSC oxygen storage component
  • Diesel oxidation catalysts are designed to oxidize CO to C0 2 and gas phase hydrocarbons (HC) and an organic fraction of diesel particulates (soluble organic fraction) to C0 2 and H 2 0.
  • Typical DOC components include platinum and optionally also palladium on a high surface area inorganic oxide support, such as alumina, silica-alumina and a zeolite.
  • a catalyzed soot filter is a filter substrate that is coated with a catalyst of similar composition and function to a DOC. It can also assist in the combustion of diesel particulate matter.
  • Typical CSF catalyst components include platinum, palladium, and a high surface area inorganic oxide.
  • Selective catalytic reduction (SCR) catalysts are catalysts that reduce NO x to N 2 by reaction with nitrogen compounds (such as ammonia or urea) or hydrocarbons (lean NO x reduction).
  • a typical SCR catalyst is comprised of a vanadia-titania catalyst, a vanadia-tungsta-titania catalyst, or a metal/zeolite catalyst such as iron/beta zeolite, copper/beta zeolite, copper/SSZ-13, copper/SAPO-34, Fe/ZSM-5, or copper/ZSM-5.
  • the SCR catalyst is typically coated onto a flow-through substrate.
  • SCRF Selective catalytic reduction filters
  • Lean NO x traps are catalysts that adsorb NO x under lean exhaust conditions, release the adsorbed NO x under rich conditions, and reduce the released NO x to form N 2 .
  • NO x traps typically include a NO x - storage component (e.g., Ba, Ca, Sr, Mg, K, Na, Li, Cs, La, Y, Pr, and Nd), an oxidation component (preferably Pt), and a reduction component (preferably Rh). These components are contained on one or more inorganic oxide supports.
  • the ferromagnetic material When used to detect the thermal deterioration of the catalyst component, the ferromagnetic material will preferably be located in close proximity to the catalyst component so that the ferromagnetic material is exposed to the same temperatures as the catalyst component. Preferably, the ferromagnetic material will be located within 12 inches (30.5 cm), more preferably within 6 inches (15.25 cm) of the catalyst component, and most preferably within the catalyst component itself.
  • the ferromagnetic material may be located within a catalyst coating of the catalyst component.
  • the ferromagnetic materials and the washcoat composition should be selected such that they are mutually compatible and do not adversely impact the catalytic activity (for example, the ferromagnetic materials should not poison the catalytic washcoat).
  • the coating When the ferromagnetic material is located within the catalyst coating, the coating will preferably be magnetized (by aligning the electron spins of the ferromagnetic material) prior to installation on the vehicle. This can be achieved by passing the finished catalyst through an external magnetic field. The magnetized catalyst may then be installed on a vehicle and the magnetic field monitored using a suitable portable means for measuring the magnetic field strength.
  • the ferromagnetic material may be located on a separate probe located within a channel of the catalyst component. It may also be located on a separate probe in close proximity of the catalyst component, preferably within 12 inches (30.5 cm), and more preferably within 6 inches (15.25 cm), of the catalyst component. When located in close proximity of the catalyst component, the separate probe is preferably located downstream of the catalyst component, such that the exhaust gas first contacts the catalyst component prior to contacting the separate probe.
  • the probe When the ferromagnetic material is located on a separate probe, the probe will preferably be magnetized prior to installation on the vehicle. This can be achieved by passing the probe through an external magnetic field. The magnetized probe may then be installed on a vehicle and the magnetic field monitored using a suitable means for measuring the magnetic field strength.
  • the means for measuring magnetic field strength is preferably located such that it is in close enough proximity to the ferromagnetic material to measure the magnetic field strength, preferably within 12 inches (30.5 cm), and more preferably within 6 inches (15.25 cm), of the ferromagnetic material.
  • the means for measuring magnetic field strength may be measured continuously, and if the magnetic field strength falls below a pre-determined value this would trigger a malfunction indicator light (MIL) to indicate the catalyst component had exceeded a deactivating temperature condition.
  • MIL malfunction indicator light
  • the invention also encompasses a method for on-board diagnostics of a catalyst component in an exhaust system for an internal combustion engine.
  • the method comprises measuring the magnetic field strength of a ferromagnetic material that is located in close proximity of the catalyst component, wherein the ferromagnetic material has a Curie temperature above which the ferromagnetic material loses its ferromagnetic properties.
  • the ferromagnetic material will be located within 12 inches (30.5 cm), more preferably within 6 inches (15.25 cm) of the catalyst component, and most preferably within the catalyst component itself.
  • the ferromagnetic material may be located within a catalyst coating of the catalyst component, as previously described.
  • the ferromagnetic material may also preferably be located on a separate probe located within a channel of the catalyst component, or on a separate probe in close proximity of the catalyst component, as previously described. When located in close proximity of the catalyst component, the separate probe is preferably located downstream of the catalyst component, such that the exhaust gas first contacts the catalyst component prior to contacting the separate probe.
  • the method then comprises determining whether the ferromagnetic material has been exposed to a temperature above its Curie temperature, as measured by a decrease in the magnetic field strength.
  • This can be used to determine if the catalyst component has been thermally deactivated by exposure to excessive temperature. For instance, if the catalyst component is susceptible to high temperature deactivation above a certain temperature, the ferromagnetic material can be specifically chosen according to its Curie temperature.
  • the ferromagnetic material useful to show deactivation of the DOC will preferably be Fe (having a Curie temperature of 770°C).
  • the Fe ferromagnetic material will still exhibit magnetic properties as measured by, e.g., a Gauss magnetometer.
  • the measured magnetic field will indicate that the DOC has not been exposed to a deactivating high temperature.
  • the Fe will lose its magnetic properties as indicated by the lack of a magnetic field measured by the magnetometer. Therefore, the DOC has been exposed to a potentially deactivating high temperature above 770°C.
  • an OBD sensor may be triggered to indicate high temperature deactivation of the catalyst component.
  • the method of the invention further comprises triggering a malfunction indicator light when the magnetic field strength decreases below a pre-determined value, such as when the magnetic field strength approaches zero.
  • a diesel oxidation catalyst according to the invention is prepared by the following method. Appropriate amounts of platinum and palladium salts are added to alumina by the incipient wetness method. The material is dried and then calcined at 500°C. The calcined material is then slurried in water and milled to a particle size d90 ⁇ 20 micron. Beta zeolite is added to the slurry such that 10% of the total solids content by mass is beta zeolite. Low particle size iron particles (d90 ⁇ 20 micron) are added to the PGM/beta zeolite slurry and the mixture is stirred in order to homogenize it. The resulting milled slurry is applied to a cordierite flow-through monolith substrate using established coating techniques. The catalyst-containing substrate is dried and calcined at 500°C to produce the diesel oxidation catalyst (DOC).
  • DOC diesel oxidation catalyst
  • the DOC is then placed in an external magnetic field of appropriate field strength to magnetize the coating.
  • the magnetized DOC catalyst is installed on a vehicle together with a magnetometer in close proximity to the catalyst canning.
  • the magnetic field strength is continually monitored during the DOC use to diagnose whether the diesel oxidation catalyst will exceed OBD emission thresholds. After high temperature exposure (in this case at a temperature >770°C), the magnetic field strength of the catalyst decreases significantly and would trigger a malfunction indicator light (MIL) warning on the vehicle dashboard.
  • MIL malfunction indicator light

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Catalysts (AREA)

Abstract

L'invention porte sur un système de diagnostic à bord pour un système d'échappement d'un moteur à combustion interne. Le système comprend un ou plusieurs matériaux ferromagnétiques et un moyen de mesure de la force de champ magnétique. L'invention concerne également un procédé de diagnostic de bord d'un composant de catalyseur dans le système d'échappement. Le procédé consiste à mesurer la force de champ magnétique d'un matériau ferromagnétique placé à proximité étroite du composant de catalyseur et à déterminer si le matériau ferromagnétique a été exposé à une température supérieure à la température de Curie du matériau ferromagnétique, mesurée par une diminution de la force de champ magnétique mesurée.
PCT/GB2013/052922 2012-11-07 2013-11-07 Système de diagnostic à bord WO2014072718A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261723393P 2012-11-07 2012-11-07
US61/723,393 2012-11-07

Publications (1)

Publication Number Publication Date
WO2014072718A1 true WO2014072718A1 (fr) 2014-05-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107817272A (zh) * 2016-09-13 2018-03-20 现代自动车株式会社 柴油燃料品质检查设备以及柴油燃料品质检查方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6160413B2 (ja) * 2013-09-30 2017-07-12 マツダ株式会社 排気浄化触媒の劣化診断装置及び劣化診断方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0135204A2 (fr) * 1983-06-15 1985-03-27 CISE- Centro Informazioni Studi Esperienze S.p.A. Appareil pour détecter des défauts à la surface et près de la surface de corps métalliques au-dessus de la température de Curie
US6506605B1 (en) * 2000-05-26 2003-01-14 Engelhard Corporation System for sensing catalyst coating loss and efficiency
US20030011374A1 (en) * 1996-09-05 2003-01-16 Dieter Seipler Sensor for the monitoring of an NOx catalyst
US20100005783A1 (en) * 2006-04-11 2010-01-14 Daimler Chrysler Ag Device for monitoring an exhaust gas catalytic converter for an internal combustion engine
DE202009008379U1 (de) * 2009-06-15 2010-12-02 Apel, Helga Tanksystem
US20120216508A1 (en) 2009-09-03 2012-08-30 Johnson Matthey Public Limited Company Emission control

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0135204A2 (fr) * 1983-06-15 1985-03-27 CISE- Centro Informazioni Studi Esperienze S.p.A. Appareil pour détecter des défauts à la surface et près de la surface de corps métalliques au-dessus de la température de Curie
US20030011374A1 (en) * 1996-09-05 2003-01-16 Dieter Seipler Sensor for the monitoring of an NOx catalyst
US6506605B1 (en) * 2000-05-26 2003-01-14 Engelhard Corporation System for sensing catalyst coating loss and efficiency
US20100005783A1 (en) * 2006-04-11 2010-01-14 Daimler Chrysler Ag Device for monitoring an exhaust gas catalytic converter for an internal combustion engine
DE202009008379U1 (de) * 2009-06-15 2010-12-02 Apel, Helga Tanksystem
US20120216508A1 (en) 2009-09-03 2012-08-30 Johnson Matthey Public Limited Company Emission control

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107817272A (zh) * 2016-09-13 2018-03-20 现代自动车株式会社 柴油燃料品质检查设备以及柴油燃料品质检查方法

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