EP1662105B1 - System zur Behandlung von NOx im Abgasstrom einer automobilen Brennkraftmaschine - Google Patents

System zur Behandlung von NOx im Abgasstrom einer automobilen Brennkraftmaschine Download PDF

Info

Publication number
EP1662105B1
EP1662105B1 EP05292350A EP05292350A EP1662105B1 EP 1662105 B1 EP1662105 B1 EP 1662105B1 EP 05292350 A EP05292350 A EP 05292350A EP 05292350 A EP05292350 A EP 05292350A EP 1662105 B1 EP1662105 B1 EP 1662105B1
Authority
EP
European Patent Office
Prior art keywords
plasma
temperature
catalyst
catalytic
temperatures
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.)
Not-in-force
Application number
EP05292350A
Other languages
English (en)
French (fr)
Other versions
EP1662105A1 (de
Inventor
François Baudin
Stéphanie Schneider
Yvane Lendresse
Sabine Calvo
Patrick Da Costa
Gérald DJEGA-MARIADASSOU
Cyril Thomas
Ahmed Khacef
Jean-Marie Cormier
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.)
Universite Pierre et Marie Curie Paris 6
Original Assignee
Universite Pierre et Marie Curie Paris 6
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 Universite Pierre et Marie Curie Paris 6 filed Critical Universite Pierre et Marie Curie Paris 6
Publication of EP1662105A1 publication Critical patent/EP1662105A1/de
Application granted granted Critical
Publication of EP1662105B1 publication Critical patent/EP1662105B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • 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
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • 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
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • F01N13/0097—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series the purifying devices are arranged in a single housing
    • 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
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0892—Electric or magnetic treatment, e.g. dissociation of noxious components
    • 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
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • 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
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • 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
    • F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/28—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being a plasma reactor
    • 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
    • F01N2370/00—Selection of materials for exhaust purification

Definitions

  • the present invention relates to a system for treating the nitrogen oxides of the exhaust gas of a motor vehicle engine, comprising, in an exhaust line thereof, means for producing non-thermal plasma at from the exhaust gases they receive at the inlet and the nitrogen oxide reduction catalyst forming means arranged at the outlet of the plasma production means.
  • the combustion of an air / fuel mixture in a motor vehicle engine produces oxides of nitrogen (nitrogen monoxide NO and nitrogen dioxide NO 2 ).
  • a technology for the treatment of NOx present in the exhaust gas uses a catalyst arranged in the exhaust line of the engine.
  • a catalyst has a permanent catalytic activity during the operation of the engine.
  • Such a catalyst uses unburnt hydrocarbons from the exhaust gases to reduce NOx at catalytic sites provided for this purpose.
  • the thermal window of catalytic activity of such a catalyst i.e., the temperature range where the catalyst is effective in reducing NOx, is relatively low.
  • its use is incompatible with the operation of a vehicle engine for particular whose exhaust temperature can vary widely.
  • the document WO 00/43469 A discloses a device and method for removing at least a portion of at least one pollutant in an exhaust gas stream containing an exhaust gas formed from the combustion of fuel in a lean-burn engine.
  • the document BE 1006164A discloses a catalyst device for the reduction of nitrogen oxides in an exhaust gas which occurs in a wide range of temperatures.
  • the object of the present invention is to solve the aforementioned problem by proposing a NOx treatment system emitted by a motor vehicle engine having a thermal window of significant catalytic activity and compatible with a substantially permanent operation of the engine lean mixture, so that such a system can be implanted in motor vehicles for particular for effective treatment of NOx.
  • a motor vehicle engine 10 is associated with means 12 for supplying fuel to its cylinders and means 14 for admitting air at its inlet.
  • the engine 10 is also associated with an exhaust line 16 of its exhaust gas comprising a reactor 18 for producing non-thermal plasma.
  • the reactor 18 comprises a cylindrical body comprising at least a first peripheral electrode connected to the ground of high voltage electrical supply means and a second central electrode, in the form of a wire, connected to a terminal of setpoint voltage of the high voltage supply means.
  • the power supply means 20 are controllable and connected to the vehicle battery, for example. They comprise a waveform generator suitable for forming electric discharges in the exhaust gas passing through the reactor 18 to thereby produce a non-thermal plasma.
  • the means 20 are adapted to deliver predetermined voltage pulses to the reactor electrodes or a sinusoidal voltage.
  • the catalyst 22 comprises a plurality of successive separate catalytic elements 22a, 22b, 22c arranged in series.
  • Each of these catalytic elements has a catalytic activity (NOx conversion rate) in a variable thermal window depending on the nature of the gases they treat, that is to say depending in particular on the composition of the gases. unburned hydrocarbon exhaust and plasma exhaust gas characteristics, as will be explained in more detail later.
  • the thermal windows of the elements 22a, 22b, 22c of the catalyst 22 are complementary, a first window being in low temperatures, a second in intermediate temperatures and a third in high temperatures.
  • the total thermal window of catalytic activity of the catalyst 22 is important, as will be explained in more detail later.
  • the operation of the motor 10 and of the components which have just been described is controlled by a unit 24 implementing a NOx treatment control strategy which maximizes the catalytic activity of the catalyst 22 for the exhaust gas temperature, while by minimizing the fuel consumption induced by the reactor 18 power supply.
  • a first temperature sensor 26 is arranged upstream of the catalyst 22 to acquire the temperature of the exhaust gas at the inlet thereof and delivers the upstream temperature acquired to the unit 24.
  • a second temperature sensor 28 is also provided downstream of the catalyst 22 to acquire the temperature of the exhaust gas leaving the latter, and delivers the downstream temperature acquired to the unit 24.
  • Means 30 for acquiring the operating point of the motor 10, for example the rotational speed thereof, the motor torque required by the driver and / or the air flow at the input of the motor 10, are also provided and deliver the operating point acquired to the unit 24.
  • These means 30 comprise for example a speed sensor for the acquisition of the rotational speed of the motor 10, a position sensor of the accelerator pedal for the acquisition of the requested torque and a flowmeter arranged at the inlet of the intake means 14 for acquiring the air flow admitted into the engine 10.
  • a second embodiment of the reactor and the catalyst is schematically presented on the figure 2 .
  • identical or similar elements are referenced by the same number.
  • the reactor 18 and the catalyst 22 are structurally similar to those of the figure 1 but are incorporated in the same body 32, that is to say that the reactor 18 is arranged inside the catalyst 22.
  • the non-thermal plasma is directly produced from the gases present in the catalyst.
  • the reaction medium bathing the catalytic elements of the catalyst comprises a concentration of reactive elements, such as free radicals for example, greater because of the time of transport thereof to the catalytic elements with respect to to this one of the embodiment of the figure 1 .
  • the catalytic element 22a upstream of the catalyst has a catalytic activity in a high temperature window, that is to say having a main catalytic activity between about 300 ° C and about 500 ° C without plasma in the treated gases, and between about 200 ° C and about 400 ° C with plasma in the treated gases.
  • the upstream catalytic element is Al 2 O 3 alumina.
  • Table 1 presents the main characteristics of alumina Al 2 O 3 illustrated in FIGS. 3A, 3B, 4A and 4B .
  • the nature of the exhaust gas treated with alumina depends on their unburned hydrocarbon composition at the engine outlet.
  • the unburned hydrocarbons present at the outlet of the engine in the exhaust gas are substantially propene.
  • the unburned hydrocarbons present at the engine outlet are a mixture of propene, propane, toluene and decane in the standard proportions of exhaust gas of a heat engine.
  • the nature of the treated exhaust gas also depends on the presence or absence of non-thermal plasma in the alumina-treated gases.
  • a first main column “Propene” of Table 1 refers to the catalytic properties of Al 2 O 3 alumina in the presence of propene as a major reducer in the exhaust gas at the engine outlet.
  • a second main column “Hydrocarbon mixture” refers to these same properties in the presence of the mixture of unburned hydrocarbons in the exhaust gas leaving the engine.
  • a first main line of Table 1 “Plasma-free” refers to the catalytic properties of alumina Al 2 O 3 in the absence of plasma in the treated exhaust gas and a second main line “With plasma” refers these same properties in the presence of plasma.
  • Each of the first and second main columns of Table 1 is divided between a first column "Window (° C)", which lists thermal windows of catalytic activities of alumina Al 2 O 3 , and a column “AC (%) which lists the minimal catalytic activities of alumina Al 2 O 3 corresponding to these thermal windows.
  • Table 1 Catalytic activity of alumina Al ⁇ sub> 2 ⁇ / sub> O ⁇ sub> 3 ⁇ / sub> depending on the temperature and the nature of the treated gases.
  • the intermediate catalytic element 22b of the catalyst 22, downstream of the upstream catalytic element 22a, has a thermal window of intermediate catalytic activity, lower than that of the first upstream catalytic element, that is to say having a catalytic activity main between about 200 ° C and about 300 ° C with or without plasma in the treated gases.
  • This intermediate catalytic element 22b is for example formed of a transition metal deposit on cerium and zirconium oxides.
  • the intermediate catalytic element 22b is of the Rh / Ce0 2 -Zr0 2 and / or Pd / Ce0 2 -Zr0 2 type .
  • Table 2 organized identically in Table 1, shows the main catalytic characteristics, as illustrated in FIGS. 5A, 5B, 6A and 6B of an element of the type Pd-Rh / Ce0 2 -Zr0 2 as a function of the temperature and the nature of the gases described previously.
  • Table 2 Catalytic activity of Pd-Rh / Ce0 ⁇ sub> 2 ⁇ / sub> -Zr0 ⁇ sub> 2 ⁇ / sub> as a function of the temperature and the nature of the gases treated.
  • the catalytic element 22c downstream of the catalyst 22, downstream of the intermediate catalytic element 22b, has a thermal window of low catalytic activity, lower than that of the intermediate catalytic element 22b, that is to say having a main catalytic activity between about 150 ° C and about 300 ° C with or without plasma in the treated gases.
  • This downstream element 22c is for example formed of a deposit of precious metal on cerium and zirconium oxides.
  • the catalytic element 22c downstream is Ag / Ce0 2 -Zr0 2 type .
  • Table 3 organized identically in Table 1, shows the main catalytic characteristics, as illustrated in FIGS. 7A, 7B, 8A and 8B of an element of the Ag / Ce0 2 -Zr0 2 type as a function of the temperature and the nature of the gases described previously.
  • Table 3 Catalytic activity of Ag / Ce0 ⁇ sub> 2 ⁇ / sub> -Zr0 ⁇ sub> 2 ⁇ / sub> as a function of the temperature and the nature of the gases treated.
  • propene Hydrocarbon mixture Window (° C) AC (%) Window (° C) AC (%) Without plasma 200-250 10 200-250 10 300-400 300-400 250-300 18 250-300 18 With plasma 150-400 20
  • thermal windows of catalytic activity of the various elements 22a, 22b, 22c are complementary and decrease in the direction of the flow of the exhaust gases in the exhaust line 16.
  • each of the elements 22a, 22b, 22c of the catalyst 22 exhibits a total catalytic activity as a function of the temperature and the nature of the treated exhaust gases as illustrated in FIGS. FIGS. 9A, 9B, 10A and 10B .
  • Table 4 organized in a manner identical to Table 1, summarizes the main characteristics of the catalyst 22.
  • Table 4 total catalytic activity of the catalyst, formed successively, in the gas flow direction, of Al ⁇ sub> 2 ⁇ / sub> O ⁇ sub> 3 ⁇ / sub>, of Pd-Rh / Ce0 ⁇ sub > 2 ⁇ / sub> -Zr0 ⁇ sub> 2 ⁇ / sub> and Ag / Ce0 ⁇ sub> 2 ⁇ / sub> -Zr0 ⁇ sub> 2 ⁇ / sub> depending on the temperature and nature of the gases treaties.
  • the catalyst 22 thus has a catalytic activity in a thermal window at least equal to [200-500] ° C., which makes it possible to obtain NOx treatment in a wide operating range of a particular vehicle engine.
  • the three catalytic elements Al 2 O 3 , Ph-Rh / CeO 2 -ZrO 2 and Ag / CeO 2 -ZrO 2 are deposited on a single support, such as cordielite, mullite, carborundum (SiC ), metal, or any type of substrate suitable for use as a catalyst support.
  • the unit 24 comprises means 40 for storing a first and a second threshold temperature T1, T2.
  • the storage means 40 are connected to first and second comparison means 42, 44 of the threshold temperatures T1, T2 at the upstream temperatures Td and downstream Td respectively acquired.
  • T1, T2 threshold temperatures are for example determined experimentally and depend in particular on the composition of catalytic elements, their precious metal charge and the catalyst volume, as well as the adjustment of the engine.
  • T1 is for example equal to 200 ° C and T2 is for example equal to 350 ° C.
  • the activation / deactivation means 46 activate the high voltage power supply of the plasma production reactor if this activation has the effect of a significant catalytic activity increase of the catalyst, for example greater than 10%.
  • the activation / deactivation means 46 does not energize the plasma generating reactor, an activation condition of this reactor being that at least one type of catalyst element present in the catalyst 22 is in a primed state.
  • the NOx are then not treated by the non-primed catalytic elements and thus pass through the catalyst without reduction in nitrogen. Indeed, the activation of the reactor would have substantially no effect on the catalytic activity of the catalyst. This phase corresponds to the cold start of the vehicle.
  • the catalytic elements are ignited and the means 46 activate the reactor for the production of plasma.
  • the three catalytic elements including alumina whose thermal window is located in the high temperatures in the absence of plasma with an evolution thereof to lower temperatures in the presence of plasma discharges in the exhaust gas, participate in the reduction of NOx exhaust gas.
  • the activation of the reactor thus results in a significant gain in the total catalytic activity of the catalyst greater than 10%, thus justifying the overconsumption of fuel induced by the activity of the reactor.
  • the means 46 control the means 20 for supplying the reactor steadily.
  • the supply means 20 are controlled by the activation / deactivation means 46 so that they deliver to the electrodes of the reactor a power of between 250 and 300 W, for example.
  • the means 46 control the supply means 20 according to the amount of NOx present in the exhaust gas and / or the temperature thereof.
  • the means 46 receive the operating point Pf of the engine and determine, for example by means of a predetermined map and stored therein, the amount of NOx emitted by the engine for the operating point. The means 46 then control the feed means 20 of the reactor so that they deliver a modulated power according to the amount of NOx determined, for example increasing in function of an increasing amount of NOx emitted by the engine.
  • the means 46 deactivate the plasma production reactor. Indeed, for temperatures greater than T2, only the high temperature catalytic element, that is to say alumina, has a catalytic activity. However, for these temperatures, the thermal window of catalytic activity of alumina is significantly greater without plasma than with plasma in the presence of the hydrocarbon mixture in the exhaust gases, as is illustrated in FIGS. Figures 4A and 4B . Since the activity gain by activation of the reactor is zero, the reactor is not activated for temperatures greater than T2. This makes it possible to reduce the fuel consumption of the engine for the production of energy necessary for the operation of the reactor supply means.
  • the means 46 are also adapted to control the operation of the motor supply means and / or the air inlet intake means of the engine in order to modify the unburned hydrocarbon composition of the exhaust gases and thus modulate the catalytic activity of the catalyst as a function of the composition of the exhaust gas in propene or in a mixture of hydrocarbons.
  • the means 46 is capable of modifying the fuel injection strategy in the engine cylinders by controlling a late injection of fuel therein, or post-injection.
  • the post-injection of fuel into the engine cylinders has the effect of significantly increasing the amount of unburned hydrocarbons in the exhaust gas, which leads to a temporary increase in the HC / NOx ratio of the amount of unburned hydrocarbons the amount of NOx in the exhaust gas, and therefore to an improvement in the conversion of NOx into nitrogen.
  • This unit implements in a simple manner a control strategy which maximizes, as a function of temperature, the catalytic activity of a catalyst comprising three complementary catalytic elements, in a broad thermal window of approximately [200, 500] ° C. while minimizing fuel over-consumption induced by the use of a plasma generating reactor.
  • system according to the invention may comprise a single sensor placed upstream of the catalyst, and the control unit is adapted to compare this acquired temperature with the aforementioned threshold temperatures for a control of the reactor supply means similar to that described previously.
  • the acquired downstream temperature being substantially that of the last catalytic element of the catalyst, which allows a control closer to the temperature thereof.
  • the catalyst may comprise 2 or more portions of catalytic element types.
  • Another variant consists in replacing the catalytic elements of Ag / CeO 2 -ZrO 2 and Pd-Rh / CeO 2 -ZrO 2 type with a material containing no precious metals, namely two elements of CeO 2 -ZrO 2 , so that the cost of the system is significantly reduced due to the absence of precious metals.
  • the catalyst comprises an alumina Al 2 O3 portion upstream of a portion of CeO 2 -ZrO 2.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Catalysts (AREA)
  • Control Of Eletrric Generators (AREA)
  • Hybrid Electric Vehicles (AREA)
  • Treating Waste Gases (AREA)

Claims (12)

  1. System zur Behandlung von Stickoxiden oder NOx im Abgasstrom eines Verbrennungsmotors (10) eines Kraftfahrzeugs, welches System in einem Abgasstrang (16) Mittel (18) zur Erzeugung eines nicht-thermischen Plasmas aus den am Einlaß aufgenommenen Abgasen und Mittel (22) zur Bildung eines Katalysators zur Verminderung von NOx enthalten, welche am Auslaß der Mittel zur Plasmaerzeugurig angeordnet sind, dadurch gekennzeichnet, dass die Mittel zur Bildung des Katalysators unterschiedliche Arten von katalytischen Elementen enthalten, welche unterschiedliche thermische Fenster katalytischer Aktivität aufweisen, welche katalytischen Elemente in der Strömungsrichtung des Gases in absteigender Reihenfolge der Temperaturen der thermischen Fenster katalytischer Aktivität angeordnet sind, welches System unter anderem umfaßt:
    - erste Mittel (26) zur Aufnahme der Temperatur des Abgases stromaufwärts der Mittel zur Bildung des Katalysators; und
    - Mittel (24) zur Steuerung der Mittel (18) zur Plasmaerzeugung entsprechend der aufgenommenen Temperatur zur Optimierung der Reduktion des NOx bei dieser Temperatur,
    welche Mittel (24) zur Steuerung die Mittel (18) zur Plasmaerzeugung derart aktivieren, dass bei der aufgenommenen Temperatur der gesamte Zuwachs katalytischer Aktivität der jeweiligen Aktivierung größer ist als eine vorbestimmte Schwelle.
  2. System gemäß Anspruch 1, dadurch gekennzeichnet, dass die Arten katalytischer Elemente derart ausgebildet sind, dass das thermische Fenster der gesamten katalytischen Aktivität der Mittel zur Bildung des Katalysators ein Fenster von 200° C bis 500° C umfaßt.
  3. System gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass die katalytischen Elemente aus der Gruppe ausgewählt sind, die aus Al2O3 oder CeO2-ZrO2 besteht, dass mit einem Übergangsmetall oder Edelmetall imprägniert ist.
  4. System gemäß Anspruch 3, dadurch gekennzeichnet, dass die katalytischen Elemente in der Strömungsrichtung des Abgasstroms aufeinanderfolgend aus Al2O3, Rh-Pd/CeO2-ZrO2 oder Ag/CeO2-ZrO2 bestehen.
  5. System gemäß Anspruch 3 oder 4, dadurch gekennzeichnet, dass die katalytischen Elemente auf einem einheitliche Träger angeordnet sind.
  6. System gemäß Anspruch 5, dadurch gekennzeichnet, dass der einheitliche Träger aus der Gruppe ausgewählt ist, die aus Cordierit, Mullit, SiC oder Metall gebildet wird.
  7. System gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass die katalytischen Elemente aus der Gruppe ausgewählt sind, die Al2O3 und CeO2-ZrO2 umfaßt.
  8. System gemäß einem der vorhergehenden Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Mittel (18) zur Erzeugung nicht-thermischen Plasmas im Inneren der Mittel (22) zur Bildung des Katalysators angeordnet sind.
  9. System gemäß einem der vorhergehenden Ansprüche, gekennzeichnet durch zweite Mittel (28) zur Temperaturaufnahme stromabwärts der Mittel (22) zur Bildung des Katalysators, wobei die Steuermittel (24) Mittel (46) zur Bestimmung des Anregungszustands der Arten katalytischer Elemente in Abhängigkeit von den aufgenommenen Temperaturen umfassen, und dass eine Bedingung zur Aktivierung der Mittel (18) zur Plasmaerzeugung darin besteht, dass zumindest eine Art von katalytischem Element angeregt ist.
  10. System gemäß Anspruch 9 in Verbindung mit einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, dass die Steuermittel Mittel (42,44) zum Vergleich der stromaufwärts gemessenen und stromabwärts gemessenen Temperaturen mit jeweils vorbestimmten ersten und zweiten Schwellentemperaturen umfassen, und dass
    - in dem Fall, in welchem die stromaufwärts gemessenen und stromabwärts gemessenen Temperaturen kleiner sind als ihre jeweiligen Schwellentemperaturen, die Mittel zur Plasmaerzeugung inaktiv sind;
    - in dem Fall, in welchem die stromaufwärts gemessene Temperatur grösser ist als die erste Schwellentemperatur und die stromabwärts gemessene Temperatur kleiner ist als die zweite Schwellentemperatur, die Mittel zur Plasmaerzeugung aktiv sind; und
    - in dem Fall, in welchem die stromaufwärts und stromabwärts gemessenen Temperaturen höher sind als ihre jeweiligen Schwellentemperaturen, die Mittel zur Plasmaerzeugung inaktiv sind.
  11. System gemäß Anspruch 10, dadurch gekennzeichnet, dass die ersten und zweiten Schwellentemperaturen jeweils im Bereich von 200° C bis 350° C liegen.
  12. System gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Steuermittel (24) unter anderem dazu vorgesehen sind, die Kraftstoffversorgung der Zylinder des Motors (10) und/oder die Luftfördermenge in den Motor (10) zur Veränderung der Zusammensetzung der Kohlenwasserstoffe der Abgase am Auslaß des Motors zu steuern.
EP05292350A 2004-11-08 2005-11-07 System zur Behandlung von NOx im Abgasstrom einer automobilen Brennkraftmaschine Not-in-force EP1662105B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR0411882A FR2877693B1 (fr) 2004-11-08 2004-11-08 SYSTEME DE TRAITEMENT DES NOx DE GAZ D'ECHAPPEMENT D'UN MOTEUR THERMIQUE DE VEHICULE AUTOMOBILE

Publications (2)

Publication Number Publication Date
EP1662105A1 EP1662105A1 (de) 2006-05-31
EP1662105B1 true EP1662105B1 (de) 2008-04-30

Family

ID=34950949

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05292350A Not-in-force EP1662105B1 (de) 2004-11-08 2005-11-07 System zur Behandlung von NOx im Abgasstrom einer automobilen Brennkraftmaschine

Country Status (4)

Country Link
EP (1) EP1662105B1 (de)
AT (1) ATE393872T1 (de)
DE (1) DE602005006363T2 (de)
FR (1) FR2877693B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8438842B2 (en) 2008-04-08 2013-05-14 Mitsubishi Electric Corporation Exhaust gas purification device

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2912385B1 (fr) 2007-02-13 2011-05-06 Gaz Transport & Technigaz Structure cylindrique composee d'elements rectangulaires.

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4032085A1 (de) * 1990-10-10 1992-04-16 Didier Werke Ag Katalysatoranordnung zur reduktion von stickoxiden
JP3922408B2 (ja) * 1997-09-16 2007-05-30 株式会社デンソー 内燃機関の排気浄化装置
EP1095702B1 (de) * 1998-06-30 2005-02-23 Toyota Jidosha Kabushiki Kaisha Verfahren und katalysator zur reinigung von abgas und verfahren zur herstellung des katalysators
WO2000043469A2 (en) * 1999-01-21 2000-07-27 Litex, Inc. Combined plasma reactor catalyst systems for effective emission control over a range of operating conditions
JP3642032B2 (ja) * 2001-03-02 2005-04-27 トヨタ自動車株式会社 内燃機関の排気浄化装置
JP4222064B2 (ja) * 2003-03-06 2009-02-12 マツダ株式会社 排気ガス浄化用触媒
JP2004305841A (ja) * 2003-04-03 2004-11-04 Honda Motor Co Ltd ＮＯｘ浄化システム

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8438842B2 (en) 2008-04-08 2013-05-14 Mitsubishi Electric Corporation Exhaust gas purification device

Also Published As

Publication number Publication date
EP1662105A1 (de) 2006-05-31
DE602005006363T2 (de) 2009-06-10
FR2877693B1 (fr) 2007-04-13
DE602005006363D1 (de) 2008-06-12
FR2877693A1 (fr) 2006-05-12
ATE393872T1 (de) 2008-05-15

Similar Documents

Publication Publication Date Title
EP1815112B1 (de) Abgassystem mit exothermerzeugungskatalysator
FR2540177A1 (fr) Regeneration des filtres catalytiques a particules et appareil pour sa mise en oeuvre
CN1540143A (zh) 内燃机的排气净化装置
FR2792036A1 (fr) Systeme d'aide a la regeneration d'un filtre a particules integre dans une ligne d'echappement d'un moteur diesel notamment de vehicule automobile
EP1581727B1 (de) Unterstützungssystem zur regeneration einesteilchenfilters in einer auslassleitung eines dieselmotors
EP1941136A2 (de) Vorrichtung zur bearbeitung von stickstoffoxiden aus kraftfahrzeugabgasen
EP1617051B1 (de) Abgasstrecke einer Brennkraftmaschine und Anlage zur Abgasreinigung
FR2831208A1 (fr) Dispositif de maitrise pour les emissions d'echappement pour un moteur a combustion interne
EP1662105B1 (de) System zur Behandlung von NOx im Abgasstrom einer automobilen Brennkraftmaschine
EP1809878A1 (de) Vorrichtung zur kontrolle des betriebszustandes eines katalytischen wandlers einer abgasleitung, die zu einem verbrennungsmotor führt, und motor mit einer solchen vorrichtung
WO2010139875A1 (fr) Moteur a combustion interne
FR2831077A1 (fr) Installation et procede pour l'epuration des gaz d'echappement avec un catalyseur d'emmagasinage des oxydes d'azote et un catalyseur a rcs
FR2981862A3 (fr) Controle du ratio no2/nox pour la scr par procede plasma
WO2008142324A1 (fr) Systeme de traitement des oxydes d'azote pour moteur a combustion interne
EP2439385A1 (de) Verfahren zur Nachbehandlung von Abgasen eines Verbrennungsmotors
FR2801635A1 (fr) Procede de gestion du fonctionnement d'un filtre a particules pour moteur a combustion
FR2802572A1 (fr) Dispositif de regeneration d'un filtre a particules d'une ligne d'echappement d'un moteur diesel
FR2943095A1 (fr) Procede de regeneration d'un filtre a particules
EP1375885B1 (de) Behandlungsverfahren der Abgase einer Otto-Brennkraftmaschine
FR2926518A1 (fr) Procede de commande d'un moteur hybride et moteur correspondant
EP1827893A1 (de) Verfahren zur regelung der regenerierung eines elektrostatischen partikelfilters
FR2846038A1 (fr) Procede de determination de la temperature interne d'un filtre a particules, procede de commande de la generation du filtre a particules, systeme de commande et filtre a particules correspondant.
FR2918901A3 (fr) Systeme de production de composes cwhyoz
FR3030618A1 (fr) Procede de gestion d'un catalyseur d'oxydation de methane et systeme de post-traitement des gaz d'echappement pour sa mise en oeuvre
FR2883199A1 (fr) Filtre a particules pour vehicule automobile et systeme et ligne d'echappement comprenant un tel filtre a particules

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20061104

17Q First examination report despatched

Effective date: 20061207

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIN1 Information on inventor provided before grant (corrected)

Inventor name: CALVO, SABINE

Inventor name: KHACEF, AHMED

Inventor name: DJEGA-MARIADASSOU, GERALD

Inventor name: THOMAS, CYRIL

Inventor name: LENDRESSE, YVANE

Inventor name: DA COSTA, PATRICK

Inventor name: BAUDIN, FRANCOIS

Inventor name: SCHNEIDER, STEPHANIE

Inventor name: CORMIER, JEAN-MARIE

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNIVERSITE PIERRE ET MARIE CURIE (PARIS VI)

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602005006363

Country of ref document: DE

Date of ref document: 20080612

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080930

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080810

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080830

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080731

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20090202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

BERE Be: lapsed

Owner name: UNIVERSITE PIERRE ET MARIE CURIE (PARIS VI)

Effective date: 20081130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081101

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091130

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091130

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080731

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20120910

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20121113

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20121123

Year of fee payment: 8

Ref country code: GB

Payment date: 20121127

Year of fee payment: 8

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20131107

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140731

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602005006363

Country of ref document: DE

Effective date: 20140603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140603

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131202

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131107