WO2013179393A1 - 内燃機関の排気浄化装置 - Google Patents
内燃機関の排気浄化装置 Download PDFInfo
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- WO2013179393A1 WO2013179393A1 PCT/JP2012/063795 JP2012063795W WO2013179393A1 WO 2013179393 A1 WO2013179393 A1 WO 2013179393A1 JP 2012063795 W JP2012063795 W JP 2012063795W WO 2013179393 A1 WO2013179393 A1 WO 2013179393A1
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- 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
- F01N3/2006—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
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- 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
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F01N3/105—General auxiliary catalysts, e.g. upstream or downstream of the main catalyst
- F01N3/106—Auxiliary oxidation catalysts
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- 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
- F01N3/2006—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
- F01N3/2033—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating using a fuel burner or introducing fuel into exhaust duct
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- 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
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- F01N3/208—Control of selective catalytic reduction [SCR], e.g. dosing of reducing agent
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- F02D41/024—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to increase temperature of the exhaust gas treating apparatus
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- F01N2610/14—Arrangements for the supply of substances, e.g. conduits
- F01N2610/1453—Sprayers or atomisers; Arrangement thereof in the exhaust apparatus
- F01N2610/146—Control thereof, e.g. control of injectors or injection valves
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- 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
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- F02D41/1446—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the characteristics of the combustion gases the characteristics being exhaust temperatures
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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- Y02T10/12—Improving ICE efficiencies
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/40—Engine management systems
Definitions
- the present invention relates to an exhaust emission control device for an internal combustion engine, and more particularly to a technique for raising the temperature of a NOx catalyst arranged in an exhaust passage of the internal combustion engine.
- an exhaust purification device for an internal combustion engine a device that arranges an oxidation catalyst or a NOx catalyst in an exhaust passage of the internal combustion engine is known.
- a technique for operating the internal combustion engine in either an exhaust temperature raising mode in which the exhaust temperature increases or an exhaust component reduction mode in which hydrocarbon (HC) in the exhaust gas decreases is known. Specifically, during the period from the start of the internal combustion engine to the activation of the catalyst, the internal combustion engine is operated in the exhaust temperature increase mode, and after the catalyst is activated, the exhaust temperature increase mode is set based on the purification performance of the catalyst and the exhaust components.
- a technique for switching the exhaust component reduction mode is known (see, for example, Patent Document 1).
- the catalyst becomes difficult to activate. Therefore, the period or opportunity for which the internal combustion engine is operated in the exhaust gas temperature raising mode increases.
- the air-fuel ratio of the air-fuel mixture is lowered (rich), the fuel ignition timing is retarded, or fuel post-injection (or after-injection) is performed. I will be broken. Therefore, when the period or opportunity when the internal combustion engine is operated in the exhaust gas temperature raising mode increases, the fuel consumption increases. Further, since the period during which the internal combustion engine is operated in a state where the catalyst is not activated becomes long, there is a possibility that the emission increases.
- the present invention has been made in view of the above situation, and an object of the present invention is to increase the temperature of the NOx catalyst in an exhaust gas purification apparatus for an internal combustion engine including a NOx catalyst disposed in an exhaust passage of the internal combustion engine.
- the present invention provides a technique capable of suppressing an increase in fuel consumption and an increase in emissions caused by the above process.
- the present invention focuses on the correlation between the temperature of the NOx catalyst and the NOx purification rate (the ratio of the NOx amount purified by the NOx catalyst to the NOx amount flowing into the NOx catalyst).
- the NOx purification rate when the NOx catalyst is in an inactive state increases as the temperature of the NOx catalyst increases.
- the ratio of the amount by which the NOx purification rate increases with respect to the temperature increase amount of the NOx catalyst (hereinafter referred to as “temperature change rate”) is not constant. Therefore, there is a case where the amount of increase in the NOx purification rate is smaller than the amount of increase in the temperature of the NOx catalyst (when the temperature change rate is small).
- the amount of increase in the NOx purification rate may increase with respect to the amount of increase in temperature of the NOx catalyst (when the temperature change rate is large).
- the amount of increase in the NOx purification rate is smaller than the amount of temperature increase of the NOx catalyst.
- the increase amount of the NOx purification rate increases with respect to the temperature increase amount of the NOx catalyst.
- the “lower limit temperature” here is, for example, a temperature at which a part of the NOx catalyst is activated (partial activation temperature).
- the “activation temperature” is a temperature at which the entire NOx catalyst is activated (complete activation temperature).
- the temperature change rate of the NOx catalyst becomes small, and therefore the period of time for performing the temperature raising process becomes long.
- the execution period of the temperature raising process tends to be long.
- the amount of fuel consumption increases and the amount of emissions (such as smoke and carbon dioxide (CO 2 )) also increases.
- the exhaust gas purification apparatus for an internal combustion engine of the present invention executes the temperature raising process of the NOx catalyst on the condition that the rate of temperature change is equal to or higher than a reference value. In other words, even when the NOx catalyst is in an inactive state, the exhaust gas purification apparatus for an internal combustion engine according to the present invention does not execute the temperature raising process of the NOx catalyst when the temperature change rate falls below the reference value. I made it.
- the exhaust gas purification apparatus for an internal combustion engine of the present invention is A NOx catalyst disposed in an exhaust passage of an internal combustion engine mounted on a vehicle; A temperature raising means for performing a temperature raising process which is a process for raising the temperature of the NOx catalyst by raising the temperature of the exhaust gas flowing into the NOx catalyst; Detecting means for detecting the temperature of the NOx catalyst; The condition is that the temperature change rate, which is the ratio of the increase amount of the NOx purification rate to the predetermined amount when the temperature of the NOx catalyst is increased by a predetermined amount from the temperature detected by the detecting means, is equal to or higher than a reference value. Control means for permitting execution of the temperature raising process, I was prepared to.
- the “predetermined amount” may be an amount that makes a difference between when the temperature change rate is large and small, and is determined in advance by an adaptation process using experiments or the like.
- the “reference value” is, for example, the minimum temperature change rate at which the amount of increase in the NOx purification rate is considered appropriate with respect to the amount of fuel consumption required to increase the temperature of the NOx catalyst by a predetermined amount. The value is determined in advance by an adaptation process using an experiment or the like.
- the temperature raising process is not executed. In other words, the temperature raising process is executed only when the temperature change rate when the temperature of the NOx catalyst rises by a predetermined amount is equal to or higher than the reference value.
- the temperature increasing process is executed when the temperature change rate is equal to or higher than the reference value, the temperature of the NOx catalyst and the NOx purification rate are rapidly increased.
- the temperature increasing process is executed on condition that the temperature change rate is equal to or higher than a reference value, NOx
- the temperature of the catalyst and the NOx purification rate can be quickly increased. As a result, the execution time of the temperature raising process can be shortened.
- the exhaust gas purification apparatus for an internal combustion engine of the present invention it is possible to suppress an increase in fuel consumption and an increase in emissions due to the temperature raising process.
- the exhaust gas purification apparatus for an internal combustion engine of the present invention it is possible to activate the NOx catalyst while suppressing an increase in fuel consumption and an increase in emissions accompanying the execution of the temperature raising process.
- the exhaust gas purification apparatus for an internal combustion engine of the present invention may further include an oxidation catalyst disposed in the exhaust passage upstream of the NOx catalyst.
- the temperature raising means may raise the temperature of the exhaust gas flowing into the NOx catalyst by supplying unburned fuel to the oxidation catalyst.
- the oxidation rate of the unburned fuel in the oxidation catalyst indicates that the temperature of the oxidation catalyst is a predetermined activity. When it is lower than the temperature (for example, the partial activation temperature), it becomes extremely small.
- the control means may permit the supply of unburned fuel to the oxidation catalyst on the condition that the temperature of the oxidation catalyst is equal to or higher than a predetermined activation temperature and the rate of temperature change is equal to or higher than the reference value.
- the temperature raising process can be executed while suppressing the amount of unburned fuel that is not oxidized in the oxidation catalyst and the NOx catalyst and is discharged into the atmosphere. Further, when the temperature raising process is performed in accordance with such conditions, a relatively large amount of unburned fuel can be supplied to the oxidation catalyst, so that the period for performing the temperature raising process can be further shortened. .
- the exhaust gas purification apparatus for an internal combustion engine of the present invention may further include a calculation means for integrating the amount of emission contained in the exhaust gas flowing out from the oxidation catalyst.
- the control means may prohibit the temperature raising process when the integrated amount of emission calculated by the computing means exceeds the comparison value.
- the “comparison value” here corresponds to, for example, an integrated amount of emissions when the temperature raising process is executed by a conventional method.
- Conventional methods include a method in which unburned fuel continues to be supplied to the oxidation catalyst during the period from the start of the internal combustion engine to the activation of the NOx catalyst, or when the temperature of the oxidation catalyst rises above a predetermined activation temperature.
- the unburned fuel is continuously supplied to the oxidation catalyst during the period until the NOx catalyst is activated.
- “Emission” is an exhaust component that increases due to the execution of the temperature raising process, and is, for example, smoke, carbon dioxide (CO 2 ), or the like. The amount of smoke and CO 2 flowing out from the oxidation catalyst per unit time can be calculated using the amount of unburned fuel supplied to the oxidation catalyst and the temperature of the oxidation catalyst as parameters.
- the exhaust gas purifying apparatus when the integrated amount of emissions calculated by the calculating means exceeds the comparison amount, the exhaust gas purifying apparatus increases even if the temperature change rate is equal to or higher than a reference value. The temperature process is not executed.
- the temperature increase is performed after the restart of the internal combustion engine.
- the process is executed again, there is a possibility that the accumulated amount of emissions becomes larger than the comparison value.
- the accumulated amount of emissions can be suppressed to the same level or lower as before.
- the amount of unburned fuel supplied to the oxidation catalyst during the temperature increase process is increased from the conventional temperature increase process, there is a possibility that the amount of emissions will be temporarily higher than the conventional temperature increase process.
- the amount of emissions (accumulated amount) in the medium to long term period can be suppressed to the same level or lower as before.
- control means of the present invention may reduce the amount of unburned fuel supplied to the oxidation catalyst when the NOx purification rate of the NOx catalyst exceeds a certain value during the temperature raising process.
- the “constant value” here is, for example, a value smaller than the NOx purification rate when the entire NOx catalyst is activated, and is equal to the NOx purification rate when most of the NOx catalyst is activated.
- the control means of the present invention may determine that the temperature change rate is equal to or higher than the reference value when the temperature detected by the detection means belongs to a predetermined temperature range.
- the “predetermined temperature range” is, for example, a temperature range in which the temperature change rate is equal to or higher than the reference value, and is a range obtained in advance by an adaptation process using an experiment or the like.
- the control means of the present invention may determine that the temperature change rate is equal to or higher than the reference value when the NOx purification rate of the NOx catalyst belongs to a predetermined purification rate range.
- the “predetermined purification rate range” is a range of the NOx purification rate in which the temperature change rate is equal to or higher than the reference value. Note that the NOx purification rate of the NOx catalyst can be calculated based on measured values of NOx sensors arranged upstream and downstream of the NOx catalyst.
- control means of the present invention calculates a temperature change rate using the exhaust gas flow rate, the exhaust air-fuel ratio, the temperature of the oxidation catalyst, and the temperature of the NOx catalyst as parameters, and the calculation result and the reference value May be compared.
- an increase in fuel consumption and an increase in emissions due to a process for raising the temperature of the NOx catalyst are reduced. Can be suppressed.
- FIG. 1 shows schematic structure of the internal combustion engine to which this invention is applied, and its intake / exhaust system. It is a figure which shows the correlation with the temperature of an oxidation catalyst, and a purification rate. It is a figure which shows the correlation with the temperature of a selective reduction catalyst, and a purification rate. It is a timing chart which shows the execution method of the temperature rising process in a 1st Example. It is a flowchart which shows the process routine performed by ECU when a temperature rising process is performed in a 1st Example. It is a timing chart which shows the execution method of the temperature rising process in 2nd Example. It is a flowchart which shows the process routine performed by ECU when a temperature rising process is performed in a 2nd Example.
- FIG. 1 is a diagram showing a schematic configuration of an internal combustion engine to which the present invention is applied.
- the internal combustion engine 1 shown in FIG. 1 is a compression ignition type internal combustion engine (diesel engine) having a plurality of cylinders.
- the internal combustion engine to which the present invention is applied is not limited to a compression ignition type internal combustion engine, but may be a spark ignition type internal combustion engine (gasoline engine) operated in a lean combustion mode.
- the intake passage 2 is a passage that guides fresh air (air) taken from the atmosphere to the cylinders of the internal combustion engine 1.
- the exhaust passage 3 is a passage for circulating burned gas (exhaust gas) discharged from the cylinder of the internal combustion engine 1.
- the throttle valve 4 is a valve mechanism that adjusts the amount of air taken into the cylinder of the internal combustion engine 1 by changing the cross-sectional area of the intake passage 2.
- the throttle valve 4 includes a valve body and an electric motor for opening and closing the valve body, and the electric motor is controlled by an ECU 10 described later.
- the first catalyst casing 5 includes an oxidation catalyst and a particulate filter inside a cylindrical casing.
- the oxidation catalyst may be supported on a catalyst carrier disposed upstream of the particulate filter, or may be supported on the particulate filter.
- the second catalyst casing 6 is a cylindrical casing in which a catalyst carrier carrying a selective reduction catalyst is accommodated.
- the catalyst carrier is, for example, a monolith type substrate having a honeycomb-shaped cross section made of cordierite or Fe—Cr—Al heat resistant steel and coated with an active component (support) of alumina or zeolite. is there.
- a noble metal catalyst for example, platinum (Pt), palladium (Pd), etc.
- selective reduction catalyst corresponds to the NO X catalyst according to the present invention.
- a catalyst carrier carrying an oxidation catalyst may be arranged downstream of the selective catalytic reduction catalyst.
- the oxidation catalyst in that case can oxidize the reducing agent that has passed through the selective reduction catalyst among the reducing agents supplied from the reducing agent addition valve 7 described later to the selective reduction catalyst.
- a reducing agent addition valve 7 for adding (injecting) NH 3 or a reducing agent which is a precursor of NH 3 into the exhaust gas. It is attached.
- the reducing agent addition valve 7 is a valve device having an injection hole that is opened and closed by the movement of a needle.
- the reducing agent addition valve 7 is connected to a reducing agent tank 71 via a pump 70.
- the pump 70 sucks the reducing agent stored in the reducing agent tank 71 and pumps the sucked reducing agent to the reducing agent addition valve 7.
- the reducing agent addition valve 7 injects the reducing agent pumped from the pump 70 into the exhaust passage 3.
- the opening / closing timing of the reducing agent addition valve 7 and the discharge pressure of the pump 70 are electrically controlled by the ECU 10.
- an aqueous solution such as urea or ammonium carbamate, or NH 3 gas can be used as the reducing agent.
- an aqueous urea solution is used as the reducing agent.
- the urea aqueous solution When the urea aqueous solution is injected from the reducing agent addition valve 7, the urea aqueous solution flows into the second catalyst casing 6 together with the exhaust gas. At that time, the urea aqueous solution receives heat from the exhaust and the second catalyst casing 6 and is thermally decomposed or hydrolyzed. When the aqueous urea solution is thermally decomposed or hydrolyzed, ammonia (NH 3 ) is generated. The ammonia (NH 3 ) thus generated is adsorbed or occluded by the selective reduction catalyst.
- Ammonia (NH 3 ) adsorbed or occluded by the selective catalytic reduction catalyst reacts with nitrogen oxide (NO x ) contained in the exhaust gas to generate nitrogen (N 2 ) or water (H 2 O). That is, ammonia (NH 3 ) functions as a reducing agent for nitrogen oxides (NO X ).
- the internal combustion engine 1 configured as described above is provided with an ECU 10.
- the ECU 10 is an electronic control unit that includes a CPU, a ROM, a RAM, a backup RAM, and the like.
- the ECU 10 is electrically connected to various sensors such as a first exhaust temperature sensor 8, a second exhaust temperature sensor 9, a crank position sensor 11, an accelerator position sensor 12, an air flow meter 13, and an A / F sensor 14.
- the first exhaust temperature sensor 8 is disposed in the exhaust passage 3 downstream from the first catalyst casing 5 and upstream from the second catalyst casing 6, and outputs an electrical signal correlated with the temperature of the exhaust gas flowing out from the first catalyst casing 5.
- the second exhaust temperature sensor 9 is disposed in the exhaust passage 3 downstream from the second catalyst casing 6 and outputs an electrical signal correlated with the temperature of the exhaust gas flowing out from the second catalyst casing 6.
- the crank position sensor 11 outputs an electrical signal correlated with the rotational position of the output shaft (crankshaft) of the internal combustion engine 1.
- the accelerator position sensor 12 outputs an electrical signal that correlates with the amount of operation of the accelerator pedal (accelerator opening).
- the air flow meter 13 outputs an electrical signal correlated with the amount of air taken into the internal combustion engine 1 (intake air amount).
- the A / F sensor 14 is disposed in the exhaust passage 3 upstream from the first catalyst casing 5 and outputs an electrical signal correlated with the air-fuel ratio of the exhaust.
- the ECU 10 is electrically connected to various devices (for example, a fuel injection valve) attached to the internal combustion engine 1, a throttle valve 4, a reducing agent addition valve 7, a pump 70, and the like.
- the ECU 10 electrically controls various devices of the internal combustion engine 1, the throttle valve 4, the reducing agent addition valve 7, the pump 70, and the like based on the output signals of the various sensors described above.
- the ECU 10 is a selective reduction type housed in the second catalyst casing 6 in addition to known controls such as fuel injection control of the internal combustion engine 1 and addition control for intermittently injecting the reducing agent from the reducing agent addition valve 7.
- the catalyst temperature increase control is executed.
- a method for executing the temperature rise control in this embodiment will be described.
- the oxidation catalyst and the selective reduction catalyst are not active, that is, the oxidation catalyst can oxidize unburned fuel components (HC, CO, etc.) in the exhaust.
- the selective catalytic reduction catalyst cannot reduce nitrogen oxide (NO x ) in the exhaust gas. Therefore, it is necessary to activate the oxidation catalyst and the selective reduction catalyst at an early stage.
- a method of activating the oxidation catalyst and the selective catalytic reduction catalyst at an early stage fuel is added to the exhaust passage 3 upstream from the oxidation catalyst, or after-injection from the fuel injection valve into the cylinder of the expansion stroke or the exhaust stroke.
- a method of executing a process (temperature increase process) for supplying an unburned fuel component to an oxidation catalyst is known. According to such a method, the temperature of the oxidation catalyst or the selective catalytic reduction catalyst can be raised by using heat generated when the unburned fuel component is oxidized by the oxidation catalyst.
- the oxidation catalyst or the selective reduction catalyst when the oxidation catalyst or the selective reduction catalyst is lower than a predetermined temperature, the amount of increase in the purification rate is less than the amount of increase in temperature.
- the relationship between the temperature (bed temperature) of the oxidation catalyst and the purification rate (oxidation rate of unburned fuel) is shown in FIG.
- the “first temperature Te1” here is a temperature at which at least a part of the oxidation catalyst housed in the first catalyst casing 5 is activated (partial activation temperature). If the temperature raising process is executed when the temperature of the oxidation catalyst is lower than the first temperature Te1, a large portion of the unburned fuel component supplied to the oxidation catalyst may be discharged into the atmosphere without being oxidized. is there.
- Figure 3 is a graph showing the relationship between the temperature and the purification rate of the selective reduction catalyst (NO X purification rate).
- the temperature of the selective reduction catalyst is lower than a predetermined temperature (second temperature) Te2
- second temperature Te2 to the temperature rise of the selective reduction catalyst
- selective reduction temperature of the catalyst is the second temperature Te2 or more, and when belonging to a range of less than the third temperature Te3, to the temperature rise of the selective reduction catalyst, increases the amount of the NO X purification rate Become more.
- the "second temperature Te2" is (ratio of the amount of NO X purification rate with respect to temperature increase of the selective catalytic reduction catalyst rises) temperature change rate when the temperature of the selective reduction catalyst rises a predetermined amount Is the lowest temperature that is equal to or higher than the reference value, for example, the temperature at which at least a part of the selective catalytic reduction catalyst accommodated in the second catalyst casing 6 is activated (partial activation temperature).
- the “third temperature Te3” is the highest temperature at which the temperature change rate when the temperature of the selective catalytic reduction catalyst increases by a predetermined amount is equal to or higher than a reference value, and is accommodated in the second catalyst casing 6, for example. This is the temperature at which the entire selective catalytic reduction catalyst is activated (complete activation temperature).
- the temperature raising process is executed on the condition that the temperature of the oxidation catalyst is equal to or higher than the first temperature Te1 and the temperature of the selective catalytic reduction catalyst is equal to or higher than the second temperature Te2 and lower than the third temperature Te3. It is desirable.
- the execution method of the temperature raising process in the present embodiment will be described along the timing chart of FIG.
- the heat of the exhaust is transferred to the oxidation catalyst and the selective reduction catalyst.
- the temperature of the oxidation catalyst rises before the selective reduction catalyst.
- the temperature of the oxidation catalyst reaches the first temperature Te1 or higher (t1 in FIG. 4)
- the temperature of the selective catalytic reduction catalyst reaches the second temperature Te2 or higher (t2 in FIG. 4).
- first period The period from the start of the internal combustion engine 1 until the temperature of the selective catalytic reduction catalyst reaches the second temperature Te2 or higher (hereinafter referred to as “first period”) is relative to the temperature increase amount of the selective catalytic reduction catalyst. ratio of the amount of NO X purification rate is increased (temperature change rate) is reduced. Therefore, during the first period, the temperature raising process is not executed (the temperature raising process flag is off (OFF)).
- a period (hereinafter referred to as “second”) from the time when the temperature of the selective catalytic reduction catalyst reaches the second temperature Te2 or higher (t2 in FIG. 4) to the time when the temperature reaches the third temperature Te3 or higher (t3 in FIG. 4).
- the temperature change rate is significantly higher than that in the first period. Therefore, during the second period, the temperature raising process is executed (the temperature raising process flag is on (ON)).
- the temperature raising process is executed in the second period, the temperature of the selective catalytic reduction catalyst rapidly rises and the temperature change rate also rapidly rises. As a result, it is possible to increase the NO X purification rate of the selective reduction catalyst in a short time.
- the amount of unburned fuel supplied to the oxidation catalyst per unit time at the time of executing the temperature raising process is the same as the conventional temperature raising process (supply of unburned fuel to the oxidation catalyst at the start of the internal combustion engine 1 or immediately after the start. It is preferable that the number of processes is increased more than when the process is started. In that case, it is possible to further increase the rising speed of the temperature increase rate and NO X purification rate of the selective reduction catalyst. As a result, even when the low load operation state is continued after the internal combustion engine 1 is started, the selective reduction catalyst can be activated quickly. Further, since the execution time of the temperature raising process is shortened, an increase in fuel consumption due to the temperature raising process can be suppressed to a small extent.
- the amount of PM or CO 2 flowing out from the oxidation catalyst in a relatively short period is larger than that in the conventional temperature raising process.
- the amount of PM and CO 2 flowing out from the oxidation catalyst can be reduced.
- the selective reduction catalyst can be activated in a short time while suppressing an increase in fuel consumption and an increase in emissions (PM and CO 2 flowing out from the oxidation catalyst). It becomes possible.
- FIG. 5 is a flowchart showing a processing routine executed by the ECU 10 when the temperature raising process is executed.
- the processing routine of FIG. 5 is stored in advance in the ROM or the like of the ECU 10 and is periodically executed by the ECU 10.
- the ECU 10 first reads the temperature of the oxidation catalyst and the temperature of the selective reduction catalyst in S101. At that time, the ECU 10 reads the output signal Tcat1 of the first exhaust temperature sensor 8 as the temperature of the oxidation catalyst, and reads the output signal Tcat2 of the second exhaust temperature sensor 9 as the temperature of the selective reduction catalyst.
- the detection means concerning this invention is implement
- the ECU 10 determines whether or not the temperature Tcat2 of the selective catalytic reduction catalyst belongs to a predetermined temperature range.
- the “predetermined temperature range” is a temperature range that is equal to or higher than the second temperature Te2 and lower than the third temperature Te3. If a negative determination is made in S102, the ECU 10 ends the execution of this processing routine. On the other hand, if a positive determination is made in S102, the ECU 10 proceeds to S103.
- the ECU 10 determines whether or not the temperature Tcat1 of the oxidation catalyst is equal to or higher than the first temperature Te1. If a negative determination is made in S103, the ECU 10 ends the execution of this processing routine. On the other hand, if an affirmative determination is made in S103, the ECU 10 proceeds to S104.
- control means concerning this invention is implement
- the ECU 10 executes a temperature raising process. That is, the ECU 10 injects fuel (after injection) from the fuel injection valve of the cylinder in the expansion stroke or the exhaust stroke. In this case, the fuel injection amount is increased as compared with the case where the conventional temperature raising process is executed.
- the temperature raising processing by such a method are performed, the temperature of the selective reduction catalyst rises rapidly, NO X purification rate also increases rapidly.
- the temperature raising means according to the present invention is realized by the ECU 10 executing the process of S104.
- the ECU 10 reads the output signal Tcat2 of the second exhaust temperature sensor 9 again.
- the ECU 10 determines whether or not the temperature Tcat2 read in S105 is equal to or higher than the third temperature Te3. If a negative determination is made in S106, the ECU 10 executes the processes subsequent to S101 again. On the other hand, if a positive determination is made in S106, the ECU 10 proceeds to S107.
- the ECU 10 ends the temperature increase process. That is, the ECU 10 ends the after injection of the fuel injection valve.
- the selective catalytic reduction catalyst can be quickly heated while suppressing an increase in fuel consumption and emission resulting from the temperature increasing process.
- the selective reduction catalyst can be activated in a short time, so that the conventional temperature increase process is executed. compared to when it is, it is possible to reduce the amount of the NO X discharged into the atmosphere.
- the example in which the temperature raising process is executed on condition that the temperature of the selective catalytic reduction catalyst belongs to the temperature range of the second temperature Te2 or higher and lower than the third temperature Te3 has been described.
- the NO x purification rate of the selective catalytic reduction catalyst may change depending on factors other than the temperature of the selective catalytic reduction catalyst. Therefore, the temperature change rate of the selective catalytic reduction catalyst may also change due to factors other than the temperature of the selective catalytic reduction catalyst.
- ECU 10 subject to the NO X purification rate of the selective reduction catalyst belongs to a predetermined purification rate range, it may perform the Atsushi Nobori process.
- ECU 10 in S102 of the processing routine in FIG. 5 described above, calculates the NO X purification rate of the selective reduction catalyst, calculated NO X purification rate by discriminating whether or not belonging to a predetermined purification rate range That's fine.
- predetermined purification rate range is the range of the NO X purification rate temperature change rate is equal to or greater than the reference value of the selective reduction catalyst is in a range determined in advance experimentally.
- the NO X purification rate of the selective catalytic reduction catalyst can be calculated using the following equation.
- Enox (Anoxin-Anoxout) / Anoxin Enox in the above formula is a NO X purification rate.
- Anoxin is the amount of the NO X flowing into the selective reduction catalyst (NO X inflow).
- Anoxout is the amount of the NO X flowing out from the selective catalytic reduction catalyst (NO X outflow).
- the NO X inflow amount Anoxin may be measured by a NO X sensor disposed in the exhaust passage 3 upstream of the selective catalytic reduction catalyst, or the operating state of the internal combustion engine 1 (fuel injection amount, intake air amount, and engine (E.g., rotation speed).
- the NO X outflow amount Anoxout may be measured by a NO X sensor disposed in the exhaust passage 3 downstream from the selective catalytic reduction catalyst.
- NO X purification rate of the selective reduction catalyst is determined whether or not it belongs to a predetermined purification rate range, it is determined whether or not the temperature change rate of the selective reduction catalyst is equal to or greater than the reference value more accurately Can do.
- the ECU 10 may calculate a temperature change rate when the temperature of the selective catalytic reduction catalyst has increased by a predetermined amount from the current temperature, and determine whether the temperature change rate is equal to or higher than a reference value. .
- the rate of temperature change at that time is the current temperature of the selective catalytic reduction catalyst, the flow rate of the exhaust, the air-fuel ratio of the exhaust, and the amount of NO 2 contained in the exhaust (preferably, the NO X contained in the exhaust. The ratio of the amount of NO 2 to the amount).
- the amount of NO 2 contained in the exhaust gas is correlated with the current temperature of the oxidation catalyst and the air-fuel ratio of the exhaust gas.
- the ECU 10 selects the current temperature of the selective catalytic reduction catalyst, the current temperature of the oxidation catalyst, the exhaust gas flow rate, and the exhaust air / fuel ratio as parameters in S102 of the processing routine of FIG.
- a temperature change rate when the temperature of the reduction catalyst increases by a predetermined amount from the current temperature may be calculated to determine whether or not the calculated temperature change rate is equal to or higher than a reference value.
- the relationship between the temperature change rate, the current temperature of the selective catalytic reduction catalyst, the current temperature of the oxidation catalyst, the flow rate of exhaust gas, and the air-fuel ratio of exhaust gas is stored in advance in the ROM of the ECU 10 as a map. Also good.
- the NO X purification rate of the selective reduction catalyst exceeds a predetermined value, so as to reduce the amount of fuel after-injection from the fuel injection valve (after injection amount) May be.
- the “constant value” here is, for example, a value smaller than the NO X purification rate when the entire selective reduction catalyst accommodated in the second catalyst casing 6 is activated, and most of the NO X catalyst is active. it is a value equivalent to the NO X purification rate when the.
- the difference between the first embodiment described above and the present embodiment is that the rate of change in temperature when the temperature of the selective catalytic reduction catalyst rises by a predetermined amount is not less than a reference value, and in addition the integration of emissions flowing out of the oxidation catalyst.
- the temperature increase process is executed on condition that the amount is equal to or less than the comparison value.
- emission is an exhaust component that increases due to execution of after injection, and is, for example, PM and / or CO 2 flowing out from the oxidation catalyst.
- the “comparison value” is an integrated amount of emissions flowing out of the oxidation catalyst when the conventional temperature raising process is executed.
- FIG. 6 is a timing chart showing a method of executing the temperature raising process in the present embodiment.
- the timing chart shown in FIG. 6 is a diagram illustrating a method of executing the temperature raising process when the internal combustion engine 1 is started and stopped three times.
- the solid line indicates data when the temperature increasing process of the present invention is executed
- the alternate long and short dash line indicates data when the conventional temperature increasing process is executed.
- the temperature Tcat2 of the selective catalytic reduction catalyst reaches the second temperature Te2 during the period from the first start of the internal combustion engine 1 (t10 in FIG. 6) to the shutdown (t13 in FIG. 6).
- the accumulated amount of PM and / or CO 2 flowing out from the oxidation catalyst (integrated PM ⁇ CO 2 amount) is smaller than the comparison value, and thus the temperature raising process is executed.
- the temperature raising process is terminated when the temperature Tcat2 of the selective catalytic reduction catalyst reaches the third temperature Te3 (t12 in FIG. 6).
- the temperature Tcat2 of the selective catalytic reduction catalyst reaches a temperature range lower than the second temperature Te2. descend. However, during the period from the second start of the internal combustion engine 1 (t14 in FIG. 6) to the operation stop (t16 in FIG. 6), the temperature Tcat2 of the selective catalytic reduction catalyst reaches the second temperature Te2 ( At t15) in FIG. 6, the accumulated PM ⁇ CO 2 amount is larger than the comparison value, so the temperature raising process is not executed.
- the comparison value in FIG. 6 is the accumulated PM ⁇ CO 2 amount when the above-described conventional temperature raising process is executed. Accumulated PM ⁇ CO 2 amount in the case of temperature increase process is executed according to the present invention, and the accumulated PM ⁇ CO 2 amount in the case of temperature increase process in the prior art is performed, as temperature of the after-injection amount and oxidation catalyst It is possible to calculate using known parameters.
- the amount of PM and / or CO 2 flowing out from the oxidation catalyst in one heating process is larger than that in the case where the conventional temperature raising process is executed.
- the temperature raising process is not executed. Therefore, the accumulated PM / CO 2 amount in a long period of time in which a plurality of start and stop operations are repeated is the conventional temperature rise. This can be reduced to a lesser extent than when processing is executed.
- the amount of accumulated PM ⁇ CO 2 over a long period of time can be reduced to a lower level than when the conventional temperature raising process is executed.
- NO X purification rate of the selective reduction catalyst when the temperature increase process is not executed in the present invention there is concern that lower than when conventional heating process is executed.
- the conventional temperature raising process is executed when the temperature change rate is small. Therefore, as shown in the period from t14 to t16 in FIG. 6, the amount of NO x discharged into the atmosphere when the temperature raising process of the present invention is not executed is the same as when the conventional temperature raising process is executed. It will amount substantially equal of the NO X discharged into the atmosphere.
- the amount of NO x discharged into the atmosphere when the temperature raising process of the present invention is executed is compared with the amount of NO x discharged into the atmosphere when the conventional temperature raising process is executed. Enough. Therefore, the amount of the NO X discharged into the atmosphere in a long time, towards the case of heating process of the present invention than when the conventional heating process is executed is executed is reduced.
- FIG. 7 is a flowchart showing a processing routine executed by the ECU 10 when the temperature raising process is executed.
- This processing routine is stored in advance in the ROM or the like of the ECU 10 and is periodically executed by the ECU 10.
- FIG. 7 the same reference numerals are assigned to the same processes as those in the processing routine of the first embodiment described above (see FIG. 5).
- the ECU 10 executes the process of S201 when an affirmative determination is made in S103 (Tcat1 ⁇ Te1).
- step S201 the ECU 10 determines whether or not the integrated PM ⁇ CO 2 amount ⁇ PM ⁇ CO 2 is smaller than the comparison value Cv.
- the accumulated PM ⁇ CO 2 amount ⁇ PM ⁇ CO 2 is sequentially calculated using the air-fuel ratio of the exhaust, the temperature of the oxidation catalyst, the after injection amount, and the like as parameters.
- the comparison value Cv is sequentially calculated using as parameters the after-injection amount assuming that the conventional temperature raising process has been executed, the air-fuel ratio of the exhaust, the temperature of the oxidation catalyst, the after-injection amount, and the like. According to such a method, the ECU 10 calculates the integrated PM ⁇ CO 2 amount ⁇ PM ⁇ CO 2 and the comparison value Cv, thereby realizing the calculating means according to the present invention.
- the temperature raising process When the temperature raising process is executed according to the procedure described above, the same effects as those of the first embodiment described above can be obtained, and the accumulated PM ⁇ CO 2 amount over a long period of time and NO X discharged into the atmosphere can be obtained. This amount can be reduced as compared with the case where the conventional temperature raising process is executed. As a result, the temperature raising process can be executed even under various conditions such as when the internal combustion engine 1 is repeatedly started and restarted in a short period of time, or when the low load operation state is continued after the internal combustion engine 1 is started. while less suppressing an increase in due to the emission, it is possible to reduce the NO X amount exhausted to the atmosphere.
- the selective reduction catalyst may be a storage reduction catalyst.
- the example in which the particulate filter is disposed in the exhaust passage 3 upstream of the selective reduction catalyst has been described.
- the particulate filter is disposed in the exhaust passage downstream of the selective reduction catalyst.
- a filter may be disposed, or the selective reduction catalyst may be supported on the particulate filter.
- the present invention is applicable as long as the oxidation catalyst is arranged in the exhaust passage 3 upstream of the selective catalytic reduction catalyst.
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Abstract
Description
車両に搭載される内燃機関の排気通路に配置されたNOx触媒と、
前記NOx触媒へ流入する排気の温度を上昇させることにより、前記NOx触媒を昇温させる処理である昇温処理を実行する昇温手段と、
前記NOx触媒の温度を検出する検出手段と、
前記NOx触媒の温度が前記検出手段により検出された温度から所定量上昇したと仮定した場合の前記所定量に対するNOx浄化率の上昇量の割合である温度変化率が基準値以上になることを条件として、前記昇温処理の実行を許可する制御手段と、
を備えるようにした。
先ず、本発明の第1の実施例について図1乃至図5に基づいて説明する。図1は、本発明が適用される内燃機関の概略構成を示す図である。
Enox=(Anoxin-Anoxout)/Anoxin
上記の式中のEnoxは、NOX浄化率である。Anoxinは、選択還元型触媒へ流入するNOXの量(NOX流入量)である。Anoxoutは、選択還元型触媒から流出するNOXの量(NOX流出量)である。
次に、本発明の第2の実施例について図6及び図7に基づいて説明する。ここでは、前述した第1の実施例と異なる構成について説明し、同様の構成については説明を省略する。
2 吸気通路
3 排気通路
4 スロットル弁
5 第1触媒ケーシング
6 第2触媒ケーシング
7 還元剤添加弁
8 第1排気温度センサ
9 第2排気温度センサ
10 ECU
11 クランクポジションセンサ
12 アクセルポジションセンサ
13 エアフローメータ
14 A/Fセンサ1
70 ポンプ
71 還元剤タンク
Claims (6)
- 車両に搭載された内燃機関の排気通路に配置されるNOX触媒と、
前記NOX触媒へ流入する排気の温度を上昇させることにより、前記NOX触媒を昇温させる処理である昇温処理を実行する昇温手段と、
前記NOX触媒の温度を検出する検出手段と、
前記NOX触媒の温度が前記検出手段により検出された温度から所定量上昇したと仮定した場合の前記所定量に対するNOX浄化率の上昇量の割合である温度変化率が基準値以上になることを条件として、前記昇温処理の実行を許可する制御手段と、
を備える内燃機関の排気浄化装置。 - 請求項1において、前記NOX触媒より上流の排気通路に配置される酸化触媒をさらに備え、
前記昇温処理は、前記酸化触媒へ未燃燃料を供給する処理であり、
前記制御手段は、前記酸化触媒の温度が所定の活性温度以上であり、且つ前記温度変化率が前記基準値以上であることを条件として、前記昇温処理の実行を許可する内燃機関の排気浄化装置。 - 請求項2において、前記酸化触媒から流出する排気に含まれるエミッションの量を積算する演算手段をさらに備え、
前記制御手段は、前記演算手段により算出されたエミッションの積算量が比較値を超えているときは、前記昇温処理の実行を禁止する内燃機関の排気浄化装置。 - 請求項2又は3において、前記制御手段は、前記昇温処理の実行中に前記NOX触媒のNOX浄化率が一定値を超えると、前記酸化触媒へ供給される未燃燃料の量を減少させる内燃機関の排気浄化装置。
- 請求項1乃至4のいずれか1項において、前記制御手段は、前記検出手段により検出された温度が所定の温度範囲に属するときに、前記温度変化率が前記基準値以上であると判定する内燃機関の排気浄化装置。
- 請求項1乃至4のいずれか一項において、前記制御手段は、前記NOX触媒のNOX浄化率が所定の浄化率範囲に属するときに、前記温度変化率が前記基準値以上であると判定する内燃機関の排気浄化装置。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12878017.8A EP2857648B8 (en) | 2012-05-29 | 2012-05-29 | Exhaust gas purification apparatus for internal combustion engine |
JP2014518128A JP6015753B2 (ja) | 2012-05-29 | 2012-05-29 | 内燃機関の排気浄化装置 |
PCT/JP2012/063795 WO2013179393A1 (ja) | 2012-05-29 | 2012-05-29 | 内燃機関の排気浄化装置 |
US14/403,982 US9212586B2 (en) | 2012-05-29 | 2012-05-29 | Exhaust gas purification apparatus for internal combustion engine |
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PCT/JP2012/063795 WO2013179393A1 (ja) | 2012-05-29 | 2012-05-29 | 内燃機関の排気浄化装置 |
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US (1) | US9212586B2 (ja) |
EP (1) | EP2857648B8 (ja) |
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WO (1) | WO2013179393A1 (ja) |
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CN107654301B (zh) * | 2016-07-25 | 2019-12-24 | 上海汽车集团股份有限公司 | 一种发动机排气歧管的温度控制方法及装置 |
FR3063521B1 (fr) * | 2017-03-06 | 2019-08-16 | Peugeot Citroen Automobiles Sa | Procede de controle d’emission d’un polluant pendant un mode de fonctionnement d’un moteur thermique le protegeant de fortes temperatures |
CN108087071B (zh) * | 2017-12-05 | 2021-09-28 | 南京依柯卡特排放技术股份有限公司 | 对dpf碳载量的判断方法 |
US11131226B2 (en) * | 2019-07-23 | 2021-09-28 | Caterpillar Inc. | Method and system for thermal control of aftertreatment |
CN111535903B (zh) * | 2020-05-22 | 2021-07-20 | 潍柴动力股份有限公司 | 清除反应器结晶的方法、装置和电子设备 |
Citations (4)
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JP2003269146A (ja) * | 2002-03-19 | 2003-09-25 | Toyota Motor Corp | 内燃機関の排気浄化装置 |
JP2008231966A (ja) * | 2007-03-19 | 2008-10-02 | Toyota Motor Corp | 圧縮着火式内燃機関の排気浄化装置 |
JP2010043583A (ja) * | 2008-08-11 | 2010-02-25 | Toyota Motor Corp | 内燃機関の排気浄化装置 |
JP2010112192A (ja) | 2008-11-04 | 2010-05-20 | Nissan Motor Co Ltd | 内燃機関の排気浄化装置 |
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JP2001164928A (ja) | 1999-12-13 | 2001-06-19 | Mazda Motor Corp | エンジンの排気浄化装置及び浄化方法 |
JP4253984B2 (ja) | 2000-02-14 | 2009-04-15 | マツダ株式会社 | ディーゼルエンジンの制御装置 |
JP4051547B2 (ja) * | 2002-07-04 | 2008-02-27 | 三菱ふそうトラック・バス株式会社 | 内燃機関の排気浄化装置 |
JP4677837B2 (ja) * | 2005-07-08 | 2011-04-27 | いすゞ自動車株式会社 | 排気ガス浄化システムの再生制御方法及び排気ガス浄化システム |
JP5287282B2 (ja) | 2009-01-20 | 2013-09-11 | いすゞ自動車株式会社 | 排気ガス浄化方法及び排気ガス浄化システム |
CN101918686B (zh) * | 2009-03-31 | 2012-12-26 | 丰田自动车株式会社 | 催化剂劣化判定装置及催化剂劣化判定方法 |
JP4665258B2 (ja) | 2010-03-04 | 2011-04-06 | 学校法人加計学園 | 人工飼育水による養殖システム |
-
2012
- 2012-05-29 EP EP12878017.8A patent/EP2857648B8/en not_active Not-in-force
- 2012-05-29 JP JP2014518128A patent/JP6015753B2/ja not_active Expired - Fee Related
- 2012-05-29 US US14/403,982 patent/US9212586B2/en not_active Expired - Fee Related
- 2012-05-29 WO PCT/JP2012/063795 patent/WO2013179393A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2003269146A (ja) * | 2002-03-19 | 2003-09-25 | Toyota Motor Corp | 内燃機関の排気浄化装置 |
JP2008231966A (ja) * | 2007-03-19 | 2008-10-02 | Toyota Motor Corp | 圧縮着火式内燃機関の排気浄化装置 |
JP2010043583A (ja) * | 2008-08-11 | 2010-02-25 | Toyota Motor Corp | 内燃機関の排気浄化装置 |
JP2010112192A (ja) | 2008-11-04 | 2010-05-20 | Nissan Motor Co Ltd | 内燃機関の排気浄化装置 |
Also Published As
Publication number | Publication date |
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EP2857648A4 (en) | 2015-05-27 |
US9212586B2 (en) | 2015-12-15 |
EP2857648A1 (en) | 2015-04-08 |
EP2857648B1 (en) | 2018-11-21 |
US20150121854A1 (en) | 2015-05-07 |
JP6015753B2 (ja) | 2016-10-26 |
JPWO2013179393A1 (ja) | 2016-01-14 |
EP2857648B8 (en) | 2019-02-27 |
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