WO2006027903A1 - 排気ガス浄化方法及び排気ガス浄化システム - Google Patents
排気ガス浄化方法及び排気ガス浄化システム Download PDFInfo
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- WO2006027903A1 WO2006027903A1 PCT/JP2005/013626 JP2005013626W WO2006027903A1 WO 2006027903 A1 WO2006027903 A1 WO 2006027903A1 JP 2005013626 W JP2005013626 W JP 2005013626W WO 2006027903 A1 WO2006027903 A1 WO 2006027903A1
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- nox
- oxygen
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- exhaust gas
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D41/00—Electrical control of supply of combustible mixture or its constituents
- F02D41/02—Circuit arrangements for generating control signals
- F02D41/021—Introducing corrections for particular conditions exterior to the engine
- F02D41/0235—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus
- F02D41/027—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to purge or regenerate the exhaust gas treating apparatus
- F02D41/0275—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to purge or regenerate the exhaust gas treating apparatus the exhaust gas treating apparatus being a NOx trap or adsorbent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9431—Processes characterised by a specific device
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9495—Controlling the catalytic process
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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
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
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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
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0871—Regulation of absorbents or adsorbents, e.g. purging
- F01N3/0885—Regeneration of deteriorated absorbents or adsorbents, e.g. desulfurization of NOx traps
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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
- F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
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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
- F01N9/00—Electrical control of exhaust gas treating apparatus
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B37/00—Engines characterised by provision of pumps driven at least for part of the time by exhaust
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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
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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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
- F01N2560/00—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics
- F01N2560/02—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics the means being an exhaust gas sensor
- F01N2560/025—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics the means being an exhaust gas sensor for measuring or detecting O2, e.g. lambda sensors
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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
- F01N2610/00—Adding substances to exhaust gases
- F01N2610/03—Adding substances to exhaust gases the substance being hydrocarbons, e.g. engine fuel
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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
- F01N2900/00—Details of electrical control or of the monitoring of the exhaust gas treating apparatus
- F01N2900/04—Methods of control or diagnosing
- F01N2900/0412—Methods of control or diagnosing using pre-calibrated maps, tables or charts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D2200/00—Input parameters for engine control
- F02D2200/02—Input parameters for engine control the parameters being related to the engine
- F02D2200/08—Exhaust gas treatment apparatus parameters
- F02D2200/0806—NOx storage amount, i.e. amount of NOx stored on NOx trap
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D41/00—Electrical control of supply of combustible mixture or its constituents
- F02D41/02—Circuit arrangements for generating control signals
- F02D41/021—Introducing corrections for particular conditions exterior to the engine
- F02D41/0235—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus
- F02D41/0295—Control according to the amount of oxygen that is stored on the exhaust gas treating apparatus
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/40—Engine management systems
Definitions
- the present invention relates to an exhaust gas purification method and an exhaust gas including a catalyst device carrying a NOx occlusion reduction type catalyst that reduces and purifies NOx (nitrogen oxides) in exhaust gas of an internal combustion engine. It relates to a purification system.
- NOx catalysts for reducing and removing NOx (nitrogen oxides) in exhaust gas from internal combustion engines such as diesel engines and some gasoline engines and various combustion devices. ing.
- NOx storage-reduction catalyst as a NOx reduction catalyst for diesel engines.
- This catalyst device is formed of a monolithic cam 30M or the like having a structure as shown in FIG. 7, and this monolithic cam 30M is formed of cordierite or stainless steel as shown in FIG. A large number of polygonal cells 30S are formed on the structural material carrier 31 thus formed. On the wall surface of the cell 30S, as shown in FIGS. 8 and 9, alumina (Al 2 O 3) zeora is used.
- a porous catalyst coat layer 34 is provided as a catalyst support layer formed of 2 3ite.
- the catalyst coat layer 34 earns a surface area in contact with the exhaust gas.
- a supported noble metal (catalytically active metal) 32 and a NOx storage material (NOx storage material: NOx storage agent: NOx absorbent) 33 are supported on the surface of the catalyst coat layer 34. This configuration generates a catalytic function.
- FIG. 10 and FIG. 11 show the arrangement of the catalyst substances 32 and 33 on the surface of the support layer of the catalyst device and the NOx occlusion reduction mechanism.
- a noble metal 32 having an oxidation function and a NOx storage material 33 having a NOx storage function are supported on the catalyst coat layer 34.
- This precious metal 32 is white gold (Pt) or the like.
- NOx occlusion material 33 is composed of alkali metals such as potassium (K), sodium (Na), lithium (Li) and cesium (Cs), alkaline earth metals such as barium (Ba) and calcium (Ca), lanthanum (La ), Formed from several forces among rare earths such as yttrium (Y).
- the catalyst device with this configuration performs the NOx occlusion function by the difference in oxygen concentration in the exhaust gas. It also serves to purify NOx emission and the released NOx.
- nitric acid and nitrogen which is also exhausted from the engine power, is oxidized to nitrogen dioxide (NO) by oxygen contained in the exhaust gas by the oxidation catalyst function of the noble metal 32.
- the nitrogen dioxide is stored in the form of nitrate in the NOx storage material 33 such as norium with NOx storage function to purify NOx.
- the NOx occlusion material 33 having the NOx occlusion function is entirely changed to nitrate, and therefore the NOx occlusion function is lost. Therefore, the engine operating conditions are changed or fuel is injected into the exhaust passage to produce rich combustion exhaust gas (rich spike gas) and send it to the catalyst.
- This rich combustion exhaust gas is an exhaust gas in which oxygen is not present in the exhaust gas, the concentration of carbon monoxide (CO) is high, and the exhaust temperature is high.
- the excess air ratio at the initial stage of rich combustion is shown in FIG.
- the rich control is performed by setting the air fuel ratio to 1.0, that is, the air fuel ratio to the stoichiometric air fuel ratio. Initially, oxygen adsorbed on the catalyst surface is released. Because of this released oxygen, in the exhaust gas The reducing agent is consumed. Therefore, a reducing agent sufficient to reduce the released NOx cannot be obtained, and the NOx reduction reaction is not sufficiently activated.
- the catalyst outlet NOx concentration Cnoxex is remarkably increased, and a large amount of unpurified NOx is released downstream of the catalyst device.
- the oxygen adsorbed on the catalyst surface does not make the air-fuel ratio near the catalyst surface rich.
- NOx cannot be reduced and NOx flows out.
- This upstream side catalytic device functions as a starting catalytic device with the main purpose of removing HC and CO components released in large quantities when the engine is started.
- oxygen at the start of the catalyst device is released during a rich spike operation for regenerating the catalyst device carrying the NOx storage reduction catalyst. This oxygen is trying to solve the problem that NOx is not purified in the early stage of regeneration and flows out downstream of the catalytic device.
- this exhaust purification device a reducing agent for consuming the total amount of oxygen released by the upstream start catalyst device is added, and a rich noise operation for regenerating the NOx storage reduction catalyst is performed.
- Storage reduction means for making the air-fuel ratio richer than the air-fuel ratio is provided. Due to this storage reduction measure, the NOx storage reduction catalyst is located near the beginning of the rich spike operation. Since the air-fuel ratio of the engine does not become richer than the stoichiometric air-fuel ratio, it is possible to prevent the NOx from being exhausted and becoming a state.
- an exhaust purification device for an internal combustion engine as described in Japanese Patent Laid-Open No. 2002-188430, for example.
- the supply amount of the reducing agent is feedback-controlled by an air-fuel ratio sensor provided on the downstream side of the catalyst device carrying the NOx storage reduction catalyst. Then, at the initial stage of the regeneration control, a predetermined period until the output value of the air-fuel ratio sensor reaches a predetermined value, that is, an oxygen (O) streak.
- the present invention has been made to solve the above problems, and an object of the present invention is to provide an exhaust gas purification method using an NOx occlusion reduction type catalyst and exhaust gas for the purification of NOx in the exhaust gas.
- the regeneration control of the NOx storage reduction catalyst takes into account the oxygen storage function and performs generation control to supply an appropriate amount of reducing agent into the exhaust gas.
- the exhaust gas purification method for achieving the above-mentioned object has stored NOx when the air-fuel ratio power lean state of the exhaust gas and occludes when it is rich.
- the amount of reducing agent that matches the amount of oxygen released in the catalyst device power at the initial stage of regeneration control is Catalytic device power Addition to the amount of reducing agent supplied to reduce released NOx is performed to perform the first-time rich control in which the target air-fuel ratio is made smaller than the stoichiometric air-fuel ratio.
- the catalyst device It is a method characterized by performing reproduction.
- the air-fuel ratio of the exhaust gas here does not necessarily mean the air-fuel ratio in the cylinder, and the amount of air supplied to the exhaust gas flowing into the catalyst device carrying the NOx storage reduction catalyst. This is the ratio to the amount of fuel (including the amount burned in the cylinder).
- the target air-fuel ratio in the first rich control is set to 0.70 to 0.98 in terms of the excess air ratio ⁇
- the target air-fuel ratio in the second rich control is set to 0.98 in the excess air ratio conversion: L 02 is preferred.
- the air-fuel ratio in the vicinity of the NOx occlusion reduction type catalyst can be maintained in a rich state in the vicinity of the theoretical air-fuel ratio in spite of oxygen release.
- sufficient reducing agent is supplied to reduce the released NOx, it is possible to prevent the raw NOx from flowing out to the downstream side of the catalyst device.
- the air-fuel ratio in the vicinity of the NOx storage reduction catalyst can be maintained in a rich state near the stoichiometric air-fuel ratio by late rich control in which the amount of reducing agent is changed to an appropriate amount. Further, when reducing the released NOx, excess unreacted reducing agent is avoided, so that unused HC and CO can be prevented from flowing out downstream of the NOx storage reduction catalyst.
- the amount of reducing agent commensurate with the amount of oxygen released from the catalyst device is determined from map data indicating the relationship between the catalyst device temperature and the oxygen storage amount.
- the regeneration control can be performed with a relatively simple algorithm.
- the map data indicating the relationship between the catalyst device temperature and the oxygen storage amount is obtained in advance by a preliminary experiment or the like, input to the control device, and referred to during the regeneration control.
- control time of the late rich control is Map data based on gin load and engine speed, or map data based on engine load and catalyst device temperature
- control time of late rich control is determined with a relatively simple algorithm be able to.
- the control time of the late rich control is determined from the NOx remaining amount of the catalyst device and the amount of HC detected downstream of the catalyst device.
- the control time of late rich control can be determined with a relatively simple algorithm.
- This NOx remaining amount is determined from a map measured in advance through tests, etc., and the exhaust gas temperature and regeneration time during the previous regeneration.
- an exhaust gas purification system for achieving the above-described object occludes NOx when the air-fuel ratio of the exhaust gas is lean, and occludes when it is rich.
- the regeneration control means is a reducing agent commensurate with the amount of oxygen released from the catalyst device at the initial stage of the regeneration control.
- First-stage rich control means for performing first-stage rich control in which the target air-fuel ratio is made smaller than the theoretical air-fuel ratio by adding the amount of NOx to the amount of reducing agent supplied to reduce the NOx released from the catalyst device.
- Ritz In the control, when it is determined from the oxygen concentration on the downstream side of the catalyst device that the release of the oxygen is completed and the release of the oxygen is determined to be complete, the target air is more effective than the previous rich control.
- late rich control means for performing late rich control in the vicinity of the stoichiometric air-fuel ratio with an increased fuel ratio.
- the rich control means determines the amount of the reducing agent corresponding to the amount of oxygen released from the catalyst device, the catalyst device temperature and the oxygen storage amount.
- the first-stage rich control and the second-stage rich control are respectively configured such that the inlet side oxygen concentration of the catalyst device becomes the oxygen concentration of each target air-fuel ratio. It is configured to feedback control.
- the late rich control means may map the control time of the late rich control based on engine load and engine speed, Alternatively, it is configured to calculate from map data based on the engine load and the catalyst device temperature.
- the late rich control means detects the control time of the late rich control on the NOx remaining amount of the catalyst device and the downstream side of the catalyst device. It is configured to be determined from the amount of HC.
- the amount of reducing agent necessary for consuming oxygen released in the initial regeneration is increased in consideration of the oxygen storage function of the catalyst device. Therefore, the rich control is performed in the first half, so that the air-fuel ratio in the vicinity of the NOx occlusion reduction catalyst can be maintained in a rich state near the theoretical air-fuel ratio in spite of the oxygen release from the catalyst device, and the released oxygen As the amount of reducing agent consumed is expected, the NOx released can be reduced with a sufficient amount of reducing agent.
- FIG. 1 is a diagram showing a configuration of an exhaust gas purification system according to an embodiment of the present invention.
- FIG. 2 is a diagram showing a configuration of control means of the exhaust gas purification system according to the embodiment of the present invention.
- FIG. 3 is a diagram showing an example of a control flow for regeneration of a catalyst device carrying a NOx storage reduction catalyst.
- FIG. 4 is a diagram schematically showing a map data configuration of control time of late rich control based on engine load and engine speed.
- FIG. 5 is a diagram showing the relationship between the remaining amount of NOx and the outflow HC.
- FIG. 6 Fuel injection control, exhaust pipe injection control, N in the control flow of FIG.
- Fig. 6 is a diagram schematically showing temporal changes in the estimated amount of Ox occlusion, the valve opening of the EGR valve, the throttle opening of the intake valve, the intake air amount, the catalyst inlet excess air ratio, and the catalyst outlet excess air ratio.
- FIG. 7 is a view showing a monolith honeycomb.
- FIG. 8 is a partially enlarged view of a monolith honeycomb.
- FIG. 9 is an enlarged view of a cell wall portion of a monolith cam.
- FIG. 10 is a diagram schematically showing the structure of the catalyst device and the mechanism of the purification in the state during lean control.
- FIG. 11 is a diagram schematically showing the structure of the catalyst device and the mechanism of purification in the state during rich control.
- FIG. 12 is a diagram schematically showing a cryogenic temperature region.
- FIG. 13 is a graph showing the relationship between catalyst device temperature and purification rate.
- An exhaust gas purification system 10 shown in FIG. 1 is configured by arranging a catalyst device 50 carrying a NOx storage reduction catalyst in an exhaust passage 20 of an engine (internal combustion engine) 1.
- the catalyst device 50 is formed of a monolith catalyst.
- a catalyst coat layer is provided on a carrier such as acid aluminum or titanium oxide. This catalyst coat layer is loaded with a noble metal catalyst (catalyst metal) such as platinum (Pt) or palladium (Pd) and a NOx storage material (NOx storage material) such as barium (Ba).
- a noble metal catalyst catalyst metal
- platinum platinum
- Pd palladium
- NOx storage material such as barium (Ba).
- the NOx occlusion material occludes NOx in the exhaust gas when the exhaust gas has a high oxygen concentration (lean air-fuel ratio). This purifies NOx in the exhaust gas.
- the oxygen concentration is low or zero, the stored NOx is released and the released NOx is reduced by the catalytic action of the noble metal catalyst. This prevents NOx from flowing into the atmosphere.
- An exhaust pipe fuel addition valve 22 is provided on the upstream side of the catalyst device 50.
- the exhaust pipe fuel addition valve 22 receives fuel from a line (not shown) during regeneration control, and supplies this fuel into the exhaust gas as a reducing agent for NOx.
- the air-fuel ratio of the exhaust gas is made smaller than the stoichiometric air-fuel ratio, and the exhaust gas is brought into a deep rich state.
- the regeneration control of the catalyst device 50 feedback control is performed so that the oxygen concentration in the exhaust gas flowing into the catalyst device 50 becomes the oxygen concentration of the target air-fuel ratio (or the excess air ratio ⁇ ).
- the supply amount of the reducing agent is adjusted.
- a catalyst inlet ⁇ (excess air ratio) sensor 51 is provided on the inlet side of the catalyst device 50.
- the catalyst outlet ⁇ for detecting the oxygen concentration downstream of the catalyst device 50 in order to determine the completion of the oxygen release at the initial stage of regeneration.
- a sensor 52 is provided. This catalyst outlet ⁇ sensor 52 Use an air excess rate sensor that can easily and accurately determine the end of oxygen release, where the output change is extremely large near Toiki (theoretical air-fuel ratio).
- a catalyst inlet ⁇ sensor 53 and a catalyst inlet exhaust gas temperature sensor 54 for detecting the catalyst device temperature of the catalyst device 50 are disposed on the inlet side of the catalyst device 50.
- a catalyst outlet ⁇ sensor 55 is disposed on the outlet side of the catalyst device 50.
- a turbine 21 a of the turbocharger 21 is disposed upstream of the catalyst device 50 in the exhaust passage 20.
- a mass air flow sensor (MAF sensor) 31 a compressor (not shown;), an intercooler (not shown), a turbocharger 21, an intake throttle valve (intake throttle valve) 32) are provided.
- an EGR passage 40 that connects the exhaust passage 20 and the intake passage 30 on the upstream side of the turbine 21a is provided.
- the EGR passage 40 is provided with an EGR cooler 41 and an EGR valve 42.
- a control device (ECU: engine control unit) 60 is provided that performs overall control of the operation of the engine 1 and also performs recovery control of the NOx purification capacity of the catalyst device 50. Detection values from the catalyst inlet sensor 51, the catalyst outlet sensor 52, the catalyst inlet NOx sensor 53, the catalyst inlet exhaust gas temperature sensor 54, the catalyst outlet NOx sensor 55, and the like are input to the control device 60.
- the control device 60 outputs a signal for controlling the EGR valve 42 of the engine 1, the fuel injection valve 61 of the common rail electronic control fuel injection device for fuel injection, the intake throttle valve 32, and the like.
- the air A passes through a mass flow sensor (MAF sensor) 31 in the intake passage 30 and a compressor (not shown) in the turbocharger 21, and is taken in by the intake throttle valve 32.
- the amount is adjusted and enters the cylinder.
- the exhaust gas G generated in the cylinder drives the turbine 21a of the turbocharger 21 in the exhaust passage 20.
- the exhaust gas G passes through the catalyst device 50 and becomes purified exhaust gas Gc, which is discharged into the atmosphere through a silencer (not shown).
- part of the exhaust gas G As EGR gas Ge, it passes through the EGR cooler 41 in the EGR passage 40, the amount is adjusted by the EGR valve 42, and is recirculated to the intake passage 30 side.
- the control device force of the exhaust gas purification system 10 is incorporated in the control device 60 of the engine 1, and the exhaust gas purification system 10 is controlled in parallel with the operation control of the engine 1.
- the control device of the exhaust gas purification system 10 includes a control means C1 for the NOx storage reduction catalyst as shown in FIG.
- This NOx storage reduction catalyst control means C1 is a means for controlling regeneration, desulfurization (sulfur purge), etc. of the catalyst device 50 carrying the NOx storage reduction catalyst, and is a regeneration control means C10. And desulfurization regeneration control means C20.
- the regeneration control means C10 performs regeneration for recovering the NOx storage capacity of the catalyst device 50 when the estimated NOx storage amount estimated to be stored in the catalyst device 50 reaches a predetermined determination value.
- NOx concentration detection means Cll, catalyst temperature detection means C12, regeneration start determination means C13, first-stage rich control means C14, oxygen release completion determination means C15, and second-stage rich control means C16 It is prepared for.
- the NOx concentration detection means C11 is a means for detecting the NOx concentration in the exhaust gas, and has a catalyst inlet NOx sensor 53 and a catalyst outlet NOx sensor 55.
- the oxygen concentration (or excess air ratio) is also detected along with the NOx concentration. It will be.
- the catalyst temperature detecting means C12 is means for detecting the temperature of the catalyst device based on the exhaust gas temperature Tg detected by the catalyst inlet exhaust gas temperature sensor 54. Strictly speaking, unlike the exhaust gas temperature Tg at the catalyst inlet, the exhaust gas temperature Tg is often used as the catalytic device temperature in consideration of the simplicity of force control that needs to be corrected. Here too, the exhaust gas temperature (catalyst inlet gas temperature) Tg is used as the catalyst device temperature. When a catalyst device temperature sensor is provided to directly measure the catalyst device temperature, the measured temperature becomes the detected catalyst device temperature as it is.
- the NOx occlusion amount has a slight effect on the temperature, so this NOx occlusion amount Rnoxl is corrected somewhat as a function, and this corrected value is cumulatively calculated to obtain the NOx occlusion estimation amount Rnox.
- This NOx occlusion estimated amount Rnox is compared with the judgment value R0 for starting regeneration control, and when the NOx occlusion estimated amount Rnox is equal to or greater than the predetermined judgment value R0, it is judged that it is the start time of regeneration control. .
- the regeneration control start determination value R0 is calculated from a map data force for a start determination value set in advance from the engine speed Ne indicating the operating state of the engine and the load Q. This map data is based on the data obtained from prior experiments, etc., and the value of the judgment value R0 for starting regeneration control is set in a map based on the engine speed Ne and the load Q.
- the first rich control means C14 determines the amount of the reducing agent (additional reducing agent amount) commensurate with the amount of oxygen released from the catalytic device 50 from map data indicating the relationship between the catalytic device temperature and the oxygen storage amount. Reducing agent amount calculating means C141 is provided. This first-stage rich control unit C14 adds the amount of additional reducing agent to the amount of reducing agent supplied to reduce NOx released from the catalyst device 50 in the early stage of regeneration control (standard reducing agent amount). This is means for performing the rich control in the first half of the rich state in which the target air-fuel ratio is smaller than the theoretical air-fuel ratio.
- This early rich control means C14 performs feedback control so that the oxygen concentration on the inlet side of the catalyst device 50 becomes the oxygen concentration of the target air-fuel ratio by a large amount of EGR by intake throttle, injection in the exhaust pipe, fuel injection control, etc. .
- intake throttle the intake throttle valve 22 and the EGR valve 42 are controlled.
- fuel injection control exhaust pipe injection by the exhaust pipe fuel addition valve 22 and post injection or main injection increase are performed.
- the amount of additional reducing agent refer to the map data that shows the relationship between the catalytic device temperature and the oxygen storage amount from the detected catalytic device temperature for the amount of reducing agent that matches the amount of oxygen released from the catalytic device 50. Then, the oxygen storage amount is calculated, the released oxygen amount is calculated from the oxygen stored amount, and the additional reduction amount corresponding to the released oxygen amount is calculated.
- the standard reducing agent amount is an engine that indicates the operating state of the engine. It is calculated from the map data for calculating the standard reducing agent amount that has been set in advance through experiments and the like from the rotation speed Ne and the load Q. This map data is based on the engine speed Ne and load Q, and the amount of reducing agent that minimizes the NOx outflow to the downstream side of the catalytic device 50 when there is no released oxygen is set as the standard reducing agent amount. It is a thing. This map data is set based on data obtained by prior experiments.
- the oxygen release completion determination means C15 is a means for determining the completion of oxygen release from the oxygen concentration downstream of the catalyst device 50 in the first rich control. This oxygen release completion determination means C15 determines that the release of oxygen is completed when the output value of the excess air ratio sensor 52 that detects the oxygen concentration downstream of the catalyst device 50 is reversed.
- the late rich control means C16 determines that the release of oxygen is complete, the late rich control means C16 increases the target air-fuel ratio more than the first rich control, and the latter half of the theoretical air-fuel ratio in the rich state shallower than the first rich control. It is means for performing rich control.
- this late rich control feedback control is performed so that the inlet side oxygen concentration of the NOx storage reduction catalyst 50 becomes the oxygen concentration of each target air-fuel ratio.
- a large amount of EGR by the intake throttle and fuel injection control such as post injection or main injection increase are performed without performing the injection into the exhaust pipe by the exhaust pipe fuel addition valve 22.
- the target air-fuel ratio is calculated based on the standard reducing agent amount that does not take into account the released oxygen.
- the control time Tr of the late rich control is calculated based on the first control time map data based on the engine load and the engine speed, or the engine load. Calculate from the second control time map data based on the catalyst device temperature.
- the first control time map data is based on the engine load and the engine speed, and the control times Tr of the late rich control are arranged in a matrix and in a map. It is a thing.
- the first control time map data is configured such that a control time corresponding to the detected engine load and engine speed can be selected.
- the second control time map data is configured in the same manner as the first control time map data.
- the optimal time point (at the time of crossing in Fig. 5) can be set as the end point Re of the late rich control. That is, the control time Tr of the late rich control can also be determined from the remaining NOx amount of the catalyst device 50 and the outflow HC amount detected on the downstream side of the catalyst device 50.
- the desulfurization regeneration control means C20 includes a desulfurization control start determination means C21 and a desulfurization control means C22.
- This desulfurization control start determination means C21 determines whether or not the sulfur purge control is started by whether or not the sulfur has accumulated until the NOx occlusion capacity is reduced, such as by integrating the sulfur (sulfur) accumulation amount. Means.
- This means C20 starts desulfurization when the sulfur accumulation amount exceeds a predetermined judgment value.
- the desulfurization control means C22 is a means for efficiently performing desulfurization while suppressing emission of carbon monoxide (CO) into the atmosphere.
- This means C22 controls the air-fuel ratio of the exhaust gas by in-pipe injection or post-injection, and also performs EGR control and intake throttle control to raise the temperature of the catalyst device 50 to a temperature capable of desulfurization.
- control means C1 of the exhaust gas purification system of the control device of the exhaust gas purification system 10 incorporated in the control device 60 of the engine 1 is The regeneration control of the catalyst device 50 is performed according to the control flow illustrated in FIG.
- the control flow of FIG. 3 is shown as being executed in parallel with other control flows of the engine when the engine 1 is operated.
- the regeneration start determination means C13 causes the catalyst inlet NOx concentration Cnoxin, the catalyst outlet NOx concentration Cnoxex, the fuel injection amount (fuel weight) Qg, and the intake air amount (step S11). Intake air weight) Calculate NOx occlusion amount Rnox from Ag. Also, in the next step S12, this NOx occlusion estimated amount Rnox is compared with the judgment value R0 for starting regeneration control, and when the NOx occlusion estimated amount Rnox becomes equal to or greater than the predetermined judgment value R0, the regeneration control is performed. It is determined that it is the start time.
- the regeneration control start determination value R0 also calculates a predetermined start determination value map data force from the engine speed Ne indicating the engine operating state and the load Q.
- step S 12 If it is determined in step S 12 that the reproduction control is not started! /, Control other than the reproduction control is performed in step S 40. After passing through control routines other than the regeneration control, the process returns to step S11. In control other than this regeneration control, various conditions If the conditions are correct, control other than regeneration control, such as desulfurization control, is performed, but if the respective conditions are not met, the control returns without performing these controls.
- control other than regeneration control such as desulfurization control
- step S12 If it is determined in step S12 that the regeneration control is started, the process goes to step S20, and the previous rich control is performed by the previous rich means C14 of the regeneration control means C10.
- the target air-fuel ratio (or the target excess air ratio ⁇ 1) of the first rich control is considered, and the oxygen released from the catalyst device 50 at the beginning of the regeneration control is considered. However, it is calculated based on the value obtained by adding the standard reducing agent amount to the additional reducing agent amount that is the amount of reducing agent commensurate with the amount of oxygen released from the catalyst device 50.
- This target air-fuel ratio is less than the theoretical air-fuel ratio / J.
- map data of the target air-fuel ratio (or target air excess ratio ⁇ 1) of the rich control in the previous period in consideration of the amount of additional reducing agent may be prepared in advance based on the engine load and the engine speed.
- the target air-fuel ratio (or target excess air ratio ⁇ 1) of the first rich control is obtained from the detected engine load and engine speed.
- the oxygen adsorption amount is substantially determined by the catalyst device temperature, and the exhaust gas temperature closely related to the catalyst device temperature is determined from the engine load and the engine speed. Instead of being based on catalyst device temperature, it can be based on engine load and engine speed.
- step S22 the oxygen concentration at the inlet side of the catalyst device 50 becomes the oxygen concentration of the target air-fuel ratio by controlling a large amount of EGR and exhaust pipe injection by post-intake and post injection or main injection increase. Feedback control.
- the air-fuel ratio of the exhaust gas is set to 0.70 to 0.98 (for example, 0.90) in terms of excess air ratio ( ⁇ ) in front of the catalyst.
- the NOx occlusion ability that is, the NOx purification capacity, is recovered by regenerating the NOx catalyst within a predetermined temperature range (power by the catalyst is approximately 200 ° C to 600 ° C).
- the first-time rich control in step S22 is performed for a predetermined time At related to the interval for determining whether oxygen release is completed, and the process goes to step S23.
- the release of oxygen that has been adsorbed and stored by the oxygen storage function of the catalyst device 50 during the rich control in the previous period is performed by the oxygen release completion determination means C15. Determine completion.
- step S23 If it is determined in step S23 that oxygen release has not been completed, the process returns to step S22, and step S22 and step S23 are performed until it is determined in step S23 that oxygen release has been completed. repeat.
- step S30 the late rich control means C16 performs late rich control in the vicinity of the stoichiometric air-fuel ratio in which the target air-fuel ratio is larger than in the previous rich control.
- step S31 the late rich control is performed.
- the target air-fuel ratio (target excess air ratio ⁇ 2) is calculated based on the value of the standard reducing agent amount that does not take into account the released oxygen.
- a control time Tr of late rich control is calculated.
- the calculation of the control time Tr is based on the map data for the first control time based on the engine load and the engine speed, or the map data for the second control time based on the engine load and the catalyst device temperature. calculate.
- the control time Tr of the late rich control is determined from the NOx remaining amount of the catalyst device 50 and the HC amount detected on the downstream side of the catalyst device 50. This NOx remaining amount is determined from a map measured in advance through tests, etc., and the exhaust gas temperature and regeneration time during the previous regeneration.
- the amount of HC the relationship between the O concentration and the amount of HC was determined from the previous test results.
- the HC amount is also calculated from the value of the excess air ratio sensor 52 at the catalyst outlet, and the control time Tr of the late rich control is determined from these maps.
- step S33 the oxygen concentration on the inlet side of the catalyst device 50 is set to the target air-fuel ratio (target air excess ratio) by controlling a large amount of EGR and exhaust pipe injection by post-intake and post injection or main injection increase. 2) Perform feedback control to achieve the oxygen concentration.
- the air-fuel ratio of the exhaust gas is set to 0.98 to L 02 (for example, 1.0) in terms of excess air ratio ( ⁇ ) in front of the catalyst.
- the NOx occlusion capacity that is, the NOx purification capacity, is restored within a predetermined temperature range (power by the catalyst is approximately 200 ° C to 600 ° C), and the NOx catalyst is regenerated.
- step S33 is completed during the control time Tr of the late rich control calculated in step S32.
- Regeneration control is performed in the rich control in step S20 and the late rich control in step S30, and when the late rich control ends, the process returns to step S11.
- control flow in Fig. 3 is repeatedly executed until the engine is stopped. If the engine key is turned off during control, an interrupt in step S13 is generated. After performing the necessary end processing (shown in the figure) at the step where this interrupt occurred, the process returns. And this control flow is complete
- the amount of reducing agent commensurate with the amount of oxygen released from the catalyst device 50 at the initial stage of the regeneration control is determined.
- rich control is performed in the previous period in which the target air-fuel ratio (excess air ratio ⁇ 1) is smaller (deeper) than the stoichiometric air-fuel ratio.
- the completion of the oxygen release is determined based on the oxygen concentration downstream of the catalyst device 50.
- the target air-fuel ratio is set larger (shallow) than in the first period rich control.
- the catalyst device 50 can be regenerated by performing late rich control in the vicinity of the theoretical air-fuel ratio (excess air ratio ⁇ 2).
- FIG. 6 shows fuel injection control ⁇ ⁇ ⁇ , post-injection pipe injection control ⁇ , NOx occlusion estimation amount C (Rnox), valve opening of the EGR valve, etc., according to the control flow of FIG.
- An example of a time series of D, intake valve throttle opening E, intake air amount F, catalyst inlet excess air ratio ⁇ in, and catalyst outlet excess air ratio ⁇ ex is schematically shown.
- the target excess air ratio ⁇ ⁇ is set to 0.70 to 0.98 ( For example, 0.90)
- injection into the exhaust pipe by the exhaust pipe fuel addition valve 22 is performed.
- the valve opening D of the EGR valve is opened, the throttle opening ⁇ of the intake valve is closed, and the intake air amount F is decreased.
- feedback control is performed so that the catalyst inlet excess air ratio ⁇ in becomes the target excess air ratio ⁇ .
- This excess air ratio ⁇ ⁇ ⁇ at the inlet of the catalyst reaches the target excess air ratio ⁇ 1 after overshooting, and this rich control is continued until the point Oe when oxygen release is completed.
- This early rich control reduces the estimated NOx storage amount C (Rnox).
- the catalyst outlet air excess rate ex rapidly decreases. Start a little.
- the first rich control is terminated and the second rich control is started.
- the target excess air rate 2 is set to 0.98-: L 02 (eg, 1.0), and fuel injection control such as post injection is continued, but the exhaust pipe fuel addition valve 2 2 The injection into the exhaust pipe due to stops. Then, feedback control is performed so that the catalyst inlet excess air rate in becomes the target excess air rate 2.
- the valve opening D of the EGR valve is closed, the throttle opening E of the intake valve is opened, and the intake air amount F is restored.
- the late rich control is terminated.
- the NOx occlusion estimated amount C (Rnox) becomes substantially zero, the NOx occlusion capacity is restored, and the regeneration control is completed.
- the exhaust gas purification system and the exhaust gas purification method of the present invention having the excellent effects described above are not limited to exhaust gases of internal combustion engines mounted on automobiles, but also various industrial machines and stationary types. It can be used very effectively as an exhaust gas purification system and exhaust gas purification method for internal combustion engine exhaust gas, factory gas, power plant gas, and the like.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Toxicology (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Combined Controls Of Internal Combustion Engines (AREA)
- Electrical Control Of Air Or Fuel Supplied To Internal-Combustion Engine (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US11/660,312 US7716918B2 (en) | 2004-09-03 | 2005-07-26 | Method of exhaust gas purification and exhaust gas purification system |
EP05767190.1A EP1793099B1 (en) | 2004-09-03 | 2005-07-26 | Method of exhaust gas purification and exhaust gas purification system |
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JP2004-256597 | 2004-09-03 | ||
JP2004256597A JP3852461B2 (ja) | 2004-09-03 | 2004-09-03 | 排気ガス浄化方法及び排気ガス浄化システム |
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US (1) | US7716918B2 (ja) |
EP (1) | EP1793099B1 (ja) |
JP (1) | JP3852461B2 (ja) |
WO (1) | WO2006027903A1 (ja) |
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JP2004232555A (ja) * | 2003-01-30 | 2004-08-19 | Toyota Motor Corp | 内燃機関の排気浄化システム |
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US7886527B2 (en) * | 2007-04-10 | 2011-02-15 | Gm Global Technology Operations, Inc. | Reductant injection control strategy |
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EP1793099B1 (en) | 2018-12-05 |
EP1793099A1 (en) | 2007-06-06 |
JP3852461B2 (ja) | 2006-11-29 |
EP1793099A4 (en) | 2010-03-17 |
US7716918B2 (en) | 2010-05-18 |
US20070256405A1 (en) | 2007-11-08 |
JP2006070834A (ja) | 2006-03-16 |
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