CN100410503C - Exhaust gas purifier for ic engine - Google Patents

Exhaust gas purifier for ic engine Download PDF

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Publication number
CN100410503C
CN100410503C CNB2005100040809A CN200510004080A CN100410503C CN 100410503 C CN100410503 C CN 100410503C CN B2005100040809 A CNB2005100040809 A CN B2005100040809A CN 200510004080 A CN200510004080 A CN 200510004080A CN 100410503 C CN100410503 C CN 100410503C
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China
Prior art keywords
catalyst element
exhaust
pore
big
little
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Chinese (zh)
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CN1648424A (en
Inventor
田村保树
田代圭介
奥村显久
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Beauty catalyst USA Ltd.
ICT Co Ltd
Mitsubishi Motors Corp
Umicore Shokubai Japan Co Ltd
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ICT Co Ltd
Mitsubishi Motors Corp
International Catalyst Technology Inc
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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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • 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
    • 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
    • F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
    • F01N3/0835—Hydrocarbons
    • 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
    • F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
    • F01N3/0857—Carbon oxides
    • 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
    • F01N2430/00—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics
    • F01N2430/06—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics by varying fuel-air ratio, e.g. by enriching fuel-air mixture
    • 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
    • F01N2510/00—Surface coverings
    • 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

Abstract

A three-way catalyst ( 30 ) comprises a microporous catalyst element ( 30 a) having a micropore group whose average pore opening size is smaller than molecular size of HC in a washcoat and a macroporous catalyst element ( 30 b) having a macropore group whose average pore opening size is larger than the molecular size of HC in a washcoat.

Description

The Exhaust gas purifying device of internal-combustion engine
Technical field
The present invention relates to a kind of Exhaust gas purifying device of internal-combustion engine, relate in particular to a kind of technology that improves the three-way catalyst purification efficiency.
Background technique
As the exhaust emission control catalyst of vehicle with internal-combustion engine, general three-way catalyst is widely used.Three-way catalyst attempts to reach oxidation and the NO of HC (hydrocarbon), CO (carbon monoxide) by exhaust air-fuel ratio being controlled near the chemically correct fuel (stoichiometric(al)) XThe reduction optimization, can promote exhaust gas purification.
Also have, exploitation recently has a kind of like this Exhaust gas purifying device, catalyzer is for example made cellular structure, with NO X, oxygen (O 2), HC and CO capture in the pore, in reducing atmosphere, HC and CO are captured in the pore, and with the NO that captures XAnd O 2Oxidation, on the other hand, in oxidizing atmosphere with NO XAnd O 2Capture in the pore, and with HC that captures and CO reductive NO X
Even also a kind of like this technology of exploitation, in porous structure, pore is diminished hinder reducing agent HC approaching to oxidation catalyst, can promote like this it only to take place to NO XThe useful reaction (for example: open the 2001-525241 communique) of purification with reference to the spy of Japan.
Yet, in common three-way catalyst, compared with HC and NO XRedox reaction, CO and NO XThe reaction velocity of redox reaction fast, if HC can be separated with CO, preferentially implement CO and NO XRedox reaction, then can make NO XPurifying property improve.
Yet because in reducing atmosphere, HC and CO in the exhaust mix, and former porous structure comprises technology that described communique discloses and can not separate and catch HC and CO, so exist the existence of big molecule HC to hinder little molecule CO and NO XRedox reaction, can not promote CO and NO that reaction velocity is fast XThe problem of redox reaction.Also exist if can not promote CO and NO like this XRedox reaction, then a part of CO and O 2Reaction causes being used for the O of oxidation HC 2Not enough problem.
Summary of the invention
The present invention makes for solving the above problems, and purpose is to provide a kind of Exhaust gas purifying device of internal-combustion engine, separates HC and CO energetically, preferential CO and the NO of taking place on catalyzer XRedox reaction, improve exhaust purification performance.
For reaching described purpose, the Exhaust gas purifying device of internal-combustion engine of the present invention is characterized in that, has three-way catalyst on the exhaust passage of internal-combustion engine, described three-way catalyst is made up of one or more catalyst elements, and the different pore group of two or more average opening sizes is arranged on the coating.
In view of the above, can capture in each catalyst element, can not have the obstruction of other compositions and implement oxidation reaction and reduction reaction respectively well, improve exhaust purification performance according to a plurality of compositions (for example oxygenant and reducing agent) that bulk of molecule screens in the exhaust.
It is desirable to, described three-way catalyst by, having on the coating on the average opening size little pore group's littler than given size the little pore catalyst element, coating has the average opening size big pore group's bigger than given size big pore catalyst element to consist of suitable.
In view of the above, in a plurality of compositions in exhaust (for example oxygenant and reducing agent), can capture in the little pore catalyst element by the composition that molecule is little, the composition that molecule is big captures in the big pore catalyst element, the component separating that just composition that can molecule is little and molecule are big is caught, can not have the obstruction of other compositions and implement oxidation reaction and reduction reaction respectively well, improve exhaust purification performance.
This occasion, it is desirable to, described three-way catalyst by, on the coating by forming by the average opening size big pore group's bigger big pore catalyst element on the average opening size little pore group's littler little pore catalyst element, the coating than the molecular dimension of this HC than the molecular dimension of HC.
In view of the above, (the O for example of a plurality of compositions in exhaust 2, NO X, HC, CO, H 2) in, especially CO that can molecule is little, O 2, NO XAnd H 2Separate capturing in the little pore catalyst element, the HC separation that molecule is big captures in the big pore catalyst element, mainly in oxidizing atmosphere, makes CO and NO XRedox reaction have precedence over HC and NO XRedox reaction, the obstruction of no HC, can promote well the reaction, can make NO XPurifying property improve.Have again, because of promoting CO and NO XRedox reaction, can be with O 2Use fully with the oxidation reaction of HC on, the purifying property of HC is improved.So, can improve exhaust purification performance comprehensively.
Also have, it is desirable to, it is that arranged in series is advisable that described little pore catalyst element and described big pore catalyst element look up in blast air side.
In view of the above, little molecule CO can be separated successively reliably with big molecule HC and capture in little pore catalyst element and the big pore catalyst element.
At this moment, it is desirable to described little pore catalyst element and be provided in exhaust-gas upstream side, described big pore catalyst element is provided in the exhaust downstream side.
In view of the above, can respectively little molecule CO be separated capturing in the little pore catalyst element of exhaust-gas upstream side, big molecule HC be separated capturing in the big pore catalyst element in exhaust downstream side, can make fast CO of reaction velocity and NO reliably in exhaust-gas upstream side XRedox reaction than HC and NO XRedox reaction preferentially implement, can make NO XPurifying property improve.Have again, because of preferential CO and the NO of implementing XRedox reaction, can be in the exhaust downstream side with O 2Use fully with the oxidation reaction of HC on, the purifying property of HC is improved.So, can improve exhaust purification performance comprehensively.
Also have, it is desirable to, described little pore catalyst element and described big pore catalyst element stratiform are configured to suitable.
In view of the above, little molecule CO can be separated capturing in little pore catalyst element and the big pore catalyst element with big molecule HC, and make when cold start-up etc. little pore catalyst element and greatly the pore catalyst element roughly heat up, make it that activity is arranged simultaneously.
At this moment, it is desirable to, described little pore catalyst element is configured in the top layer side, and described big pore catalyst element is configured in the internal layer side.
In view of the above, can respectively little molecule CO be separated capturing in the little pore catalyst element of top layer side, big molecule HC be separated capturing in the big pore catalyst element of internal layer side, can implement fast CO of reaction velocity and NO reliably in the top layer side XRedox reaction and have precedence over HC and NO XRedox reaction, can make NO XPurifying property improve.Have again, because of preferential CO and the NO of implementing XRedox reaction, can be in the internal layer side with O 2Use fully with the oxidation reaction of HC on, the purifying property of HC is improved.Thus, can improve exhaust purification performance comprehensively.
Have again, it is desirable to, the air fuel ratio mean of calculating that the exhaust air-fuel ratio that flows into described three-way catalyst is periodically changed between rare air fuel ratio and dense air fuel ratio is arranged.
In view of the above, can periodically produce oxidizing atmosphere and reducing atmosphere, little molecule CO that for example will capture in reducing atmosphere and big molecule HC are used in the redox reaction in the oxidizing atmosphere, then in reducing atmosphere, repeatedly these little molecule CO and big molecule HC are carried out continuous capturing, the exhaust purification performance that can keep efficiently.
This occasion switched to oxidizing atmosphere before the seizure amount of the medium and small molecule CO of reducing atmosphere reaches the amount of breaking once, big molecule NO in oxidizing atmosphere XThe seizure amount reach and switch to reducing atmosphere before the amount of breaking once and be advisable, the exhaust purification performance that can more keep all the time efficiently thus.
Description of drawings
The feature of this invention comprises other purpose and advantage, will make an explanation in the description of drawings below.In the accompanying drawing, identical reference character is represented same or parts roughly the same in institute's drawings attached, wherein::
Fig. 1 is the structural representation that carries the exhaust gas purifier for internal combustion engine of the present invention the 1st embodiment on vehicle;
Fig. 2 is 1/4th ones (a) of the unit lattice of the little pore catalyst element of expression, is coated in the expanded view (b) of this catalyzer of/4th ones and the expanded view (c) of a particle on the washcoat (w/c);
Fig. 3 is 1/4th ones (a) of the unit lattice of the big pore catalyst element of expression, is coated in the expanded view (b) of this catalyzer of/4th ones and the expanded view (c) of a particle on the washcoat (w/c);
Fig. 4 is illustrated in pore opening size (solid line) on the little pore catalyst element and the frequency of the pore opening size (dotted line) on the big pore catalyst element distributes and each average opening size X and average opening size Y;
Fig. 5 is expression the 1st embodiment's O 2The flow chart of the control program of F/B control;
Fig. 6 is other embodiments' of expression the 1st embodiment the figure of three-way catalyst;
Fig. 7 is the figure of expression the 2nd embodiment's three-way catalyst;
Fig. 8 is other embodiments' of expression the 2nd embodiment the figure of three-way catalyst;
Fig. 9 is 1/4th ones figure of expression the 3rd embodiment's three-way catalyst unit lattice;
Figure 10 is 1/4th ones figure of expression the 4th embodiment's three-way catalyst unit lattice;
Figure 11 is the flow chart of control program of the 5th embodiment's A/F conversion control.
Embodiment
Below, with reference to the accompanying drawings example of the present invention is described.
At first, the 1st embodiment is described.
With reference to Fig. 1, be the structural representation that carries the exhaust gas purifier for internal combustion engine of the present invention on vehicle, below, the structure of this Exhaust gas purifying device is described.
As shown in the drawing, on the cylinder head 2 of I. C. engine body (for example be petrol engine, below, abbreviate motor as) 1, spark plug 4 is installed on each cylinder, spark plug 4 is connected with the spark coil 8 of output HIGH voltage.
On cylinder head 2, on each cylinder, be formed with suction port, in order to be communicated with each suction port, an end of intake manifold 10 is connected with it respectively.Electro-magneto fuel injector 6 is installed on the intake manifold 10, and Fuelinjection nozzle 6 is connected with the fuel supplying device that fuel tank is arranged (figure does not show) by fuel pipe 7.
The upstream side of the Fuelinjection nozzle 6 on intake manifold 10 is provided with and regulates the electromagnetic type throttle valve 14 that sucks air quantity, is provided with the throttle opening sensor (TPS) 16 of the valve opening that detects throttle valve 14 simultaneously.Have again, clamp in the upstream of throttle valve 14 and measure rare air flow sensor 18 of going into air quantity.
Again, on the cylinder head 2, be formed with relief opening on each cylinder, in order to be communicated with each relief opening, an end of gas exhaust manifold 12 is connected with it respectively.
The other end of gas exhaust manifold 12 is connected with outlet pipe (exhaust passage) 20, clamp on this outlet pipe 20 as the exhaust emission control catalyst device make unitary, the carrier cross section is cancellate three-way catalyst 30.
As reactive metal in copper (Cu), cobalt (Co), silver (Ag), platinum (Pt), rhodium (Rh), the palladium (Pd) any one arranged on the coating of the carrier surface of this three-way catalyst 30.
Have, three-way catalyst 30 is formed with a large amount of pores except reactive metal is arranged on coating again.In detail, three-way catalyst 30 be by, the average opening size of the pore little pore group's littler than the molecular dimension (given size) of HC little pore catalyst element 30a arranged and form by the average opening size big pore group's bigger big pore catalyst element 30b than the molecular dimension of HC.Little pore catalyst element 30a is configured in exhaust-gas upstream side, big pore catalyst element 30b and little pore catalyst element 30a in series are configured in the exhaust downstream side.
Just, with reference to Fig. 2, / 4th ones (a) that represent little pore catalyst element 30a unit lattice, and expression is coated in the expanded view (b) of this catalyzer of/4th ones and the expanded view (c) of a particle on the coating (w/c), as shown in the drawing, on the coating of little pore catalyst element 30a, be formed with the opening size little pore S littler in a large number than the molecular dimension of HC.
Also have, with reference to Fig. 3, / 4th ones (a) that represent big pore catalyst element 30b unit lattice, and expression is coated in the expanded view (b) of this catalyzer of/4th ones and the expanded view (c) of a particle on the coating (w/c), as shown in the drawing, on the coating of big pore catalyst element 30b, be formed with the opening size big pore L bigger in a large number than the molecular dimension of HC.
Promptly, with reference to Fig. 4, being illustrated in the pore opening size (solid line) on the little pore catalyst element 30a and the frequency of the pore opening size (dotted line) on the big pore catalyst element 30b distributes, represent average opening size X and average opening size Y respectively, on little pore catalyst element 30a and big pore catalyst element 30b, between the average opening size of pore, difference is set like this.So three-way catalyst 30 can will be on the little pore catalyst element 30a of exhaust-gas upstream side, CO, the O littler than the molecular dimension of HC 2, NO X, H 2Seizure in little pore S, can on the big pore catalyst element 30b in exhaust downstream side, the big HC of molecular dimension catches in big pore L.
For example, the opening size of pore is by impregnating method or CVD (Chemical Vapor Deposition: chemical vapor deposition) control such as method.
Little pore catalyst element 30a for example is zeolite 3A, Ca-silk zeolite etc., its diameter is 3～
Figure C20051000408000071
About.Again, big pore catalyst element 30b for example is zeolite 5A, ZSM-5, β etc., its diameter is 5～
Figure C20051000408000072
About.In addition, big pore catalyst element 30b also can be that in addition general catalyzer is (for example, with Al 2O 3Deng the catalyzer that is primary coil).
Material as having implemented effective fine pore control has zeolite, SAPO (SAPO), ALPO (aluminium phosphate), is not limited thereto, if the material of different fine pore is arranged, also can use any material except that above-mentioned, if can screen HC and CO, NO X, H 2Deng material, also can use the virtually any size except that above-mentioned, the material of shape.
Upstream side at the three-way catalyst 30 of outlet pipe 20 is equipped with the air-fuel ratio sensor 22 that detects exhaust air-fuel ratio (exhaust A/F) according to the oxygen concentration in the exhaust.Air-fuel ratio sensor 22 uses O 2Sensor also can use linear A/F sensor (LAFS) etc.
ECU (electric control device) 40 has: input output unit, storage device (ROM, RAM, fixedness RAM etc.), central processing unit (CPU), timer etc., carry out Comprehensive Control to comprising motor 1 at interior Exhaust gas purifying device by this ECU40.
The input side of ECU40 is except being connected with described TPS16, air flow sensor 18, air-fuel ratio sensor 22, also be connected with the various sensors such as CKP 42 of the crank angle of detection of engine 1, input is from the detection information of these sensors.In addition, detect engine rotary speed Ne according to crank angle information from CKP 42.
On the other hand, the outlet side of ECU is connected with various output units such as described Fuelinjection nozzle 6, spark coil 8, throttle valve 14, according to the fuel injection amount that goes out from the detection information calculations of various sensors, fuel injection time, firing time etc. respectively to these output units output.
In detail, according to air fuel ratio being set at suitable target air-fuel ratio (target A/F) from various sensor detection information, the fuel that will meet this target A/F amount sprays from combustion amount injection valve 6 in good time, again throttle valve 14 is adjusted to appropriate aperture, utilizes spark plug 4 to implement spark ignition in good time.
In more detail, according to the information from air-fuel ratio sensor 22, exhaust A/F carries out O in order to reach target A/F (for example, stoichiometric(al)) 2Feedback (O 2F/B) control, correspondingly fuel injection amount also changes, and in fact exhaust A/F periodically changes (air fuel ratio mean of calculating) round target A/F in dense air fuel ratio (dense A/F) side and rare air fuel ratio (rare A/F) side.
Below, the effect of the Exhaust gas purifying device of the present invention of above-mentioned formation is described.
With reference to Fig. 5, O 2The control program flowcharting of F/B control describes along this flow chart below.
At first, in step S10, foundation is O from air-fuel ratio sensor 22 2The information of sensor is that rare A/F or dense A/F judge to exhaust A/F now.According to judgement, be the occasion of rare A/F, then in step S12, carry out dense running.Increment correction fuel injection amount specifically.
If carry out dense running like this, then exhaust A/F becomes dense A/F, contains a large amount of HC and CO in the exhaust, and then three-way catalyst 30 is a reducing atmosphere.
As described later, because before three-way catalyst 30 becomes reducing atmosphere, catching in the little pore S of little pore catalyst element 30a has the molecular dimension NO littler than HC XAnd O 2So, in case three-way catalyst 30 becomes reducing atmosphere, these NO then XAnd O 2Be released, with CO, the HC generation redox reaction in the exhaust.At this moment, because CO and NO XThe reaction velocity of redox reaction than HC and NO XRedox reaction fast, so d/d NO XWith the CO preferential reaction, d/d on the other hand O 2Just react well with HC.
And, if NO XAnd O 2Fully discharge, then the little pore S of the little pore catalyst element 30a of exhaust upstream side catches the molecular dimension CO littler than HC, H well 2, on the other hand, the big pore L of the big pore catalyst element 30b in exhaust downstream side catches the big HC of molecular dimension well.In other words, in three-way catalyst 30, CO and HC separated energetically capturing among little pore catalyst element 30a and the big pore catalyst element 30b respectively.
, according to the judgement of step S10, be judged as the occasion of dense A/F, then in step S14, carry out rare running specifically thereafter.Decrement correction fuel injection amount specifically.
If carry out rare running like this, then exhaust A/F becomes rare A/F, contains a large amount of O in the exhaust 2And NO X, then three-way catalyst 30 is an oxidizing atmosphere.
As mentioned above, the CO that is captured, H 2, HC discharges, with O in the exhaust 2And NO XThe generation redox reaction.At this moment, because as mentioned above, CO and HC separated seizure respectively discharge CO, H in the little pore catalyst element 30a of exhaust-gas upstream side in little pore catalyst element 30a and big pore catalyst element 30b 2, simultaneously, CO and NO XThe reaction velocity of redox reaction than HC and NO XRedox reaction fast, so CO that in the little pore catalyst element 30a of exhaust-gas upstream side, discharges and the NO in the exhaust XPreferentially and reliably react.And, by like this CO is used with NO XReaction in, HC that on the big pore catalyst element 30b in exhaust downstream side, discharges and the O in the exhaust 2Reaction fully.
Just, the 1st embodiment's Exhaust gas purifying device passes through O 2Thereby F/B control makes exhaust A/F conversion between rare A/F and dense A/F produce oxidizing atmosphere and reducing atmosphere well, in reducing atmosphere, the good repeatedly continuous capturing of the state that separates with HC with CO to three-way catalyst 30, in oxidizing atmosphere, the CO of release, H 2The obstruction ground of the HC that is not discharged and the NO in the exhaust XPreferentially reaction reliably improves NO XPurifying property.Also have, because such CO, H 2Use with NO XReaction on, so HC that discharges and the O in the exhaust 2Reaction also improves the purifying property of HC fully.Thus, improve and highly keep comprehensively the exhaust purification performance of three-way catalyst 30.
In addition, here, as shown in Figure 1, linking all-in-one-piece three-way catalyst 30 with little pore catalyst element 30a fully on the blast air direction with big pore catalyst element 30b is that example is described, but little pore catalyst element 30a and big pore catalyst element 30b be necessary to be linked, as other embodiment, as shown in Figure 6, little pore catalyst element 30a and big pore catalyst element 30b can separate on the blast air direction.
Below, the 2nd embodiment is described.
In the 2nd embodiment, have only with three-way catalyst 301 to replace three-way catalyst 30 this point different with described the 1st embodiment.
As shown in Figure 7, three-way catalyst 301 by, big pore catalyst element 301a and the average opening size little pore catalyst element 301b littler than the molecular dimension of HC that the average opening size of pore is bigger than the molecular dimension of HC form, big pore catalyst element 301a is configured in exhaust-gas upstream side, and little pore catalyst element 301b is configured in the exhaust downstream side.Just, in three-way catalyst 301, the configuration of little pore catalyst element and big pore catalyst element is opposite with above-mentioned three-way catalyst 30.
Below, object is configured in exhaust-gas upstream side with big pore catalyst element 301a like this, and the effect that little pore catalyst element 301b is configured in the occasion in exhaust downstream side describes.
At O 2Carry out dense running in the F/B control, three-way catalyst 301 is reducing atmosphere, and is same as described above, the NO of seizure XAnd O 2Be released, with CO, the HC generation redox reaction in the exhaust.At this moment, because CO and NO XThe reaction velocity of redox reaction than HC and NO XRedox reaction fast, so the still NO that discharges XWith the CO preferential reaction, on the other hand, the O of release 2React well with HC.
Like this, NO XAnd O 2After discharging fully, then the big pore L of the big pore catalyst element 301a of exhaust-gas upstream side catches the big HC of molecular dimension well, on the other hand, the little pore S of the little pore catalyst element 301b in exhaust downstream side catches the molecular dimension CO littler than HC, H well 2, same as described above, in three-way catalyst 301, HC is separated respectively energetically with CO to be caught in big pore catalyst element 301a and little pore catalyst element 301b.
On the other hand, carry out rare running, three-way catalyst 301 is an oxidizing atmosphere, the HC of described seizure, CO and H 2Be released, with the O in the exhaust 2, NO XRedox reaction takes place.At this moment, HC and CO are separated respectively as mentioned above captures among big pore catalyst element 301a and the little pore catalyst element 301b, so, in the big pore catalyst element 301a of exhaust-gas upstream side, the HC of release and the O in the exhaust 2Reaction well, in the little pore catalyst element 301b in exhaust downstream side, the CO of release, H 2The obstruction ground of the HC that is not discharged and the NO in the exhaust XReaction well.
Thus, with NO XPurifying property and the purifying property of HC improve simultaneously, improve the exhaust purification performance of three-way catalyst 301 comprehensively.
In addition, this occasion also is that big pore catalyst element 301a and little pore catalyst element 301b not necessity connect to one, as other embodiment, as shown in Figure 8, big pore catalyst element 301a and little pore catalyst element 301b can separate on the blast air direction.
Below, the 3rd embodiment is described.
In the 3rd embodiment, have only with three-way catalyst 302 to replace three-way catalyst 30 this point different with described the 1st embodiment.
With reference to Fig. 9, / 4th ones of its expression three-way catalyst 302 unit lattice, this three-way catalyst 302 by, little pore catalyst element 302a and the average opening size of the pore big pore catalyst element 302b bigger than the molecular dimension of HC that the average opening size of pore is littler than the molecular dimension of HC form stratiform, little pore catalyst element 302a is configured in the top layer side, and big pore catalyst element 302b is configured in the internal layer side.
Below, object is configured in the top layer side with little pore catalyst element 302a like this, and the effect that big pore catalyst element 302b is configured in the occasion of internal layer side describes.
At O 2Carry out dense running in the F/B control, three-way catalyst 302 is reducing atmosphere, and is same as described above, the NO of seizure XAnd O 2Be released, with CO, the HC generation redox reaction in the exhaust.At this moment, because CO and NO XThe reaction velocity of redox reaction than HC and NO XRedox reaction fast, so the still NO that discharges XWith the CO preferential reaction, on the other hand, the O of release 2React well with HC.
Like this, NO XAnd O 2After discharging fully, then the little pore S of the little pore catalyst element 302a of top layer side catches the molecular dimension CO littler than HC, H well 2On the other hand, the big pore L of the big pore catalyst element 302b of internal layer side catches the big HC of molecular dimension well by the gap in the little pore catalyst element 302a, same as described above, in three-way catalyst 302, HC is separated respectively energetically with CO to be caught in little pore catalyst element 302a and big pore catalyst element 302b.
On the other hand, carry out rare running, three-way catalyst 302 is an oxidizing atmosphere, the HC of described seizure, CO and H 2Be released, with the O in the exhaust 2, NO XRedox reaction takes place.At this moment, HC and CO are separated respectively as mentioned above captures among little pore catalyst element 302a and the big pore catalyst element 302b, discharges CO, H in the little pore catalyst element 302a of top layer side 2, simultaneously, CO and NO XThe reaction velocity of redox reaction than HC and NO XRedox reaction fast, so the CO, the H that in the little pore catalyst element 302a of top layer side, discharge 2With the NO in the exhaust XPreferentially and reliably react.And, by like this CO is used with NO XReaction on, HC that in the big pore catalyst element 302b of internal layer side, discharges and the O in the exhaust 2Reaction fully.
Thus, with NO XPurifying property and the purifying property of HC improve simultaneously, improve the exhaust purification performance of three-way catalyst 302 comprehensively.
Also have, if will like this little pore catalyst element 302a and big pore catalyst element 302b be formed stratiform, then when motor 1 cold start etc., little pore catalyst element 302a and big pore catalyst element 302b roughly heat up simultaneously, obtain good activity.
Below, the 4th embodiment is described.
In the 4th embodiment, have only with three-way catalyst 303 to replace three-way catalyst 302 this point different with described the 3rd enforcement.
With reference to Figure 10, / 4th ones of its expression three-way catalyst 303 unit lattice, this three-way catalyst 303 by, big pore catalyst element 303a and the average opening size little pore catalyst element 303b littler than the molecular dimension of HC that the average opening size of pore is bigger than the molecular dimension of HC form stratiform, big pore catalyst element 303a is configured in the top layer side, and little pore catalyst element 303b is configured in the internal layer side.Just, in three-way catalyst 303, the configuration of little pore catalyst element and big pore catalyst element is opposite with described three-way catalyst 302.
Below, object is configured in the top layer side with big pore catalyst element 303a like this, and the effect that little pore catalyst element 303b is configured in the occasion of internal layer side describes.
At O 2Carry out dense running in the F/B control, three-way catalyst 303 is reducing atmosphere, and is same as described above, the NO of seizure XAnd O 2Be released, with CO, the HC generation redox reaction in the exhaust.At this moment, because CO and NO XThe reaction velocity of redox reaction than HC and NO XRedox reaction fast, so the still NO that discharges XWith the CO preferential reaction, on the other hand, the O of release 2React well with HC.
Like this, NO XAnd O 2After discharging fully, then the big pore L of the big pore catalyst element 303a of top layer side catches the big HC of molecular dimension well, on the other hand, the little pore S of the little pore catalyst element 303b of internal layer side catches the molecular dimension CO littler than HC well, same as described above, in three-way catalyst 303, HC is separated respectively energetically with CO to be caught in big pore catalyst element 303a and little pore catalyst element 303b.
On the other hand, carry out rare running, three-way catalyst 303 is an oxidizing atmosphere, and HC, the CO of described seizure are released, with the O in the exhaust 2, NO XRedox reaction takes place.At this moment, because HC and CO is separated respectively captures among big pore catalyst element 303a and the little pore catalyst element 303b as mentioned above, so HC that in the big pore catalyst element 303a of top layer side, discharges and the O in the exhaust 2Reaction well.The much NO that hinders in ground and the exhaust of the HC that the CO that discharges in the little pore catalyst element 303b of internal layer side is not discharged XReaction more well.
Thus, with NO XPurifying property and the purifying property of HC improve simultaneously, improve the exhaust purification performance of three-way catalyst 303 comprehensively.
Also have, this occasion also is, if will like this big pore catalyst element 303a and little pore catalyst element 303b be formed stratiform, when motor 1 cold start etc., big pore catalyst element 303a and little pore catalyst element 303b roughly heat up simultaneously, obtain good activity.
Then, the 5th embodiment is described.
In the 5th embodiment, have only and carry out A/F conversion (air fuel ratio mean of calculating) forcibly and replace O 2F/B control this point is different with described the 1st embodiment.
With reference to Figure 11, the control program flowcharting of A/F conversion control describes along this flow chart below.
At first, in step 20, judge timer whether timing stipulated time t1.The CO seizure amount that stipulated time t1 for example is arranged on the little pore catalyzer 30a of the prediction three-way catalysts 30 such as experiment by in advance reaches capacity state promptly The amount of breaking onceTime in.Just, in step S20, judge whether the seizure amount of CO is the state that is about to reach the amount of breaking once.
The result that step 20 is judged is negative (No), concludes the occasion that does not also have through stipulated time t1, can judge and can fully catch CO, enters step S22, carries out or continue dense running.On the other hand, judged result is concluded the occasion of having passed through stipulated time t1 for affirming (Yes), enters step S24.
In step S24, judge timer whether timing stipulated time t2, stipulated time t2-t1 for example is arranged on the NO of the little pore catalyzer 30a of the prediction three-way catalysts 30 such as experiment by in advance XThe seizure amount reaches capacity state in i.e. time of the amount of breaking once.Just, in step S24, judge NO XThe seizure amount whether be the state that is about to reach the amount of breaking once.
The result that step 24 is judged is negative (No), concludes the occasion that does not also have through stipulated time t2, can judge and can fully catch NO X, enter step S26, carry out or continue rare running.On the other hand, judged result is concluded the occasion of having passed through stipulated time t2 for affirming (Yes), enters step S28, and timer is reset to 0.Like this, after, dense running and rare running implemented repeatedly.
Just, in the 5th embodiment, do not reach in the scope of the amount of breaking once, exhaust A/F is changed between dense A/F and rare A/F expeditiously at the CO of three-way catalyst 30 and the seizure amount of NOX.
Thereby, in the 5th embodiment's Exhaust gas purifying device, thereby by the A/F conversion and control make exhaust A/F expeditiously between rare A/F and dense A/F conversion produce oxidizing atmosphere and reducing atmosphere well, in reducing atmosphere, the good repeatedly continuous capturing of the state that separates with HC with CO is in three-way catalyst 30, in oxidizing atmosphere, the NO in the obstruction of the HC that the CO of release or not ground and the exhaust XPreferentially reaction reliably improves NO XPurifying property.Also have because like this CO is used with NO XReaction on, so HC that discharges and the O in the exhaust 2Reaction also improves the purifying property of HC fully.Thus, the final exhaust purification performance that improves and keep well all the time comprehensively three-way catalyst 30.
In addition, here, be illustrated with described the 1st embodiment's three-way catalyst 30, but be not limited thereto, described the 2nd to the 4th embodiment's three-way catalyst 301,302,303 also can be applicable to the 5th embodiment.
In addition, in described example, the different little pore catalyst element and the big pore catalyst elements of average opening size of pore is set on three-way catalyst, with CO and HC is that two compositions in the exhaust separate, but also can be according to catching the average opening size of refinement pore of composition, the catalyst element (pore group) of configuration more than three, the composition more than three in the separation off gas.Also have, the composition in the separation off gas is not limited to CO and HC, can appropriately select as required about this separated component.
Also have, in described example, motor 1 has adopted petrol engine, but motor 1 also can be a diesel engine.
More than the present invention is described, apparent, the present invention can be changed in every way.These change and can not be counted as breaking away from aim of the present invention and scope, and all will be included in the scope of claims described later conspicuous all such modifications of technician in the art.

Claims (2)

1. the Exhaust gas purifying device of an internal-combustion engine is characterized in that,
On the exhaust passage of internal-combustion engine, have three-way catalyst (30,301,302,303),
Described three-way catalyst is made up of one or more catalyst element, and the different pore group of two or more average opening sizes is arranged on the coating,
Described three-way catalyst by, have on the coating can molecular dimension is littler than the molecular dimension of hydrocarbon CO, O 2, NO X, H 2The little pore group's that the average opening size that separates is little little pore catalyst element (30a, 301b, 302a, big pore catalyst element (30b, 301a, 302b that the big big pore group of the average opening size that can catch described hydrocarbon 303b), is arranged on the coating, 303a) form
Described little pore catalyst element (30a) is provided in exhaust-gas upstream side, and described big pore catalyst element (30b) is provided in the exhaust downstream side.
2. the Exhaust gas purifying device of internal-combustion engine as claimed in claim 1 is characterized in that,
The air fuel ratio mean of calculating that further has the air fuel ratio that makes the exhaust that flows into described three-way catalyst periodically between rare air fuel ratio and dense air fuel ratio, to change.
CNB2005100040809A 2004-01-08 2005-01-07 Exhaust gas purifier for ic engine Expired - Fee Related CN100410503C (en)

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JP2005193171A (en) 2005-07-21

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