JP2005042687A - Exhaust emission control device and emission control method - Google Patents

Exhaust emission control device and emission control method Download PDF

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JP2005042687A
JP2005042687A JP2003280391A JP2003280391A JP2005042687A JP 2005042687 A JP2005042687 A JP 2005042687A JP 2003280391 A JP2003280391 A JP 2003280391A JP 2003280391 A JP2003280391 A JP 2003280391A JP 2005042687 A JP2005042687 A JP 2005042687A
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exhaust gas
filter
ceramic honeycomb
catalyst
partition wall
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JP4412641B2 (en )
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Hiroshi Funahashi
Hirohisa Suwabe
博 舟橋
博久 諏訪部
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Hino Motors Ltd
Hitachi Metals Ltd
日立金属株式会社
日野自動車株式会社
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/18Exhaust 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
    • F01N3/20Exhaust 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
    • F01N3/2066Selective catalytic reduction [SCR]
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00Exhaust 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
    • F01N13/009Exhaust 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2340/00Dimensional characteristics of the exhaust system, e.g. length, diameter or volume of the apparatus; Spatial arrangements of exhaust apparatuses
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00Surface coverings
    • F01N2510/06Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0682Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00Adding substances to exhaust gases
    • F01N2610/02Adding substances to exhaust gases the substance being ammonia or urea
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/0231Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using special exhaust apparatus upstream of the filter for producing nitrogen dioxide, e.g. for continuous filter regeneration systems [CRT]
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/103Oxidation catalysts for HC and CO only
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/20Exhaust after-treatment
    • Y02T10/24Selective Catalytic Reactors for reduction in oxygen rich atmosphere

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compact exhaust emission control device and an exhaust emission control method, which efficiently remove NOx and particulate substance contained in exhaust gas, in the exhaust emission control device of a diesel engine and which can reduce pressure loss in the whole exhaust emission control device. <P>SOLUTION: The exhaust emission control device is constructed such that a filter and a SCR (Selective Catalytic Reduction) catalyst are arranged in this order from an upstream side in an exhaust passage of the diesel engine. The ceramic honeycomb filter has a porous ceramic honeycomb structure in which desired flow passages are sealed. At least one sealed portion on an exhaust gas inflow side of the filter is arranged apart from an exhaust gas inflow side end surface. Catalyst material is carried on at least a part of partition walls and/or the sealed portions. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、ディーゼルエンジンから排出される、窒素酸化物(以下NO xとも略記する)及び粒子状物質を含有する排気ガスを浄化するディーゼルエンジンの排気ガス浄化装置に関するものである。 The present invention is discharged from a diesel engine, to a exhaust gas purifying device for a diesel engine for purifying nitrogen oxides (also hereinafter NO x abbreviated) and an exhaust gas containing particulate matter.

ディーゼルエンジンはその燃費効率の高さから、欧州を中心に需要が増大している。 Diesel engines because of its high fuel efficiency, the demand in Europe is increasing. しかしながら、ディーゼルエンジンの排気ガス中に含まれている粒子状物質(PM:Particulate Matter)及び窒素酸化物(NO x )の人体の健康に与える影響が大きいことから、このPM及びNO xの低減技術が種々検討されている。 However, particulate matter contained in exhaust gas from diesel engines (PM: Particulate Matter) and nitrogen oxides since health Influence of the human body is large (NO x), technology for reducing the PM and NO x There has been studied. この排気ガス中のPM及びNO xを低減する排気ガス浄化装置として、例えば、特許文献1に記載の発明には、NO及び粒子状物質を含む燃焼排気ガスを処理する改良されたSCR(Selective Catalytic Reduction)機構であって、前記NO x中のNOの少なくとも一部をNO に効果的に転化する酸化触媒と、粒子状物質トラップと、還元剤流体の供給源、及びSCR触媒をこの順序で組み合わせてなる、SCR機構が開示されている。 As an exhaust gas purification apparatus for reducing PM and NO x in the exhaust gas, for example, in the invention described in Patent Document 1, NO and particulate matter handling combustion exhaust gas containing an improved SCR (Selective Catalytic a reduction) mechanism, at least a portion of NO in said NO x and an oxidation catalyst effectively converted to NO 2, and particulate trap, a source of reductant fluid, and the SCR catalyst in that order combination comprising, SCR mechanism is disclosed. ここでSCRとは、選択的接触還元のことで、高温の排気ガスを、窒素系還元剤、特にアンモニアまたは、尿素の存在下で触媒上を通過させる方法である。 Here, the SCR is by selective catalytic reduction, the hot exhaust gases, nitrogen-based reducing agent, in particular ammonia or a method to pass over the catalyst in the presence of urea. この発明では、酸化触媒により排気ガス中のNOがNO に効果的に転化され、粒子状物質トラップで排気ガス中の粒子状物質の少なくとも一部がNO の存在下で比較的低い温度で燃焼除去される。 In the present invention, NO in the exhaust gas by the oxidation catalyst can be effectively converted to NO 2, at a relatively low temperature in the presence of at least a portion of the particulate matter in the exhaust gas in the particulate trap NO 2 It is burned and removed. 更に、NO 含有量の高くなった排気ガスに対して、窒素系還元剤を添加してガス混合物を形成し、このガス混合物をSCR触媒上に通過させることにより、NO がN に転化される。 Furthermore, with respect to raised exhaust gas NO 2 content, the addition of nitrogen-based reducing agent to form a gas mixture, converting the gas mixture by passing on the SCR catalyst, NO x is in N 2 It is. この発明によれば、SCR触媒の上流に配置した酸化触媒、及び粒子状物質トラップが、SCR機構によるNO xからN への転化率を増加するのに特に有効であるとされている。 According to the present invention, an oxidation catalyst disposed upstream of the SCR catalyst, and particulate matter trap, it is said to be particularly effective in increasing the conversion rate of the N 2 from the NO x by SCR mechanism. この発明では、酸化触媒には、例えば、セラミックまたは金属製の、スルー−フローハニカム担体上に担持された白金触媒が特に好適とされており、粒子状物質トラップには、一般的にセラミックから製造されるウオール−フローフィルターが好ましいとされ、SCR触媒には、スルー−フローハニカム担体上に担持されたV /WO /TiO 触媒が好ましいとされている。 In this invention, the oxidation catalyst, for example, made of ceramic or metal, through - manufacturing are the flow honeycomb support on supported on the platinum catalyst is particularly preferred, the particulate trap, generally from ceramic is a flow filter is preferred, the SCR catalyst, the through - - wall being flow honeycomb support V 2 supported on O 5 / WO 3 / TiO 2 catalyst is preferred.

また、特許文献2に記載の発明には、図4にこの発明に係わる実施の形態のディーゼルエンジンの排気ガス浄化装置を示すエンジンの排気系の構成図を示すように、ディーゼルエンジンの排気通路2に、NO を還元浄化するSCR触媒5を配設すると共に、該SCR触媒の上流側に、上流側から順に酸化触媒3と、該酸化触媒3の触媒作用により排気ガス中の硫黄分が酸化されて生じるサルフェート分を捕集できるフィルタ4を直列に配設したことを特徴とするディーゼルエンジンの排気ガス浄化装置が開示されている。 Further, the invention described in Patent Document 2, as shown a block diagram of an exhaust system of an engine showing an exhaust gas purification system for a diesel engine of the embodiment according to the present invention in FIG. 4, the exhaust of diesel engines passage 2 to, with disposing the SCR catalyst 5 reduces and purifies NO x, upstream of the SCR catalyst, the oxidation catalyst 3 in order from the upstream side, the sulfur content in the exhaust gas by the catalytic action of the oxidation catalyst 3 is oxidized exhaust gas purifying device for a diesel engine is disclosed, wherein a filter 4 is disposed in series which can collect the sulfate fraction occurring it is. そして、フィルタ4とSCR触媒5の間の排気通路2に還元剤供給装置6が設けてある。 Then, the reducing agent supply device 6 to the exhaust passage 2 between the filter 4 and the SCR catalyst 5 is provided. この発明の構成によれば、排気ガス中に含まれる硫黄分を排気ガス中のダストと共に捕集し、下流側のSCR触媒5が硫黄分やPM等のダストにより、被毒するのを防止できるので、効率よくNO を還元浄化でき、排気ガスによる公害を低減できるとしている。 According to the configuration of the present invention, the sulfur contained in the exhaust gas was collected with the dust in the exhaust gas, SCR catalyst 5 on the downstream side by the dust, such as sulfur and PM, can be prevented from poisoning so it can be efficiently reduce and purify NO x, are the pollution can be reduced by the exhaust gas. この発明において、酸化触媒3は、例えば、コージェライト製モノリス担体にアルミナの触媒担持層をコーティングにより形成し、この担持層に白金等の触媒成分を担持させたものが使用され、フィルタ4は、多数の排気通路が互いに平行に形成されたコージェライト製のハニカムフィルタやアルミナ等のセラミック不織布からなるフィルタ等を使用することができ、更に、SCR触媒5は、担体をAl 、TiO 等で形成し、活性体として触媒金属をPt、V 、Fe 、CuO、Mn 、Cr 、MoO 等で形成する。 In the present invention, the oxidation catalyst 3, for example, is formed by coating a catalyst support layer of alumina cordierite monolithic support, which was supported catalyst component such as platinum is used for this carrier layer, filter 4, the consists of a number of exhaust passages cordierite honeycomb filter and a ceramic non-woven fabric such as alumina which is formed in parallel to each other filter or the like can be used, further, SCR catalyst 5, the carrier Al 2 O 3, TiO 2 formed in or the like to form a catalytic metal Pt, V 2 O 5, Fe 2 O 3, CuO, in Mn 2 O 3, Cr 2 O 3, MoO 3 or the like as the active substance.

特表2002−502927号公報 JP-T 2002-502927 JP 特開2000−303826号公報 JP 2000-303826 JP

上記従来技術である特許文献1及び2に記載されているディーゼルエンジンから排出される排気ガスの浄化装置では、排気ガス通路に、酸化触媒、フィルタ、還元剤流体の供給源、及びSCR触媒の各装置が直列に配置されており、多くの場合、酸化触媒及びSCR触媒には触媒物質が担持されたセラミックハニカム構造体が、またフィルタにはセラミックハニカム構造体の所望の流路を両端部で目封止したセラミックハニカムフィルタ、或いはセラミック不織布からなるフィルタ等が使用されている。 Above purification apparatus for exhaust gas discharged from a diesel engine described in Patent Documents 1 and 2 is a prior art, the exhaust gas passage, an oxidation catalyst, a filter, a source of reductant fluid, and each of the SCR catalyst device are arranged in series, often, the eye at both ends ceramic honeycomb structure catalyst material is supported on the oxidation catalyst and the SCR catalyst, but also the desired flow paths of the ceramic honeycomb structure in the filter sealed ceramic honeycomb filter or filters and the like made of ceramic nonwoven is used. このため、排気ガス浄化装置の圧力損失は、2種類のハニカム構造体の圧力損失、セラミックハニカムフィルタ、又はセラミック不織布からなるフィルタの圧力損失が加算されたものとなり、装置全体の圧力損失が大きくなって、エンジン出力や燃費の低下につながるという問題がある。 Therefore, the pressure loss of the exhaust gas purifying device, the pressure loss of the two honeycomb structures, ceramic honeycomb filters, or pressure loss of the filter is to have been added consisting of a ceramic nonwoven, increases the pressure loss of the entire device Te, there is a problem that leads to a decrease in engine output and fuel economy. また、例えば特許文献2の図2に記載されているような、従来の排気ガス浄化装置では、酸化触媒とフィルタが排気通路によって、直列に配置されていることから、酸化触媒における触媒反応により高温となった排気ガスが、酸化触媒とフィルタ間の排気通路を通過する間に温度が低下してフィルタに流入し、特に低速走行時のように浄化装置に流入する排気ガス温度自体が低い場合は、フィルタ内の温度が、粒子状物質を十分に燃焼させる温度に達しない場合があり、未燃焼の粒子状物質がフィルタに残存して、フィルタの圧力損失が上昇するという問題の発生する場合もあった。 Further, for example, as described in Figure 2 of Patent Document 2, in the conventional exhaust gas purifying apparatus, by the oxidation catalyst and the filter exhaust passage, because it is arranged in series, a high temperature by catalytic reaction in the oxidation catalyst by now, the exhaust gas, when the temperature while passing through the exhaust passage between the oxidizing catalyst and the filter flows into the filter decreases, especially low exhaust gas temperature itself flowing into purifier such as during low-speed traveling , the temperature in the filter, may not reach the temperature to sufficiently burn the particulate matter, and particulate matter unburned remains in the filter, even if the pressure loss of the filter may occur a problem that increases there were.

また、ハニカム構造体やセラミックハニカムフィルタ又はセラミック不織布からなるフィルタ等の装置は、浄化性能を確保するために一定量の体積が必要であることから、従来技術のように2種類のハニカム構造体、セラミックハニカムフィルタ又はセラミック不織布からなるフィルタ、及び還元剤供給装置の4種類の装置を直列に配置した場合、取り付けスペースが膨大になり、例えばディーゼル車輌への搭載が困難になるという問題もあり、小型で低圧力損失、且つ高効率の排気ガス浄化装置が求められていた。 The device such as a filter made of a honeycomb structure, a ceramic honeycomb filter or ceramic nonwoven, since it is required a certain amount of volume in order to ensure the purification performance, two types of the honeycomb structure as in the prior art, ceramic honeycomb filter or filter made of ceramic nonwovens, and if the four devices of the reducing agent supply device arranged in series, the mounting space becomes huge, for example also a problem that mounting of the diesel vehicle becomes difficult, size in low pressure loss, and a high efficiency of the exhaust gas purification device it has been demanded.
本発明の目的は、上記従来技術の問題を解決し、小型で低圧力損失の排気ガス浄化装置を提供することにある。 An object of the present invention is to solve the above-mentioned prior art problems and to provide an exhaust gas purification device with low pressure loss small.

本発明者らは、排気ガス中のNO xと粒子状物質を効果的に低減しつつ、排気ガス浄化装置全体の圧力損失の低減及び小型化について、鋭意検討を行った結果、SCR触媒の上流に配置される、フィルタの構造を最適化することが有効であることを見出し、本発明に想到した。 The present inventors, while reducing the NO x and particulate matter in the exhaust gas effectively, the reduction and miniaturization of the pressure loss of the entire exhaust gas purification device, extensive studies were carried out result, upstream of the SCR catalyst it is disposed, optimizing the structure of the filter found that it is effective, and conceived the present invention.

本発明の排気ガス浄化装置は、ディーゼルエンジンから排出される窒素酸化物及び粒子状物質を含有する排気ガスを浄化する装置であって、多孔質セラミックハニカム構造体の所望の流路を目封止したセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているフィルタと、SCR触媒とを、この順序で配置したことを特徴とする。 Exhaust gas purifying apparatus of the present invention is an apparatus for purifying exhaust gas containing nitrogen oxides and particulate matter discharged from a diesel engine, plugging the desired flow paths of the porous ceramic honeycomb structural body and the ceramic honeycomb filter, with at least one exhaust gas inlet side plugged portions are spaced apart from the exhaust gas inlet-side end, a catalyst material is supported on at least a portion of the partition wall and / or the plugging portion and in which filter, and SCR catalyst, characterized by being arranged in this order.

さらに本発明の排気ガス浄化装置において、前記セラミックハニカムフィルタの排気ガス流入側目封止部端面が、セラミックハニカムフィルタの流入側端面から該セラミックハニカムフィルタ全長の0.7倍以下の長さの区間に配置されていることが好ましい。 In addition exhaust gas purifying apparatus of the present invention, the ceramic exhaust gas inflow side plugged end face of the honeycomb filter, a ceramic honeycomb from the inlet-side end of the filter of 0.7 times the length of the ceramic honeycomb filter full length interval it is preferably arranged in. また、前記セラミックハニカムフィルタに担持される触媒物質が白金族金属を含んでなることが好ましい。 Further, it is preferable that the catalytic material is supported on the ceramic honeycomb filter comprising a platinum group metal. 更には、前記セラミックハニカムフィルタに担持される触媒物質を、排気ガス流出側に比べ排気ガス流入側に多く担時させることが好ましい。 Furthermore, the catalyst material is supported on the ceramic honeycomb filter, be much 担時 the exhaust gas inlet side than on the exhaust gas outlet side preferably.

本発明の排気ガス浄化方法は、ディーゼルエンジンから排出される窒素酸化物及び粒子状物質を含有する排気ガスを浄化する装置に配設されたセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持され、前記排気ガス中の粒子状物質を前記セラミックハニカムフィルタ内で燃焼させ、前記フィルタの排気ガス排出側に配設されたSCR触媒中に導入する排気ガス中のNO/NO のモル比を1/2〜2/1にすることを特徴とする。 Exhaust gas purification method of the present invention, the ceramic honeycomb filter disposed in an apparatus for purifying exhaust gas containing nitrogen oxides and particulate matter discharged from a diesel engine, at least one exhaust gas inlet side eyes sealed with stopper portion is spaced apart from the exhaust gas inlet-side end, a catalyst material is supported on at least a portion of the partition wall and / or the plugging portion, the particulate matter in the exhaust gas the ceramic honeycomb in the filter in burned, characterized in that the molar ratio of 1/2 to 2/1 of NO / NO 2 in the exhaust gas introduced into the exhaust gas discharge side SCR catalyst disposed in the filter.

本発明の排気ガス浄化装置及び排気ガス浄化方法の作用、効果について、本発明の排気ガス浄化装置を示すエンジンの排気系の構成図である図1を用いて説明する。 The action of the exhaust gas purifying apparatus and an exhaust gas purification method of the present invention, the effects will be described with reference to FIG. 1 is a configuration diagram of an exhaust system of an engine showing an exhaust gas purifying apparatus of the present invention.
本発明のディーゼルエンジンから排出される窒素酸化物(NO )及び粒子状物質を含有する排気ガスを浄化する装置は、多孔質セラミックハニカム構造体の所望の流路を目封止したセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているフィルタ11と、SCR触媒5とを、この順序で配置している。 Apparatus for purifying exhaust gas containing nitrogen oxides (NO x) and particulate matter emitted from a diesel engine of the present invention, a ceramic honeycomb filter plugging a desired flow path of the porous ceramic honeycomb structural body of, together with at least one exhaust gas inlet side plugged portions are spaced apart from the exhaust gas inlet side end surface, the filter catalyst material on at least a portion of the partition wall and / or the plugging portion is supported 11 When, the SCR catalyst 5, are arranged in this order. このため、酸化触媒、フィルタ、還元剤の供給源、SCR触媒を、この順序で配置した従来技術の排気ガス浄化装置の圧力損失が、酸化触媒に用いられるハニカム構造体の圧力損失、セラミックハニカムフィルタ、又はセラミック不織布からなるフィルタの圧力損失、及びSCR触媒に用いられるハニカム構造体の圧力損失の合計となり、装置全体の圧力損失が大きくなっているのに対し、本発明の排気ガス浄化装置の圧力損失は、セラミックハニカムフィルタの圧力損失とSCR触媒に用いられるハニカム構造体の圧力損失の合計にすぎないので、排気ガス通路全体の圧力損失を小さくすることができ、エンジン出力や燃費の低下を防ぐことができるのと共に、排ガス浄化装置全体の小型化が可能となる。 Therefore, an oxidation catalyst, a filter, a source of reductant, the SCR catalyst, the pressure loss of the exhaust gas purifying apparatus of the prior art arranged in this order, a pressure loss of the honeycomb structure used in the oxidation catalyst, ceramic honeycomb filters , or the pressure loss of the filter made of ceramic nonwovens, and the sum of the pressure loss of the honeycomb structure used in the SCR catalyst, while the pressure loss of the entire device is large, the pressure of the exhaust gas purifying apparatus of the present invention losses, since only a total pressure loss of the honeycomb structure used in the pressure loss of the ceramic honeycomb filter and the SCR catalyst, it is possible to reduce the pressure loss in the entire exhaust gas passage, preventing the reduction of the engine output and fuel efficiency together we can be, it is possible to miniaturize the entire exhaust gas purifying apparatus.

ここで、本発明の排気ガス浄化装置において、多孔質セラミックハニカム構造体の所望の流路を目封止したセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているフィルタ11を用いる理由と作用、効果について以下説明する。 Here, in the exhaust gas purifying apparatus of the present invention, the desired flow paths of the ceramic honeycomb filter plugging the at least one exhaust gas inlet side plugged portions exhaust gas inlet side end surface of the porous ceramic honeycomb structural body together are arranged farther away, it acts as the reason for using a filter 11 in which the catalyst substance is supported on at least a portion of the partition wall and / or the plugging portions, the effect will be described below.
図2は、本発明の排気ガス浄化装置に用いられるフィルタ11の一例の模式断面図である。 Figure 2 is a schematic sectional view of an example of the filter 11 used in the exhaust gas purifying apparatus of the present invention. フィルタ11は、流路方向垂直断面が略円状又は略楕円状で、外周壁20と、この外周壁20の内周側で隔壁30により囲まれた多数の流路40を有する多孔質セラミックハニカム構造体10の流路40の所望部位に目封止部50、52により交互に目封止している。 Filter 11, flow path direction vertical cross section a substantially circular or substantially elliptical shape, a porous ceramic honeycomb having an outer peripheral wall 20, a number of channels 40 surrounded by partitions 30 on the inner peripheral side of the outer peripheral wall 20 It is sealed plugged alternately by plugged portion 50, 52 to the desired site of the channel 40 of the structure 10. そして、少なくとも一つの排気ガス流入側の目封止部端面51は、セラミックハニカムフィルタの流入側端面12に対して、排気ガス流出側に離れて配置されており、隔壁及び/または目封止部の少なくとも一部には触媒物質60が担持されている。 Then, the plugged end face 51 of the at least one exhaust gas inlet side, to the inlet-side end 12 of the ceramic honeycomb filter are spaced apart in the exhaust gas outlet side, the partition wall and / or the plugging portion the catalytic material 60 is supported on the at least a portion of.

このような構造を有するハニカムフィルタにおいて排気ガスは、流入側端面12で開口している流路41、及び42から流入する。 Such exhaust gas in the honeycomb filter having a structure flows from the channel 41, and 42 are open at inlet-side end 12. このうち流路42から流入した排気ガス91は、流入側目封止部50があることから、隔壁31中に形成された細孔(図示せず)を通過して隣接する流路41に排出され、この流路41に流入側端面12から流入した排気ガス90と合流後、流路41を流出側端面13に向かって進行し、この流路の流出側端面には、流出側目封止部52があるために、隔壁32に形成された細孔(図示せず)を通過して隣接する流路である流出側端面13で開口している流路43から排出(矢印92で示す)される。 Exhaust gas 91 flowing from the inner flow path 42 is discharged since there is inflow side plugged portions 50, the flow path 41 adjacent through the pores formed in the partition wall 31 (not shown) is, after the confluence with the exhaust gas 90 that has flowed from the inlet-side end 12 in the passage 41, and travels toward the channel 41 to the outflow end face 13, the outflow side end face of the flow path, the outflow-side plugging because of the part 52, the pores formed in the partition wall 32 through the (not shown) discharged from the flow channel 43 which is open at the outflow side end face 13 is adjacent flow path (indicated by arrow 92) It is. なお、排気ガスのうちの一部は、流入側目封止部50及び流出側目封止部52に形成されている細孔(図示せず)を通過して、排出されるものもある。 A part of the exhaust gas is passed through the pores formed in the inflow side plugged portions 50 and the outflow-side plugging portion 52 (not shown), others are discharged. この間、排気ガス中の粒子状物質は、主に流路41〜43、及び隔壁31〜32を通過する際に、多孔質隔壁に捕集されると共に、隔壁及び/または目封止部の少なくとも一部には端持された触媒物質の作用により燃焼され効率よく排気ガスが浄化される。 During this time, the particulate matter in the exhaust gas is mainly the flow path 41 to 43, and when passing through the partition wall 31-32, while being trapped in the porous partition, at least the septum and / or plugging portion some are burned efficiently exhaust gas is purified by the action of the catalyst material which is Tanji.

従来技術では、排気ガス浄化装置の小型化ができないという問題に加えて、酸化触媒における触媒反応により高温となった排気ガスが、酸化触媒とフィルタ間の排気通路2を通過する際に温度が低下し、低温の排気ガスとなってフィルタに流入し、特に低速走行時のような浄化装置に流入する排気ガス温度自体が低い場合に、フィルタ内の温度が、粒子状物質を十分に燃焼させる温度に達せず、未燃焼の粒子状物質がフィルタに残存、特に未燃焼の粒子状物質が温度の低いフィルタ入口端部に多く残存して、流路を閉塞させることによるフィルタの圧力損失が上昇するという問題もあった。 In the prior art, in addition to the problem of being unable to reduce the size of the exhaust gas purifying device, the exhaust gas temperature has become high by the catalytic reaction in the oxidation catalyst, the temperature is lowered as it passes through the exhaust passage 2 between the oxidation catalyst and the filter and the temperature when entering into the filter becomes low-temperature exhaust gas, the exhaust gas temperature itself flowing into the particular purification device, such as during low speed running low, the temperature in the filter, to sufficiently burn the particulate matter not reached, the residual particulate matter of the unburned filter, particulate matter unburned especially with many remaining lower filter inlet end temperature, pressure loss of the filter due to occlude the flow path is increased there was also a problem. これに対して、本発明の排気ガス浄化装置は、少なくとも一つの流入側目封止部50がセラミックハニカムフィルタ11の流入側端面からフィルタ内部に離れて配置されていることから、排気ガスが流入側目封止部50より流入側に配置された隔壁31に担持された触媒物質による触媒反応により、高温とされるため、フィルタ内部の温度を前記触媒物質の活性下限温度以上に維持し易くなる。 In contrast, the exhaust gas purifying apparatus of the present invention, since at least one of the inflow-side plugging portion 50 is spaced apart from the inlet-side end of the ceramic honeycomb filter 11 inside the filter, the exhaust gas inlet the catalytic reaction using supported catalyst material in the partition wall 31 disposed on the inflow side from the side plugged portions 50, because it is a high temperature, tends to maintain the temperature inside the filter to more active lower limit temperature of the catalytic material . このため、本発明の排気ガス浄化装置は、排ガス中の粒子状物質を効率よく燃焼させることができ、特に流入側目封止部での未燃焼粒子状物質の堆積による圧力損失の上昇を防ぐことが出来るという効果も有する。 Therefore, the exhaust gas purifying apparatus of the present invention can be combusted efficiently the particulate matter in the exhaust gas, prevents the increase of pressure loss due to particularly the deposition of unburned particulate matter in the inflow-side plugging portion it also has an effect that can be.

さらに、従来技術である酸化触媒、フィルタ、還元剤の供給源、SCR触媒の装置の組合せにより構成される排気ガス浄化装置に対して、上記のように、本発明の少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているフィルタ、SCR触媒の組合せにより構成される排気ガス浄化装置の圧力損失が低減できる理由は、以下のように考えられる。 Furthermore, the prior art is that the oxidation catalyst, the filter, a source of reductant for the exhaust gas purification apparatus constituted by a combination of the apparatus of the SCR catalyst, as described above, at least one exhaust gas inlet side of the present invention with plugged portions are spaced apart from the exhaust gas inlet side end surface, the filter catalyst material is supported on at least a portion of the partition wall and / or the plugging portion, the exhaust constituted by the combination of the SCR catalyst why the pressure loss of the gas purifier can be reduced, it is considered as follows.
一般に排気ガス浄化装置に用いられるセラミックハニカム構造体の圧力損失は、(1)排気ガス流路の流入口及び流出口で排気ガスが圧縮或いは膨張することにより生じる圧力損失、(2)排気ガス流路内での流路抵抗による圧力損失の合計で表される。 Generally the pressure loss of the ceramic honeycomb structure used in the exhaust gas purifying apparatus, (1) the pressure loss caused by the exhaust gas compressed or expanded at the inlet and outlet of the exhaust gas passage, (2) the exhaust gas stream represented by the sum of the pressure loss due to flow resistance in the road. セラミックハニカムフィルタでは、上記に更に(3)隔壁を排気ガスが通過する際の圧力損失が加算される。 The ceramic honeycomb filter, pressure loss when the further (3) the partition wall of the exhaust gas passes are added. このため、従来技術の酸化触媒が担持されたハニカム構造体、セラミックハニカムフィルタ、SCR触媒が担持されたハニカム構造体から構成される排ガス装置を本発明のように少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているセラミックハニカムフィルタ及びSCR触媒が担持されたハニカム構造体から構成される排気ガス浄化装置とすることにより、従来技術の酸化触媒での排気ガス流路流入側及び流出口の圧力損失及び流路抵抗による圧力損失が発生しなくなるため、排気ガス浄化装置全体の圧力損失を低減することが可能となる。 Therefore, the honeycomb structure oxidation catalyst is carried in the prior art, ceramic honeycomb filter, at least one exhaust gas inlet side first sealed as in the present invention configured exhaust system of the honeycomb structure SCR catalyst is supported with stopper portion is spaced apart from the exhaust gas inlet side end surface, the partition wall and / or a honeycomb structure ceramic honeycomb filter and the SCR catalyst in which the catalyst substance is supported on at least a part of which is carried in the plugging portion with the exhaust gas purification device comprising, the pressure loss due to pressure loss and the flow path resistance of the conventional exhaust gas passage of the oxidation catalyst technology inlet side and the outlet is not generated, the entire exhaust gas purifying device it is possible to reduce the pressure loss. また、図1に示す本発明の排気ガス浄化装置では、排気ガス通路2の長さ自体を、図4に示す従来の排気ガス浄化装置に比べて短縮することができるため、排気ガス浄化装置の全体の圧力損失を小さくすることができ、且つ排気ガス浄化装置を小型化することができる。 Further, the exhaust gas purifying apparatus of the present invention is shown in Figure 1, the length itself exhaust gas passage 2, it is possible to shorten as compared with the conventional exhaust gas purifying apparatus shown in FIG. 4, the exhaust gas purifying device it is possible to reduce the overall pressure drop, and the exhaust gas purifying device can be miniaturized.

本発明の排気ガス浄化方法は、ディーゼルエンジンから排出される窒素酸化物及び粒子状物質を含有する排気ガスを浄化する装置に配設されたセラミックハニカムフィルタの少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持され、前記排気ガス中の粒子状物質を前記セラミックハニカムフィルタ内で燃焼させ、前記フィルタの排気ガス排出側に配設されたSCR触媒中に導入する排気ガス中のNO/NO のモル比を1/2〜2/1にすることを特徴としている。 Exhaust gas purification method of the present invention, at least one exhaust gas inlet side plugged ceramic honeycomb filter disposed in an apparatus for purifying exhaust gas containing nitrogen oxides and particulate matter discharged from a diesel engine with part is spaced apart from the exhaust gas inlet-side end, a catalyst material is supported on at least a portion of the partition wall and / or the plugging portion, the particulate matter in the exhaust gas within the ceramic honeycomb filter burned, it is characterized in that the molar ratio of NO / NO 2 in the exhaust gas introduced into the exhaust gas discharge side SCR catalyst disposed in the filter 1 / 2-2 / 1. このため、SCR触媒上におけるNO及びNO 等のNO xからN への転化率が増加し、NO xの浄化効率が改善される効果も有している。 Therefore, conversion to N 2 is increased from NO and NO 2 or the like of the NO x in the SCR catalyst, the effect also has the purification efficiency of the NO x can be improved. これは、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているセラミックハニカムフィルタにおいて、担持された触媒物質の触媒作用により、粒子状物質の燃焼が行われることから、フィルタから排出される粒子状物質が燃焼浄化された後の排気ガス中に、NO及びNO が含まれ、且つこのNO及びNO のモル比をNO/NO で1/2〜2/1とした排気ガスが得られ易くなり、これに、窒素系還元剤であるアンモニアまたは、尿素を添加してガス混合物を形成し、このガス混合物がSCR触媒上に導入されると、NO xからN への転化率が増加し、排気ガス浄化装置でのNO xの浄化効率が改善されるためで This ceramic least one exhaust gas inlet side plugged portion is spaced apart from the exhaust gas inlet side end surface, the catalytic material is supported on at least a portion of the partition wall and / or the plugging portion in the honeycomb filter, by the catalytic action of the supported catalyst material, since the burning of the particulate matter is performed, the exhaust gas after particulate matter discharged from the filter is burned clean, NO and NO 2 is It included, and the molar ratio of NO and NO 2 in the NO / NO 2 1 / 2~2 / 1 and the exhaust gas is easily obtained that, to this, ammonia or a nitrogen-based reducing agent, adding urea to form a gas mixture, this gas mixture is introduced into the SCR catalyst increases the conversion of from the NO x to N 2, because the purification efficiency of the NO x in the exhaust gas purification device is improved so る。 That.

従来技術の排気ガス浄化装置では、酸化触媒、フィルタ、還元剤の供給源、SCR触媒をこの順序で配置して、酸化触媒が排気ガスの温度を上昇させると共に、NO xをNO に転化させ、酸化触媒の後に配置されたフィルタが粒子状物質をNO を用いて燃焼させ、更にSCR触媒においてNO xを浄化していたのに対し、本発明の排気ガス浄化装置及び排気ガス浄化方法によれば、フィルタ11で排気ガス中の粒子状物質を効率的に燃焼させると共に、排気ガス中のNO/NO 比を適切に調整させて、このフィルタから排出された排気ガスを、SCR触媒においてNO xを効率的に低減できるため、従来技術の排気ガス浄化装置に比べて排気ガス浄化装置全体の圧力損失を低減できるのと共に浄化性能を高めることが可能となる。 In the exhaust gas purifying apparatus of the prior art, the oxidation catalyst, the filter, the source of the reducing agent, place the SCR catalyst in that order, with the oxidation catalyst raises the temperature of the exhaust gas, it is converted to NO x to NO 2 the filter particulate matter, which is placed after the oxidation catalyst is burned with NO 2, to further had to purify the NO x in the SCR catalyst, the exhaust gas purifying apparatus and an exhaust gas purification method of the present invention According, the particulate matter in the exhaust gas in the filter 11 causes efficient combustion, suitably by adjusting the NO / NO 2 ratio in the exhaust gas, the exhaust gas discharged from the filter, the SCR catalyst since the NO x can be efficiently reduced, it is possible to improve the purification performance with can reduce the pressure loss of the entire exhaust gas purification device than the exhaust gas purifying apparatus of the prior art.

本発明の排気ガス浄化装置に配設されるセラミックハニカムフィルタの排気ガス流入側目封止部端面が、セラミックハニカムフィルタの流入側端面から該セラミックハニカムフィルタ全長の0.7倍以下の長さの区間に配置されていることが好ましいのは、流入側端面12から該セラミックハニカムフィルタ全長の0.7倍の長さの区間を越えて配置すると、セラミックハニカムフィルタの全体の長さには制約があるため、排気ガス流入側目封止部より流出側の隔壁32の面積が、隔壁31に比べて少なくなるため、ハニカムフィルタ全体の圧力損失が上昇することもあるからである。 Exhaust gas inflow side plugged end face of the ceramic honeycomb filter disposed in an exhaust gas purifying apparatus of the present invention, the inlet-side end of the ceramic honeycomb filter of 0.7 times the length of the ceramic honeycomb filter full length the it is preferably arranged in the section, when the inlet-side end 12 is arranged beyond the period of 0.7 times the length of the ceramic honeycomb filter overall length, overall restrictions on the length of the ceramic honeycomb filter there therefore, the area of ​​the partition wall 32 of the exhaust gas inlet side first outflow side of the sealing portion, to become smaller than the partition wall 31, since the pressure loss of the whole honeycomb filter sometimes rises. また、更に好ましい流入側目封止部端面51の配置区間は、セラミックハニカムフィルタ流入側端面12から該セラミックハニカムフィルタ全長の0.1〜0.4倍の長さの区間である。 Also, further preferred arrangement section of the inlet side plugged end face 51 is 0.1 to 0.4 times the length section of the ceramic honeycomb filter entire length of ceramic honeycomb filter inlet-side end 12.

次に、本発明の排気ガス浄化装置に配設されるセラミックハニカムフィルタに担持される触媒物質が、白金族金属を含んでなることが好ましいのは、白金族金属を含む触媒物質が、主に排気ガスの酸化反応を促進し、排気ガスの温度を上昇させることから、フィルタ内部温度を前記触媒物質の活性下限温度以上に維持することがより確実にできるからである。 The catalyst material is supported on a ceramic honeycomb filter disposed in an exhaust gas purifying apparatus of the present invention, the preferably contains a platinum group metal, the catalytic material comprising platinum group metals, mainly promotes the oxidation reaction of the exhaust gases, since raising the temperature of the exhaust gas, to maintain the filter internal temperature above activation lower limit temperature of the catalytic material is because it more reliably. このため、排ガス中の粒子状物質を効率よく燃焼させることができ、特に流入側目封止部での未燃焼粒子状物質の堆積による圧力損失の上昇を防ぐことが出来る。 Therefore, it is possible to burn efficiently the particulate matter in the exhaust gas, it is possible to prevent an increase in pressure loss due to particularly the deposition of unburned particulate matter in the inflow-side plugging portion. 尚、白金族金属を含む触媒物質は、たとえば、Pt、Pd、Ru、Rh又はその組合せ、白金族金属酸化物等が含まれるが、アルカリ土類金属酸化物や希土類酸化物等を含んでも良い。 The catalyst substance containing a platinum group metal, e.g., Pt, Pd, Ru, Rh or combinations thereof, including but platinum group metal oxides may include alkaline earth metal oxides and rare earth oxides . また、白金族金属を含む触媒物質には、公知のγアルミナ等の活性アルミナからなる高比表面積材料が含まれると、白金族金属等と排気ガスとの接触面積を大きくすることができ、排気ガスの浄化効率を高めることができることから好ましい。 Further, the catalytic material comprising platinum group metals and contains a high specific surface area material consisting of activated alumina such as a known γ-alumina, it is possible to increase the contact area of ​​the platinum group metal or the like and the exhaust gas, the exhaust It preferred because it is possible to enhance the purification efficiency of the gas.

また、本発明の排気ガス浄化装置に配設されるセラミックハニカムフィルタの排気ガス流入側の隔壁に担持された触媒物質の活性度が、排気ガス流出側の隔壁に担持された触媒物質の活性度に比べて高いことが好ましいのは、流入側目封止部50より流入側に配置された隔壁31に担持された触媒物質上で、排気ガスの触媒反応が促進され、その反応熱を多くすることができ、フィルタ内部温度を前記触媒物質の活性下限温度以上に維持することがより確実にできるからである。 The exhaust the activity of the catalyst material supported on the exhaust gas inflow side of the partition wall of the ceramic honeycomb filter disposed in the gas purification device, the activity of the supported catalyst material on the partition walls of the exhaust gas outlet side of the present invention compared to to be higher is the supported catalyst material in which the partition wall 31 arranged on the inflow side than the inflow side plugged portion 50, catalytic reaction of the exhaust gas is promoted, increasing the reaction heat it can be, because the filter internal temperature can is more reliably be maintained above activity lower limit temperature of the catalyst material. このため、排ガス中の粒子状物質を効率よく燃焼させることができ、特に流入側目封止部での未燃焼粒子状物質の堆積による圧力損失の上昇を防ぐことが出来る。 Therefore, it is possible to burn efficiently the particulate matter in the exhaust gas, it is possible to prevent an increase in pressure loss due to particularly the deposition of unburned particulate matter in the inflow-side plugging portion. ここで、排気ガス流入側の隔壁に担持された触媒物質の活性度が、排気ガス流出側の隔壁に担持された触媒物質の活性度に比べて高いというのは、例えば流入側目封止部より排気ガス流入側である隔壁に担持された触媒物質中の白金族金属を含む触媒物質の含有量や、助触媒物質であるアルカリ土類金属酸化物、希土類酸化物、或いはベース金属触媒の含有量を、排気ガス流出側の隔壁に担持された触媒物質に比べて多く担持させ、担持された触媒全体として見た時に、触媒の性能が高いことを意味する。 Here, the activity of the exhaust gas inlet side of the supported catalyst material in the partition wall, because higher than the activity of the supported catalyst material on the partition walls of the exhaust gas outflow side, for example, the inflow-side plugging portion the content and the catalytic material containing a platinum group metal catalyst substance supported on the partition wall is more exhaust gas inlet side, an alkaline earth metal oxide as the promoter material, rare earth oxide, or containing a base metal catalyst amounts, is often carried compared to carried on the exhaust gas outflow side of the partition wall catalyst material, when viewed as a whole supported catalysts, it means that the catalyst performance is high.
例えば、本発明の排気ガス浄化装置において、セラミックハニカムフィルタの流入側目封止部より排気ガス流入側の隔壁に担持された触媒物質中の白金族金属含有量を、排気ガス流出側の隔壁に担持された触媒物質中の白金族金属含有量よりも多くすることにより、長期に亘り圧力損失の上昇を防ぐことができる。 For example, the exhaust gas purifying apparatus of the present invention, the platinum group metal content of the exhaust gas inlet side of the catalyst material supported on the partition wall from the inlet side plugged portions of the ceramic honeycomb filter, the exhaust gas outflow side of the partition wall by more than a platinum group metal content of the supported catalyst substance, it is possible to prevent an increase in pressure loss for a long time.

また、本発明の排気ガス浄化装置に配設されるセラミックハニカムフィルタの流入側目封止部50より排気ガス流入側である隔壁には、酸化触媒である、Pt、Pd、Ru、Rh等の白金族金属を含む触媒物質の含有量を多く担持し、排気ガス流出側の隔壁32には、助触媒であるベース金属触媒、典型的には酸化ランタン、酸化セシウム、酸化バナジウム類よりなる触媒物質及び白金族金属を含む触媒物質を多く担持させることにより、微粒子の燃焼が効率よく行われるため、長期に亘り圧力損失の上昇を防ぐことができる。 Further, the partition wall is an exhaust gas inlet side than the inflow side plugged portions 50 of the ceramic honeycomb filter disposed in an exhaust gas purifying apparatus of the present invention is the oxidation catalyst, Pt, Pd, Ru, and Rh, etc. and many carried the content of the catalytic material comprising platinum group metals, the exhaust gas outflow side of the partition wall 32, the base metal catalyst is a cocatalyst, typically lanthanum oxide, cesium oxide, catalyst material consisting of vanadium oxide compound and by many carrying a catalytic material comprising platinum group metals, the combustion of the particulate is efficiently, it is possible to prevent an increase in pressure loss for a long time.

また、本発明の排気ガス浄化装置は、多孔質セラミックハニカム構造体の所望の流路を目封止したセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているフィルタと、窒素酸化物(NO )を浄化させるSCR触媒を、この順序で配置して、ディーゼルエンジンから排出されるNO 及び粒子状物質を浄化しているが、SCR触媒の上流には還元剤の供給源を設けて、還元剤を排気ガスに添加した後、この排気ガスをSCR触媒に供給する。 The exhaust gas purifying apparatus of the present invention, the ceramic honeycomb filter plugging a desired flow path of the porous ceramic honeycomb structural body, at least one exhaust gas inlet side plugged portions is the exhaust gas inlet side end surface is spaced apart, the filter catalyst material on at least a portion of the partition wall and / or the plugging portion is supported, nitrogen oxides SCR catalyst for purifying (NO x), are arranged in this order Te, although purifies NO x and particulate matter discharged from a diesel engine, upstream of the SCR catalyst is provided a source of reducing agent, after the addition of the reducing agent to the exhaust gas, the exhaust gas supplied to the SCR catalyst. また、SCR触媒の下流に、未反応のまま或いは複生成物としてアンモニアが発生する場合は、SCR触媒の下流側にアンモニアの浄化触媒を配置しても良い。 Further, downstream of the SCR catalyst, if ammonia is generated as a left or a double product Unreacted may be arranged purifying catalyst of ammonia downstream of the SCR catalyst.

本発明の排気ガス浄化装置に備えられるハニカム構造のフィルタは、隔壁の気孔率が、50%〜80%、隔壁の平均細孔径が10〜40μmであると好ましい。 Filter of a honeycomb structure provided in the exhaust gas purifying apparatus of the present invention, the porosity of the partition walls is 50% to 80%, an average pore diameter of the partition walls is preferably a 10 to 40 [mu] m. ハニカムフィルタの隔壁の気孔率が50%未満であると、隔壁を排気ガスが通過する際の通気抵抗が大きくなるため、フィルタの圧力損失が大きくなり、排気ガス浄化装置全体の圧力損失も大きくなるからである。 When the porosity of the honeycomb filter septum is less than 50%, the airflow resistance when the partition walls the exhaust gas passes increases, the pressure loss of the filter increases, the greater the pressure loss of the entire exhaust gas purifying device it is from. 一方、気孔率が80%を超えると、フィルタの強度が低下し、排気ガス浄化用装置として使用された際の、機械的応力や振動により破損するおそれがあるからである。 On the other hand, when the porosity exceeds 80%, the strength of the filter is reduced, when used as an exhaust gas purifying device, there is a possibility of damage by mechanical stress and vibration. ハニカムフィルタの気孔率は、好ましくは、60〜75%である。 The porosity of the honeycomb filter is preferably from 60 to 75%.

ハニカムフィルタの隔壁の平均細孔径が10μm未満であると、隔壁を排気ガスが通過する際の通気抵抗が大きくなるため、フィルタの圧力損失が大きくなり、排気ガス浄化装置全体の圧力損失も大きくなるからである。 When the average pore diameter of the honeycomb filter septum is less than 10 [mu] m, since the airflow resistance when the partition walls the exhaust gas passes increases, the pressure loss of the filter increases, the greater the pressure loss of the entire exhaust gas purifying device it is from. 一方、平均細孔径が40μmを超えると、フィルタの強度が低下し、排気ガス浄化用装置として使用された際の、機械的応力や振動により破損するおそれがあるからである。 On the other hand, when the average pore diameter exceeds 40 [mu] m, the strength of the filter is reduced, when used as an exhaust gas purifying device, there is a possibility of damage by mechanical stress and vibration. 尚、ハニカムフィルタの平均細孔径のより好ましい範囲は、15〜25μmである。 A more preferred range of the average pore diameter of the honeycomb filter is 15 to 25 [mu] m.

本発明の排気ガス浄化装置に備えられる、ハニカムフィルタの隔壁厚は、0.1〜0.5mmが好ましく、隔壁のピッチは1.2mm以上が好ましい。 Provided in an exhaust gas purifying apparatus of the present invention, a partition wall thickness of the honeycomb filter is preferably 0.1 to 0.5 mm, the pitch of the partition walls is preferably at least 1.2 mm. 隔壁厚が0.1mm未満では、ハニカムフィルタの強度が低下し、好ましくない。 Partition wall thickness is less than 0.1mm is, the strength of the honeycomb filter is lowered, unfavorably. 一方、隔壁厚が0.5mmを超えると、排気ガスに対する隔壁の通気抵抗が大きくなるため、ハニカムフィルタの圧力損失が大きくなるからである。 On the other hand, when the wall thickness exceeds 0.5 mm, since the flow resistance of the partition walls is increased relative to the exhaust gas, because the pressure loss of the honeycomb filter becomes large. より好ましい隔壁厚さは、0.2〜0.4mmである。 More preferred wall thickness is 0.2 to 0.4 mm. また、隔壁のピッチが1.2mm未満であると、ハニカムフィルタの入口の開口面積が小さくなることから、ハニカムフィルタ入口の圧力損失が大きくなるためである。 Further, the pitch of the partition walls is less than 1.2 mm, since the inlet opening area of ​​the honeycomb filter is reduced, because the pressure loss of the honeycomb filter inlet is increased.

上記、排気ガス浄化装置に備えられるハニカムフィルタの隔壁を構成する材料としては、本発明が主にディーゼルエンジンの排気ガスを浄化するために使用されるため、耐熱性に優れた材料を使用することが好ましく、コージェライト、アルミナ、ムライト、窒化珪素、炭化珪素及びLASからなる群から選ばれた少なくとも1種を主結晶とするセラミック材料を用いることが好ましい。 Above, as the material constituting the partition walls of the honeycomb filter provided in an exhaust gas purification device, since the present invention is used mainly for purifying the exhaust gas of diesel engines, the use of a material excellent in heat resistance preferably, cordierite, alumina, mullite, silicon nitride, at least one selected from the group consisting of silicon carbide and LAS be a ceramic material mainly crystalline preferable. 中でも、コージェライトを主結晶とするハニカム構造体は、安価で耐熱性、耐食性に優れ、また低熱膨張であることから最も好ましい。 Among them, a honeycomb structure of cordierite as a main crystal, inexpensive and excellent in heat resistance and corrosion resistance, and most preferred because of its low thermal expansion.

次に本発明の排気ガス浄化装置に使用される、多孔質セラミックハニカム構造体の所望の流路を目封止したセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されているセラミックハニカムフィルタ11の目封止部の形成方法の一例を図3を用いて説明する。 Then used in an exhaust gas purifying apparatus of the present invention, the ceramic honeycomb filter plugging a desired flow path of the porous ceramic honeycomb structural body, at least one exhaust gas inlet side plugged portions the exhaust gas inflow an example of a method for forming plugging portions in the ceramic honeycomb filter 11 is disposed away from the side edge will be described with reference to FIG. ハニカム構造体の排気ガス流入側端面に図3に示すように市松模様に樹脂製スラリー導入通路81を設けた樹脂製のマスク80を装着し、図3のA部拡大図の矢印で示すようにスラリー導入通路81を通してスラリー状の目封止材53を導入し、ハニカム構造体の流路の一部に充填する。 The resin mask 80 having a resinous slurry introducing passage 81 in a checkered pattern as shown in FIG. 3 on the exhaust gas inlet side end face of the honeycomb structure is mounted, as indicated by the arrows in enlarged view of a portion A of FIG 3 introducing a slurry of the plugging material 53 through the slurry inlet passage 81 to fill a part of the flow path of the honeycomb structure. その後、スラリー状の目封止材53中に含まれる水分はハニカム構造体の隔壁に吸水され目封止材が隔壁に着肉して行き保形性が得られるようになると、固化していないスラリーを排出し、樹脂製マスクを除去後、固化した目封止材の乾燥を行う。 Thereafter, the slurry plugging material is moisture contained in 53 is absorbed by the partition walls of the honeycomb structure plugging material so shape retention continue to adheres to the partition wall is obtained, unsolidified the slurry was discharged, after removal of the resin mask, and drying of the solidified plugging materials. このとき樹脂製スラリー導入通路81内に存在するスラリー状の目封止材は隔壁からの吸水が無いことから固化しないため、スラリ−導入通路の長さを調整することにより、排気ガス流入側目封止部のハニカム構造体流入側端面からの形成位置を決定することができる。 At this time slurry plugging material present in the resinous slurry introducing passage 81 is not solidified because there is no absorption of water from the partition wall, the slurry - by adjusting the length of the induction passage, an exhaust gas inflow side th it is possible to determine the forming position from the honeycomb structure inlet-side end of the sealing portion. 一方、流出側の端面は、端部に目封止部を形成し、その後、目封止材の焼成を行い、隔壁と目封止材を一体化せしめる。 On the other hand, the end face of the outlet side, forming the plugging portions in the end, then, the resulting mixture was fired in a plugging material, allowed to integrate the partition wall and the plugging material.

なお、その他の方法としては、注射針状の管をハニカム構造体の端部から流路の所定位置まで挿入し、この管を通して所定位置に所定量のペースト状の目封止材を導入後、乾燥、焼成させる方法や、セラミックチップをハニカム構造体の内部に埋め込み、焼成させる方法等を採用することができる。 As the other method, the needle-shaped tube is inserted from the end portion of the honeycomb structure to a predetermined position of the flow channel, after introducing a predetermined amount of paste-like plugging material to a predetermined position through the tube, drying, and a method of firing, embedding a ceramic chip inside of the honeycomb structure, it is possible to employ a method or the like to be fired.
更には、両端が目封止された従来構造のセラミックハニカムフィルタの排気ガス流入側端面に目封止が施されていないセラミックハニカム構造体を配置させ、両者を一体化せしめることにより、製造することも可能である。 Furthermore, both ends to place the ceramic honeycomb structure is plugged on the exhaust gas inlet side end face of the ceramic honeycomb filters of conventional structure plugged not applied, by allowed to integrate both, to produce it is also possible.

本発明の排気ガス浄化装置に備えられるSCR触媒は、外周壁と外周壁の内側で軸方向に多孔質隔壁により仕切られた多数の流通孔を有するセラミックハニカム構造体の隔壁表面にSCR触媒物質を担持して形成されると良い。 SCR catalyst provided in an exhaust gas purifying apparatus of the present invention, the SCR catalyst material on the partition wall surface of a ceramic honeycomb structure having a large number of circulation holes partitioned by porous partition walls in the axial direction inside the outer peripheral wall and the outer peripheral wall it may be formed by carrying. 特に、本発明の排気ガス浄化装置は、 In particular, the exhaust gas purifying apparatus of the present invention,
多孔質セラミックハニカム構造体の所望の流路を目封止したセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているフィルタとSCR触媒とが、この順序で配置されており、セラミックハニカムフィルタで粒子状物質を効率的に燃焼させ、更にこのフィルタから排出された排気ガスを、SCR触媒においてNO xを効率的に低減させているため、SCR触媒に用いられる、セラミックハニカム構造体の幾何学的表面積は大きい方が好ましい。 Ceramic honeycomb filter plugging a desired flow path of the porous ceramic honeycomb structural body, together with at least one exhaust gas inlet side plugged portions are spaced apart from the exhaust gas inlet side end surface, the partition wall and / or a filter and the SCR catalyst in which the catalyst substance is supported on at least a portion of the plugging portions are disposed in this order, effectively by burning particulate matter in a ceramic honeycomb filter, further from the filter the exhaust gas discharged, since the effectively reduce NO x in the SCR catalyst, used in the SCR catalyst, the geometric surface area of the ceramic honeycomb structure is larger is preferable. このため、ハニカム構造体の隔壁厚は、0.05〜0.25mmが好ましく、隔壁のピッチは0.8〜1.6mmが好ましい。 Therefore, a partition wall thickness of the honeycomb structure is preferably 0.05 to 0.25 mm, the pitch of the partition walls 0.8~1.6mm is preferred. 隔壁厚が0.05mm未満では、ハニカムフィルタの強度が低下し、好ましくなく、隔壁厚が0.25mmを超えると、排気ガスに対する通気抵抗が大きくなるため、ハニカム構造体の圧力損失が大きくなるからである。 The partition wall thickness is less than 0.05 mm, the strength of the honeycomb filter is lowered, not preferred, the wall thickness exceeds 0.25 mm, since the airflow resistance is increased relative to the exhaust gas, because the pressure loss of the honeycomb structure increases it is. より好ましい隔壁厚さは、0.08〜0.15mmである。 More preferred partition wall thickness is 0.08~0.15Mm. また、隔壁のピッチが0.8mm未満であると、ハニカム構造体の入口の開口面積が小さくなることから、ハニカム構造体の圧力損失が大きくなるためであり、隔壁のピッチが1.6mmを越えると、幾何学的表面積が小さくなり、SCR触媒の浄化性能が低下するためである。 Further, the pitch of the partition walls is less than 0.8 mm, since the inlet opening area of ​​the honeycomb structure is small, because the pressure loss of the honeycomb structure increases, the pitch of the partition walls exceeds 1.6mm When the geometric surface area is reduced, because the purification performance of the SCR catalyst is decreased. より好ましい隔壁のピッチは、0.9〜1.3mmである。 Pitch more preferred partition wall is 0.9~1.3Mm.

また、本発明の排気ガス浄化装置に備えられるSCR触媒に用いられるセラミックハニカム構造体が、上記のような隔壁厚さ、隔壁ピッチを有している場合には、ハニカム構造体の隔壁の気孔率は、25%〜45%、隔壁の平均細孔径は、1〜10μmであると好ましい。 Moreover, the ceramic honeycomb structure used in the SCR catalyst provided in an exhaust gas purifying apparatus of the present invention, the above-described partition wall thickness, in the case where a partition wall pitch, the porosity of the partition walls of the honeycomb structure from 25% to 45%, an average pore diameter of the partition walls, if it is 1~10μm preferred. ハニカム構造体の隔壁の気孔率が25%未満であると、SCR触媒物質が担持しにくくなり、浄化性能が低下する場合があるからであり、気孔率が45%を超えると、隔壁の厚さが0.05〜0.25mmと薄いため、ハニカム構造体の強度が低下し、排気ガス浄化用装置として使用された際の、機械的応力や振動により破損するおそれがあるからである。 When the porosity of the partition walls of the honeycomb structure is less than 25% SCR catalytic material is less likely to carry, is because the purification performance may be deteriorated, when the porosity exceeds 45%, the thickness of the partition wall there thinner and 0.05 to 0.25 mm, strength of the honeycomb structure is decreased, when used as an exhaust gas purifying device, there is a possibility of damage by mechanical stress and vibration.

また、本発明の排気ガス浄化装置に備えられるSCR触媒に用いられるセラミックハニカム構造体の平均細孔径が1μm未満であると、SCR触媒物質が担持しにくくなり、浄化性能が低下する場合があるからであり、平均細孔径が10μmを超えると、隔壁の厚さが0.05〜0.25mmと薄いため、ハニカム構造体の強度が低下し、排気ガス浄化用装置として使用された際の、機械的応力や振動により破損するおそれがあるからである。 When the average pore size of the ceramic honeycomb structures used in the SCR catalyst provided in an exhaust gas purifying apparatus of the present invention is less than 1 [mu] m, it becomes difficult SCR catalytic material supported, because the purification performance may deteriorate , and the the average pore diameter exceeds 10 [mu] m, the thickness of the partition wall is thin and 0.05 to 0.25 mm, strength of the honeycomb structure is decreased, when used as an exhaust gas purifying device, the machine This is because fear is to be damaged by stress and vibration.

本発明の排気ガス浄化装置に備えられるSCR触媒に用いられるセラミックハニカム構造体の隔壁を構成する材料としては、本発明が主にディーゼルエンジンの排気ガスを浄化するために使用されるため、耐熱性に優れた材料を使用することが好ましく、コージェライト、アルミナ、ムライト、窒化珪素、炭化珪素及びLASからなる群から選ばれた少なくとも1種を主結晶とするセラミック材料を用いることが好ましい。 As a material for forming the partition walls of the ceramic honeycomb structure used in the SCR catalyst provided in an exhaust gas purifying apparatus of the present invention, since the present invention is used mainly for purifying exhaust gas from diesel engines, heat resistance it is preferred to use a material excellent in, cordierite, alumina, mullite, silicon nitride, at least one selected from the group consisting of silicon carbide and LAS be a ceramic material mainly crystalline preferable. 中でも、コージェライトを主結晶とするハニカム構造体は、安価で耐熱性、耐食性に優れ、また低熱膨張であることから最も好ましい。 Among them, a honeycomb structure of cordierite as a main crystal, inexpensive and excellent in heat resistance and corrosion resistance, and most preferred because of its low thermal expansion.

本発明の排気ガス浄化装置に備えられるSCR触媒に用いられる触媒物質としては、V 、WO 、TiO が好適であり、これらに加えてPt、Fe 、CuO、Mn 、Cr 、MoO 等を用いてもよい。 The catalyst material used in the SCR catalyst provided in an exhaust gas purifying apparatus of the present invention, V 2 O 5, WO 3 , TiO 2 is preferred, Pt in addition to these, Fe 2 O 3, CuO, Mn 2 O 3, Cr 2 O 3, MoO 3 or the like may be used.

以上の説明のように、本発明の排気ガス浄化装置によれば、排気ガス中の粒子状物資及びNO xの有害成分を効果的に低減でき、且つ排気ガス浄化装置に必要な部品数を減らすことができる。 As described above, according to the exhaust gas purifying apparatus of the present invention, harmful components of the particulate materials and NO x in the exhaust gas can be effectively reduced, and reduce the number of parts required for the exhaust gas purifying device be able to. また、圧力損失の原因になる部品数が少ないため、排気ガス浄化装置全体としての圧力損失を低減できるという大きな効果と、従来技術の排気ガス浄化装置に比べ小型化が可能となる。 Further, since a small number of components that cause the pressure loss, a great effect of reducing the pressure loss of the whole exhaust gas purifying apparatus, size reduction is possible as compared to the exhaust gas purifying apparatus of the prior art.

(実施例) (Example)
本発明に係わるディーゼルエンジンの排気ガス浄化装置の実施の形態の排気ガス浄化装置における、フィルター11の製造方法について、模式断面図の図3を用いて説明する。 In the exhaust gas purifying apparatus according to an embodiment of the exhaust gas purifying device for a diesel engine according to the present invention, a method for manufacturing the filter 11 will be described with reference to FIG. 3 of the schematic cross-sectional view.
カオリン、タルク、シリカ、水酸化アルミ、アルミナなどのコージェライト生成原料粉末に、成形助剤と造孔剤を添加し、規定量の水を注入して更に十分な混合を行い、ハニカム構造に押出成形可能な坏土を調整した。 Kaolin, talc, silica, aluminum hydroxide, cordierite generation material powder such as alumina, was added a molding aid and a pore-forming agent, performs more thorough mixing by injecting a specified amount of water, extruded into a honeycomb structure the moldable clay was prepared. そして、公知の押出成形用金型を用い押出成形し、外周壁と、この外周壁の内周側で隔壁により囲まれた断面が四角形状の流路を有するハニカム構造の成形体を作製し、乾燥後焼成を行い、直径267mm、全長L305mm、隔壁のピッチ1.50mmで、隔壁厚さ0.3mmの隔壁構造を有し、隔壁の気孔率が65%、平均細孔径が20μmのセラミックハニカム構造体10を作製した。 The extruded using known extrusion molding die, prepare an outer peripheral wall, a section surrounded by the partition wall on the side of the inner periphery of the outer peripheral wall of the formed body of honeycomb structure having a rectangular flow channel, and dried after firing, diameter 267 mm, total length L305mm, a pitch 1.50mm partition wall has a partition wall structure of the partition wall thickness 0.3 mm, porosity of the partition walls 65%, an average pore diameter of 20μm of the ceramic honeycomb structure the body 10 was prepared.

次に、図3に示すようにハニカム構造体の排気ガス流入側端面に市松模様にスラリー導入通路81を設けた樹脂製のマスク80を装着し、スラリー導入通路を通してスラリー状の目封止材を導入、ハニカム構造体の流路の一部に充填した。 Next, mounting the resin mask 80 having a slurry introducing passage 81 in a checkerboard pattern on the exhaust gas inlet side end face of the honeycomb structure as shown in FIG. 3, the slurry plugging material through the slurry inlet passage introduced, it was charged to a portion of the flow path of the honeycomb structure. その後、目封止材が隔壁に着肉して、保形性が得られた後、樹脂製マスクを除去し、目封止材53の乾燥を行った。 Then adheres plugging material in the partition wall, after the shape retention is obtained, removing the resin mask, it was dried in plugging material 53. 一方、ハニカム構造体の排気ガス流出側端面の目封止部は、端面にマスキングフィルムを接着剤で貼り付けた後、市松模様となるように穿孔し、続いて、スラリー状の目封止材を端面より導入して目封止部を形成した。 Meanwhile, the plugged portion of the exhaust gas outflow side end face of the honeycomb structure, after attaching a masking film with an adhesive to the end surface, perforated so that the checkered pattern, followed by slurry plugging material It was formed plugging portions is introduced from the end face. 次いで、バッチ式焼成炉を用いて温度制御しつつ目封止材の焼成を行い、ハニカムフィルタ11を得た。 Then, the resulting mixture was fired in a plugging material with temperature control using a batch type firing furnace, to obtain a honeycomb filter 11. この時の、排気ガス流入側目封止部の排気ガス流入側端面51とハニカムフィルタ端面12の間の距離Xは100mmとなるようにした。 At this time, the distance X between the exhaust gas inlet side end face 51 and the honeycomb filter end face 12 of the exhaust gas inflow side plugged portion was set to be 100 mm.

前記のハニカムフィルタに対して、白金(Pt)、酸化セリウム、及び活性アルミナからなる触媒物質を隔壁表面及び隔壁中の細孔内部、更には目封止部表面及び目封止部中の細孔内部に担持させた。 With respect to the honeycomb filter, platinum (Pt), cerium oxide, and within the pores of the catalyst material the partition surface and the partition wall made of active alumina, more pores of the plugged portion surface and the plugged portions in It was carried on the inside. 担持量はPt量で2g/L(ハニカムフィルタ容積1Lに対して2g担持の意味)とした。 Carrying amount was 2g / L in volume Pt ​​(meaning of 2g bearing against a honeycomb filter volume 1L).
上記のように作成したフィルタ11を、図2に示すように、エンジン1の排気通路2に、フィルタ11、アンモニア等を噴出できる還元剤供給装置6、SCR触媒5を設けて配置する。 The filter 11 was prepared as described above, as shown in FIG. 2, an exhaust passage 2 of the engine 1, the filter 11 is disposed with a reducing agent supply device 6, SCR catalyst 5 which can eject the ammonia. ここで、SCR触媒5には、直径267mm、全長L200mm、隔壁のピッチ1.06mmで、隔壁厚さ0.11mmの隔壁構造を有し、隔壁の気孔率が30%、平均細孔径が5μmのコージェライト質セラミックハニカム構造体に、V 、WO 、TiO を担持して、形成した。 Here, the SCR catalyst 5, the diameter 267 mm, total length L200mm, a pitch 1.06mm partition wall has a partition wall structure of the partition wall thickness 0.11 mm, a partition wall porosity of 30%, an average pore diameter of 5μm of the cordierite ceramic honeycomb structural body, carrying the V 2 O 5, WO 3, TiO 2, was formed. そして、還元剤供給装置6はアンモニア水や液体アンモニアや尿素水溶液を還元剤タンク6aから排気通路2内に噴霧できる還元剤噴射弁6bを備えて形成した。 Then, the reducing agent supply device 6 was formed with a reducing agent injection valve 6b that can be sprayed from the reducing agent tank 6a into the exhaust passage 2 aqueous ammonia or liquid ammonia or aqueous urea solution.

以上の構成による本発明の排気ガス浄化装置は、外径267mm、全長305mmの多孔質セラミックハニカム構造体の所望の流路を目封止したセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているセラミックハニカムフィルタ11及び外径267mm、全長200mmのセラミックハニカム構造体に触媒物質が担持されているSCR触媒5とをこの順序で配置しており、それぞれの容積は、セラミックハニカムフィルタが17077cm 、SCR触媒が11198cm であり、排気ガス装置全体に必要なセラミックハニカム構造体の長さは505mm、容積は28275cm Above exhaust gas purification apparatus of the present invention by the configuration of the outer diameter 267 mm, the ceramic honeycomb filter plugging a desired flow path of the porous ceramic honeycomb structural body of the full-length 305 mm, at least one exhaust gas inlet side eyes sealed with stopper portion is spaced apart from the exhaust gas inlet side end surface, the partition wall and / or the plugged portion of the ceramic honeycomb filter 11 catalytic material is supported on at least a portion and an outer diameter 267 mm, the total length 200mm ceramic the SCR catalyst 5 in the honeycomb structure catalyst material is supported and arranged in this order, each of the volume, the ceramic honeycomb filter is 17077Cm 3, the SCR catalyst is 11198Cm 3, it required the entire exhaust system the length of the ceramic honeycomb structure 505 mm, volume and 28275Cm 3 なる。 Become.

以上の構成による排気ガス浄化装置は、エンジン1の下流側の排気通路2に、上流側から順に、多孔質セラミックハニカム構造体の所望の流路を目封止したセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているフィルタ11、アンモニア等を噴出できる還元剤供給装置6、SCR触媒5を設けて構成されていることから、次のように浄化される。 The exhaust gas purification device by the configuration described above, the exhaust passage 2 downstream of the engine 1, in order from the upstream side, of the ceramic honeycomb filter plugging a desired flow path of the porous ceramic honeycomb structural body, at least one of together with the exhaust gas inlet side plugged portions are spaced apart from the exhaust gas inlet side end surface, the filter 11 the catalytic material is supported on at least a portion of the partition wall and / or the plugging portion, and ammonia jet because it is constituted by providing a reducing agent supply device 6, SCR catalyst 5 which can be purified as follows. フィルタ11への粒子状物質の捕集量が多くなると、フィルタの目詰まりによる圧力損失の上昇を避けるため、ディーゼルエンジン1の運転状態に応じて、触媒物質を担持させたフィルタ上への微粒子の堆積量を推定した上で、フィルタの上流側に燃料を未燃のまま噴射して、前記触媒物質上で、燃料の酸化反応を促し、その反応熱によりフィルタの内部温度を前記触媒物質の活性下限温度以上に維持させ、堆積した微粒子を燃焼させる。 When trapping amount of the particulate matter to the filter 11 increases, in order to avoid an increase in pressure loss due to clogging of the filter, in accordance with the operation state of the diesel engine 1, the fine particles onto the filter supporting a catalyst substance on the deposit amount was estimated, the fuel on the upstream side of the filter by injecting unburned, wherein on the catalyst material, encourage fuel oxidation reaction, the activity of the catalyst material the internal temperature of the filter by its reaction heat It is maintained above the lower limit temperature, burning the deposited particulate. この時、セラミックハニカムフィルタ11の排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されているため、目封止部の温度が触媒物質の活性化温度以上に維持され、排気ガス流入側目封止部の流入側端面への微粒子堆積による、流路閉塞を原因とする、フィルタ11の圧力損失上昇を低減させることが可能となる。 At this time, since the exhaust gas inflow side plugged portions of the ceramic honeycomb filter 11 is spaced apart from the exhaust gas inlet side end surface, the temperature of the plugging portion is maintained at or above the activation temperature of the catalyst material, the exhaust by particle deposition on the inflow side end face on the gas inlet side plugged portions, caused by the passage closing, it is possible to reduce the pressure loss rise of the filter 11. また、このような構成のフィルタから排出される排気ガス中に、NO及びNO が含まれ、且つ、このNO及びNO のモル比をNO/NO で1/2〜2/1とした排気ガスが得られ易いため、これに、還元剤供給装置から還元剤であるアンモニアを添加してガス混合物を形成し、このガス混合物をSCR触媒上に導入させると、NO xからN への転化率が増加し、NO がN に高効率で転化されて浄化される。 Further, the exhaust gas discharged from such configuration of the filter, include NO and NO 2, and, the molar ratio of NO and NO 2 was at 1 / 2~2 / 1 NO / NO 2 liable exhaust gases is obtained, in which, with the addition of ammonia as a reducing agent from the reducing agent supply device to form a gas mixture, when the introduction of this gas mixture on the SCR catalyst, from the NO x to N 2 conversion is increased, NO x is purified is converted with high efficiency into N 2.

(従来例) (Conventional example)
従来例について、図4を用いて説明する。 Examples of conventional, will be described with reference to FIG.
カオリン、タルク、シリカ、水酸化アルミ、アルミナなどのコージェライト生成原料粉末に、成形助剤を添加し、規定量の水を注入して更に十分な混合を行い、ハニカム構造に押出成形可能な坏土を調整した。 Kaolin, talc, silica, aluminum hydroxide, cordierite generation material powder such as alumina, is added a forming aid, make more thorough mixing by injecting a specified amount of water, extruded formable into a honeycomb structure 坏to adjust the soil. そして、公知の押出成形用金型を用い押出成形し、外周壁と、この外周壁の内周側で隔壁により囲まれた断面が四角形状の流路を有するハニカム構造の成形体を作製し、乾燥後焼成を行い、外径267mm、全長152mm、隔壁のピッチ1.46mmで、隔壁厚さ0.2mmの隔壁構造を有し、隔壁の気孔率が35%、平均細孔径が5μmのセラミックハニカム構造体を作製した。 The extruded using known extrusion molding die, prepare an outer peripheral wall, a section surrounded by the partition wall on the side of the inner periphery of the outer peripheral wall of the formed body of honeycomb structure having a rectangular flow channel, and dried after firing, the outer diameter 267 mm, total length 152 mm, with a pitch 1.46mm partition wall has a partition wall structure of the partition wall thickness 0.2 mm, 35% porosity of the partition walls, the average pore diameter of 5μm ceramic honeycomb to prepare a structure.
前記のセラミックハニカム構造体に対して、白金(Pt)、酸化セリウム、及び活性アルミナからなる触媒物質を隔壁表面及び隔壁中の細孔内部、担持させた。 To the ceramic honeycomb structural body, platinum (Pt), cerium oxide, and within the pores of the catalytic material surface of the partition walls and septum consisting of activated alumina, it was supported. 担持量はPt量で2g/Lとし、ハニカム構造体にPt、酸化セリウム、及び活性アルミナからなる触媒物質を含有する酸化触媒3を作成した。 Loading amount was set to 2 g / L in weight Pt, Pt on the honeycomb structure was prepared cerium oxide, and an oxidation catalyst 3 containing a catalyst material consisting of activated alumina.
一方、実施例と同様の方法により、外径267mm、全長305mm、隔壁のピッチ1.5mm、隔壁厚さ0.3mmの隔壁構造を有し、隔壁の気孔率が65%、平均細孔径が20μmのセラミックハニカム構造体を作製した。 On the other hand, by a method similar to the embodiment, the outer diameter 267 mm, total length 305 mm, pitch 1.5mm of the partition walls having a partition wall structure of the partition wall thickness 0.3 mm, porosity of the partition walls 65%, an average pore diameter of 20μm the ceramic honeycomb structural body was manufactured. 次に、ハニカム構造体の排気ガス流入側端面にマスキングフィルムを接着剤で貼り付け、市松模様となるように穿孔し、この孔からスラリー状の目封止材を導入、ハニカム構造体の端部に充填した。 Then, paste masking film with an adhesive on the exhaust gas inlet side end face of the honeycomb structure, perforated so that the checkered pattern, introducing the slurry plugging material from the hole, the end portion of the honeycomb structure It was filled in. その後、目封止材が隔壁に着肉して、保形性が得られた後、マスキングフィルムを除去し、目封止材の乾燥を行った。 Thereafter, the plugging material is then adheres to the partition wall, after the shape retention is obtained, removing the masking film, was dried for plugging material. 同様に、ハニカム構造体の排気ガス流出側端面にも目封止部を形成した後、バッチ式焼成炉を用いて温度制御しつつ目封止材の焼成を行い、セラミックハニカム構造体の所望の流路を端部で目封止した。 Similarly, after forming the plugging portions in the exhaust gas outlet side end face of the honeycomb structure, the resulting mixture was fired in plugging material with temperature control using a batch type firing furnace, the desired ceramic honeycomb structural body plugging at the end of the flow path. 更に、Pt、酸化セリウム、及び活性アルミナからなる触媒物質を隔壁表面及び隔壁中の細孔内部、更には目封止部表面及び目封止部中の細孔内部に担持させたセラミックハニカムフィルタ4を得た。 Furthermore, Pt, cerium oxide, and the internal pores in the catalyst material surface of the partition walls and the partition wall made of active alumina, ceramic honeycomb filter 4 further is supported inside the pores in the plugging portion surface and the plugged portions It was obtained. 担持量はPt量で2g/Lとした。 Carrying amount was 2 g / L in amount Pt.
更に、実施例と同様の方法で、直径267mm、全長L200mm、隔壁のピッチ1.06mmで、隔壁厚さ0.11mmの隔壁構造を有し、隔壁の気孔率が30%、平均細孔径が5μmのコージェライト質セラミックハニカム構造体に、、V 、WO 、TiO を担持して、形成した。 Further, in the same manner as in Example, the diameter 267 mm, total length L200mm, a pitch 1.06mm partition wall has a partition wall structure of the partition wall thickness 0.11 mm, a partition wall porosity of 30%, an average pore size of 5μm cordierite ceramic honeycomb structure ,, V 2 O 5, carries a WO 3, TiO 2, was formed.
上記のように作成したフィルタ4を、図4に示すように、エンジン1の排気通路2に、酸化触媒3、フィルタ4、アンモニア等を噴出できる還元剤供給装置6、SCR触媒5を設けて配置する。 The filter 4 created as above, as shown in FIG. 4, an exhaust passage 2 of an engine 1, an oxidation catalyst 3, the filter 4, provided with a reducing agent supply device 6, SCR catalyst 5 which can eject the ammonia arrangement to. また、還元剤供給装置6はアンモニア水や液体アンモニアや尿素水溶液を元剤タンク6aから排気通路2内に噴霧できる還元剤噴射弁6bを備えて形成される。 Further, the reducing agent supply device 6 is formed with a reducing agent injection valve 6b that can be sprayed aqueous ammonia or liquid ammonia or urea solution from Motozai tank 6a into the exhaust passage 2.

以上の構成による従来例の排気ガス浄化装置は、セラミックハニカム構造体に酸化触媒物質が担持された酸化触媒3、多孔質セラミックハニカム構造体の所望の流路を両端部で目封止し、かつ隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているセラミックハニカムフィルタ4、セラミックハニカム構造体に触媒物質が担持されているSCR触媒5とをこの順序で配置しており、それぞれの外径、全長、容積は、酸化触媒3が外径267mm、全長152mm、容積8510cm 、セラミックハニカムフィルタ4が外径267mm、全長305mm、容積17077cm 、SCR触媒5が外径267mm、全長200mm、容積11198cm であり、排気ガス装置全体に必要なセラミックハニカム構造体の長 Or more exhaust gas purification device of a conventional example of the configuration, the ceramic honeycomb structure is oxidized catalytic material supported oxidation catalyst 3, plugging at both ends of the desired flow paths of the porous ceramic honeycomb structural body, and ceramic honeycomb filter 4 in which the catalyst substance is supported on at least a portion of the partition wall and / or the plugging portion, the catalytic material has been arranged and the SCR catalyst 5 which is carried in this order on a ceramic honeycomb structural body, the outer diameters, the total length, is the volume, the oxidation catalyst 3 is an outer diameter of 267 mm, total length 152 mm, volume 8510Cm 3, a ceramic honeycomb filter 4 outer diameter 267 mm, total length 305 mm, volume 17077Cm 3, SCR catalyst 5 is an outer diameter of 267 mm, the total length 200 mm, a volume 11198cm 3, the length of the ceramic honeycomb structure required entire exhaust gas system は657mm、容積は36785cm となる。 Is 657mm, the volume becomes a 36785cm 3.

以上の構成による従来例の排気ガス浄化装置は、エンジン1の下流側の排気通路2に、上流側から順に、酸化触媒3、多孔質セラミックハニカム構造体の所望の流路を両端部で目封止し、且つ隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているフィルタ4、アンモニア等を噴出できる還元剤供給装置6、SCR触媒5を設けて構成されていることから、次のように浄化される。 Above conventional example of the configuration of the exhaust gas purifying device, the exhaust passage 2 downstream of the engine 1, in order from the upstream side, eyes sealed at both ends of the desired flow path of the oxidation catalyst 3, a porous ceramic honeycomb structure sealed, and because the catalyst material is formed by providing a reducing agent supply device 6, SCR catalyst 5 which can eject the filter 4 and ammonia that is supported on at least a portion of the partition wall and / or the plugging portion It is purified as follows. フィルタ4への粒子状物質の捕集量が多くなると、フィルタの目詰まりによる圧力損失の上昇を避けるため、ディーゼルエンジン1の運転状態に応じて、触媒物質を担持させたフィルタ上への微粒子の堆積量を推定した上で、酸化触媒3の上流側に燃料を未燃のまま噴射して、前記酸化触媒物質上で、燃料の酸化反応を促すとともに、排気ガス中のNOをNO に効果的に転化させ、前記反応熱によりフィルタ4の内部温度を上昇させ、セラミックハニカムフィルタ4で排気ガス中の粒子状物質の少なくとも一部がNO の存在下で比較的低い温度で燃焼除去させる。 When trapping amount of the particulate matter to the filter 4 increases, in order to avoid an increase in pressure loss due to clogging of the filter, in accordance with the operation state of the diesel engine 1, the fine particles onto the filter supporting a catalyst substance on the deposit amount was estimated, the fuel is injected unburned upstream of the oxidation catalyst 3, on the oxidation catalyst material, encourages the oxidation reaction of the fuel, the effect of NO in the exhaust gas to NO 2 to be converted, said raising the internal temperature of the filter 4 by the heat of reaction, at least a portion of the particulate matter in the exhaust gas is burned off at relatively low temperatures in the presence of NO 2 in the ceramic honeycomb filter 4. 更に、NO 含有量の高くなった排気ガスに対して、窒素系還元剤を添加してガス混合物を形成し、このガス混合物をSCR触媒上に通過させることにより、窒素酸化物(NO )がN に転化されて、浄化される。 Furthermore, with respect to raised exhaust gas NO 2 content, the addition of nitrogen-based reducing agent to form a gas mixture, by passing the gas mixture over an SCR catalyst, nitrogen oxides (NO x) There is converted to N 2, it is purified. 但し、この従来例の排気ガス浄化装置では、酸化触媒3とセラミックハニカムフィルタ4が排気通路によって、直列に配置されていることから、酸化触媒における触媒反応により高温となった排気ガスが、酸化触媒とフィルタ間の排気通路を通過する間に温度が低下してフィルタに流入し、特に低速走行時のように浄化装置に流入する排気ガス温度自体が低い場合は、フィルタ内の温度が、粒子状物質を十分に燃焼させる温度に達しない場合があり、未燃焼の粒子状物質が特にフィルタの中でも最も温度の低くなるフィルタ流入側目封止部端面に残存して、流路を閉塞させて、フィルタの圧力損失を上昇させるという問題が発生した。 However, the exhaust gas purifying apparatus of this conventional example, by the oxidation catalyst 3 and the ceramic honeycomb filter 4 is an exhaust passage, because it is arranged in series, the exhaust gas temperature has become high by the catalytic reaction in the oxidation catalyst, oxidation catalyst and flows into the filter temperature decreases while passing through the exhaust passage between the filter, when the exhaust gas temperature itself flowing is low especially purifier such as during low-speed running, the temperature in the filter, particulate may not reach the temperature to sufficiently burn the material was remaining on the filter inlet side plugged end face of the most temperature lower also in particular particulate matter unburned filter, to block the flow path, problem of increasing pressure loss of the filter occurs. また、このような構成のフィルタから排出される排気ガス中のNO/NO のモル比は1/3〜4/1と広い範囲のモル比の排気ガスが得られるため、これに、還元剤供給装置から還元剤であるアンモニアを添加してガス混合物を形成し、このガス混合物をSCR触媒上に導入させると、モル比によってはNO xからN への転化率が低下する場合もある。 Moreover, since the exhaust gas in a molar ratio of such a molar ratio of NO / NO 2 in the exhaust gas discharged from the configuration of the filter is wide and 1 / 3-4 / 1 range is obtained, in which a reducing agent adding ammonia as a reducing agent from the supply device to form a gas mixture, when the introduction of this gas mixture on the SCR catalyst, by molar ratio in some cases conversion to N 2 is reduced from the NO x.

以上、説明したように本発明の実施例による排気ガス浄化装置では、フィルタ11が、触媒物質の作用により粒子状物質を効果的に燃焼浄化する機能を有しているため、本発明の排気ガス浄化装置は、フィルター11、及びSCR触媒5とで構成され、排気ガス装置全体に必要なセラミックハニカム構造体の長さは505mm、容積は28275cm であるのに対し、比較例の排気ガス浄化装置では、排気ガス装置全体に必要なセラミックハニカム構造体の長さは657mm、容積は36785cm であり、本発明の排気ガス浄化装置によれば、粒子状物質及び窒素酸化物(NO )の浄化率を高く維持できるとともに、排気ガス浄化装置全体の圧力損失を低減できるという大きな効果が得られる。 Above, the exhaust gas purification apparatus according to an exemplary embodiment of the present invention as described, since the filter 11 has a function to effectively burn purifying the particulate matter by the action of the catalyst material, the exhaust gas of the present invention purifier is composed of a filter 11, and the SCR catalyst 5, the length of the ceramic honeycomb structure required entire exhaust gas system is 505 mm, while the volume is 28275Cm 3, an exhaust gas purification apparatus of the comparative example So the length of the ceramic honeycomb structure required entire exhaust gas system 657Mm, volume was 36785Cm 3, according to the exhaust gas purifying apparatus of the present invention, the purification of particulate matter and nitrogen oxides (NO x) with the rate can be kept high, a large effect is obtained that can reduce the pressure loss of the entire exhaust gas purification device. また本発明の排気ガス浄化装置に必要なハニカム構造体はフィルター11、及びSCR触媒5となるため、従来技術のように酸化触媒、セラミックハニカムフィルタ、SCR触媒を配設した排気ガス浄化装置に比べ圧力損失が低く押さえられることから、浄化装置全体の小型化が可能となる。 The honeycomb structure required exhaust gas purifying apparatus of the present invention is to become a filter 11, and the SCR catalyst 5, compared with the oxidation catalyst, ceramic honeycomb filter, the exhaust gas purifying device which is disposed an SCR catalyst as in the prior art since the pressure loss is kept low, it is possible to miniaturize the entire purification apparatus.

本発明の排気ガス浄化装置を示すディーゼルエンジンの排気系の構成図である。 It is a configuration diagram of an exhaust system of a diesel engine showing an exhaust gas purifying apparatus of the present invention. 本発明の実施の形態でのハニカムフィルタの模式断面図である。 It is a schematic cross-sectional view of the honeycomb filter in the embodiments of the present invention. ハニカム構造体に目封止材を導入している状況を示す模式断面図である It is a schematic sectional view showing a situation that deploy plugging material into the honeycomb structure 従来の排気ガス浄化装置を示すディーゼルエンジンの排気系の構成図である。 It is a configuration diagram of an exhaust system of a diesel engine showing a conventional exhaust gas purification device.

符号の説明 DESCRIPTION OF SYMBOLS

1:エンジン 2:排気通路 3:酸化触媒 4:フィルタ 5:SCR触媒 6:還元剤供給装置 7:排気ガス10:ハニカム構造体11:ハニカムフィルタ12:流入側端面13:流出側端面20:外周壁30:隔壁31:流入側目封止部より流入側の隔壁32:流入側目封止部より流出側の隔壁40:流路41:流入側端面で開口している流路42:流入側端面で開口している流路43:排気ガス流出側に開口した流路50:流入側目封止部51:流入側目封止部端面52:流出側目封止部53:目封止材60:触媒物質70:未燃焼微粒子80:マスク81:スラリー導入通路90:排気ガスの流入91:排気ガスの流入92:排気ガスの流出X:目封止部形成位置 1: Engine 2: exhaust passage 3: the oxidation catalyst 4: Filter 5: SCR catalyst 6: reducing agent feeder 7: exhaust gas 10: honeycomb structure 11: honeycomb filter 12: inlet-side end 13: outflow-side end surface 20: outer peripheral walls 30: partition wall 31: inlet-side plugging portions than the inflow side of the partition wall 32: inlet-side plugging portions than the outflow side of the partition wall 40: passage 41: open at the inflow side end face and the channel 42: inlet side flow path is open at an end face 43: exhaust gas outflow side open flow paths 50: inflow side plugged portions 51: inflow side plugged end face 52: outflow-side plugging portion 53: plugging material 60: catalyst material 70: unburned particulates 80: mask 81: slurry introducing passage 90: flow of exhaust gases 91: flow of exhaust gas 92: outflow of exhaust gas X: forming plugged portions located

Claims (5)

  1. ディーゼルエンジンから排出される窒素酸化物及び粒子状物質を含有する排気ガスを浄化する装置であって、多孔質セラミックハニカム構造体の所望の流路を目封止したセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持されているフィルタと、SCR触媒とを、この順序で配置したことを特徴とする排気ガス浄化装置。 An apparatus for purifying an exhaust gas containing nitrogen oxides and particulate matter exhausted from diesel engines, ceramic honeycomb filters plugging a desired flow path of the porous ceramic honeycomb structural body, at least one of together with the exhaust gas inlet side plugged portions are spaced apart from the exhaust gas inlet side end surface, and a filter catalyst material is supported on at least a portion of the partition wall and / or the plugging portion, and a SCR catalyst the exhaust gas purification apparatus characterized by being arranged in this order.
  2. 前記セラミックハニカムフィルタの排気ガス流入側目封止部端面が、セラミックハニカムフィルタの流入側端面から該セラミックハニカムフィルタ全長の0.7倍以下の長さの区間に配置されていることを特徴とする請求項1に記載の排気ガス浄化装置。 Exhaust gas inflow side plugged end face of the ceramic honeycomb filter, characterized in that it is arranged in a section of 0.7 times the length of the ceramic honeycomb filter total length from the inflow side end face of the ceramic honeycomb filter exhaust gas purifying apparatus according to claim 1.
  3. 前記セラミックハニカムフィルタに担持される触媒物質が白金族金属を含んでなることを特徴とする請求項1乃至2のいずれかに記載の排気ガス浄化装置。 Exhaust gas purifying apparatus according to any one of claims 1 to 2 catalyst material which is supported on the ceramic honeycomb filter is characterized in that it comprises a platinum group metal.
  4. 前記セラミックハニカムフィルタの排気ガス流入側の隔壁に担持された触媒物質の活性度が、排気ガス流出側の隔壁に担持された触媒物質の活性度に比べ高いことを特徴とする請求項1乃至3のいずれかに記載のセラミックハニカムフィルタ。 The ceramic honeycomb activity of the catalyst material supported on the exhaust gas inflow side of the partition wall of the filter, according to claim 1, wherein the higher than in the activity of supported on the partition walls of the exhaust gas outlet side catalyst material the ceramic honeycomb filter according to any one of.
  5. ディーゼルエンジンから排出される窒素酸化物及び粒子状物質を含有する排気ガスを浄化する装置に配設されたセラミックハニカムフィルタの、少なくとも一つの排気ガス流入側目封止部が排気ガス流入側端面より離れて配置されていると共に、隔壁及び/または目封止部の少なくとも一部に触媒物質が担持され、前記排気ガス中の粒子状物質を前記セラミックハニカムフィルタ内で燃焼させ、前記フィルタの排気ガス排出側に配設されたSCR触媒中に導入する排気ガス中のNO/NO のモル比を1/2〜2/1にすることを特徴とする排気ガス浄化方法。 Ceramic honeycomb filter disposed in an apparatus for purifying exhaust gas containing nitrogen oxides and particulate matter discharged from a diesel engine, at least one exhaust gas inlet side plugged portions is the exhaust gas inlet side end surface is spaced apart, the catalyst material is supported on at least a portion of the partition wall and / or the plugging portion, the particulate matter in the exhaust gas is combusted in the ceramic honeycomb filter, the exhaust gas of the filter exhaust gas purification method, characterized in that the molar ratio of NO / NO 2 in the exhaust gas introduced into the SCR catalyst disposed on the discharge side to the 1/2 to 2/1.
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JP2006212591A (en) * 2005-02-07 2006-08-17 Isuzu Motors Ltd Exhaust gas purifying system and exhaust gas purifying method using the same
JP2006233935A (en) * 2005-02-28 2006-09-07 Hitachi Metals Ltd Exhaust emission control device
JP2008057337A (en) * 2006-08-29 2008-03-13 Hino Motors Ltd Exhaust emission control device
JP2008121629A (en) * 2006-11-15 2008-05-29 Mitsubishi Fuso Truck & Bus Corp Exhaust emission control device
WO2008096548A1 (en) 2007-02-09 2008-08-14 Hino Motors, Ltd. Exhaust purification apparatus
JP2009510333A (en) * 2005-10-06 2009-03-12 エミテック ゲゼルシヤフト フユア エミツシオンス テクノロギー ミツト ベシユレンクテル ハフツング Reduction process and apparatus of the nitrogen oxide component contained in the exhaust gas of an internal combustion engine
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RU2455505C2 (en) * 2007-02-21 2012-07-10 Вольво Ластвагнар Аб System of exhaust gas advanced treatment
US8371109B2 (en) 2007-07-31 2013-02-12 Hino Motors, Ltd. Exhaust emission control device
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JP4507901B2 (en) * 2005-02-07 2010-07-21 いすゞ自動車株式会社 Exhaust gas purification system and an exhaust gas purification method
JP2006212591A (en) * 2005-02-07 2006-08-17 Isuzu Motors Ltd Exhaust gas purifying system and exhaust gas purifying method using the same
JP2006233935A (en) * 2005-02-28 2006-09-07 Hitachi Metals Ltd Exhaust emission control device
JP2009510333A (en) * 2005-10-06 2009-03-12 エミテック ゲゼルシヤフト フユア エミツシオンス テクノロギー ミツト ベシユレンクテル ハフツング Reduction process and apparatus of the nitrogen oxide component contained in the exhaust gas of an internal combustion engine
JP2008057337A (en) * 2006-08-29 2008-03-13 Hino Motors Ltd Exhaust emission control device
JP2008121629A (en) * 2006-11-15 2008-05-29 Mitsubishi Fuso Truck & Bus Corp Exhaust emission control device
JP2015158206A (en) * 2006-12-01 2015-09-03 ビーエーエスエフ コーポレーション Zone coated filter, and emission treatment systems and methods
KR101812438B1 (en) * 2006-12-01 2017-12-26 바스프 카탈리스트 엘엘씨 Zone coated filter, emission treatment systems and methods
JP2010511829A (en) * 2006-12-01 2010-04-15 ビーエーエスエフ、カタリスツ、エルエルシーBASF Catalysts LLC Regionally coated filters exhaust treatment system and method
US8245503B2 (en) 2007-02-09 2012-08-21 Hino Motors, Ltd. Exhaust emission control device
WO2008096548A1 (en) 2007-02-09 2008-08-14 Hino Motors, Ltd. Exhaust purification apparatus
RU2455505C2 (en) * 2007-02-21 2012-07-10 Вольво Ластвагнар Аб System of exhaust gas advanced treatment
US8371109B2 (en) 2007-07-31 2013-02-12 Hino Motors, Ltd. Exhaust emission control device
JP2014080979A (en) * 2007-12-12 2014-05-08 Basf Corp Exhaust processing method
US9863297B2 (en) 2007-12-12 2018-01-09 Basf Corporation Emission treatment system
US9993771B2 (en) 2007-12-12 2018-06-12 Basf Corporation Emission treatment catalysts, systems and methods

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