【０００１】[0001]
【産業上の利用分野】この発明は、エンジンの排気ポー
トより排出されるＨＣ（炭化水素）、ＣＯ（一酸化炭
素）、ＮＯｘ（窒素酸化物）の有害ガスを浄化するよう
な排気ガス浄化装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas purifying apparatus for purifying harmful gases such as HC (hydrocarbon), CO (carbon monoxide) and NOx (nitrogen oxide) discharged from an exhaust port of an engine. Regarding
【０００２】[0002]
【従来の技術】従来、上述例の排気ガス浄化装置として
は、例えば特開平２−１３５１２６号公報に記載の装置
がある。2. Description of the Related Art Conventionally, as an exhaust gas purifying apparatus of the above-mentioned example, there is an apparatus described in JP-A-2-135126.
【０００３】すなわち、エンジン排気系に介設された排
気ガス浄化装置であって、排気上流側にはＨＣ吸着剤を
収納したＨＣトラッパを設け、このＨＣトラッパの下流
に排気管路を介して離間状に接続された排気下流側のキ
ャスタリストケースに三元触媒を収納した触媒コンバー
タを配設し、上記ＨＣ吸着剤としてゼオライトをコート
したモノリス担体の一部に１種類以上の触媒金属（具体
的にはＰｔ）を担持させたＨＣ吸着剤を用いた排気ガス
浄化装置である。That is, in an exhaust gas purifying apparatus provided in an engine exhaust system, an HC trapper containing an HC adsorbent is provided on the exhaust upstream side, and is separated downstream of this HC trapper via an exhaust pipe line. A catalytic converter containing a three-way catalyst is provided in a caster case on the downstream side of the exhaust gas that is connected in a circular pattern, and one or more types of catalytic metal (specifically, a part of the monolith carrier coated with zeolite as the HC adsorbent is used). Is an exhaust gas purification device using an HC adsorbent carrying Pt).
【０００４】この従来の排気ガス浄化装置によればＰｔ
（白金）の担持によりＨＣ種のうちのオレフィン、パラ
フィンの浄化は可能であるが、ＨＣ種のうちのアロマ分
の浄化が不可能な問題点があった。According to this conventional exhaust gas purifying apparatus, Pt
By carrying (platinum), it is possible to purify olefins and paraffins of HC species, but there is a problem that the aroma components of HC species cannot be purified.
【０００５】排気ガス中のＨＣ種は大別してオレフィン
族炭化水素（olefinic hydrocarbon、一般式ＣｎＨｚｎ
で示され、１個の二重結合をもっている鎖状炭化水素の
ことで以下単にオレフィンと略記する）と、パラフィン
族炭化水素（paraffin hydrocarbon、一般式ＣｎＨｚｎ
＋2 で示される炭化水素で、不飽和結合と環構造をもた
ない化合物のことで以下単にパラフィンと略記する）
と、芳香族炭化水素（aromatic hydrocarbor、ベンゼン
核をもつ化合物のことで以下単にアロマ分と略記する）
とがあり、本発明者等による諸種の研究の結果、排気ガ
ス中の成分は図８のａに示すように上記アロマ分が約半
分を占め、オレフィン、パラフィンの含有量は比較的少
ないことが判明した。HC species in exhaust gas are roughly classified into olefinic hydrocarbons (general formula: CnHzn).
, Which is a chain hydrocarbon having one double bond and is abbreviated as olefin hereinafter) and paraffin hydrocarbon (general formula CnHzn).
A hydrocarbon represented by +2, which is a compound that does not have an unsaturated bond and ring structure and is simply referred to as paraffin hereinafter)
And aromatic hydrocarbons (aromatic hydrocarbor, a compound with a benzene nucleus, abbreviated as "aromatic component" below)
As a result of various studies conducted by the present inventors, the components in the exhaust gas are about half of the aroma components as shown in a of FIG. 8, and the olefin and paraffin contents are relatively low. found.
【０００６】[0006]
【発明が解決しようとする課題】この発明の請求項１記
載の発明（第１発明）は、排気ガス中のＨＣを吸着する
ＨＣ吸着剤に対して、アロマ分浄化効果の高いＰｄ（パ
ラジウム）を成分に有する三元触媒を所定間隔を隔てて
近接配置することで、冷間時に排出された未燃ＨＣをＨ
Ｃ吸着剤で一旦吸着させ、ＨＣ吸着剤の温度上昇により
ＨＣ吸着剤から放出された未燃ＨＣを上述のＰｄを主成
分とする三元触媒で燃焼浄化させ、特に排気ガス中の成
分の約半分を占めるアロマ分を良好に浄化することがで
き、またＨＣ吸着剤とＰｄを成分に有する三元触媒を所
定間隔を隔てて近接配置することで、高温条件下におけ
るＨＣ吸着剤と三元触媒との間の反応を防止して、両者
（ＨＣ吸着剤および三元触媒）の耐熱性を向上させるこ
とができる排気ガス浄化装置の提供を目的とする。The invention according to claim 1 of the present invention (first invention) is Pd (palladium) having a high aroma-purifying effect on the HC adsorbent that adsorbs HC in exhaust gas. By arranging three-way catalysts containing as a component close to each other at a predetermined interval, unburned HC discharged during cold is
Once adsorbed by the C adsorbent, the unburned HC released from the HC adsorbent due to the temperature rise of the HC adsorbent is burned and purified by the above-mentioned three-way catalyst containing Pd as a main component. It is possible to satisfactorily purify the aroma component which occupies half, and by arranging the HC adsorbent and the three-way catalyst having Pd as a component in close proximity to each other at a predetermined interval, the HC adsorbent and the three-way catalyst under high temperature conditions can be obtained. It is an object of the present invention to provide an exhaust gas purifying apparatus capable of preventing the reaction between the two and the two (HC adsorbent and three-way catalyst) to be improved in heat resistance.
【０００７】この発明の請求項２記載の発明は、上記請
求項１記載の発明の目的と併せて、ＨＣ吸着剤の直下流
にＰｄを成分に有する三元触媒を配置することで、冷間
時に排出された未燃ＨＣをＨＣ吸着剤で一旦吸着させ、
ＨＣ吸着剤の温度上昇によりＨＣ吸着剤から放出された
未燃ＨＣを直下流に位置する上述のＰｄを成分に有する
三元触媒で燃焼浄化させ、特に排気ガス中の成分の約半
分を占めるアロマ分を略全部浄化することができる排気
ガス浄化装置の提供を目的とする。The invention according to claim 2 of the present invention has the object of the invention according to claim 1 described above, and by arranging a three-way catalyst containing Pd as a component immediately downstream of the HC adsorbent, The unburned HC that is sometimes discharged is once adsorbed by the HC adsorbent,
The unburned HC released from the HC adsorbent due to the temperature rise of the HC adsorbent is burned and purified by a three-way catalyst having Pd as a component located immediately downstream, and in particular, an aroma that occupies about half of the components in the exhaust gas. It is an object of the present invention to provide an exhaust gas purification device that can purify almost all of the amount.
【０００８】この発明の請求項３記載の発明（第２発
明）は、周囲がパラジウムに対して反応しにくい耐火性
多孔質体で囲繞された囲繞構造のＨＣ吸着剤粒子と、ア
ロマ分浄化効果の高いＰｄ（パラジウム）を成分に有す
る三元触媒とが複合された複合触媒をエンジンの排気系
に介設することで、冷間時に排出された未然ＨＣをＨＣ
吸着剤で一旦吸着させ、ＨＣ吸着剤の温度上昇によりＨ
Ｃ吸着剤から放出された未然ＨＣを上述のＰｄを成分に
有する三元触媒で燃焼浄化させ、特に排気ガス中の成分
の約半分を占めるアロマ分を良好に浄化することがで
き、かつＰｄに対して反応しにくい耐火性多孔質体でＨ
Ｃ吸着剤粒子を囲繞することで、ＨＣ吸着剤がＰｄと反
応するのを防止して、ＨＣ吸着剤およびＰｄの熱劣化を
防止しつつ、ＨＣ吸着剤とＰｄとの複合化により初期浄
化性能の向上を図ることができる排気ガス浄化装置の提
供を目的とする。The invention according to claim 3 (the second invention) of the present invention is a HC adsorbent particle having a surrounding structure surrounded by a refractory porous body which is hard to react with palladium, and an aroma content purifying effect. By installing a composite catalyst, which is a composite of a three-way catalyst containing Pd (palladium), which has a high content, in the exhaust system of the engine, it is possible to reduce the amount of HC that is already emitted during cold conditions to HC.
Once it is adsorbed by the adsorbent, the temperature rise of the HC adsorbent causes H
The HC released from the C adsorbent can be burned and purified by the above-mentioned three-way catalyst having Pd as a component, and in particular, the aroma component occupying about half of the components in the exhaust gas can be satisfactorily purified, and Pd It is a refractory porous material that is hard to react with H
By surrounding the C adsorbent particles, the HC adsorbent is prevented from reacting with Pd and thermal deterioration of the HC adsorbent and Pd is prevented, while the initial purification performance is achieved by combining the HC adsorbent and Pd. It is an object of the present invention to provide an exhaust gas purification device capable of improving the exhaust gas.
【０００９】この発明の請求項４記載の発明は、上記請
求項１もしくは３記載の発明の目的と併せて、ＨＣ吸着
剤粒子を、ＦＡＵ型ゼオライト、β型ゼオライト、ＭＡ
Ｚ型ゼオライト、ＡＦＹ型ゼオライト、ＭＦＩ型ゼオラ
イトのうちの少なくとも１つに設定することで、他のＨ
Ｃ吸着剤を用いるものと比較してアロマ分の吸着効果の
向上を図ることができる排気ガス浄化装置の提供を目的
とする。According to the invention of claim 4 of the present invention, in addition to the object of the invention of claim 1 or 3, HC adsorbent particles are mixed with FAU type zeolite, β type zeolite, MA
By setting at least one of Z-type zeolite, AFY-type zeolite, and MFI-type zeolite, other H
It is an object of the present invention to provide an exhaust gas purifying device capable of improving the adsorption effect of aroma components as compared with the one using a C adsorbent.
【００１０】この発明の請求項５記載の発明は、上記請
求項３記載の発明の目的と併せて、Ｐｄに対して反応し
にくい耐火性多孔質体を、アルミナ、シリカ、酸化セリ
ウム（いわゆるセリア）のうちの少なくとも１つに設定
することで、ＨＣ吸着剤粒子とＰｄとが反応するのを良
好に防止して、ＨＣ吸着剤およびＰｄの熱劣化を確実に
防止することができる排気ガス浄化装置の提供を目的と
する。According to the invention of claim 5 of the present invention, in addition to the object of the invention of claim 3, a refractory porous body which is difficult to react with Pd is made of alumina, silica, cerium oxide (so-called ceria). By setting at least one of the above), it is possible to favorably prevent the HC adsorbent particles from reacting with Pd, and to reliably prevent thermal deterioration of the HC adsorbent and Pd. The purpose is to provide a device.
【００１１】この発明の請求項６記載の発明は、上記請
求項２記載の発明の目的と併せて、同項記載の排気ガス
浄化装置の上流および下流の少なくとも一方にＰｔ−Ｒ
ｈ（白金−ロジウム）を主成分とする三元触媒を配置す
ることで、Ｐｄによりアロマ分を浄化し、Ｐｔ−Ｒｈに
よりオレフィン、パラフィンを浄化して、全てのＨＣ種
を良好に浄化することができる排気ガス浄化装置の提供
を目的とする。According to a sixth aspect of the present invention, in addition to the object of the second aspect of the invention, Pt-R is provided at least at one of the upstream side and the downstream side of the exhaust gas purifying apparatus.
By arranging a three-way catalyst containing h (platinum-rhodium) as a main component, Pd is used to purify aroma components, Pt-Rh is used to purify olefins and paraffins, and all HC species are favorably purified. An object of the present invention is to provide an exhaust gas purifying device capable of achieving the
【００１２】この発明の請求項７記載の発明は、上記請
求項３記載の発明の目的と併せて、上述の複合触媒の上
流および下流の少なくとも一方にＰｔ−Ｒｈ（白金−ロ
ジウム）を主成分とする三元触媒を配置することで、複
合触媒内のＰｄによりアロマ分を浄化し、Ｐｔ−Ｒｈに
よりオレフィン、パラィンを浄化して、全てのＨＣ種を
良好に浄化することができる排気ガス浄化装置の提供を
目的とする。According to the invention of claim 7 of the present invention, in addition to the object of the invention of claim 3, Pt-Rh (platinum-rhodium) is a main component in at least one of the upstream side and the downstream side of the composite catalyst. By arranging the three-way catalyst, the aroma component is purified by Pd in the composite catalyst, the olefin and the line are purified by Pt-Rh, and all the HC species can be purified satisfactorily. The purpose is to provide a device.
【００１３】この発明の請求項８記載の発明は、上記請
求項１，２，３，５，６もしくは７記載の発明の目的と
併せて、ＨＣ吸着剤として細孔径が７．４オングストロ
ーム以上のゼオライトを用いることで、ＨＣ種の約半分
を占めるアロマ分のベンゼン環を良好にトラップするこ
とができる排気ガス浄化装置の提供を目的とする。The invention according to claim 8 of the present invention, together with the object of the invention according to claim 1, 2, 3, 5, 6 or 7, has a pore diameter of 7.4 angstroms or more as an HC adsorbent. It is an object of the present invention to provide an exhaust gas purifying apparatus that can favorably trap a benzene ring for an aroma that accounts for about half of HC species by using zeolite.
【００１４】この発明の請求項９記載の発明は、上記請
求項１，２，３，５，６もしくは７記載の発明の目的と
併せて、ＨＣ吸着剤として細孔径が７．４オングストロ
ーム以上のゼオライトで、ＦＡＵ型ゼオライト、β型ゼ
オライト、ＭＡＺ型ゼオライトの内の少なくとも１つに
設定することで、ＨＣ種の約半分を占めるアロマ分のベ
ンゼン環を良好にトラップすることができる排気ガス浄
化装置の提供を目的とする。In addition to the object of the invention described in claim 1, 2, 3, 5, 6 or 7, the invention described in claim 9 of the present invention has a pore diameter of 7.4 angstroms or more as an HC adsorbent. Exhaust gas purifying device capable of favorably trapping the benzene ring of aroma that accounts for about half of HC species by setting at least one of FAU type zeolite, β type zeolite and MAZ type zeolite as the zeolite For the purpose of providing.
【００１５】[0015]
【課題を解決するための手段】この発明の請求項１記載
の発明（第１発明）は、エンジンの排気系に介設される
排気ガス浄化装置であって、排気ガス中のＨＣを吸着す
るＨＣ吸着剤に対して、少なくともＰｄを成分に有する
三元触媒が所定間隔を隔てて近接配置された排気ガス浄
化装置であることを特徴とする。The invention according to claim 1 (first invention) of the present invention is an exhaust gas purifying device provided in an exhaust system of an engine, and adsorbs HC in the exhaust gas. The exhaust gas purifying device is characterized in that a three-way catalyst containing at least Pd as a component is disposed close to the HC adsorbent at a predetermined distance.
【００１６】この発明の請求項２記載の発明は、上記請
求項１記載の発明の構成と併せて、排気ガス中のＨＣを
吸着するＨＣ吸着剤と、該ＨＣ吸着剤の直下流に配置さ
れた少なくともＰｄを成分に有する三元触媒とを備えた
排気ガス浄化装置であることを特徴とする。According to a second aspect of the present invention, in addition to the configuration of the first aspect of the invention, an HC adsorbent that adsorbs HC in the exhaust gas is arranged and immediately downstream of the HC adsorbent. Further, the exhaust gas purifying apparatus is provided with a three-way catalyst having at least Pd as a component.
【００１７】この発明の請求項３記載の発明（第２発
明）は、排気ガス中のＨＣを吸着するＨＣ吸着剤粒子の
周囲がパラジウムに対して反応しにくい耐火性多孔質体
で囲繞された囲繞構造のＨＣ吸着剤粒子と、少なくとも
Ｐｄを成分に有する三元触媒とが複合された複合触媒を
設け、上記複合触媒をエンジンの排気系に介設した排気
ガス浄化装置であることを特徴とする。According to a third aspect of the present invention (the second invention), the periphery of the HC adsorbent particles for adsorbing HC in the exhaust gas is surrounded by a refractory porous body which is difficult to react with palladium. An exhaust gas purifying apparatus comprising a composite catalyst, which comprises a composite of HC adsorbent particles having a surrounding structure, and a three-way catalyst containing at least Pd as a component, and the composite catalyst is provided in an exhaust system of an engine. To do.
【００１８】この発明ノ請求項４記載の発明は、上記請
求項１もしくは３記載の発明の構成と併せて、上記排気
ガス中のＨＣを吸着するＨＣ吸着剤粒子を、ＦＡＵ型ゼ
オライト、β型ゼオライト、ＭＡＺ型ゼオライト、ＡＦ
Ｙ型ゼオライト、ＭＦＩ型ゼオライトのうち少なくとも
１つに設定した排気ガス浄化装置であることを特徴とす
る。The present invention as set forth in claim 4 is, in addition to the constitution of the invention as set forth in claim 1 or 3, wherein the HC adsorbent particles for adsorbing HC in the exhaust gas are FAU type zeolite or β type. Zeolite, MAZ type zeolite, AF
The exhaust gas purifying device is characterized in that at least one of Y-type zeolite and MFI-type zeolite is set.
【００１９】この発明の請求項５記載の発明は、上記請
求項３記載の発明の構成と併せて、上記Ｐｄに対して反
応しにくい耐火性多孔質体を、アルミナ、シリカ、酸化
セリウムのうち少なくとも１つに設定した排気数浄化装
置であることを特徴とする。According to the invention of claim 5 of the present invention, in addition to the constitution of the invention of claim 3, a refractory porous body which is difficult to react with Pd is selected from alumina, silica and cerium oxide. It is characterized in that it is an exhaust gas number purification device set to at least one.
【００２０】この発明の請求項６記載の発明は、上記請
求項２記載の排気ガス浄化装置の上流および下流の少な
くとも一方にＰｔ−Ｒｈを主成分とする三元触媒が配置
された排気ガス浄化装置であることを特徴とする。The invention according to claim 6 of the present invention is exhaust gas purification in which a three-way catalyst containing Pt-Rh as a main component is arranged at least upstream or downstream of the exhaust gas purification device according to claim 2. It is a device.
【００２１】この発明の請求項７記載の発明は、上記請
求項３記載の発明の構成と併せて、上記複合触媒の上流
および下流の少なくとも一方にＰｔ−Ｒｈを主成分とす
る三元触媒が配置された排気ガス浄化装置であることを
特徴とする。According to a seventh aspect of the present invention, in addition to the configuration of the third aspect of the invention, a three-way catalyst containing Pt-Rh as a main component is provided on at least one of the upstream side and the downstream side of the composite catalyst. The exhaust gas purifying device is arranged.
【００２２】この発明の請求項８記載の発明は、上記請
求項１，２，３，５，６もしくは７記載の発明の構成と
併せて、排気ガス中のＨＣを吸着するＨＣ吸着剤を、細
孔径７．４オングストローム以上のゼオライトで構成し
た排気ガス浄化装置であることを特徴とする。According to the invention of claim 8 of the present invention, in addition to the constitution of the invention of claim 1, 2, 3, 5, 6 or 7, an HC adsorbent for adsorbing HC in exhaust gas is provided. The exhaust gas purifier is made of zeolite having a pore size of 7.4 angstroms or more.
【００２３】この発明の請求項９記載の発明は、上記請
求項１，２，３，５，６もしくは７記載の発明の構成と
併せて、排気ガス中のＨＣを吸着するＨＣ吸着剤を、細
孔径７．４オングストローム以上のゼオライトで、ＦＡ
Ｕ型ゼオライト、β型ゼオライト、ＭＡＺ型ゼオライト
の内の少なくとも１つに設定した排気ガス浄化装置であ
ることを特徴とする。According to a ninth aspect of the present invention, in addition to the constitution of the first, second, third, fifth, sixth or seventh aspect of the present invention, an HC adsorbent for adsorbing HC in exhaust gas is provided. Zeolite with a pore size of 7.4 Å or more
The exhaust gas purifying device is characterized by being set to at least one of U-type zeolite, β-type zeolite, and MAZ-type zeolite.
【００２４】[0024]
【発明の作用及び効果】この発明の請求項１記載の発明
（第１発明）によれば、排気ガス中のＨＣを吸着するＨ
Ｃ吸着剤に対して、アロマ分浄化効果の高いＰｄ（パラ
ジウム）を成分に有する三元触媒を所定間隔を隔てて近
接配置したので、冷間時に排出された未燃ＨＣをＨＣ吸
着剤で一旦吸着させ、ＨＣ吸着剤の温度上昇によりＨＣ
吸着剤から放出された未燃ＨＣを上述のＰｄを成分に有
する三元触媒で燃焼浄化させ、特に排気ガス中の成分の
約半分を占めるアロマ分を図８のＣに示す如く良好に浄
化することができ、またＨＣ吸着剤とＰｄを主成分とす
る三元触媒を所定間隔を隔てて近接配置したので、高温
条件下におけるＨＣ吸着剤と三元触媒との間の反応を防
止して、両者（ＨＣ吸着剤および三元触媒）の耐熱性を
向上させることができる効果がある。According to the invention (first invention) of claim 1 of the present invention, H which adsorbs HC in the exhaust gas
Since a three-way catalyst containing Pd (palladium), which has a high aroma-purifying effect, as a component was placed close to the C adsorbent at a predetermined interval, the unburned HC discharged during cold operation was temporarily absorbed by the HC adsorbent. Adsorb the HC by increasing the temperature of the HC adsorbent
The unburned HC released from the adsorbent is burned and purified by the above-mentioned three-way catalyst having Pd as a component, and in particular, the aroma component occupying about half of the components in the exhaust gas is satisfactorily purified as shown in C of FIG. Further, since the HC adsorbent and the three-way catalyst containing Pd as the main component are closely arranged at a predetermined interval, the reaction between the HC adsorbent and the three-way catalyst under high temperature conditions is prevented, There is an effect that the heat resistance of both (HC adsorbent and three-way catalyst) can be improved.
【００２５】ここで、上述のＰｄはＰｔに対して反応温
度が低く、表面活性度が高いと共に、アロマ分のベンゼ
ン環を分解する能力が高い。この分解されたアロマ分は
酸化されやすくなることから、浄化性能にすぐれてい
る。Here, the above-mentioned Pd has a low reaction temperature with respect to Pt, has a high surface activity, and has a high ability to decompose the benzene ring of an aromatic component. The decomposed aroma component is easily oxidized, so that it has excellent purification performance.
【００２６】この発明の請求項２記載の発明によれば、
上記請求項１記載の発明の効果と併せて、ＨＣ吸着剤の
直下流にＰｄを成分に有する三元触媒を配置したので、
冷間時に排出された未燃ＨＣをＨＣ吸着剤で一旦吸着さ
せ、ＨＣ吸着剤の温度上昇によりＨＣ吸着剤から放出さ
れた未燃ＨＣを直下流に位置する上述のＰｄを成分に有
する三元触媒で燃焼浄化させ、特に排気ガス中の成分の
約半分を占めるアロマ分を略全部浄化することができる
効果がある。According to the second aspect of the present invention,
In addition to the effect of the invention described in claim 1, since the three-way catalyst having Pd as a component is arranged immediately downstream of the HC adsorbent,
The unburned HC discharged during cold is temporarily adsorbed by the HC adsorbent, and the unburned HC released from the HC adsorbent due to the temperature rise of the HC adsorbent is the ternary component having the above-mentioned Pd located immediately downstream. It is effective in purifying by combustion with a catalyst, and in particular, purifying almost all of the aroma components which account for about half of the components in the exhaust gas.
【００２７】この発明の請求項３記載の発明（第２発
明）によれば、周囲がＰｄ（パラジウム）に対して反応
しにくい耐火性多孔質体で囲繞された囲繞構造のＨＣ吸
着剤粒子と、アロマ分浄化効果の高いＰｄ（パラジウ
ム）を成分に有する三元触媒とが複合された複合触媒を
エンジンの排気系に介設したので、冷間時に排出された
未然ＨＣをＨＣ吸着剤で一旦吸着させ、ＨＣ吸着剤の温
度上昇によりＨＣ吸着剤から放出された未然ＨＣを上述
のＰｄを成分に有する三元触媒で燃焼浄化させ、特に排
気ガス中の成分の約半分を占めるアロマ分を良好に浄化
することができ、かつＰｄに対して反応しにくい耐火性
多孔質体でＨＣ吸着剤粒子を囲繞することで、ＨＣ吸着
剤がＰｄと反応するのを防止して、ＨＣ吸着剤およびＰ
ｄの熱劣化を防止しつつ、ＨＣ吸着剤とＰｄとの複合化
により、ＨＣ吸着剤とＰｄとが極近接位置に存在し、Ｈ
ＣがＰｄに接触しやすくなり、かつＰｄに熱が伝わりや
すいので、初期浄化性能の向上を図ることができる効果
がある。According to the third aspect of the present invention (the second invention), the HC adsorbent particles having a surrounding structure are surrounded by a refractory porous material which is hard to react with Pd (palladium). Since a composite catalyst in which a three-way catalyst containing Pd (palladium), which has a high aroma component purification effect, as a component is combined, is provided in the exhaust system of the engine, the HC that has already been discharged during cold is temporarily absorbed by the HC adsorbent. By adsorbing, the HC released from the HC adsorbent due to the temperature rise of the HC adsorbent is burnt and purified by a three-way catalyst having the above-mentioned Pd as a component, and especially the aroma component that accounts for about half of the component in the exhaust gas is good. By surrounding the HC adsorbent particles with a refractory porous material that can be purified to Pd and is hard to react with Pd, the HC adsorbent is prevented from reacting with Pd, and the HC adsorbent and Pd are prevented.
While preventing the thermal deterioration of d, by combining the HC adsorbent and Pd, the HC adsorbent and Pd exist in a close proximity position, and H
Since C easily contacts Pd and heat is easily transferred to Pd, there is an effect that the initial purification performance can be improved.
【００２８】この発明の請求項４記載の発明によれば、
上記請求項１もしくは３記載の発明の効果と併せて、Ｈ
Ｃ吸着剤粒子を、ＦＡＵ型ゼオライト、β型ゼオライ
ト、ＭＡＺ型ゼオライト、ＡＦＹ型ゼオライト、ＭＦＩ
型ゼオライトのうちの少なくとも１つに設定したので、
他のＨＣ吸着剤を用いるものと比較してアロマ分の吸着
効果の向上を図ることができる効果がある。According to the invention of claim 4 of the present invention,
In addition to the effect of the invention described in claim 1 or 3,
C adsorbent particles are FAU type zeolite, β type zeolite, MAZ type zeolite, AFY type zeolite, MFI
Since it was set to at least one of the type zeolite,
There is an effect that the adsorption effect of the aroma component can be improved as compared with the case where another HC adsorbent is used.
【００２９】この発明の請求項５記載の発明によれば、
上記請求項３記載の発明の効果と併せて、Ｐｄに対して
反応しにくい耐火性多孔質体を、アルミナ、シリカ、酸
化セリウム（いわゆるセリア）のうちの少なくとも１つ
に設定したので、ＨＣ吸着剤粒子とＰｄとが反応するの
を良好に防止して、ＨＣ吸着剤およびＰｄの熱劣化を確
実に防止することができる効果がある。According to the invention of claim 5 of the present invention,
In addition to the effect of the invention described in claim 3, since the refractory porous body that is difficult to react with Pd is set to at least one of alumina, silica, and cerium oxide (so-called ceria), HC adsorption There is an effect that it is possible to satisfactorily prevent the agent particles and Pd from reacting with each other and to reliably prevent thermal deterioration of the HC adsorbent and Pd.
【００３０】この発明の請求項６記載の発明によれば、
上記請求項２記載の発明の効果と併せて、同項記載の排
気ガス浄化装置の上流および下流の少なくとも一方にＰ
ｔ−Ｒｈ（白金−ロジウム）を主成分とする三元触媒を
配置したので、Ｐｄによりアロマ分を浄化し、Ｐｔ−Ｒ
ｈによりオレフィン、パラフィンを浄化して、全てのＨ
Ｃ種を良好に浄化することができる効果がある。According to the invention of claim 6 of the present invention,
In addition to the effect of the invention described in claim 2, P is provided on at least one of the upstream side and the downstream side of the exhaust gas purifying apparatus according to the same claim.
Since a three-way catalyst containing t-Rh (platinum-rhodium) as a main component was arranged, the aroma component was purified by Pd, and Pt-R
Purifies olefins and paraffins by h to remove all H
There is an effect that the C type can be satisfactorily purified.
【００３１】この発明の請求項７記載の発明によれば、
上記請求項３記載の発明の効果と併せて、上述の複合触
媒の上流および下流の少なくとも一方にＰｔ−Ｒｈ（白
金−ロジウム）を主成分とする三元触媒を配置したの
で、複合触媒内のＰｄによりアロマ分を浄化し、Ｐｔ−
Ｒｈによりオレフィン、パラィンを浄化して、全てのＨ
Ｃ種を良好に浄化することができる効果がある。According to the invention of claim 7 of the present invention,
In addition to the effect of the invention described in claim 3, a three-way catalyst containing Pt-Rh (platinum-rhodium) as a main component is arranged at least at one of the upstream side and the downstream side of the above-mentioned composite catalyst. Aroma component is purified by Pd, Pt-
Purifies olefins and lines with Rh and all H
There is an effect that the C type can be satisfactorily purified.
【００３２】この発明の請求項８記載の発明によれば、
上記請求項１，２，３，５，６もしくは７記載の発明の
効果と併せて、ＨＣ吸着剤として細孔径が７．４オング
ストローム以上のゼオライトを用いたので、ＨＣ種の約
半分を占めるアロマ分のベンゼン環を良好にトラップす
ることができる効果がある。According to the invention of claim 8 of the present invention,
In addition to the effect of the invention described in claim 1, 2, 3, 5, 6 or 7, since a zeolite having a pore size of 7.4 angstroms or more is used as the HC adsorbent, an aroma occupying about half of the HC species. There is an effect that a minute benzene ring can be favorably trapped.
【００３３】すなわち、ベンゼン環の大きな六角形の平
行辺間の距離が５．１オングストローム、対向する各頂
点間の距離が５．８オングストロームであり、このベン
ゼン環の大きさに対して適度の大きさの細孔径（７．４
オングストローム）により、ベンゼン環の良好なトラッ
プを図ることができる。That is, the distance between the parallel sides of the large hexagon of the benzene ring is 5.1 angstroms, and the distance between the opposite vertices is 5.8 angstroms, which is an appropriate size for the size of this benzene ring. Pore diameter (7.4
Å) enables good trapping of the benzene ring.
【００３４】この発明の請求項９記載の発明によれば、
上記請求項１，２，３，５，６もしくは７記載の発明の
効果と併せて、上記ＨＣ吸着剤を細孔径が７．４オング
ストローム以上のゼオライトで、ＦＡＵ型ゼオライト、
β型ゼオライト、ＭＡＺ型ゼオライトのうちの少なくと
も１つに設定したので、ＨＣ種の約半分を占めるアロマ
分のベンゼン環をこれらのゼオライトにより良好にトラ
ップすることができる効果がある。According to the invention of claim 9 of the present invention,
In addition to the effect of the invention described in claim 1, 2, 3, 5, 6 or 7, the HC adsorbent is a zeolite having a pore size of 7.4 angstroms or more, which is a FAU type zeolite,
Since at least one of β-type zeolite and MAZ-type zeolite is set, there is an effect that the benzene ring of the aroma which occupies about half of the HC species can be favorably trapped by these zeolites.
【００３５】[0035]
【実施例】この発明の一実施例を以下図面に基づいて詳
述する。 （第１実施例）図面はエンジンの排気系に介設される排
気ガス浄化装置を示し、図１において、排気ガス浄化装
置としての触媒コンバータ１は、車両のアンダフロア位
置に配設されると共に、この触媒コンバータ１は前後両
端に接合フランジ部２，３を備え、排気ガス入口４にコ
ーン部５を介してキャタリストケース６の前端側を接続
し、このキャタリストケース６の後端側はコーン部７を
介して排気ガス出口８に接続している。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described in detail below with reference to the drawings. (First Embodiment) The drawing shows an exhaust gas purifying device provided in an exhaust system of an engine. In FIG. 1, a catalytic converter 1 as an exhaust gas purifying device is arranged at an underfloor position of a vehicle. The catalytic converter 1 is provided with joint flange portions 2 and 3 at both front and rear ends, and the front end side of the catalyst case 6 is connected to the exhaust gas inlet 4 via the cone portion 5, and the rear end side of the catalyst case 6 is It is connected to the exhaust gas outlet 8 via the cone portion 7.
【００３６】上述のキャタリストケース６内の上流側と
しての前段にはＨＣ種のうちのオレフィン、パラフィン
の浄化効果が高いＰｔ−Ｒｈ系三元触媒９（特性につい
ては図８のｂ参照）を配置し、中段には排気ガス中のＨ
Ｃを吸着するＨＣ吸着剤１０を配置し、このＨＣ吸着剤
１０に対して所定間隔（例えば約１cm）を隔てた後段に
はアロマ分の浄化効果が高いＰｄ系三元触媒１１（特性
については図８のｃ参照）を配置している。A Pt-Rh-based three-way catalyst 9 (see FIG. 8b for characteristics) having a high purification effect on olefins and paraffins of HC species is provided upstream of the catalyst case 6 as an upstream side. It is arranged, and H in the exhaust gas is in the middle
An HC adsorbent 10 that adsorbs C is arranged, and a Pd-based three-way catalyst 11 (for the characteristics, which has a high aroma purification effect) is provided in the latter stage after a predetermined interval (for example, about 1 cm) from the HC adsorbent 10. (See FIG. 8c).
【００３７】ここで上述のＨＣ吸着剤１０としてはその
細孔径が７．４オングストローム以上のＦＡＵ型ゼオラ
イト（ケイバン比８０）を用いている。このように構成
した触媒コンバータ１を車両に取付け、ＦＴＰモード
（ＣＶＳ４モードと同意で米国標準走行モードのこと）
中のＹ１モード（冷間時のモード）を実車走行テスト
し、Ｙ１モードの０〜６０秒までのＨＣ浄化率における
初期浄化率および９００℃、５０時間大気熱処理後の浄
化率を実測した結果、次の如き良好な浄化率を得ること
ができた。Here, as the above-mentioned HC adsorbent 10, a FAU type zeolite (Cayban ratio 80) having a pore diameter of 7.4 angstrom or more is used. The catalytic converter 1 configured in this way is attached to the vehicle, and the FTP mode (the CVS4 mode is synonymous with the US standard traveling mode)
As a result of actually testing the Y1 mode (mode during cold) in the actual vehicle, and measuring the initial purification rate in the HC purification rate of 0 to 60 seconds in the Y1 mode and the purification rate after atmospheric heat treatment at 900 ° C. for 50 hours, The following good purification rates could be obtained.
【００３８】Ｙ１モードの０〜６０秒までのＨＣ浄化率 初期………７４．３％ 熱処理後…７０．８％ このように図１に示す実施例（請求項２，４，６，８に
対応する実施例）によれば、ＨＣ吸着剤１０の直下流に
Ｐｄ系三元触媒１１を配置したので、冷間時に排出され
た未燃ＨＣをＨＣ吸着剤１０で一旦吸着させ、ＨＣ吸着
剤１０の温度上昇により該ＨＣ吸着剤１０から放出され
た未燃ＨＣを直下流に位置する上述のＰｄ系三元触媒１
１で燃焼浄化させるので、特に排気ガス中の成分の約半
分を占めるアロマ分を略全部浄化することができる効果
がある。HC purification rate from 0 to 60 seconds in Y1 mode Initial stage 74.3% After heat treatment 70.8% Thus, the embodiment shown in FIG. 1 (claims 2, 4, 6 and 8) According to the corresponding embodiment), since the Pd-based three-way catalyst 11 is arranged immediately downstream of the HC adsorbent 10, the HC adsorbent 10 once adsorbs the unburned HC discharged during cold, and The unburned HC released from the HC adsorbent 10 due to the temperature rise of the above-mentioned Pd-based three-way catalyst 1 located immediately downstream
Since it is burnt and purified by 1, it is particularly effective in purifying almost all of the aroma component which accounts for about half of the components in the exhaust gas.
【００３９】また上述のＨＣ吸着剤１０とＰｄ系三元触
媒１１とを所定間隔（具体的には約１cm）を隔てて近接
配置したので、高温条件下におけるＨＣ吸着剤１０とＰ
ｄ系三元触媒１１との間の反応を防止することができ
て、両者（ＨＣ吸着剤１０およびＰｄ系三元触媒１１）
の耐熱性を向上させることができる効果がある。Further, since the above-mentioned HC adsorbent 10 and the Pd-based three-way catalyst 11 are placed close to each other with a predetermined distance (specifically, about 1 cm), the HC adsorbent 10 and P under high temperature conditions
A reaction with the d-based three-way catalyst 11 can be prevented, and both (HC adsorbent 10 and Pd-based three-way catalyst 11) can be prevented.
There is an effect that the heat resistance of can be improved.
【００４０】さらに、上述のＨＣ吸着剤１０とＰｄ系三
元触媒１１との組合せ構成体の上流にＰｔ−Ｒｈ系三元
触媒９を配置したので、このＰｔ−Ｒｈによりオレフィ
ン、パラフィンを浄化（図８のｂ参照）し、上述のＰｄ
でアロマ分を浄化（図８のｃ参照）するので、全てのＨ
Ｃ種を良好に浄化することができる効果がある。Further, since the Pt-Rh-based three-way catalyst 9 is arranged upstream of the combination structure of the HC adsorbent 10 and the Pd-based three-way catalyst 11, the Pt-Rh purifies olefins and paraffins ( 8b), and the above-mentioned Pd
Aroma is purified with (see c in Figure 8), so all H
There is an effect that the C type can be satisfactorily purified.
【００４１】加えて、ＨＣ吸着剤１０としてはアロマ分
の吸着効果が高いＦＡＵ型ゼオライトを用いたので、他
のＨＣ吸着剤すなわちＭＯＲ（モルデナイト）、ＦＥＲ
（フェリエライト）、ＣＨＡ（シャバサイト）を用いる
ものと比較してアロマ分の吸着効果の向上を図ることが
できる効果がある。In addition, since FAU type zeolite having a high aroma adsorption effect was used as the HC adsorbent 10, other HC adsorbents such as MOR (mordenite) and FER were used.
(Ferrierite) and CHA (chabazite) are effective compared with those using CHA (chabazite).
【００４２】また上述のＨＣ吸着剤１０としては細孔径
が７．４オングストローム以上のゼオライト（ＦＡＵ型
ゼオライト）を用いたので、ＨＣ種の約半分を占めるア
ロマ分のベンゼン環を良好にトラップすることができる
効果がある。Since the above-mentioned HC adsorbent 10 is a zeolite (FAU type zeolite) having a pore size of 7.4 angstroms or more, a benzene ring for aroma which accounts for about half of HC species should be well trapped. There is an effect that can be.
【００４３】さらに上記実施例で示す如くＰｔ−Ｒｈ系
三元触媒９をＨＣ吸着剤１０およびＰｄ系三元触媒１１
の上流に配置した場合には、前段のＰｔ−Ｒｈ系三元触
媒９を通過して温度低下させた排気ガスを中段のＨＣ吸
着剤１０に導くことにより、ＨＣ吸着効果の向上を図
り、さらに前段のＰｄ−Ｒｈ系三元触媒９がライトオフ
（活性化）することで未然ＨＣが燃焼して、前段のＰｔ
−Ｒｈ系三元触媒９の温度が上昇し、この温度が中段の
ＨＣ吸着剤１０を介して後段のＰｄ三元触媒１１に伝熱
することにより、後段のＰｄ系三元触媒１１が早くライ
トオフして、ＨＣ吸着剤１０から放出されはじめたＨ
Ｃ、特にアロマ分を早いタイミングで浄化することがで
き、ＨＣ浄化率、特にアロマ分の浄化率の大幅な向上を
図ることができる。Further, as shown in the above embodiment, the Pt-Rh-based three-way catalyst 9 is replaced with the HC adsorbent 10 and the Pd-based three-way catalyst 11.
In the case of arranging it upstream of the above, by introducing the exhaust gas whose temperature has passed through the Pt—Rh-based three-way catalyst 9 in the preceding stage to the HC adsorbent 10 in the intermediate stage, the HC adsorbing effect is further improved, Light-off (activation) of the Pd-Rh-based three-way catalyst 9 in the preceding stage causes HC to burn, which leads to Pt in the preceding stage.
-The temperature of the Rh-based three-way catalyst 9 rises, and this temperature is transferred to the Pd-based three-way catalyst 11 in the subsequent stage via the HC adsorbent 10 in the middle stage, so that the Pd-based three-way catalyst 11 in the subsequent stage is quickly written. H that is turned off and begins to be released from the HC adsorbent 10
C, especially the aroma component can be purified at an early timing, and the HC purification rate, especially the aroma component purification rate, can be greatly improved.
【００４４】なお、上述のＦＡＵ型ゼオライトの他に使
用可能なゼオライトは次の通りである。すなわち、β型
ゼオライト、ＭＡＺ型ゼオライト、などの細孔径が７．
４オングストローム以上のゼオライトが使用可能であ
る。Zeolites that can be used in addition to the above-mentioned FAU type zeolite are as follows. That is, the pore size of β-type zeolite, MAZ-type zeolite, etc. is 7.
Zeolites of 4 Å or more can be used.
【００４５】またＡＦＹ型ゼオライト、ＭＦＩ型ゼオラ
イトはアロマ分も吸収するが、オレフィン、パラフィン
も吸収することができ、よって最もアロマ分を吸収する
ことができるＦＡＵ型ゼオライトと混合すれば、アロマ
分、オレフィン、パラフィンをより一層完全に吸収でき
る。AFY-type zeolite and MFI-type zeolite also absorb aroma components, but they can also absorb olefins and paraffins, and therefore, when mixed with FAU-type zeolite which can absorb most aroma components, aroma components, Can absorb olefin and paraffin more completely.
【００４６】また、これらの各種ゼオライトを用いる場
合には、イオン交換、担持、含浸等で金属修飾が施され
ているものでもよく、イオン交換種、含浸種等にはＰｄ
（パラジウム）、Ｐｔ（白金）、Ｒｈ（ロジウム）、Ｃ
ｏ（コバルト）、Ｎｉ（ニッケル）、Ｆｅ（鉄）等が有
効であり、ゼオライトをモノリス（monolith、単体）に
ウオッシュコートして調製する際に用いられるバインダ
は水和アルミナ、シリカゾルなどを用いることができ
る。因に各金属修飾を行なったＦＡＵ型ゼオライト１ｇ
当りのトルエン（toluen、Ｃ6Ｈ5ＣＨ3、アロマ分の
うちの１つ）の吸着量を示すと、次の［表１］の通りで
ある。In the case of using these various zeolites, those modified with metal by ion exchange, loading, impregnation, etc. may be used.
(Palladium), Pt (Platinum), Rh (Rhodium), C
O (cobalt), Ni (nickel), Fe (iron), etc. are effective, and hydrated alumina, silica sol, etc. should be used as the binder when the zeolite is wash-coated on the monolith (monolith) You can 1 g of FAU type zeolite with each metal modification
The adsorbed amount of toluene (toluen, C6 H5 CH3 , and one of the aroma components) per unit is shown in the following [Table 1].
【００４７】[0047]
【表１】[Table 1]
【００４８】（第２実施例）図２は排気ガス浄化装置の
他の実施例を示し、この第２実施例においては、触媒コ
ンバータ１２のキャタリストケース６の上流側としての
前段に排気ガス中のＨＣを吸着するＨＣ吸着剤１３を配
置し、このＨＣ吸着剤１３に対して所定間隔（例えば約
１cm）を隔てた後段にアロマ分の浄化効果が高いＰｄ系
三元触媒１１を配置している。(Second Embodiment) FIG. 2 shows another embodiment of the exhaust gas purifying apparatus. In this second embodiment, the exhaust gas is provided in the upstream stage of the catalytic converter 12 upstream of the catalyst case 6. The HC adsorbent 13 for adsorbing HC is disposed, and the Pd-based three-way catalyst 11 having a high aroma purification effect is disposed downstream of the HC adsorbent 13 at a predetermined interval (for example, about 1 cm). There is.
【００４９】ここで上述のＨＣ吸着剤１３としてはその
細孔径が７．４オングストローム以上のＦＡＵ型ゼオラ
イトおよびＭＦＩ型ゼオライトを混合したものを用いて
いる。なお、図２において図１と同一の部分には同一番
号を付して、その詳しい説明を省略している。Here, as the HC adsorbent 13, a mixture of FAU type zeolite and MFI type zeolite having a pore diameter of 7.4 angstroms or more is used. In FIG. 2, the same parts as those in FIG. 1 are designated by the same reference numerals, and detailed description thereof will be omitted.
【００５０】このように構成した触媒コンバータ１２を
車両に取付け、ＦＴＰモード（ＣＶＳ４モードと同意で
米国標準走行モードのこと）中のＹ１モードを実車走行
テストし、Ｙ１モードの０〜６０秒までのＨＣ浄化率に
おける初期浄化率および９００℃、５０時間大気熱処理
後の浄化率を実測した結果、次の如き良好な浄化率を得
ることができた。The catalytic converter 12 thus constructed is attached to a vehicle, and the actual vehicle running test is conducted in the Y1 mode in the FTP mode (which is the US standard running mode which is synonymous with the CVS4 mode). As a result of actually measuring the initial purification rate in the HC purification rate and the purification rate after the atmospheric heat treatment at 900 ° C. for 50 hours, the following good purification rate could be obtained.
【００５１】Ｙ１モードの０〜６０秒までのＨＣ浄化率 初期………６３．４％ 熱処理後…５８．４％ このように図２に示す実施例（請求項２，４，８に対応
する実施例）によれば、ＨＣ吸着剤１３の直下流にＰｄ
系三元触媒１１を配置したので、冷間時に排出された未
燃ＨＣをＨＣ吸着剤１３で一旦吸着させ、ＨＣ吸着剤１
３の温度上昇により該ＨＣ吸着剤１３から放出された未
燃ＨＣを直下流に位置する上述のＰｄ系三元触媒１１で
燃焼浄化させるので、特に排気ガス中の成分の約半分を
占めるアロマ分を略全部浄化することができる効果があ
る。HC purification rate from 0 to 60 seconds in Y1 mode Initial stage ... 63.4% After heat treatment ... 58.4% Thus, the embodiment shown in FIG. 2 (corresponding to claims 2, 4 and 8) According to the embodiment, Pd is provided immediately downstream of the HC adsorbent 13.
Since the system three-way catalyst 11 is arranged, the unburned HC discharged during cold is once adsorbed by the HC adsorbent 13,
Since the unburned HC released from the HC adsorbent 13 due to the temperature rise of 3 is burnt and purified by the above-mentioned Pd-based three-way catalyst 11 located immediately downstream, the aroma component occupying about half of the components in the exhaust gas in particular. It has the effect of purifying almost all.
【００５２】また上述のＨＣ吸着剤１３とＰｄ系三元触
媒１１とを所定間隔（具体的には約１cm）を隔てて近接
配置したので、高温条件下におけるＨＣ吸着剤１３とＰ
ｄ系三元触媒１１との間の反応を防止することができ
て、両者（ＨＣ吸着剤１３およびＰｄ系三元触媒１１）
の耐熱性を向上させることができる効果がある。Further, since the above-mentioned HC adsorbent 13 and the Pd-based three-way catalyst 11 are placed close to each other with a predetermined space (specifically, about 1 cm), the HC adsorbent 13 and P under high temperature conditions are arranged.
A reaction with the d-based three-way catalyst 11 can be prevented, and both (HC adsorbent 13 and Pd-based three-way catalyst 11) can be prevented.
There is an effect that the heat resistance of can be improved.
【００５３】加えて、ＨＣ吸着剤１３としてはアロマ分
の吸着効果が高いゼオライトを用いたので、他のＨＣ吸
着剤すなわちＭＯＲ（モルデナイト）、ＦＥＲ（フェリ
エライト）、ＣＨＡ（シャバサイト）を用いるものと比
較してアロマ分の吸着効果の向上を図ることができる効
果がある。In addition, since a zeolite having a high aroma adsorption effect is used as the HC adsorbent 13, another HC adsorbent, that is, MOR (mordenite), FER (ferrierite), CHA (chabazite) is used. There is an effect that the absorption effect of the aroma component can be improved as compared with.
【００５４】（第３実施例）図３は排気ガス浄化装置の
さらに他の実施例を示し、この第３実施例においては、
排気ガス中のＨＣを吸着するＨＣ吸着剤粒子の周囲がＰ
ｄ（パラジウム）に対して反応しにくい耐火性多孔質体
で囲繞された囲繞構造のＨＣ吸着剤粒子と、Ｐｄ（パラ
ジウム）を主成分とする三元触媒とが複合された複合触
媒１５を設け、この複合触媒１５を触媒コンバータ１４
のキャタリストケース６の下流側としての後段に配置
し、キャタリストケース６の上流側としての前段にはＰ
ｔ−Ｒｈ系三元触媒９を配置している。なお、図３にお
いて全図と同一の部分には同一番号を付して、その詳し
い説明を省略している。(Third Embodiment) FIG. 3 shows still another embodiment of the exhaust gas purifying apparatus. In this third embodiment,
Around the HC adsorbent particles that adsorb HC in the exhaust gas, P
Provided is a composite catalyst 15 in which HC adsorbent particles having a surrounding structure surrounded by a refractory porous body that does not easily react with d (palladium) and a three-way catalyst containing Pd (palladium) as a main component are combined. , The composite catalyst 15 into the catalytic converter 14
Of the catalyst case 6 at the downstream side of the catalyst case 6, and at the upstream side of the catalyst case 6 at the upstream side of P.
A t-Rh-based three-way catalyst 9 is arranged. Note that, in FIG. 3, the same parts as those in all the drawings are denoted by the same reference numerals, and detailed description thereof is omitted.
【００５５】この実施例においては、上述のＨＣ吸着剤
粒子としてはゼオライト粒子を用い、Ｐｄ（パラジウ
ム）に対して反応しにくい耐火性多孔質体としてはＡｌ
2Ｏ3（アルミナ）、ＳｉＯ2（silica、シリカ）、Ｃ
ｅＯ2（cerium oxide、酸化セリウム、いわゆるセリ
ア）のうちのアルミナを用いる。In this embodiment, zeolite particles are used as the above HC adsorbent particles, and Al is used as the refractory porous material that does not easily react with Pd (palladium).
2 O3 (alumina), SiO2 (silica, silica), C
Alumina of eO2 (cerium oxide, cerium oxide, so-called ceria) is used.
【００５６】ここで上述の複合触媒１５の製造方法につ
いて述べると、まずゼオライト６０ｇ（約１モル）に対
して硝酸アルミニウムおよび水和物１８７ｇ（約０．５
モル）（但し、硝酸アルミニウム：水和物の混合比率は
１モル：９モルとする）を混合し、この混合物に対して
イオン交換水２００mlを加えて、撹拌し、懸濁液（いわ
ゆるスラリー）を得る。The method for producing the above-mentioned composite catalyst 15 will be described. First, 60 g of zeolite (about 1 mol) and 187 g of aluminum hydrate and about 0.5 g of hydrate (about 0.5 mol).
Mol) (however, the mixing ratio of aluminum nitrate: hydrate is 1 mol: 9 mol), and 200 ml of ion-exchanged water is added to this mixture and stirred to obtain a suspension (so-called slurry). To get
【００５７】次に、上述の懸濁液を１６０℃にてスプレ
ードライ手段で乾燥させた後に、６００℃で焼成する
と、ゼオライトの周囲がアルミナ（Ａｌ2Ｏ3）で囲繞
されたＨＣ吸着剤を得ることができる。次に上述のＨＣ
吸着剤にＰｄ（パラジウム）を５〜１０ｇ／リットル、
ＣｅＯ2（セリア）を４０〜１００ｇ／リットルを含浸
担持させると、上記複合触媒１５を得ることができる。
上述の含浸担持方法としては、硝酸パラジウム、硝酸セ
リウムの溶液をＨＣ吸着剤に含浸させ、３００℃で２時
間焼成した。Next, the above suspension was dried at 160 ° C. by a spray drying means and then calcined at 600 ° C. to obtain an HC adsorbent in which the periphery of the zeolite was surrounded by alumina (Al2 O3 ). Obtainable. Next, the above-mentioned HC
5 to 10 g / liter of Pd (palladium) as an adsorbent,
The composite catalyst 15 can be obtained by impregnating and carrying 40 to 100 g / liter of CeO2 (ceria).
As the above-mentioned impregnating and supporting method, a solution of palladium nitrate and cerium nitrate was impregnated into the HC adsorbent and calcined at 300 ° C. for 2 hours.
【００５８】上述の製造方法に用いるゼオライトはＭＦ
Ｉ型、ＦＡＵ型などのゼオライトである。また加えるア
ルミニウム源は水溶性であり、焼成後にアルミニウムの
対イオンが脱離するもの（例えば酢酸アルミニウムな
ど）を用いる。なお炭酸アルミニウムなどの非水溶性の
アルミニウム源を酸で溶解させて用いることも可能であ
る。The zeolite used in the above manufacturing method is MF
These are zeolites such as I type and FAU type. The aluminum source to be added is water-soluble, and a counter ion of aluminum is desorbed after firing (eg, aluminum acetate). It is also possible to use a water-insoluble aluminum source such as aluminum carbonate dissolved in an acid.
【００５９】さらに上述のアルミニウム源の量はゼオラ
イト１モルに対して０．０５モル〜０．５モルの範囲
（図４、図５参照）が望ましい。すなわちアルミニウム
源の量が上記範囲より過少な場合には効果がなくなり、
上記範囲より過多の時には吸着能が低下する。Further, the amount of the above-mentioned aluminum source is preferably in the range of 0.05 mol to 0.5 mol per 1 mol of zeolite (see FIGS. 4 and 5). That is, when the amount of the aluminum source is less than the above range, the effect is lost,
If the amount exceeds the above range, the adsorptivity will decrease.
【００６０】上述のイオン交換水の量はゼオライト１モ
ルに対して１００〜３００mlが望ましい。すなわちイオ
ン交換水の量が上記範囲より過少な時は懸濁液の粘度が
高くなって、乾燥が困難となり、上記範囲より過多の時
には乾燥に長時間がかかる。The amount of the above ion-exchanged water is preferably 100 to 300 ml per mol of zeolite. That is, when the amount of ion-exchanged water is less than the above range, the viscosity of the suspension becomes high and drying becomes difficult, and when it is more than the above range, it takes a long time to dry.
【００６１】また上述のスプレードライ手段による乾燥
温度は１５０〜２００℃が望ましい。すなわち乾燥温度
が上記範囲より低い場合には乾燥不能となり、上記範囲
より高い場合には硝酸塩等が分解を始めるので危険であ
る。The drying temperature by the above spray drying means is preferably 150 to 200 ° C. That is, when the drying temperature is lower than the above range, it becomes impossible to dry, and when the drying temperature is higher than the above range, nitrates and the like start to decompose, which is dangerous.
【００６２】さらに上述の焼成温度（熱処理温度）は５
００〜６００℃が望ましい。すなわち焼成温度が上記範
囲より低い場合にはアルミニウム塩が分解せず、上記範
囲より高い場合には生成したアルミナがシンタリング
（sintering 、塊状になること）を起こし、貴金属とし
てのＰｄ（パラジウム）含浸後の活性が向上しない。Further, the above-mentioned firing temperature (heat treatment temperature) is 5
The temperature is preferably 00 to 600 ° C. That is, when the firing temperature is lower than the above range, the aluminum salt is not decomposed, and when the firing temperature is higher than the above range, the produced alumina causes sintering and becomes impregnated with Pd (palladium) as a noble metal. Later activity does not improve.
【００６３】上述の如く調製された複合触媒１５のアル
ミニウム量に対するトルエン吸着量を図４にアルミニウ
ム量に対する熱処理後ライトオフ性能を図５に、熱処理
温度に対するライトオフ性能を図６にそれぞれ示す。な
お、図５、図６中における（Ｔ５０）はＨＣを５０％浄
化する温度のことである。The toluene adsorption amount with respect to the aluminum amount of the composite catalyst 15 prepared as described above is shown in FIG. 4, the light-off performance after heat treatment with respect to the aluminum amount is shown in FIG. 5, and the light-off performance with respect to the heat treatment temperature is shown in FIG. In addition, (T50) in FIGS. 5 and 6 is a temperature at which HC is purified by 50%.
【００６４】また上記の如く構成された第３実施例の触
媒コンバータ１４（図３参照）と、ゼオライトの周りを
アルミナで囲繞してない複合触媒１７を有する比較例の
触媒コンバータ１６（図７参照）とを車両に取付けて、
ＦＴＰモード（ＣＶＳ４モードと同意で米国標準走行モ
ードのこと）中のＹ１モードをそれぞれ実車走行テスト
し、Ｙ１モードの０〜６０秒までのＨＣ浄化率における
初期浄化率（フレッシュ）および８００℃、５０時間大
気熱処理後の浄化率を実測した結果を次の［表２］に示
す。Further, the catalytic converter 14 of the third embodiment (see FIG. 3) constructed as described above, and the catalytic converter 16 of the comparative example having the composite catalyst 17 in which zeolite is not surrounded by alumina (see FIG. 7) ) And are attached to the vehicle,
Each of the Y1 modes in the FTP mode (which is the same as the CVS4 mode, which is the US standard driving mode) was tested by actual vehicles, and the initial purification rate (fresh) and the 800 ° C., 50 ° C. of the HC purification rate from 0 to 60 seconds in the Y1 mode were tested. The following table 2 shows the results of the actual measurement of the purification rate after the heat treatment in air for 1 hour.
【００６５】[0065]
【表２】[Table 2]
【００６６】上述の［表２］からも明らかなように、第
３実施例のものは比較例に対して初期浄化率および熱処
理後浄化率の何れにおいても優れている。As is clear from the above [Table 2], the third example is superior to the comparative example in both the initial purification rate and the post-heat treatment purification rate.
【００６７】このように図３に示す第３実施例（請求項
３，４，５，７，８に対応する実施例）によれば、周囲
がＰｄ（パラジウム）に対して反応しにくい耐火性多孔
質体で囲繞された囲繞構造のＨＣ吸着剤粒子と、アロマ
分浄化効果の高いＰｄ（パラジウム）を主成分とする三
元触媒とが複合された複合触媒１５をエンジンの排気系
に介設したので、冷間時に排出された未然ＨＣをＨＣ吸
着剤で一旦吸着させ、ＨＣ吸着剤の温度上昇によりＨＣ
吸着剤から放出された未然ＨＣを上述のＰｄを主成分と
する三元触媒（ＨＣ吸着剤に対して極近接位置に存在す
るＰｄ）で燃焼浄化させ、特に排気ガス中の成分の約半
分を占めるアロマ分を良好に浄化することができ、かつ
Ｐｄに対して反応しにくい耐火性多孔質体でＨＣ吸着剤
粒子を囲繞することで、ＨＣ吸着剤がＰｄと反応するの
を防止して、ＨＣ吸着剤およびＰｄの熱劣化を防止しつ
つ、ＨＣ吸着剤とＰｄとの複合化により初期浄化性能の
向上を図ることができる効果がある。As described above, according to the third embodiment shown in FIG. 3 (the embodiment corresponding to claims 3, 4, 5, 7, and 8), the fire resistance of the surroundings is difficult to react with Pd (palladium). A composite catalyst 15 in which an HC adsorbent particle having a surrounding structure surrounded by a porous body and a three-way catalyst containing Pd (palladium) as a main component having a high aroma-removing effect are combined is provided in an engine exhaust system. As a result, the HC that had been discharged during cold conditions was once adsorbed by the HC adsorbent and the temperature of the HC adsorbent rose
The HC released from the adsorbent is burned and purified by the above-mentioned three-way catalyst containing Pd as a main component (Pd existing in a close proximity to the HC adsorbent), and in particular, about half of the components in the exhaust gas are removed. The HC adsorbent is prevented from reacting with Pd by surrounding the HC adsorbent particles with a refractory porous material that can purify the aroma occupying well and that is difficult to react with Pd. It is possible to improve the initial purification performance by combining the HC adsorbent and Pd while preventing thermal deterioration of the HC adsorbent and Pd.
【００６８】また、ＨＣ吸着剤粒子を、ＦＡＵ型ゼオラ
イト、β型ゼオライト、ＭＡＺ型ゼオライト、ＡＦＹ型
ゼオライト、ＭＦＩ型ゼオライトのうちの少なくとも１
つに設定したので、他のＨＣ吸着剤を用いるものと比較
してアロマ分の吸着効果の向上を図ることができる効果
がある。The HC adsorbent particles are at least one of FAU type zeolite, β type zeolite, MAZ type zeolite, AFY type zeolite and MFI type zeolite.
Since it is set to one, there is an effect that the aroma component adsorption effect can be improved as compared with the case where another HC adsorbent is used.
【００６９】さらに、Ｐｄに対して反応しにくい耐火性
多孔質体を、アルミナ、シリカ、酸化セリウム（いわゆ
るセリア）のうちの少なくとも１つに設定したので、Ｈ
Ｃ吸着剤粒子とＰｄとが反応するのを良好に防止して、
ＨＣ吸着剤およびＰｄの熱劣化を確実に防止することが
できる効果がある。Further, since the refractory porous body which is hard to react with Pd is set to at least one of alumina, silica and cerium oxide (so-called ceria), H
Satisfactorily preventing the reaction between the C adsorbent particles and Pd,
There is an effect that the heat deterioration of the HC adsorbent and Pd can be surely prevented.
【００７０】加えて、上述の複合触媒の上流および下流
の少なくとも一方にＰｔ−Ｒｈ（白金−ロジウム）を主
成分とする三元触媒を配置したので、複合触媒内のＰｄ
によりアロマ分を浄化し、Ｐｔ−Ｒｈによりオレフィ
ン、パラィンを浄化して、全てのＨＣ種を良好に浄化す
ることができる効果がある。In addition, since the three-way catalyst containing Pt-Rh (platinum-rhodium) as a main component is arranged at least one of the upstream side and the downstream side of the composite catalyst, Pd in the composite catalyst is
Has the effect of purifying aroma components, and purifying olefins and lines with Pt-Rh, and purifying all HC species satisfactorily.
【００７１】また、ＨＣ吸着剤として細孔径が７．４オ
ングストローム以上のゼオライトすなわちＦＡＵ型ゼオ
ライト、β型ゼオライト、ＭＡＺ型ゼオライトを用いた
ので、ＨＣ種の約半分を占めるアロマ分のベンゼン環を
良好にトラップすることができる効果がある。As the HC adsorbent, zeolite having a pore size of 7.4 angstroms or more, that is, FAU type zeolite, β type zeolite, and MAZ type zeolite was used. There is an effect that can be trapped in.
【００７２】この発明の構成と、上述の実施例との対応
において、この発明のＰｄ（パラジウム）を成分に有す
る三元触媒は、実施例のＰｄ系三元触媒１１に対応し、
以下同様に、Ｐｔ−Ｒｈ（白金・ロジウム）を主成分と
する三元触媒は、Ｐｄ−Ｒｈ系三元触媒９に対応する
も、この発明は、上述の実施例の構成のみに限定される
ものではない。In the correspondence between the constitution of the present invention and the above-mentioned embodiment, the three-way catalyst having Pd (palladium) as a component of the present invention corresponds to the Pd-based three-way catalyst 11 of the embodiment,
Similarly, a three-way catalyst containing Pt-Rh (platinum / rhodium) as a main component corresponds to the Pd-Rh-based three-way catalyst 9, but the present invention is limited to the configurations of the above-described embodiments. Not a thing.
【００７３】例えば、上述のＰｄに対して反応しにくい
耐火性多孔質体すなわちアルミナ、シリカ、酸化セリウ
ムに対して、Ｌａ（ランタン）やＢａ（バリウム）など
を添加して、耐熱性の向上を図ってもよく、Ｐｄ（パラ
ジウム）に対してＰｔ（白金）、Ｒｈ（ロジウム）を１
〜４０％添加して、耐久性の向上を図ってもよい。For example, La (lanthanum) or Ba (barium) is added to the refractory porous material which is difficult to react with Pd, that is, alumina, silica and cerium oxide, to improve heat resistance. Pt (platinum) and Rh (rhodium) can be added to 1 for Pd (palladium).
-40% may be added to improve durability.
【図１】本発明の排気ガス浄化装置を示す断面図。FIG. 1 is a cross-sectional view showing an exhaust gas purification device of the present invention.
【図２】本発明の排気ガス浄化装置の他の実施例を示す
断面図。FIG. 2 is a sectional view showing another embodiment of the exhaust gas purifying apparatus of the present invention.
【図３】本発明の排気ガス浄化装置のさらに他の実施例
を示す断面図。FIG. 3 is a sectional view showing still another embodiment of the exhaust gas purifying apparatus of the present invention.
【図４】アルミニウム量に対するトルエン吸着量を示す
特性図。FIG. 4 is a characteristic diagram showing the amount of toluene adsorbed on the amount of aluminum.
【図５】アルミニウム量に対する熱処理後ライトオフ性
能を示す特性図。FIG. 5 is a characteristic diagram showing the light-off performance after heat treatment with respect to the amount of aluminum.
【図６】熱処理温度に対するライトオフ性能を示す特性
図。FIG. 6 is a characteristic diagram showing light-off performance with respect to heat treatment temperature.
【図７】比較例の排気ガス浄化装置を示す断面図。FIG. 7 is a cross-sectional view showing an exhaust gas purification device of a comparative example.
【図８】生ガスの組成とＰｔ−Ｒｈ触媒およびＰｄ触媒
通過後の排気ガスの組成とを比較して示す説明図。FIG. 8 is an explanatory view showing a composition of raw gas and a composition of exhaust gas after passing through a Pt-Rh catalyst and a Pd catalyst, for comparison.
９…Ｐｔ−Ｒｈ系三元触媒 １０…ＨＣ吸着剤 １１…Ｐｄ系三元触媒 １３…ＨＣ吸着剤 １５…複合触媒 9 ... Pt-Rh-based three-way catalyst 10 ... HC adsorbent 11 ... Pd-based three-way catalyst 13 ... HC adsorbent 15 ... Composite catalyst
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｄ 53/94 Ｆ０１Ｎ 3/08 ＺＡＢ Ａ (72)発明者 重津 雅彦 広島県安芸郡府中町新地３番１号 マツダ 株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl.6 Identification number Internal reference number FI Technical display location B01D 53/94 F01N 3/08 ZAB A (72) Inventor Masahiko Shigetu Shinchi Fuchu-cho, Aki-gun, Hiroshima Prefecture No. 3 in Mazda Motor Corporation
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15167694AJP3586890B2 (en) | 1994-06-08 | 1994-06-08 | Exhaust gas purification device |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15167694AJP3586890B2 (en) | 1994-06-08 | 1994-06-08 | Exhaust gas purification device |
| Publication Number | Publication Date |
|---|---|
| JPH07332073Atrue JPH07332073A (en) | 1995-12-19 |
| JP3586890B2 JP3586890B2 (en) | 2004-11-10 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15167694AExpired - Fee RelatedJP3586890B2 (en) | 1994-06-08 | 1994-06-08 | Exhaust gas purification device |
| Country | Link |
|---|---|
| JP (1) | JP3586890B2 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6191061B1 (en) | 1997-04-23 | 2001-02-20 | Toyota Jidosha Kabushiki Kaisha | Method of purifying exhaust gas and catalyst for purifying exhaust gas |
| JP2002089251A (en)* | 2000-09-19 | 2002-03-27 | Toyota Motor Corp | Exhaust gas purification device for internal combustion engine |
| US6447735B1 (en) | 1998-04-30 | 2002-09-10 | Nissan Motor Co., Ltd. | Exhaust purifier and manufacturing method of same |
| JP2002336632A (en)* | 1997-05-08 | 2002-11-26 | Takasago Thermal Eng Co Ltd | Filter and cleaning equipment |
| KR20030096889A (en)* | 2002-06-18 | 2003-12-31 | 현대자동차주식회사 | Catalyst for prevention of poison for automobile |
| US6729129B2 (en) | 2001-10-25 | 2004-05-04 | Nissan Motor Co., Ltd. | Exhaust gas purifying system |
| KR100440025B1 (en)* | 2001-12-10 | 2004-07-14 | 현대자동차주식회사 | Catalyst apparatus to reduce hydrocarbon |
| KR100482872B1 (en)* | 2001-12-14 | 2005-04-14 | 현대자동차주식회사 | Apparatus for purifying |
| JP2011525579A (en)* | 2008-02-05 | 2011-09-22 | ビー・エイ・エス・エフ、コーポレーション | Gasoline engine exhaust gas treatment system with particulate trap |
| WO2024048578A1 (en)* | 2022-09-01 | 2024-03-07 | 日本碍子株式会社 | Acidic-gas adsorption device |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6191061B1 (en) | 1997-04-23 | 2001-02-20 | Toyota Jidosha Kabushiki Kaisha | Method of purifying exhaust gas and catalyst for purifying exhaust gas |
| JP2002336632A (en)* | 1997-05-08 | 2002-11-26 | Takasago Thermal Eng Co Ltd | Filter and cleaning equipment |
| US6447735B1 (en) | 1998-04-30 | 2002-09-10 | Nissan Motor Co., Ltd. | Exhaust purifier and manufacturing method of same |
| JP2002089251A (en)* | 2000-09-19 | 2002-03-27 | Toyota Motor Corp | Exhaust gas purification device for internal combustion engine |
| US6729129B2 (en) | 2001-10-25 | 2004-05-04 | Nissan Motor Co., Ltd. | Exhaust gas purifying system |
| KR100440025B1 (en)* | 2001-12-10 | 2004-07-14 | 현대자동차주식회사 | Catalyst apparatus to reduce hydrocarbon |
| KR100482872B1 (en)* | 2001-12-14 | 2005-04-14 | 현대자동차주식회사 | Apparatus for purifying |
| KR20030096889A (en)* | 2002-06-18 | 2003-12-31 | 현대자동차주식회사 | Catalyst for prevention of poison for automobile |
| JP2011525579A (en)* | 2008-02-05 | 2011-09-22 | ビー・エイ・エス・エフ、コーポレーション | Gasoline engine exhaust gas treatment system with particulate trap |
| WO2024048578A1 (en)* | 2022-09-01 | 2024-03-07 | 日本碍子株式会社 | Acidic-gas adsorption device |
| Publication number | Publication date |
|---|---|
| JP3586890B2 (en) | 2004-11-10 |
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