JPH07155613A - Exhaust gas purifying catalyst - Google Patents
Exhaust gas purifying catalystInfo
- Publication number
- JPH07155613A JPH07155613A JP5304127A JP30412793A JPH07155613A JP H07155613 A JPH07155613 A JP H07155613A JP 5304127 A JP5304127 A JP 5304127A JP 30412793 A JP30412793 A JP 30412793A JP H07155613 A JPH07155613 A JP H07155613A
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- powder
- mfi
- weight
- zeolite
- Prior art date
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、内燃機関の排ガス浄化
装置に使用される炭化水素（ＨＣ）を吸着して浄化する
排気浄化用触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas purification catalyst for adsorbing and purifying hydrocarbons (HC) used in an exhaust gas purification apparatus for an internal combustion engine.
【０００２】[0002]
【従来の技術】従来ＨＣを吸着して浄化する排気浄化用
触媒としては特開平２−１３５１２６号公報に開示され
ているようなものがある。2. Description of the Related Art As a conventional exhaust gas purification catalyst for adsorbing and purifying HC, there is one disclosed in JP-A-2-135126.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記公
報において、炭化水素吸着材としてモルデナイトおよび
Ｙ型ゼオライトを用いて炭化水素を吸着除去している
が、モルデナイトおよびＹ型ゼオライトは、細孔径が大
きく、炭素数の多い芳香族およびその他の炭化水素は吸
着するが、炭素数の少ない（Ｃ2 〜Ｃ3 ）炭化水素は吸
着されず、排出されてしまう。さらに、コールドスター
ト時には炭化水素と水との競争吸着になるため、Ｓｉ／
２Ａｌ比が低いモルデナイト等では、炭化水素を充分吸
着できない。However, in the above publication, hydrocarbons are adsorbed and removed by using mordenite and Y-type zeolite as the hydrocarbon adsorbent. However, mordenite and Y-type zeolite have large pore diameters, Although aromatics and other hydrocarbons having a large number of carbons are adsorbed, hydrocarbons having a small number of carbons (C 2 to C 3 ) are not adsorbed and are discharged. Furthermore, since it is a competitive adsorption between hydrocarbons and water during cold start, Si /
For example, mordenite having a low 2Al ratio cannot sufficiently adsorb hydrocarbons.
【０００４】[0004]
【課題を解決するための手段】本発明は、このような従
来の問題点に着目してなされたもので、ＭＦＩ型ゼオラ
イト（Ｓｉ／２Ａｌ＝１０〜４０）に金属を担持するこ
とを特徴とし、このことによって炭素数の少ない炭化水
素を化学吸着することができるようになった。Ｓｉ／２
Ａｌが４０よりも大きい場合にはＭＦＩ型ゼオライト中
の酸点が少なく、金属の交換率が小さい。一方Ｓｉ／２
Ａｌが１０未満のＭＦＩ型ゼオライトは、合成する際に
複生成物（モルデナイト）が生成するため一般的に存在
は知られていない。また、ハイシリカのゼオライトを併
用することによって、水の影響を受けにくく炭素数の多
い炭化水素を有効に吸着することが可能になった。SUMMARY OF THE INVENTION The present invention has been made in view of such conventional problems, and is characterized in that a metal is supported on MFI type zeolite (Si / 2Al = 10-40). As a result, it becomes possible to chemisorb hydrocarbons having a small number of carbon atoms. Si / 2
When Al is larger than 40, the number of acid sites in the MFI zeolite is small and the metal exchange rate is small. On the other hand, Si / 2
MFI-type zeolite having an Al content of less than 10 is not generally known to exist because a multi-product (mordenite) is produced during synthesis. Further, by using the high silica zeolite in combination, it becomes possible to effectively adsorb hydrocarbons having a large number of carbons which are hardly affected by water.
【０００５】このゼオライトの担持方法は、２種類以上
のゼオライトをブレンドしても、多層構造にしても、上
下流に配置してもよい。また、このゼオライトの担持比
については、排ガス中の成分比および基材中の金属の担
持量の影響もあるため、金属を担持したＭＦＩ型ゼオラ
イト（Ｓｉ／２Ａｌ＝１０〜４０）とＨ型ＭＦＩ型ゼオ
ライト（Ｓｉ／２Ａｌ＝５０〜２０００）、モルデナイ
ト（Ｓｉ／２Ａｌ＝３０〜２０００）、ＵＳＹ型ゼオラ
イト（Ｓｉ／２Ａｌ＝１０〜３００）およびβ−ゼオラ
イト（Ｓｉ／２Ａｌ＝４０〜２０００）との比率は、
１：３〜３：１の範囲で用いることが必要である。また
金属を担持したＭＦＩ型ゼオライトと併用するＨ型ＭＦ
Ｉ型ゼオライト（Ｓｉ／２Ａｌ＝５０〜２０００）、モ
ルデナイト（Ｓｉ／２Ａｌ＝３０〜２０００）、ＵＳＹ
型ゼオライト（Ｓｉ／２Ａｌ＝１０〜３００）およびβ
−ゼオライト（Ｓｉ／２Ａｌ＝４０〜２０００）にも、
金属を１種類以上担持してもよい。金属はイオン交換、
含浸担持法、蒸発乾固法により担持させることができ
る。担持する金属の量はゼオライトの重量に対して、
０．５〜１５％が好ましく、１５％以上担持するとゼオ
ライトの細孔閉塞の原因となる。また、０．５％以下の
担持量では効果がえられない。This zeolite loading method may be a blend of two or more kinds of zeolites, a multilayer structure, or upstream and downstream arrangements. In addition, since the loading ratio of this zeolite is influenced by the component ratio in the exhaust gas and the loading amount of the metal in the base material, the MFI type zeolite (Si / 2Al = 10-40) loaded with the metal and the H type MFI are supported. Type zeolite (Si / 2Al = 50 to 2000), mordenite (Si / 2Al = 30 to 2000), USY type zeolite (Si / 2Al = 10 to 300) and β-zeolite (Si / 2Al = 40 to 2000) The ratio is
It is necessary to use in the range of 1: 3 to 3: 1. H-type MF used in combination with MFI-type zeolite carrying metal
I-type zeolite (Si / 2Al = 50-2000), mordenite (Si / 2Al = 30-2000), USY
Type zeolite (Si / 2Al = 10-300) and β
-For zeolite (Si / 2Al = 40-2000),
One or more metals may be supported. Metal is ion exchanged,
It can be supported by the impregnation supporting method or the evaporation dryness method. The amount of supported metal is based on the weight of zeolite,
0.5 to 15% is preferable, and if 15% or more is supported, it will cause pore blockage of zeolite. In addition, the effect cannot be obtained with a loading amount of 0.5% or less.
【０００６】[0006]
【作用】次に作用を説明する。内燃機関の排ガスを浄化
するために、排気ガス浄化用触媒が現在使用されている
が、排気ガスの有害成分のうちの炭化水素の排気浄化能
は排気ガスの温度の影響を強く受け、３００℃以上の温
度にならないと貴金属触媒により浄化されないため、コ
ールドスタート時には多量の炭化水素が排出されてしま
う。このような、コールドスタート時に排出される炭化
水素を除去するためには炭化水素を吸着する吸着材を用
いることが必要となる。また、ゼオライト類は、均一な
細孔を有する結晶性の多孔性物質であり、混合物中から
その細孔入口を通過できる大きさの分子だけを選択的
に、細孔内に吸着する特性を持ち、ゼオライトの種類に
よって有効細孔径は異なる。この特性により、コールド
スタート時に排出される炭化水素を吸着し、触媒反応が
発生しない温度領域での排ガス中のＨＣを低減する。ま
た、自動車の排ガス中には多種の炭化水素が排出され
る。本発明者等はハイシリカのモルデナイト（Ｓｉ／２
Ａｌ＝３０〜２０００）、ＵＳＹ型ゼオライト（Ｓｉ／
２Ａｌ＝１０〜３００）、β−ゼオライト（Ｓｉ／２Ａ
ｌ＝４０〜２０００）、ＭＦＩ型ゼオライト（Ｓｉ／２
Ａｌ＝５０〜２０００）にＰｄまたはＡｇもしくは両方
を担持したＭＦＩ型ゼオライト（Ｓｉ／２Ａｌ＝１０〜
４０）を併用することにより、炭素数の多い芳香族また
はその他の分子径の大きい炭化水素に加え、今までの吸
着されなかった炭素数の少ない炭化水素（Ｃ2 〜Ｃ3 ）
を化学吸着することを可能にし、炭化水素吸着能が向上
することをみいだした。また、ハイシリカのゼオライト
を用いることにより、水の影響を受け難くなり、さらに
吸着能が向上した。なお、上記のハイシリカのモルデナ
イト、ＵＳＹ型ゼオライト、β−ゼオライトおよびＭＦ
Ｉ型ゼオライトに関して、Ｓｉ／２Ａｌの値が上記の範
囲より低い場合には水の吸着が多くなり、金属を加えな
いと炭化水素を吸着しなくなってしまう。またこの値が
上記の範囲より高い場合には、炭化水素の吸着量が減少
してしまう。[Operation] Next, the operation will be described. Exhaust gas purifying catalysts are currently used to purify exhaust gas from internal combustion engines, but the exhaust gas purifying ability of hydrocarbons among harmful components of exhaust gas is strongly affected by the temperature of the exhaust gas and is 300 ° C. If it does not reach the above temperature, it will not be purified by the precious metal catalyst, so a large amount of hydrocarbons will be emitted at the cold start. In order to remove such hydrocarbons discharged at cold start, it is necessary to use an adsorbent that adsorbs hydrocarbons. Zeolites are crystalline porous substances having uniform pores, and have the property of selectively adsorbing into the pores only molecules that are large enough to pass through the pore inlet from the mixture. , The effective pore size depends on the type of zeolite. Due to this characteristic, hydrocarbons discharged at cold start are adsorbed, and HC in exhaust gas in a temperature range where a catalytic reaction does not occur is reduced. In addition, various kinds of hydrocarbons are emitted into the exhaust gas of automobiles. The present inventors have found that high silica mordenite (Si / 2
Al = 30 to 2000), USY type zeolite (Si /
2Al = 10-300), β-zeolite (Si / 2A
1 = 40 to 2000), MFI type zeolite (Si / 2
MFI type zeolite (Si / 2Al = 10 to Al = 50 to 2000) carrying Pd or Ag or both.
40) together with aromatic hydrocarbons having a large number of carbon atoms or other hydrocarbons having a large molecular diameter, and hydrocarbons having a small number of carbon atoms (C 2 to C 3 ) which have not been adsorbed until now.
It has been found that it makes it possible to chemically adsorb, and that the hydrocarbon adsorption capacity is improved. In addition, the use of high silica zeolite made it less likely to be affected by water and further improved the adsorption capacity. The high silica mordenite, USY type zeolite, β-zeolite and MF
Regarding the I-type zeolite, when the value of Si / 2Al is lower than the above range, the amount of water adsorbed is large, and the hydrocarbon is not adsorbed unless a metal is added. If this value is higher than the above range, the amount of adsorbed hydrocarbon will decrease.
【０００７】[0007]
【実施例】以下本発明を実施例、比較例および試験例に
より説明する。なお、すべての実施例および比較例を通
じて、「部」は特記しない限り「重量部」を示す。 実施例１ 第１にＰｄをイオン交換したＭＦＩ型ゼオライト（以下
Ｐｄ／ＭＦＩと記す）（金属担持量１重量％、Ｓｉ／２
Ａｌ＝３０）５０部、ＵＳＹ型ゼオライト（以下ＵＳＹ
と記す、Ｓｉ／２Ａｌ＝１２）５０部、シリカゾル（固
形分２０％）６５部および水６５部を磁性ポットに仕込
み、振動ミル装置で４０分間もしくは、ユニバーサルボ
ールミル装置で６．５時間混合粉砕して、ウォッシュコ
ートスラリーを製造した。コーディライト製モノリス担
体を吸引コート法で吸水処理した後、前記で製造したス
ラリーを担体断面全体に均一に投入し吸引コート法で余
分なスラリーを除去した。その後、乾燥を行い４００℃
で約１時間仮焼成した。EXAMPLES The present invention will be described below with reference to Examples, Comparative Examples and Test Examples. Throughout all of the examples and comparative examples, "part" means "part by weight" unless otherwise specified. Example 1 First, an MFI-type zeolite in which Pd was ion-exchanged (hereinafter referred to as Pd / MFI) (metal loading amount: 1% by weight, Si / 2)
Al = 30) 50 parts, USY type zeolite (hereinafter USY
, 50 parts of Si / 2Al = 12), 65 parts of silica sol (solid content 20%) and 65 parts of water were charged in a magnetic pot, and mixed and ground for 40 minutes with a vibration mill device or for 6.5 hours with a universal ball mill device. To produce a washcoat slurry. After the cordierite monolith carrier was subjected to water absorption treatment by a suction coating method, the slurry produced above was uniformly added to the entire cross section of the carrier and the excess slurry was removed by a suction coating method. Then, dry it at 400 ℃
It was calcined for about 1 hour.
【０００８】これにより、Ｐｄ／ＭＦＩとＵＳＹ型ゼオ
ライトとの混合ゼオライトが約９０ｇ／Ｌコート量で担
体にコートされた。上記のウォッシュコート、乾燥およ
び焼成をさらに２回繰り返して合計約２００ｇ／Ｌの構
造の異なる２種のゼオライト（Ｐｄ／ＭＦＩおよびＵＳ
Ｙ）を混合したものをコートし空気雰囲気中で６５０℃
で４時間焼成を行い吸着材１を得た。As a result, a mixed zeolite of Pd / MFI and USY type zeolite was coated on the carrier at a coating amount of about 90 g / L. The above washcoating, drying and calcination were repeated two more times to obtain a total of about 200 g / L of two kinds of zeolites having different structures (Pd / MFI and US
Y) is mixed and coated in an air atmosphere at 650 ° C
Then, the adsorbent 1 was obtained by firing for 4 hours.
【０００９】実施例２ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｐｄをイオン交
換したＵＳＹ型ゼオライト（以下Ｐｄ／ＵＳＹと記す）
（金属担持量１重量％，Ｓｉ／２Ａｌ＝１２）粉末５０
部、シリカゾル（固形分２０％）６５部および水６５部
を磁性ボールミルに投入し、混合粉砕したスラリーを吸
引コート法でコーティングし、乾燥焼成してコート量が
約２００ｇ／Ｌになるようにコーティングを行い吸着材
２を得た。Example 2 In the same manner as in Example 1, 50 parts of Pd / MFI (metal loading amount 1% by weight, Si / 2Al = 30) powder, USY type zeolite having Pd ion-exchanged (hereinafter referred to as Pd / USY)
(Metal supported amount 1% by weight, Si / 2Al = 12) Powder 50
Part, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, and the slurry obtained by mixing and pulverizing is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. The adsorbent 2 was obtained.
【００１０】実施例３ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ａｇをイオン交
換したＵＳＹ型ゼオライト（以下Ａｇ／ＵＳＹと記す）
（金属担持量２重量％，Ｓｉ／２Ａｌ＝１２）粉末５０
部、シリカゾル（固形分２０％）６５部および水６５部
を磁性ボールミルに投入し、混合粉砕したスラリーを吸
引コート法でコーティングし、乾燥焼成してコート量が
約２００ｇ／Ｌになるようにコーティングを行い吸着材
３を得た。Example 3 In the same manner as in Example 1, 50 parts of Pd / MFI (metal loading amount 1% by weight, Si / 2Al = 30) powder, USY type zeolite ion-exchanged with Ag (hereinafter referred to as Ag / USY).
(Metal supported amount 2% by weight, Si / 2Al = 12) Powder 50
Part, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, and the slurry obtained by mixing and pulverizing is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. The adsorbent 3 was obtained.
【００１１】実施例４ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｈ型ＭＦＩ（Ｓ
ｉ／２Ａｌ＝７００）粉末５０部、シリカゾル（固形分
２０％）６５部および水６５部を磁性ボールミルに投入
し、混合粉砕したスラリーを吸引コート法でコーティン
グし、乾燥焼成してコート量が約２００ｇ／Ｌになるよ
うにコーティングを行い、吸着材４を得た。Example 4 In the same manner as in Example 1, 50 parts of Pd / MFI (metal loading amount 1% by weight, Si / 2Al = 30) powder, H-type MFI (S
50 parts of i / 2Al = 700) powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, dried and baked to obtain a coating amount of about Coating was performed so as to be 200 g / L to obtain an adsorbent 4.
【００１２】実施例５ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｐｄ／ＭＦＩ
（金属担持量１重量％，Ｓｉ／２Ａｌ＝７００）粉末５
０部、シリカゾル（固形分２０％）６５部および水６５
部を磁性ボールミルに投入し、混合粉砕したスラリーを
吸引コート法でコーティングし、乾燥焼成してコート量
が約２００ｇ／Ｌになるようにコーティングを行い、吸
着材５を得た。Example 5 In the same manner as in Example 1, 50 parts of Pd / MFI (metal loading amount 1% by weight, Si / 2Al = 30) powder, Pd / MFI
(Metal supported amount 1% by weight, Si / 2Al = 700) Powder 5
0 part, silica sol (solid content 20%) 65 parts and water 65
Parts were put into a magnetic ball mill, the mixed and pulverized slurry was coated by a suction coating method, and dried and baked so that the coating amount was about 200 g / L to obtain an adsorbent 5.
【００１３】実施例６ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ａｇ／ＭＦＩ
（金属担持量２重量％，Ｓｉ／２Ａｌ＝７００）粉末５
０部、シリカゾル（固形分２０％）６５部および水６５
部を磁性ボールミルに投入し、混合粉砕したスラリーを
吸引コート法でコーティングし、乾燥焼成してコート量
が約２００ｇ／Ｌになるようにコーティングを行い、吸
着材６を得た。Example 6 In the same manner as in Example 1, 50 parts of Pd / MFI (metal loading amount 1% by weight, Si / 2Al = 30) powder, Ag / MFI
(Metal supported amount 2% by weight, Si / 2Al = 700) Powder 5
0 part, silica sol (solid content 20%) 65 parts and water 65
Part was put into a magnetic ball mill, and the mixed and pulverized slurry was coated by a suction coating method and dried and baked so that the coating amount was about 200 g / L to obtain an adsorbent 6.
【００１４】実施例７ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｈ型モルデナイ
ト（Ｓｉ／２Ａｌ＝１００）粉末５０部、シリカゾル
（固形分２０％）６５部および水６５部を磁性ボールミ
ルに投入し、混合粉砕したスラリーを吸引コート法でコ
ーティングし、乾燥焼成してコート量が約２００ｇ／Ｌ
になるようにコーティングを行い、吸着材７を得た。Example 7 In the same manner as in Example 1, 50 parts of Pd / MFI (1 wt% metal loading, Si / 2Al = 30) powder, 50 parts of H-type mordenite (Si / 2Al = 100) powder, silica sol ( 65 parts of solid content (20%) and 65 parts of water are charged into a magnetic ball mill, and the mixed and pulverized slurry is coated by a suction coating method, dried and baked to obtain a coating amount of about 200 g / L.
Was coated to obtain an adsorbent 7.
【００１５】実施例８ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｐｄをイオン交
換したモルデナイト（以下Ｐｄ／モルデナイトと記す）
（金属担持量１重量％，Ｓｉ／２Ａｌ＝１００）粉末５
０部、シリカゾル（固形分２０％）６５部および水６５
部を磁性ボールミルに投入し、混合粉砕したスラリーを
吸引コート法でコーティングし、乾燥焼成してコート量
が約２００ｇ／Ｌになるようにコーティングを行い、吸
着材８を得た。Example 8 In the same manner as in Example 1, 50 parts of Pd / MFI (1 wt% metal loading, Si / 2Al = 30) powder, mordenite ion-exchanged with Pd (hereinafter referred to as Pd / mordenite)
(Metal supported amount 1% by weight, Si / 2Al = 100) Powder 5
0 part, silica sol (solid content 20%) 65 parts and water 65
Parts were put in a magnetic ball mill, the mixed and pulverized slurry was coated by a suction coating method, dried and baked so that the coating amount was about 200 g / L, and an adsorbent 8 was obtained.
【００１６】実施例９ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ａｇをイオン交
換したモルデナイト（以下Ａｇ／モルデナイトと記す）
（金属担持量２重量％，Ｓｉ／２Ａｌ＝１００）粉末５
０部、シリカゾル（固形分２０％）６５部および水６５
部を磁性ボールミルに投入し、混合粉砕したスラリーを
吸引コート法でコーティングし、乾燥焼成してコート量
が約２００ｇ／Ｌになるようにコーティングを行い、吸
着材９を得た。Example 9 In the same manner as in Example 1, 50 parts of Pd / MFI (metal loading amount 1% by weight, Si / 2Al = 30) powder, mordenite ion-exchanged with Ag (hereinafter referred to as Ag / mordenite).
(Metal supported amount 2% by weight, Si / 2Al = 100) Powder 5
0 part, silica sol (solid content 20%) 65 parts and water 65
Part was put into a magnetic ball mill, and the mixed and pulverized slurry was coated by a suction coating method, and dried and baked so that the coating amount was about 200 g / L, whereby an adsorbent 9 was obtained.
【００１７】実施例１０ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、β−ゼオライト
（Ｓｉ／２Ａｌ＝８０）粉末５０部、シリカゾル（固形
分２０％）６５部および水６５部を磁性ボールミルに投
入し、混合粉砕したスラリーを吸引コート法でコーティ
ングし、乾燥焼成してコート量が約２００ｇ／Ｌになる
ようにコーティングを行い、吸着材１０を得た。Example 10 In the same manner as in Example 1, 50 parts of Pd / MFI (1 wt% metal loading, Si / 2Al = 30) powder, 50 parts of β-zeolite (Si / 2Al = 80) powder, silica sol ( 65 parts of solid content (20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L, and adsorption is performed. Material 10 was obtained.
【００１８】実施例１１ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｐｄをイオン交
換したβ−ゼオライト（以下Ｐｄ／β−ゼオライトと記
す）（金属担持量１重量％，Ｓｉ／２Ａｌ＝８０）粉末
５０部、シリカゾル（固形分２０％）６５部および水６
５部を磁性ボールミルに投入し、混合粉砕したスラリー
を吸引コート法でコーティングし、乾燥焼成してコート
量が約２００ｇ／Ｌになるようにコーティングを行い、
吸着材１１を得た。Example 11 In the same manner as in Example 1, 50 parts of Pd / MFI (1 wt% metal loading, Si / 2Al = 30) powder, β-zeolite ion-exchanged with Pd (hereinafter referred to as Pd / β-zeolite) (Note) (50% by weight of metal supported, Si / 2Al = 80) powder, 65 parts of silica sol (solid content 20%) and water 6
5 parts were put into a magnetic ball mill, the mixed and pulverized slurry was coated by a suction coating method, and dried and baked so that the coating amount became about 200 g / L,
Adsorbent 11 was obtained.
【００１９】実施例１２ 実施例１と同様にしてＰｄ／ＭＦＩ（金属担持量１重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ａｇをイオン交
換したβ−ゼオライト（以下Ａｇ／β−ゼオライトと記
す）（金属担持量２重量％，Ｓｉ／２Ａｌ＝８０）粉末
５０部、シリカゾル（固形分２０％）６５部および水６
５部を磁性ボールミルに投入し、混合粉砕したスラリー
を吸引コート法でコーティングし、乾燥焼成してコート
量が約２００ｇ／Ｌになるようにコーティングを行い、
吸着材１２を得た。Example 12 In the same manner as in Example 1, 50 parts of Pd / MFI (1 wt% metal loading, Si / 2Al = 30) powder, β-zeolite ion-exchanged with Ag (hereinafter referred to as Ag / β-zeolite) (Note) (metal loading 2% by weight, Si / 2Al = 80) powder 50 parts, silica sol (solid content 20%) 65 parts and water 6
5 parts were put into a magnetic ball mill, the mixed and pulverized slurry was coated by a suction coating method, and dried and baked so that the coating amount became about 200 g / L,
The adsorbent 12 was obtained.
【００２０】実施例１３ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｈ型ＵＳＹ（Ｓ
ｉ／２Ａｌ＝１２）粉末５０部、シリカゾル（固形分２
０％）６５部および水６５部を磁性ボールミルに投入
し、混合粉砕したスラリーを吸引コート法でコーティン
グし、乾燥焼成してコート量が約２００ｇ／Ｌになるよ
うにコーティングを行い、吸着材１３を得た。Example 13 In the same manner as in Example 1, 50 parts of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, H-type USY (S
i / 2Al = 12) powder 50 parts, silica sol (solid content 2
(0%) 65 parts and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. Got
【００２１】実施例１４ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｐｄ／ＵＳＹ
（金属担持量１重量％，Ｓｉ／２Ａｌ＝１２）粉末５０
部、シリカゾル（固形分２０％）６５部および水６５部
を磁性ボールミルに投入し、混合粉砕したスラリーを吸
引コート法でコーティングし、乾燥焼成してコート量が
約２００ｇ／Ｌになるようにコーティングを行い、吸着
材１４を得た。Example 14 In the same manner as in Example 1, 50 parts by weight of Ag / MFI (metal loading amount 2% by weight, Si / 2Al = 30) powder, Pd / USY.
(Metal supported amount 1% by weight, Si / 2Al = 12) Powder 50
Part, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, and the slurry obtained by mixing and pulverizing is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. Then, the adsorbent 14 was obtained.
【００２２】実施例１５ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ａｇ／ＵＳＹ
（金属担持量２重量％，Ｓｉ／２Ａｌ＝１２）粉末５０
部、シリカゾル（固形分２０％）６５部および水６５部
を磁性ボールミルに投入し、混合粉砕したスラリーを吸
引コート法でコーティングし、乾燥焼成してコート量が
約２００ｇ／Ｌになるようにコーティングを行い、吸着
材１５を得た。Example 15 In the same manner as in Example 1, 50 parts by weight of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, Ag / USY.
(Metal supported amount 2% by weight, Si / 2Al = 12) Powder 50
Part, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, and the slurry obtained by mixing and pulverizing is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. Then, the adsorbent 15 was obtained.
【００２３】実施例１６ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｈ型ＭＦＩ（Ｓ
ｉ／２Ａｌ＝７００）粉末５０部、シリカゾル（固形分
２０％）６５部および水６５部を磁性ボールミルに投入
し、混合粉砕したスラリーを吸引コート法でコーティン
グし、乾燥焼成してコート量が約２００ｇ／Ｌになるよ
うにコーティングを行い、吸着材１６を得た。Example 16 In the same manner as in Example 1, 50 parts by weight of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, H-type MFI (S
50 parts of i / 2Al = 700) powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, dried and baked to obtain a coating amount of about The adsorbent 16 was obtained by performing coating so that the amount was 200 g / L.
【００２４】実施例１７ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｐｄ／ＭＦＩ
（金属担持量１重量％，Ｓｉ／２Ａｌ＝７００）粉末５
０部、シリカゾル（固形分２０％）６５部および水６５
部を磁性ボールミルに投入し、混合粉砕したスラリーを
吸引コート法でコーティングし、乾燥焼成してコート量
が約２００ｇ／Ｌになるようにコーティングを行い、吸
着材１７を得た。Example 17 In the same manner as in Example 1, 50 parts by weight of Ag / MFI (metal loading amount 2% by weight, Si / 2Al = 30) powder, Pd / MFI
(Metal supported amount 1% by weight, Si / 2Al = 700) Powder 5
0 part, silica sol (solid content 20%) 65 parts and water 65
Parts were put into a magnetic ball mill, the mixed and pulverized slurry was coated by a suction coating method, and dried and baked so that the coating amount was about 200 g / L, whereby an adsorbent 17 was obtained.
【００２５】実施例１８ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ａｇ／ＭＦＩ
（金属担持量２重量％，Ｓｉ／２Ａｌ＝７００）粉末５
０部、シリカゾル（固形分２０％）６５部および水６５
部を磁性ボールミルに投入し、混合粉砕したスラリーを
吸引コート法でコーティングし、乾燥焼成してコート量
が約２００ｇ／Ｌになるようにコーティングを行い、吸
着材１８を得た。Example 18 In the same manner as in Example 1, 50 parts by weight of Ag / MFI (metal supporting amount: 2% by weight, Si / 2Al = 30) powder, Ag / MFI
(Metal supported amount 2% by weight, Si / 2Al = 700) Powder 5
0 part, silica sol (solid content 20%) 65 parts and water 65
Part was put into a magnetic ball mill, and the mixed and pulverized slurry was coated by a suction coating method and dried and baked so that the coating amount was about 200 g / L, whereby an adsorbent 18 was obtained.
【００２６】実施例１９ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｈ型モルデナイ
ト（Ｓｉ／２Ａｌ＝１００）粉末５０部、シリカゾル
（固形分２０％）６５部および水６５部を磁性ボールミ
ルに投入し、混合粉砕したスラリーを吸引コート法でコ
ーティングし、乾燥焼成してコート量が約２００ｇ／Ｌ
になるようにコーティングを行い、吸着材１９を得た。Example 19 In the same manner as in Example 1, 50 parts by weight of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, 50 parts of H-type mordenite (Si / 2Al = 100) powder, silica sol ( 65 parts of solid content (20%) and 65 parts of water are charged into a magnetic ball mill, and the mixed and pulverized slurry is coated by a suction coating method, dried and baked to obtain a coating amount of about 200 g / L.
Coating was performed so as to obtain the adsorbent 19.
【００２７】実施例２０ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｐｄ／モルデナ
イト（金属担持量１重量％，Ｓｉ／２Ａｌ＝１００）粉
末５０部、シリカゾル（固形分２０％）６５部および水
６５部を磁性ボールミルに投入し、混合粉砕したスラリ
ーを吸引コート法でコーティングし、乾燥焼成してコー
ト量が約２００ｇ／Ｌになるようにコーティングを行
い、吸着材２０を得た。Example 20 In the same manner as in Example 1, 50 parts of Ag / MFI (metal loading amount 2% by weight, Si / 2Al = 30) powder, Pd / mordenite (metal loading amount 1% by weight, Si / 2Al = 100) ) 50 parts of powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, dried and baked to a coating amount of about 200 g / L. The coating was performed as described above to obtain an adsorbent 20.
【００２８】実施例２１ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ａｇ／モルデナ
イト（金属担持量２重量％，Ｓｉ／２Ａｌ＝１００）粉
末５０部、シリカゾル（固形分２０％）６５部および水
６５部を磁性ボールミルに投入し、混合粉砕したスラリ
ーを吸引コート法でコーティングし、乾燥焼成してコー
ト量が約２００ｇ／Ｌになるようにコーティングを行
い、吸着材２１を得た。Example 21 In the same manner as in Example 1, 50 parts of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, Ag / mordenite (metal loading 2% by weight, Si / 2Al = 100). ) 50 parts of powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, dried and baked to a coating amount of about 200 g / L. The coating was performed as described above to obtain the adsorbent 21.
【００２９】実施例２２ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、β−ゼオライト
（Ｓｉ／２Ａｌ＝８０）粉末５０部、シリカゾル（固形
分２０％）６５部および水６５部を磁性ボールミルに投
入し、混合粉砕したスラリーを吸引コート法でコーティ
ングし、乾燥焼成してコート量が約２００ｇ／Ｌになる
ようにコーティングを行い、吸着材２２を得た。Example 22 In the same manner as in Example 1, 50 parts of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, 50 parts of β-zeolite (Si / 2Al = 80) powder, silica sol ( 65 parts of solid content (20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L, and adsorption is performed. Material 22 was obtained.
【００３０】実施例２３ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ｐｄ／β−ゼオ
ライト（金属担持量１重量％，Ｓｉ／２Ａｌ＝８０）粉
末５０部、シリカゾル（固形分２０％）６５部および水
６５部を磁性ボールミルに投入し、混合粉砕したスラリ
ーを吸引コート法でコーティングし、乾燥焼成してコー
ト量が約２００ｇ／Ｌになるようにコーティングを行
い、吸着材２３を得た。Example 23 As in Example 1, 50 parts of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, Pd / β-zeolite (metal loading 1% by weight, Si / 2Al) = 80) 50 parts of powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, and the mixed and pulverized slurry is coated by a suction coating method, dried and baked to give a coating amount of about 200 g / L. Coating was performed to obtain an adsorbent 23.
【００３１】実施例２４ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末５０部、Ａｇ／β−ゼオ
ライト（金属担持量２重量％，Ｓｉ／２Ａｌ＝８０）粉
末５０部、シリカゾル（固形分２０％）６５部および水
６５部を磁性ボールミルに投入し、混合粉砕したスラリ
ーを吸引コート法でコーティングし、乾燥焼成してコー
ト量が約２００ｇ／Ｌになるようにコーティングを行
い、吸着材２４を得た。Example 24 As in Example 1, 50 parts of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, Ag / β-zeolite (metal loading 2% by weight, Si / 2Al) = 80) 50 parts of powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, and the mixed and pulverized slurry is coated by a suction coating method, dried and baked to give a coating amount of about 200 g / L. Coating was performed to obtain an adsorbent 24.
【００３２】実施例２５ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末７５部、ＵＳＹ（Ｓｉ／
２Ａｌ＝１２）粉末２５部、シリカゾル（固形分２０
％）６５部および水６５部を磁性ボールミルに投入し、
混合粉砕したスラリーを吸引コート法でコーティング
し、乾燥焼成してコート量が約２００ｇ／Ｌになるよう
にコーティングを行い、吸着材２５を得た。Example 25 In the same manner as in Example 1, 75 parts by weight of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, USY (Si / Si /
2Al = 12) powder 25 parts, silica sol (solid content 20
%) 65 parts and 65 parts of water are charged into a magnetic ball mill,
The mixed and pulverized slurry was coated by a suction coating method, dried and baked so that the coating amount was about 200 g / L, and an adsorbent 25 was obtained.
【００３３】実施例２６ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末７５部、Ｐｄ／ＵＳＹ
（金属担持量１重量％，Ｓｉ／２Ａｌ＝１２）粉末２５
部、シリカゾル（固形分２０％）６５部および水６５部
を磁性ボールミルに投入し、混合粉砕したスラリーを吸
引コート法でコーティングし、乾燥焼成してコート量が
約２００ｇ／Ｌになるようにコーティングを行い、吸着
材２６を得た。Example 26 As in Example 1, 75 parts by weight of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, Pd / USY
(Metal supported amount 1% by weight, Si / 2Al = 12) Powder 25
Part, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, and the slurry obtained by mixing and pulverizing is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. Then, the adsorbent 26 was obtained.
【００３４】実施例２７ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末７５部、Ａｇ／ＵＳＹ
（金属担持量２重量％，Ｓｉ／２Ａｌ＝１２）粉末２５
部、シリカゾル（固形分２０％）６５部および水６５部
を磁性ボールミルに投入し、混合粉砕したスラリーを吸
引コート法でコーティングし、乾燥焼成してコート量が
約２００ｇ／Ｌになるようにコーティングを行い、吸着
材２７を得た。Example 27 In the same manner as in Example 1, 75 parts by weight of Ag / MFI (metal loading amount 2% by weight, Si / 2Al = 30) powder, Ag / USY.
(Metal supported amount 2% by weight, Si / 2Al = 12) Powder 25
Part, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, and the slurry obtained by mixing and pulverizing is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. Then, the adsorbent 27 was obtained.
【００３５】実施例２８ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末２５部、ＵＳＹ（Ｓｉ／
２Ａｌ＝１２）粉末７５部、シリカゾル（固形分２０
％）６５部および水６５部を磁性ボールミルに投入し、
混合粉砕したスラリーを吸引コート法でコーティング
し、乾燥焼成してコート量が約２００ｇ／Ｌになるよう
にコーティングを行い、吸着材２８を得た。Example 28 In the same manner as in Example 1, 25 parts by weight of Ag / MFI (metal loading amount 2% by weight, Si / 2Al = 30) powder, USY (Si / Si /
2Al = 12) powder 75 parts, silica sol (solid content 20
%) 65 parts and 65 parts of water are charged into a magnetic ball mill,
The mixed and pulverized slurry was coated by a suction coating method, dried and fired so that the coating amount was about 200 g / L to obtain an adsorbent 28.
【００３６】実施例２９ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末２５部、Ｐｄ／ＵＳＹ
（金属担持量１重量％，Ｓｉ／２Ａｌ＝１２）粉末７５
部、シリカゾル（固形分２０％）６５部および水６５部
を磁性ボールミルに投入し、混合粉砕したスラリーを吸
引コート法でコーティングし、乾燥焼成してコート量が
約２００ｇ／Ｌになるようにコーティングを行い、吸着
材２９を得た。Example 29 In the same manner as in Example 1, 25 parts by weight of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, Pd / USY.
(Metal supported amount 1% by weight, Si / 2Al = 12) Powder 75
Part, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, and the slurry obtained by mixing and pulverizing is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. Then, the adsorbent 29 was obtained.
【００３７】実施例３０ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末２５部、Ａｇ／ＵＳＹ
（金属担持量２重量％，Ｓｉ／２Ａｌ＝１２）粉末７５
部、シリカゾル（固形分２０％）６５部および水６５部
を磁性ボールミルに投入し、混合粉砕したスラリーを吸
引コート法でコーティングし、乾燥焼成してコート量が
約２００ｇ／Ｌになるようにコーティングを行い、吸着
材３０を得た。Example 30 In the same manner as in Example 1, 25 parts by weight of Ag / MFI (metal loading amount 2% by weight, Si / 2Al = 30) powder, Ag / USY.
(Metal supported amount 2% by weight, Si / 2Al = 12) Powder 75
Part, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, and the slurry obtained by mixing and pulverizing is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. Then, the adsorbent 30 was obtained.
【００３８】実施例３１ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝１０）粉末５０部、ＵＳＹ（Ｓｉ／
２Ａｌ＝１２）粉末５０部、シリカゾル（固形分２０
％）６５部および水６５部を磁性ボールミルに投入し、
混合粉砕したスラリーを吸引コート法でコーティング
し、乾燥焼成してコート量が約２００ｇ／Ｌになるよう
にコーティングを行い、吸着材３１を得た。Example 31 50 parts by weight of Ag / MFI (metal loading 2% by weight, Si / 2Al = 10) powder, USY (Si / Si)
2Al = 12) powder 50 parts, silica sol (solid content 20
%) 65 parts and 65 parts of water are charged into a magnetic ball mill,
The admixture 31 was obtained by coating the mixed and pulverized slurry by a suction coating method and drying and firing so that the coating amount was about 200 g / L.
【００３９】実施例３２ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝４０）粉末５０部、ＵＳＹ（Ｓｉ／
２Ａｌ＝１２）粉末５０部、シリカゾル（固形分２０
％）６５部および水６５部を磁性ボールミルに投入し、
混合粉砕したスラリーを吸引コート法でコーティング
し、乾燥焼成してコート量が約２００ｇ／Ｌになるよう
にコーティングを行い、吸着材３２を得た。Example 32 In the same manner as in Example 1, 50 parts by weight of Ag / MFI (metal loading amount 2% by weight, Si / 2Al = 40) powder, USY (Si / Si /
2Al = 12) powder 50 parts, silica sol (solid content 20
%) 65 parts and 65 parts of water are charged into a magnetic ball mill,
The mixed and pulverized slurry was coated by a suction coating method, dried and baked so that the coating amount was about 200 g / L, and an adsorbent 32 was obtained.
【００４０】実施例３３ 実施例１と同様にして含浸法によってＡｇを担持したＭ
ＦＩゼオライト（金属担持量２重量％，Ｓｉ／２Ａｌ＝
３０）粉末５０部、Ｈ型ＵＳＹ（Ｓｉ／２Ａｌ＝１２）
粉末５０部、シリカゾル（固形分２０％）６５部および
水６５部を磁性ボールミルに投入し、混合粉砕したスラ
リーを吸引コート法でコーティングし、乾燥焼成してコ
ート量が約２００ｇ／Ｌになるようにコーティングを行
い、吸着材３３を得た。Example 33 M carrying Ag by the impregnation method in the same manner as in Example 1
FI zeolite (metal loading 2% by weight, Si / 2Al =
30) 50 parts of powder, H type USY (Si / 2Al = 12)
50 parts of powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are put into a magnetic ball mill, and the mixed and pulverized slurry is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. Was coated to obtain an adsorbent 33.
【００４１】実施例３４ 実施例１と同様にして蒸発乾固法によってＡｇを担持し
たＭＦＩゼオライト（金属担持量２重量％，Ｓｉ／２Ａ
ｌ＝３０）粉末５０部、ＵＳＹ（Ｓｉ／２Ａｌ＝１２）
粉末５０部、シリカゾル（固形分２０％）６５部および
水６５部を磁性ボールミルに投入し、混合粉砕したスラ
リーを吸引コート法でコーティングし、乾燥焼成してコ
ート量が約２００ｇ／Ｌになるようにコーティングを行
い、吸着材３４を得た。Example 34 MFI zeolite supporting Ag by the dry evaporation method in the same manner as in Example 1 (metal loading: 2% by weight, Si / 2A).
1 = 30) powder 50 parts, USY (Si / 2Al = 12)
50 parts of powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are put into a magnetic ball mill, and the mixed and pulverized slurry is coated by a suction coating method, and dried and baked so that the coating amount becomes about 200 g / L. Was coated to obtain an adsorbent 34.
【００４２】実施例３５ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末１００部、シリカゾル
（固形分２０％）６５部および水６５部を磁性ボールミ
ルに投入し、混合粉砕したスラリーを吸引コート法でコ
ーティングし、乾燥焼成してコート量が約１００ｇ／Ｌ
になるようにコーティングを行った。次に、ＵＳＹ（Ｓ
ｉ／２Ａｌ＝１２）粉末１００部、シリカゾル（固形分
２０％）６５部および水６５部を磁性ボールミルに投入
し、混合粉砕したスラリーを吸引コート法でコーティン
グし、乾燥焼成してコート量が約１００ｇ／Ｌになるよ
うにコーティングを行い、吸着材３５を得た。Example 35 In the same manner as in Example 1, 100 parts of Ag / MFI (metal supporting amount 2% by weight, Si / 2Al = 30) powder, 65 parts of silica sol (solid content 20%) and 65 parts of water were magnetic ball milled. The mixture is mixed and pulverized and coated by a suction coating method, dried and baked to give a coating amount of about 100 g / L.
Coating was performed. Next, USY (S
100 parts of i / 2Al = 12) powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, dried and baked to obtain a coating amount of about Coating was performed so as to be 100 g / L to obtain an adsorbent 35.
【００４３】実施例３６ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％，Ｓｉ／２Ａｌ＝３０）粉末１００部、シリカゾル
（固形分２０％）６５部および水６５部を磁性ボールミ
ルに投入し、混合粉砕したスラリーを吸引コート法でハ
ニカム担体の前方１／２にコーティングし、乾燥焼成し
てコート量が約１００ｇ／Ｌになるようにコーティング
を行った。次に、ＵＳＹ（Ｓｉ／２Ａｌ＝１２）粉末１
００部、シリカゾル（固形分２０％）６５部および水６
５部を磁性ボールミルに投入し、混合粉砕したスラリー
を吸引コート法でハニカム担体の後方１／２にコーティ
ングし、乾燥焼成してコート量が約１００ｇ／Ｌになる
ようにコーティングを行い、吸着材３６を得た。Example 36 In the same manner as in Example 1, 100 parts of Ag / MFI (metal loading 2% by weight, Si / 2Al = 30) powder, 65 parts of silica sol (solid content 20%) and 65 parts of water were magnetic ball milled. Then, the slurry pulverized and mixed and pulverized was coated on the front half of the honeycomb carrier by a suction coating method, and dried and baked so that the coating amount was about 100 g / L. Next, USY (Si / 2Al = 12) powder 1
00 parts, silica sol (solid content 20%) 65 parts and water 6
5 parts of the mixture was put into a magnetic ball mill, and the slurry obtained by mixing and pulverizing was coated on the rear half of the honeycomb carrier by a suction coating method, and dried and baked so that the coating amount was about 100 g / L. I got 36.
【００４４】実施例３７ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ（金属担持量２重量％、Ｓｉ／２Ａｌ＝３
０）粉末５０部、Ｈ型ＵＳＹ粉末（Ｓｉ／２Ａｌ＝１
２）２５部、Ｈ型ＭＦＩ型（Ｓｉ／２Ａｌ＝７００）粉
末２５部、シリカゾル（固形分２０％）６５部および水
６５部を磁性ボールミルに投入し、混合粉砕したスラリ
ーを吸引コート法でコーティングし、乾燥焼成してコー
ト量が約２００ｇ／Ｌになるようにコーティングを行
い、吸着材３７を得た。Example 37 MFI carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading: 2% by weight, Si / 2Al = 3)
0) 50 parts of powder, H type USY powder (Si / 2Al = 1
2) 25 parts, 25 parts of H-type MFI type (Si / 2Al = 700) powder, 65 parts of silica sol (solid content 20%) and 65 parts of water were charged into a magnetic ball mill, and the mixed and pulverized slurry was coated by a suction coating method. Then, it was dried and baked so that the coating amount was about 200 g / L to obtain an adsorbent 37.
【００４５】実施例３８ 実施例１と同様にしてイオン交換法によってＰｄとＡｇ
とを担持したＭＦＩ型ゼオライト（Ｐｄ担持量１重量
％、Ａｇ担持量１重量％、Ｓｉ／２Ａｌ＝３０）粉末５
０部、Ｈ型ＵＳＹ粉末（Ｓｉ／２Ａｌ＝１２）５０部、
シリカゾル（固形分２０％）６５部および水６５部を磁
性ボールミルに投入し、混合粉砕したスラリーを吸引コ
ート法でコーティングし、乾燥焼成してコート量が約２
００ｇ／Ｌになるようにコーティングを行い、吸着材３
８を得た。Example 38 Pd and Ag were prepared by the ion exchange method in the same manner as in Example 1.
Powder of MFI type zeolite carrying and (1% by weight of Pd, 1% by weight of Ag, Si / 2Al = 30)
0 part, H-type USY powder (Si / 2Al = 12) 50 parts,
65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, dried and baked to a coating amount of about 2
Adsorbent 3 is coated so that it becomes 00g / L.
Got 8.
【００４６】実施例３９ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末５０部、ＵＳＹ粉末（Ｓｉ／２Ａｌ
＝１２）２５部、β−ゼオライト（Ｓｉ／２Ａｌ＝８
０）粉末２５部、シリカゾル（固形分２０％）６５部お
よび水６５部を磁性ボールミルに投入し、混合粉砕した
スラリーを吸引コート法でコーティングし、乾燥焼成し
てコート量が約２００ｇ／Ｌになるようにコーティング
を行い、吸着材３９を得た。Example 39 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount: 2% by weight, Si /
2Al = 30) powder 50 parts, USY powder (Si / 2Al)
= 12) 25 parts, β-zeolite (Si / 2Al = 8
0) 25 parts of powder, 65 parts of silica sol (solid content 20%) and 65 parts of water were charged into a magnetic ball mill, and the mixed and pulverized slurry was coated by a suction coating method, dried and baked to a coating amount of about 200 g / L. Coating was performed so as to obtain an adsorbent 39.
【００４７】実施例４０ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末５０部、ＵＳＹ粉末（Ｓｉ／２Ａｌ
＝１２）２５部、モルデナイト（Ｓｉ／２Ａｌ＝１０
０）粉末２５部、シリカゾル（固形分２０％）６５部お
よび水６５部を磁性ボールミルに投入し、混合粉砕した
スラリーを吸引コート法でコーティングし、乾燥焼成し
てコート量が約２００ｇ／Ｌになるようにコーティング
を行い、吸着材４０を得た。Example 40 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount 2% by weight, Si /
2Al = 30) powder 50 parts, USY powder (Si / 2Al)
= 12) 25 parts, mordenite (Si / 2Al = 10
0) 25 parts of powder, 65 parts of silica sol (solid content 20%) and 65 parts of water were charged into a magnetic ball mill, and the mixed and pulverized slurry was coated by a suction coating method, dried and baked to a coating amount of about 200 g / L. Coating was performed so that the adsorbent 40 was obtained.
【００４８】実施例４１ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末５０部、Ｈ型ＭＦＩ粉末（Ｓｉ／２
Ａｌ＝７００）２５部、β−ゼオライト（Ｓｉ／２Ａｌ
＝８０）粉末２５部、シリカゾル（固形分２０％）６５
部および水６５部を磁性ボールミルに投入し、混合粉砕
したスラリーを吸引コート法でコーティングし、乾燥焼
成してコート量が約２００ｇ／Ｌになるようにコーティ
ングを行い、吸着材４１を得た。Example 41 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount: 2% by weight, Si /
2Al = 30) powder 50 parts, H type MFI powder (Si / 2
Al = 700) 25 parts, β-zeolite (Si / 2Al
= 80) powder 25 parts, silica sol (solid content 20%) 65
Parts and 65 parts of water were charged into a magnetic ball mill, the mixed and pulverized slurry was coated by a suction coating method, and dried and baked so that the coating amount was about 200 g / L to obtain an adsorbent 41.
【００４９】実施例４２ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末５０部、β−ゼオライト粉末（Ｓｉ
／２Ａｌ＝８０）２５部、モルデナイト（Ｓｉ／２Ａｌ
＝１００）粉末２５部、シリカゾル（固形分２０％）６
５部および水６５部を磁性ボールミルに投入し、混合粉
砕したスラリーを吸引コート法でコーティングし、乾燥
焼成してコート量が約２００ｇ／Ｌになるようにコーテ
ィングを行い、吸着材４２を得た。Example 42 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount: 2% by weight, Si /
2Al = 30) powder 50 parts, β-zeolite powder (Si
/ 2Al = 80) 25 parts, mordenite (Si / 2Al)
= 100) powder 25 parts, silica sol (solid content 20%) 6
5 parts of water and 65 parts of water were charged into a magnetic ball mill, the mixed and pulverized slurry was coated by a suction coating method, and dried and baked so that the coating amount was about 200 g / L, and an adsorbent 42 was obtained. .
【００５０】実施例４３ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末５０部、Ｈ型ＭＦＩ粉末（Ｓｉ／２
Ａｌ＝８０）２５部、モルデナイト（Ｓｉ／２Ａｌ＝１
００）粉末２５部、シリカゾル（固形分２０％）６５部
および水６５部を磁性ボールミルに投入し、混合粉砕し
たスラリーを吸引コート法でコーティングし、乾燥焼成
してコート量が約２００ｇ／Ｌになるようにコーティン
グを行い、吸着材４３を得た。Example 43 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount: 2% by weight, Si /
2Al = 30) powder 50 parts, H type MFI powder (Si / 2
Al = 80) 25 parts, mordenite (Si / 2Al = 1
00) 25 parts of powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, dried and baked to a coating amount of about 200 g / L. Coating was performed so that the adsorbent 43 was obtained.
【００５１】実施例４４ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末２５部、ＭＦＩ粉末（Ｓｉ／２Ａｌ
＝７００）２５部、β−ゼオライト（Ｓｉ／２Ａｌ＝８
０）粉末２５部、ＵＳＹ（Ｓｉ／２Ａｌ＝１２）粉末２
５部、シリカゾル（固形分２０％）６５部および水６５
部を磁性ボールミルに投入し、混合粉砕したスラリーを
吸引コート法でコーティングし、乾燥焼成してコート量
が約２００ｇ／Ｌになるようにコーティングを行い、吸
着材４４を得た。Example 44 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount: 2% by weight, Si /
2Al = 30) powder 25 parts, MFI powder (Si / 2Al)
= 700) 25 parts, β-zeolite (Si / 2Al = 8
0) powder 25 parts, USY (Si / 2Al = 12) powder 2
5 parts, silica sol (solid content 20%) 65 parts and water 65
Parts were put into a magnetic ball mill, and the mixed and pulverized slurry was coated by a suction coating method and dried and baked so that the coating amount was about 200 g / L, whereby an adsorbent 44 was obtained.
【００５２】実施例４５ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末２５部、β−ゼオライト粉末（Ｓｉ
／２Ａｌ＝８０）２５部、モルデナイト（Ｓｉ／２Ａｌ
＝１００）粉末２５部、Ｈ型ＭＦＩ粉末（Ｓｉ／２Ａｌ
＝７００）２５部、シリカゾル（固形分２０％）６５部
および水６５部を磁性ボールミルに投入し、混合粉砕し
たスラリーを吸引コート法でコーティングし、乾燥焼成
してコート量が約２００ｇ／Ｌになるようにコーティン
グを行い、吸着材４５を得た。Example 45 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount: 2% by weight, Si /
2 Al = 30) powder 25 parts, β-zeolite powder (Si
/ 2Al = 80) 25 parts, mordenite (Si / 2Al)
= 100) powder 25 parts, H-type MFI powder (Si / 2Al
= 700) 25 parts, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, dried and baked to a coating amount of about 200 g / L. The coating was performed so that an adsorbent 45 was obtained.
【００５３】実施例４６ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末２５部、Ｈ型ＭＦＩ粉末（Ｓｉ／２
Ａｌ＝８０）２５部、モルデナイト（Ｓｉ／２Ａｌ＝１
００）粉末２５部、ＵＳＹ（Ｓｉ／２Ａｌ＝１２）粉末
２５部、シリカゾル（固形分２０％）６５部および水６
５部を磁性ボールミルに投入し、混合粉砕したスラリー
を吸引コート法でコーティングし、乾燥焼成してコート
量が約２００ｇ／Ｌになるようにコーティングを行い、
吸着材４６を得た。Example 46 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount: 2% by weight, Si /
2 Al = 30) powder 25 parts, H type MFI powder (Si / 2
Al = 80) 25 parts, mordenite (Si / 2Al = 1
00) powder 25 parts, USY (Si / 2Al = 12) powder 25 parts, silica sol (solid content 20%) 65 parts and water 6
5 parts were put into a magnetic ball mill, the mixed and pulverized slurry was coated by a suction coating method, and dried and baked so that the coating amount became about 200 g / L,
The adsorbent 46 was obtained.
【００５４】比較例１ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％、Ｓｉ／２Ａｌ＝３０）粉末１５部、ＵＳＹ（Ｓｉ／
２Ａｌ＝１２）粉末８５部、シリカゾル（固形分２０
％）６５部および水６５部を磁性ボールミルに投入し、
混合粉砕したスラリーを吸引コート法でコーティング
し、乾燥焼成してコート量が約２００ｇ／Ｌになるよう
にコーティングを行い、吸着材４７を得た。Comparative Example 1 In the same manner as in Example 1, 15 parts of Ag / MFI (metal loading amount 2% by weight, Si / 2Al = 30) powder, USY (Si / Si /
2Al = 12) powder 85 parts, silica sol (solid content 20
%) 65 parts and 65 parts of water are charged into a magnetic ball mill,
The mixed and pulverized slurry was coated by a suction coating method, dried and baked so that the coating amount was about 200 g / L, and an adsorbent 47 was obtained.
【００５５】比較例２ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％、Ｓｉ／２Ａｌ＝３０）粉末８５部、ＵＳＹ（Ｓｉ／
２Ａｌ＝１２）粉末１５部、シリカゾル（固形分２０
％）６５部および水６５部を磁性ボールミルに投入し、
混合粉砕したスラリーを吸引コート法でコーティング
し、乾燥焼成してコート量が約２００ｇ／Ｌになるよう
にコーティングを行い、吸着材４８を得た。Comparative Example 2 In the same manner as in Example 1, 85 parts by weight of Ag / MFI (metal loading amount 2% by weight, Si / 2Al = 30) powder, USY (Si / Si /
2Al = 12) powder 15 parts, silica sol (solid content 20
%) 65 parts and 65 parts of water are charged into a magnetic ball mill,
The mixed and pulverized slurry was coated by a suction coating method, dried and baked so that the coating amount was about 200 g / L, and an adsorbent 48 was obtained.
【００５６】比較例３ 実施例１と同様にしてＡｇ／ＭＦＩ（金属担持量２重量
％、Ｓｉ／２Ａｌ＝１００）粉末５０部、ＵＳＹ（Ｓｉ
／２Ａｌ＝６）粉末５０部、シリカゾル（固形分２０
％）６５部および水６５部を磁性ボールミルに投入し、
混合粉砕したスラリーを吸引コート法でコーティング
し、乾燥焼成してコート量が約２００ｇ／Ｌになるよう
にコーティングを行い、吸着材４９を得た。Comparative Example 3 In the same manner as in Example 1, 50 parts by weight of Ag / MFI (metal loading amount 2% by weight, Si / 2Al = 100) powder, USY (Si
/ 2Al = 6) powder 50 parts, silica sol (solid content 20
%) 65 parts and 65 parts of water are charged into a magnetic ball mill,
The mixed and pulverized slurry was coated by a suction coating method, dried and baked so that the coating amount was about 200 g / L, and an adsorbent 49 was obtained.
【００５７】比較例４ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝１００）粉末５０部、ＵＳＹ（Ｓｉ／２Ａｌ＝
１２）粉末５０部、シリカゾル（固形分２０％）６５部
および水６５部を磁性ボールミルに投入し、混合粉砕し
たスラリーを吸引コート法でコーティングし、乾燥焼成
してコート量が約２００ｇ／Ｌになるようにコーティン
グを行い、吸着材５０を得た。Comparative Example 4 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount: 2% by weight, Si /
2Al = 100) powder 50 parts, USY (Si / 2Al =
12) 50 parts of powder, 65 parts of silica sol (solid content 20%) and 65 parts of water are charged into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, dried and baked to a coating amount of about 200 g / L. Coating was performed so as to obtain an adsorbent 50.
【００５８】比較例５ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末５０部、Ｈ型ＭＦＩ（Ｓｉ／２Ａｌ
＝３０）粉末５０部、シリカゾル（固形分２０％）６５
部および水６５部を磁性ボールミルに投入し、混合粉砕
したスラリーを吸引コート法でコーティングし、乾燥焼
成してコート量が約２００ｇ／Ｌになるようにコーティ
ングを行い、吸着材５１を得た。Comparative Example 5 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount 2% by weight, Si /
2Al = 30) powder 50 parts, H type MFI (Si / 2Al
= 30) powder 50 parts, silica sol (solid content 20%) 65
Parts and 65 parts of water were charged into a magnetic ball mill, the mixed and pulverized slurry was coated by a suction coating method, and dried and baked to a coating amount of about 200 g / L to obtain an adsorbent 51.
【００５９】比較例６ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末５０部、モルデナイト（Ｓｉ／２Ａ
ｌ＝１０）粉末５０部、シリカゾル（固形分２０％）６
５部および水６５部を磁性ボールミルに投入し、混合粉
砕したスラリーを吸引コート法でコーティングし、乾燥
焼成してコート量が約２００ｇ／Ｌになるようにコーテ
ィングを行い、吸着材５２を得た。Comparative Example 6 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount 2% by weight, Si /
2Al = 30) powder 50 parts, mordenite (Si / 2A)
l = 10) powder 50 parts, silica sol (solid content 20%) 6
5 parts of water and 65 parts of water were charged into a magnetic ball mill, the mixed and pulverized slurry was coated by a suction coating method, and dried and baked so that the coating amount was about 200 g / L, and an adsorbent 52 was obtained. .
【００６０】比較例７ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末５０部、ＵＳＹ粉末（Ｓｉ／２Ａｌ
＝７）５０部、シリカゾル（固形分２０％）６５部およ
び水６５部を磁性ボールミルに投入し、混合粉砕したス
ラリーを吸引コート法でコーティングし、乾燥焼成して
コート量が約２００ｇ／Ｌになるようにコーティングを
行い、吸着材５３を得た。Comparative Example 7 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount 2% by weight, Si /
2Al = 30) powder 50 parts, USY powder (Si / 2Al)
= 7) 50 parts, 65 parts of silica sol (solid content 20%) and 65 parts of water are put into a magnetic ball mill, the mixed and pulverized slurry is coated by a suction coating method, dried and baked to a coating amount of about 200 g / L. Coating was performed so that the adsorbent 53 was obtained.
【００６１】比較例８ 実施例１と同様にしてイオン交換法によってＡｇを担持
したＭＦＩ型ゼオライト（金属担持量２重量％、Ｓｉ／
２Ａｌ＝３０）粉末５０部、β−ゼオライト粉末（Ｓｉ
／２Ａｌ＝３０）５０部、シリカゾル（固形分２０％）
６５部および水６５部を磁性ボールミルに投入し、混合
粉砕したスラリーを吸引コート法でコーティングし、乾
燥焼成してコート量が約２００ｇ／Ｌになるようにコー
ティングを行い、吸着材５４を得た。Comparative Example 8 MFI type zeolite carrying Ag by the ion exchange method in the same manner as in Example 1 (metal loading amount: 2% by weight, Si /
2Al = 30) powder 50 parts, β-zeolite powder (Si
/ 2Al = 30) 50 parts, silica sol (solid content 20%)
65 parts of water and 65 parts of water were charged into a magnetic ball mill, and the mixed and pulverized slurry was coated by a suction coating method, and dried and baked so that the coating amount was about 200 g / L, and an adsorbent 54 was obtained. .
【００６２】試験例 各実施例および比較例について車両（排気量２０００ｃ
ｃ）を用いて、表１に示すＨＣ排出特性を有するＬＡ−
４モードエミッションの最初の１分間のＨＣ吸着率を評
価した。その結果を表２に示す。Test Example Vehicles (displacement 2000c
LA- having the HC emission characteristics shown in Table 1 using c)
The HC adsorption rate for the first minute of 4-mode emission was evaluated. The results are shown in Table 2.
【００６３】[0063]
【表１】 [Table 1]
【００６４】[0064]
【表２】 [Table 2]
【００６５】[0065]
【発明の効果】以上説明してきたように、本発明におい
て、モルデナイト（Ｓｉ／２Ａｌ＝３０〜２０００）、
ＵＳＹ（Ｓｉ／２Ａｌ＝１０〜３００）、ＭＦＩ型（Ｓ
ｉ／２Ａｌ＝５０〜２０００）、β−ゼオライト（Ｓｉ
／２Ａｌ＝４０〜２０００）に、ＰｄまたはＡｇもしく
は両方を担持したＭＦＩ型（Ｓｉ／２Ａｌ＝１０〜４
０）を併用することにより、炭素数の多い芳香族または
その他の分子径の大きい炭化水素に加え、今まで吸着さ
れなかった炭素数の少ない炭化水素（Ｃ2 〜Ｃ3 ）を吸
着することが可能になった。また、ハイシリカのゼオラ
イトを用いることにより、水の影響を受け難くなり、さ
らに炭化水素吸着能が向上した。As described above, in the present invention, mordenite (Si / 2Al = 30 to 2000),
USY (Si / 2Al = 10-300), MFI type (S
i / 2Al = 50-2000), β-zeolite (Si
/ 2Al = 40-2000) with Pd or Ag or both supported on the MFI type (Si / 2Al = 10-4)
When used in combination with 0), hydrocarbons with a small number of carbons (C 2 to C 3 ) that have not been adsorbed until now can be adsorbed in addition to aromatics with a large number of carbons or other hydrocarbons with a large molecular diameter. It became possible. In addition, by using the high silica zeolite, it became difficult to be affected by water, and the hydrocarbon adsorption capacity was further improved.
Claims (4)
類以上コーティングしたことを特徴とする内燃機関の排
気中の炭化水素を浄化するための排気浄化用触媒。1. An exhaust gas purification catalyst for purifying hydrocarbons in the exhaust gas of an internal combustion engine, characterized in that a honeycomb carrier is coated with two or more kinds of different zeolites.
型ＭＦＩ型ゼオライト（Ｓｉ／２Ａｌ＝５０〜２００
０）、モルデナイト（Ｓｉ／２Ａｌ＝３０〜２００
０）、ＵＳＹ型ゼオライト（Ｓｉ／２Ａｌ＝１０〜３０
０）およびβ−ゼオライト（Ｓｉ／２Ａｌ＝４０〜２０
００）の少なくとも１種類と、ＰｄまたはＡｇもしくは
両方を担持したＭＦＩ型ゼオライト（Ｓｉ／２Ａｌ＝１
０〜４０）とを用いたことを特徴とする請求項１記載の
排気浄化用触媒。2. H as a zeolite that adsorbs hydrocarbons
Type MFI type zeolite (Si / 2Al = 50-200
0), mordenite (Si / 2Al = 30 to 200)
0), USY type zeolite (Si / 2Al = 10 to 30)
0) and β-zeolite (Si / 2Al = 40 to 20)
00) and at least one of Pd and Ag or both of them are supported on the MFI type zeolite (Si / 2Al = 1).
0-40) was used, The exhaust gas purification catalyst according to claim 1.
＝５０〜２０００）、モルデナイト（Ｓｉ／２Ａｌ＝３
０〜２０００）、ＵＳＹ型ゼオライト（Ｓｉ／２Ａｌ＝
１０〜３００）およびβ−ゼオライト（Ｓｉ／２Ａｌ＝
４０〜２０００）と、ＰｄまたはＡｇもしくは両方を担
持したＭＦＩ型ゼオライト（Ｓｉ／２Ａｌ＝１０〜４
０）との重量比が１：３〜３：１であることを特徴とす
る請求項１記載の排気浄化用触媒。3. H-type MFI-type zeolite (Si / 2Al
= 50 to 2000), mordenite (Si / 2Al = 3)
0-2000), USY type zeolite (Si / 2Al =
10-300) and β-zeolite (Si / 2Al =
40-2000) and Pd or Ag or both MFI type zeolite (Si / 2Al = 10-4).
The exhaust purification catalyst according to claim 1, wherein the weight ratio with respect to 0) is 1: 3 to 3: 1.
０〜２０００）、モルデナイト（Ｓｉ／２Ａｌ＝３０〜
２０００）、ＵＳＹ型ゼオライト（Ｓｉ／２Ａｌ＝１０
〜３００）およびβ−ゼオライト（Ｓｉ／２Ａｌ＝４０
〜２０００）が、Ｈ型あるいはＰｄまたはＡｇのいずれ
かまたは両方を担持されていることを特徴とする請求項
１記載の排気浄化用触媒。4. MFI-type zeolite (Si / 2Al = 5
0-2000), mordenite (Si / 2Al = 30-
2000), USY type zeolite (Si / 2Al = 10)
~ 300) and β-zeolite (Si / 2Al = 40)
To 2000) are loaded with either or both of H type, Pd, and Ag, and the exhaust purification catalyst according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30412793A JP3500675B2 (en) | 1993-10-14 | 1993-12-03 | Exhaust gas purification catalyst |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-256982 | 1993-10-14 | ||
| JP25698293 | 1993-10-14 | ||
| JP30412793A JP3500675B2 (en) | 1993-10-14 | 1993-12-03 | Exhaust gas purification catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07155613A true JPH07155613A (en) | 1995-06-20 |
| JP3500675B2 JP3500675B2 (en) | 2004-02-23 |
Family
ID=26542998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30412793A Expired - Lifetime JP3500675B2 (en) | 1993-10-14 | 1993-12-03 | Exhaust gas purification catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3500675B2 (en) |
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| EP0867218A2 (en) * | 1997-03-26 | 1998-09-30 | Ngk Insulators, Ltd. | System for exhaust gas purification |
| WO1999013981A1 (en) * | 1997-09-12 | 1999-03-25 | Toyota Jidosha Kabushiki Kaisha | Exhaust emission control catalyst |
| EP0909579A1 (en) * | 1997-10-15 | 1999-04-21 | Ngk Insulators, Ltd. | Adsorbent material or adsorbent comprising porous material for automobile exhaust gas purification |
| EP0947236A1 (en) * | 1998-03-20 | 1999-10-06 | Engelhard Corporation | Catalyzed hydrocarbon trap material and method of making the same |
| US6042797A (en) * | 1997-07-02 | 2000-03-28 | Tosoh Corporation | Adsorbent for ethylene, method for adsorbing and removing ethylene and method for purifying an exhaust gas |
| US6147023A (en) * | 1997-10-28 | 2000-11-14 | Toyota Jidosha Kabushiki Kaisha | Hydrocarbon-adsorbent |
| WO2001043854A1 (en) * | 1999-12-14 | 2001-06-21 | Engelhard Corporation | Compositions for abatement of volatile organic compounds and apparatus and methods using the same |
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| US6171557B1 (en) | 1997-03-26 | 2001-01-09 | Ngk Insulators, Ltd. | System for exhaust gas purification |
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| EP0867218A2 (en) * | 1997-03-26 | 1998-09-30 | Ngk Insulators, Ltd. | System for exhaust gas purification |
| US6042797A (en) * | 1997-07-02 | 2000-03-28 | Tosoh Corporation | Adsorbent for ethylene, method for adsorbing and removing ethylene and method for purifying an exhaust gas |
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| WO1999013981A1 (en) * | 1997-09-12 | 1999-03-25 | Toyota Jidosha Kabushiki Kaisha | Exhaust emission control catalyst |
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| US6147023A (en) * | 1997-10-28 | 2000-11-14 | Toyota Jidosha Kabushiki Kaisha | Hydrocarbon-adsorbent |
| US6074973A (en) * | 1998-03-20 | 2000-06-13 | Engelhard Corporation | Catalyzed hydrocarbon trap material and method of making the same |
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| EP1129774A1 (en) * | 1998-10-28 | 2001-09-05 | Toyota Jidosha Kabushiki Kaisha | Adsorbent for hydrocarbon and catalyst for exhaust gas purification |
| EP1129774A4 (en) * | 1998-10-28 | 2003-04-16 | Toyota Motor Co Ltd | Adsorbent for hydrocarbon and catalyst for exhaust gas purification |
| WO2001043854A1 (en) * | 1999-12-14 | 2001-06-21 | Engelhard Corporation | Compositions for abatement of volatile organic compounds and apparatus and methods using the same |
| JPWO2014069676A1 (en) * | 2012-11-01 | 2016-09-08 | 日本碍子株式会社 | Ceramic separation membrane structure and repair method thereof |
| US9782729B2 (en) | 2012-11-01 | 2017-10-10 | Ngk Insulators, Ltd. | Ceramic separation membrane structure, and repair method thereof |
| US9968916B2 (en) | 2013-10-30 | 2018-05-15 | Johnson Matthey Public Limited Company | Three-way catalyst and its use in exhaust systems |
| EP3077112B1 (en) * | 2013-12-06 | 2022-02-16 | Johnson Matthey Public Limited Company | Exhaust gas catalyst containing two different palladium-molecular sieve catalysts |
| WO2020205444A1 (en) * | 2019-03-29 | 2020-10-08 | Exxonmobil Chemical Patents Inc. | Catalysts and processes for converting aromatics |
| US12011705B2 (en) | 2021-01-08 | 2024-06-18 | Johnson Matthey Public Limited Company | Method and composition |
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