JP2682404B2 - Method for producing hydrocarbon adsorbent and catalyst - Google Patents
Method for producing hydrocarbon adsorbent and catalystInfo
- Publication number
- JP2682404B2 JP2682404B2 JP5273779A JP27377993A JP2682404B2 JP 2682404 B2 JP2682404 B2 JP 2682404B2 JP 5273779 A JP5273779 A JP 5273779A JP 27377993 A JP27377993 A JP 27377993A JP 2682404 B2 JP2682404 B2 JP 2682404B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- catalyst
- alumina
- same manner
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 80
- 229930195733 hydrocarbon Natural products 0.000 title claims description 30
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 30
- 239000003463 adsorbent Substances 0.000 title claims description 22
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 76
- 239000010457 zeolite Substances 0.000 claims description 47
- 229910021536 Zeolite Inorganic materials 0.000 claims description 46
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000001179 sorption measurement Methods 0.000 claims description 34
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- 239000010948 rhodium Substances 0.000 claims description 24
- 229910052680 mordenite Inorganic materials 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 79
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 31
- 239000007787 solid Substances 0.000 description 31
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 30
- 229910017604 nitric acid Inorganic materials 0.000 description 30
- 229910052573 porcelain Inorganic materials 0.000 description 30
- 239000011268 mixed slurry Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 229910004298 SiO 2 Inorganic materials 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 241000555745 Sciuridae Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000005909 Kieselgur Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910018967 Pt—Rh Inorganic materials 0.000 description 2
- -1 ZSM-5 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、自動車等の内燃機関か
ら排出される排ガスの浄化装置に使用される炭化水素吸
着材および吸着触媒の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrocarbon adsorbent and an adsorbent catalyst for use in a device for purifying exhaust gas discharged from an internal combustion engine such as an automobile.
【０００２】[0002]
【従来の技術】自動車等の内燃機関の排ガス浄化用触媒
としては、一酸化炭素（ＣＯ）及び炭化水素（ＨＣ）の
酸化と、窒素酸化物（ＮＯx ) の還元を同時に行なう三
元触媒が汎用されている。このような触媒は、例えば特
公昭５８−２０３０７号公報にもみられるように、耐火
性担体上のアルミナコート層に、パラジウム（Ｐｄ）、
白金（Ｐｔ）およびロジウム（Ｒｈ）等の貴金属、及び
場合により助触媒成分としてセリウム（Ｃｅ）、ランタ
ン（Ｌａ）等の希土類金属またはニッケル（Ｎｉ）等の
ベースメタル酸化物を添加したものがほとんどである。2. Description of the Related Art As a catalyst for purifying exhaust gas of an internal combustion engine of an automobile or the like, a three-way catalyst which simultaneously oxidizes carbon monoxide (CO) and hydrocarbons (HC) and reduces nitrogen oxides (NO x ). It is commonly used. Such a catalyst can be obtained by, for example, palladium (Pd), in an alumina coat layer on a refractory carrier, as seen in Japanese Patent Publication No. 58-20307.
In most cases, a noble metal such as platinum (Pt) and rhodium (Rh), and optionally a rare earth metal such as cerium (Ce) and lanthanum (La) or a base metal oxide such as nickel (Ni) is added as a promoter component. Is.
【０００３】かかる触媒は、排ガス温度とエンジンの設
定空燃比の影響を強く受ける。自動車用触媒が浄化能を
発揮する排ガス温度としては、一般に３００℃以上必要
であり、また空撚比は、ＨＣとＣＯの酸化とＮＯx の還
元のバランスがとれる理論空撚比（Ａ／Ｆ＝14.6) 付近
で触媒が最も有効に働く。従って、従来の三元触媒を用
いる排ガス浄化装置を取り付けた自動車では、三元触媒
が有効に働くような位置に設置されており、また排気系
の酸素濃度を検出して、混合気を理論空撚比付近に保つ
ようフィードバック制御が行なわれている。[0003] Such a catalyst is strongly affected by the exhaust gas temperature and the set air-fuel ratio of the engine. The exhaust gas temperature at which the automobile catalyst exerts its purifying ability is generally required to be 300 ° C. or higher, and the air twist ratio is a theoretical air twist ratio (A / F) that balances the oxidation of HC and CO and the reduction of NO x. The catalyst works most effectively around = 14.6). Therefore, a conventional automobile equipped with an exhaust gas purification device that uses a three-way catalyst is installed at a position where the three-way catalyst works effectively, and the oxygen concentration in the exhaust system is detected to create a theoretical air-fuel mixture. Feedback control is performed to keep it near the twist ratio.
【０００４】従来の三元触媒をエキゾ−ストマニホール
ド直後に設置しても、排ガス温度が低い（３００℃以
下）エンジン始動直後には触媒活性が低く、始動直後
（コールドスタート時）に排出されるＨＣは浄化されず
にそのまま排出されてしまうおそれがある。Even if the conventional three-way catalyst is installed immediately after the exhaust manifold, the catalyst activity is low immediately after the engine starts when the exhaust gas temperature is low (300 ° C. or less) and is discharged immediately after the start (cold start). HC may be discharged as it is without being purified.
【０００５】上記の課題を解決するための排ガス浄化装
置として、触媒コンバータの排気上流側にコールドＨＣ
を吸着するための吸着材を納めたＨＣトラッパーを配置
したもの（特開平２−２１１２４５号公報、特開平２−
１３５１２６号公報）が提案されている。As an exhaust gas purifying apparatus for solving the above problems, cold HC is provided on the upstream side of the exhaust of a catalytic converter.
In which an HC trapper containing an adsorbent for adsorbing is adsorbed (Japanese Patent Application Laid-Open No. 2-212145, Japanese Patent Application Laid-Open No. 2-212145).
Japanese Patent No. 135126) has been proposed.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記の
特開平２−２１１２４５号公報に開示されて吸着材で
は、 (1) ゼオライト層中に小孔を形成するために発泡剤を
用いているが、発泡剤ではハニカムコート時に目づまり
をおこしやすく、コーティング性が悪い。また、特開平
２−１３５１２６号公報に開示されている吸着材では、 (2) バインダーに使用しているアルミナゾルでは粒子
径が細かく、小孔を形成することができない。 (3) 更に、ゼオライト層中に細孔を形成するために、
ケイソウ土を分散混入させた触媒が、特開平５−２２８
３７１号公報に開示されている。このケイソウ土中の細
孔（８〜１００Å）によりゼオライト活性点までのガス
拡散性の向上を意図しているが、ケイソウ土自身細孔を
持っておらず、好ましい細孔径は１０±２Åとされてお
り、小さすぎ、またケイソウ土では耐久性が不十分であ
る。またこの触媒はＮＯx 浄化に用いるものである。However, in the adsorbent disclosed in Japanese Unexamined Patent Publication (Kokai) No. 2-212145, (1) a foaming agent is used to form small pores in the zeolite layer. The foaming agent tends to cause clogging during honeycomb coating, resulting in poor coating properties. Further, in the adsorbent disclosed in JP-A-2-135126, (2) the alumina sol used as the binder has a fine particle size and cannot form small pores. (3) Furthermore, in order to form pores in the zeolite layer,
A catalyst in which diatomaceous earth is dispersed and mixed is disclosed in JP-A-5-228.
It is disclosed in Japanese Patent No. 371. The pores (8 to 100 Å) in the diatomaceous earth are intended to improve the gas diffusivity up to the zeolite active point, but the diatomaceous earth itself has no pores, and the preferable pore diameter is 10 ± 2 Å It is too small and its durability is insufficient with diatomaceous earth. Further, this catalyst is used for NO x purification.
【０００７】[0007]
【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、ゼオライト二次
粒子よりも大きいアルミナ粒子をゼオライトスラリー中
に混合することでゼオライト層中に小孔ができ、炭化水
素のゼオライト細孔中までの拡散が良くなり、吸着能力
が向上することを知見したことに基づくものである。従
って本発明はゼオライト粉末にシリカゾル、水およびア
ルミナ粉末を加えてスラリーとなし、次いで該スラリー
をモノリス担体に塗布し、乾燥後、焼成してコート層を
形成することを特徴とする炭化水素吸着材の製造方法に
関するものである。Means for Solving the Problems The present invention has been made in view of such conventional problems. In the zeolite layer, alumina particles larger than secondary zeolite particles are mixed in the zeolite slurry. This is based on the finding that small pores are formed, the diffusion of hydrocarbons into the zeolite pores is improved, and the adsorption capacity is improved. Therefore, the present invention is characterized in that silica sol, water and alumina powder are added to zeolite powder to form a slurry, and then the slurry is applied to a monolith carrier, dried and then baked to form a coat layer. The present invention relates to a manufacturing method of.
【０００８】[0008]
【作用】本発明の方法によると、吸着材にコート層内部
まで炭化水素が効率良く拡散するようにゼオライト層中
に小孔を設けられる。そのために、ゼオライトスラリー
中にゼオライトの二次粒子より大きく、粒子間の間隔が
１００〜１５０Åのアルミナ粒子を混合し、ハニカム担
体に塗布する。ゼオライトとアルミナの混合比は１：１
〜１０：１の範囲で用いるのが望ましい。アルミナの分
量を増やすとハニカム担体にコートできる量が限られて
いるためゼオライト量が減少しＨＣ吸着量が減少する。
ゼオライトはスラリー調製のしやすさやコーティング性
などの点から平均粒子径0.5 〜３μm 程度の粉末を用い
るのが好ましく、小孔を形成するために混合するアルミ
ナは、アルミナの大きさが均一ではなく分布をもってい
るため平均粒子径が４〜６μm 程度の粉末を用いるのが
好ましい。このようにして形成される小孔はゼオライト
粒子と４〜６μm のアルミナとバインダーでつくられる
空間であり、１〜１０μm となっている。According to the method of the present invention, small pores are provided in the zeolite layer in the adsorbent so that hydrocarbons can be efficiently diffused into the coating layer. Therefore, alumina particles having a size larger than the secondary particles of zeolite and having an interval between the particles of 100 to 150Å are mixed in the zeolite slurry and applied to the honeycomb carrier. Mixing ratio of zeolite and alumina is 1: 1
It is desirable to use in the range of 10: 1. If the amount of alumina is increased, the amount that can be coated on the honeycomb carrier is limited, so the amount of zeolite decreases and the amount of HC adsorption decreases.
Zeolite is preferably a powder having an average particle size of 0.5 to 3 μm from the viewpoint of ease of slurry preparation and coating properties. The alumina mixed to form the small pores has a non-uniform alumina size. Therefore, it is preferable to use a powder having an average particle diameter of about 4 to 6 μm. The small pores formed in this way are spaces formed by zeolite particles, 4 to 6 μm of alumina and a binder, and are 1 to 10 μm.
【０００９】ゼオライトには多くの種類があるが、本発
明の方法に用いるゼオライトとしては、常温ないし比較
的高い温度まで水の存在雰囲気下でも十分なＨＣ吸着能
を有し、かつ耐久性の高いものを適宜選択する。この内
炭化水素の吸着量から考えてシリカ／アルミナのモル比
が５０〜２０００であるゼオライトを用いるのが好まし
い。例えば、モネデナイト、ＵＳＹ、βゼオライト、Ｚ
ＳＭ−５が挙げられる。排ガス中の多種類のＨＣを効率
良く吸着するためには、細孔径や細孔構造の異なるゼオ
ライトを２種以上混合するのがより好ましい。Although there are many kinds of zeolite, the zeolite used in the method of the present invention has a sufficient HC adsorbing ability even at room temperature to a relatively high temperature in the presence of water and has a high durability. Choose one as appropriate. Considering the adsorption amount of hydrocarbons, it is preferable to use zeolite having a silica / alumina molar ratio of 50 to 2000. For example, mondenite, USY, β zeolite, Z
SM-5 is mentioned. In order to efficiently adsorb many kinds of HC in the exhaust gas, it is more preferable to mix two or more kinds of zeolites having different pore sizes and pore structures.
【００１０】また、本発明の方法で得られる吸着材のみ
でも十分な吸着能力を有するのが、排気系に装着して実
用化するためには温度の上昇とともに脱離するＨＣを浄
化する性能を追加した、吸着層（ゼオライト層）の上に
三元触媒層をコーティングする方法で得られる自己浄化
タイプの炭化水素吸着触媒がより好ましい。Further, the adsorbent obtained by the method of the present invention alone has a sufficient adsorbing ability. In order to put the adsorbent into the exhaust system and put it into practical use, the adsorbent must have the ability to purify HC that desorbs as the temperature rises. A self-cleaning type hydrocarbon adsorption catalyst obtained by a method of coating an additional adsorption layer (zeolite layer) with a three-way catalyst layer is more preferable.
【００１１】[0011]
【実施例】以下、本発明を実施例、比較例および試験例
によりさらに詳細に説明する。例において、部は特記し
ない限り重量部を表す。 実施例１ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）１００部、アル
ミナ１００部、シリカゾル（固形分２０％）２１５部、
１０％硝酸１４７部及び水４６部を磁性ポットに仕込
む、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。コーディエ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１時間仮焼成した。The present invention will be described below in more detail with reference to Examples, Comparative Examples and Test Examples. In the examples, parts are parts by weight unless otherwise stated. Example 1 100 parts of USY (SiO 2 / Al 2 O 3 = 50), 100 parts of alumina, 215 parts of silica sol (solid content 20%),
A washcoat slurry was manufactured by mixing 147 parts of 10% nitric acid and 46 parts of water into a magnetic pot and mixing and pulverizing for 40 minutes with a vibration mill device or for 6.5 hours with a universal ball mill device. The cordierite monolithic carrier was subjected to water absorption treatment by a suction coating method, and then the produced slurry 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 to 400
It was calcined at ℃ for 1 hour.
【００１２】これにより、ＵＳＹとアルミナが約６０ｇ
／Ｌコート量で担体にコートされた。上記ウォッシュコ
ート、乾燥、焼成をさらに２回繰り返して合計１５０ｇ
／Ｌのゼオライトにアルミナ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, about 60 g of USY and alumina
The carrier was coated with a coating amount of / L. The washcoat, drying and baking are repeated twice more for a total of 150g.
/ L zeolite was coated with a mixture of alumina and calcined in an air atmosphere at 650 ° C. for 4 hours to obtain (Adsorbent-1).
【００１３】実施例２ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）１００部、アル
ミナ５０部、シリカゾル（固形分２０％）２１５部、１
０％硝酸１１７部、水２部を磁器ポットに仕込み、実施
例１と同方法でＵＳＹとアルミナの混合スラリーを製造
した。そして、実施例１と同方法でモノリス担体上に１
５０ｇ／Ｌコートし、乾燥、６５０℃で３時間焼成を行
い、（吸着材−２）を得た。Example 2 100 parts of USY (SiO 2 / Al 2 O 3 = 50), 50 parts of alumina, 215 parts of silica sol (solid content 20%), 1
117 parts of 0% nitric acid and 2 parts of water were charged in a porcelain pot, and a mixed slurry of USY and alumina was produced by the same method as in Example 1. Then, in the same manner as in Example 1, 1 on the monolith carrier.
50 g / L coating, drying and baking at 650 ° C. for 3 hours were performed to obtain (Adsorbent-2).
【００１４】実施例３ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）５０部、ＺＳＭ
−５（ＳｉＯ2 ／Ａｌ 2 Ｏ3 ＝７００）５０部、アルミ
ナ５０部、シリカゾル（固形分２０％）２１５部、１０
％硝酸１１７部、水２部を磁器ポットに仕込み、実施例
１と同方法でＵＳＹ、ＺＳＭ−５、アルミナ混合スラリ
ーを製造した。そして、同方法でモノリス担体上に１５
０ｇ／Ｌコートし、乾燥、６５０℃で４時間焼成を行
い、（吸着材−３）を得た。Example 3 USY (SiOTwo/ AlTwoOThree= 50) 50 copies, ZSM
-5 (SiOTwo/ Al TwoOThree= 700) 50 parts, aluminum
50 parts, silica sol (solid content 20%) 215 parts, 10
% 117% nitric acid and 2 parts water were charged in a porcelain pot,
USY, ZSM-5, alumina mixed slurry in the same manner as 1.
Was manufactured. Then, in the same manner, 15
Coat with 0 g / L, dry and bake at 650 ° C for 4 hours.
(Adsorbent-3) was obtained.
【００１５】実施例４ βゼオライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）５０部、
ＺＳＭ−５（ＳｉＯ2／Ａｌ2 Ｏ3 ＝７００）５０部、
アルミナ５０部、シリカゾル（固形分２０％）２１５
部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でβゼオライト、ＺＳＭ−５、ア
ルミナ混合スラリーを製造した。そして、同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、６５０℃で
３時間焼成を行い、（吸着材−４）を得た。Example 4 50 parts of β zeolite (SiO 2 / Al 2 O 3 = 50),
ZSM-5 (SiO 2 / Al 2 O 3 = 700) 50 parts,
Alumina 50 parts, silica sol (solid content 20%) 215
, 10% nitric acid (117 parts) and water (2 parts) were charged into a porcelain pot, and a β-zeolite, ZSM-5, and alumina mixed slurry was produced in the same manner as in Example 1. Then, the monolith carrier was coated with 150 g / L by the same method, dried and baked at 650 ° C. for 3 hours to obtain (Adsorbent-4).
【００１６】実施例５ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）５０部、ＺＳＭ
−５（ＳｉＯ2 ／Ａｌ 2 Ｏ3 ＝７００）５０部、アルミ
ナ５０部、シリカゾル（固形分２０％）２１５部、１０
％硝酸１１７部、水２部を磁器ポットに仕込み、実施例
３と同方法でＵＳＹ、ＺＳＭ−５、アルミナ混合スラリ
ーを製造した。そして、同方法でモノリス担体上に１５
０ｇ／Ｌコートし、乾燥、焼成を行なった。次に、Ｐｔ
を担持した活性セリア粉末（以下、Ｐｔ／ＣｅＯ2 と記
す）１００部、アルミナ５０部、２％硝酸１５０部を磁
器ポットに仕込み、前記と同様にしてウォッシュコート
スラリーを製造し、同方法でＵＳＹ、ＺＳＭ−５、アル
ミナ混合層の上に１００ｇ／ＬのＰｔ触媒層をコート
し、乾燥後、空気雰囲気中６５０℃で４時間の焼成を行
なった。さらに、Ｒｈを担持したアルミナ粉末（以下、
Ｒｈ／Ａｌ2 Ｏ3 と記す）１００部、アルミナ５０部、
２％硝酸１５０部を磁器ポットに仕込み、前記と同様に
してウォッシュコートスラリーを製造し、同方法でＰｔ
／ＣｅＯ2 層の上に５０ｇ／ＬのＲｈ／Ａｌ2 Ｏ3 触媒
層をコートし、乾燥後、空気雰囲気中６５０℃で４時間
の焼成を行い、（吸着触媒−１）を得た。Example 5 USY (SiOTwo/ AlTwoOThree= 50) 50 copies, ZSM
-5 (SiOTwo/ Al TwoOThree= 700) 50 parts, aluminum
50 parts, silica sol (solid content 20%) 215 parts, 10
% 117% nitric acid and 2 parts water were charged in a porcelain pot,
USY, ZSM-5, alumina mixed slurry in the same manner as 3
Was manufactured. Then, in the same manner, 15
It was coated with 0 g / L, dried and baked. Next, Pt
Activated ceria powder carrying (hereinafter, Pt / CeOTwoAnd
100 parts, alumina 50 parts, 2% nitric acid 150 parts
Put in a pot and wash coat as above
A slurry is prepared and USY, ZSM-5, Al
Coat 100g / L Pt catalyst layer on Mina mixing layer
Then, after drying, calcination is performed in an air atmosphere at 650 ° C for 4 hours.
became. Furthermore, alumina powder supporting Rh (hereinafter,
Rh / AlTwoOThree100 parts, alumina 50 parts,
Charge 150 parts of 2% nitric acid into a porcelain pot, and in the same manner as above
To produce a washcoat slurry, and use the same method to produce Pt.
/ CeOTwo50g / L Rh / Al on the layerTwoOThreecatalyst
After coating the layers and drying, air atmosphere at 650 ° C for 4 hours
Was fired to obtain (Adsorption catalyst-1).
【００１７】実施例６ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）５０部、ＺＳＭ
−５（ＳｉＯ2 ／Ａｌ 2 Ｏ3 ＝７００）を５０部、アル
ミナ５０部、シリカゾル（固形分２０％）２１５部、１
０％硝酸１１７部、水２部を磁器ポットに仕込み、実施
例３と同方法でＵＳＹ、ＺＳＭ−５、アルミナ混合スラ
リーを製造した。そして、同方法でモノリス担体上に１
５０ｇ／Ｌコートし、乾燥、焼成を行なった。次に、Ｐ
ｄを担持した活性アルミナ粉末（以下、Ｐｄ／Ａｌ2 Ｏ
3 と記す）１００部、アルミナ５０部、２％硝酸１５０
部を磁器ポットに仕込み、実施例５と同方法でウォッシ
ュコートスラリーを製造し、同コート方法でＵＳＹ、Ｚ
ＳＭ−５、アルミナ層の上に１００ｇ／ＬのＰｄ触媒層
をコートし、乾燥後、空気雰囲気中６５０℃で３時間の
焼成を行なった。さらに、実施例５と同方法でＲｈ／Ａ
ｌ2 Ｏ3 触媒層をＰｄ／Ａｌ2 Ｏ3 層上に５０ｇ／Ｌコ
ートし、乾燥、焼成を行い、（吸着触媒−２）を得た。Example 6 USY (SiOTwo/ AlTwoOThree= 50) 50 copies, ZSM
-5 (SiOTwo/ Al TwoOThree= 700), 50 copies, al
Mina 50 parts, silica sol (solid content 20%) 215 parts, 1
Pour porcelain pot with 117 parts of 0% nitric acid and 2 parts of water
USY, ZSM-5, alumina mixed slurry in the same manner as in Example 3.
Manufactured Lee. And 1 on the monolith carrier in the same way
It was coated with 50 g / L, dried and baked. Next, P
Activated alumina powder carrying d (hereinafter referred to as Pd / AlTwoO
Three100 parts, alumina 50 parts, 2% nitric acid 150
Part was placed in a porcelain pot and washed in the same manner as in Example 5.
Of the same coating method to produce USY, Z
SM-5, 100 g / L Pd catalyst layer on alumina layer
Coating, and after drying, leave it in an air atmosphere at 650 ° C for 3 hours.
Firing was performed. Further, in the same manner as in Example 5, Rh / A
lTwoOThreeCatalyst layer is Pd / AlTwoOThree50g / L on the layer
The resulting product was dried, dried and calcined to obtain (Adsorption catalyst-2).
【００１８】実施例７ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）１００部、アル
ミナ５０部、シリカゾル（固形分２０％）２１５部、１
０％硝酸１１７部、水２部を磁性ポットに仕込み、実施
例１と同方法でＵＳＹとアルミナの混合スラリーを製造
した。そして、実施例１と同方法でモノリス担体上に１
５０ｇ／Ｌコートし、乾燥焼成を行なった。次に、実施
例５と同方法でＵＳＹ、アルミナ層の上に１００ｇ／Ｌ
のＰｔ／ＣｅＯ2 触媒層をコートし、乾燥、焼成を行な
った。さらに、実施例５と同方法でＵＳＹ、アルミナ層
の上に１００ｇ／ＬのＰｔ／ＣｅＯ2 触媒層をコート
し、乾燥、焼成を行なった。さらに、実施例５と同方法
でＰｔ／ＣｅＯ2 層の上にＲｈ／Ａｌ2 Ｏ3 触媒層を５
０ｇ／Ｌコートし、乾燥、焼成を行い、（吸着触媒−
３）を得た。Example 7 100 parts of USY (SiO 2 / Al 2 O 3 = 50), 50 parts of alumina, 215 parts of silica sol (solid content 20%), 1
117 parts of 0% nitric acid and 2 parts of water were charged into a magnetic pot, and a mixed slurry of USY and alumina was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, 1 on the monolith carrier.
It was coated with 50 g / L and dried and baked. Next, in the same manner as in Example 5, 100 g / L on USY and the alumina layer.
Was coated with the Pt / CeO 2 catalyst layer, and dried and baked. Further, 100 g / L of Pt / CeO 2 catalyst layer was coated on USY and alumina layers by the same method as in Example 5, dried and fired. Furthermore, in the same manner as in Example 5, 5 Rh / Al 2 O 3 catalyst layers were formed on the Pt / CeO 2 layer.
Coating with 0 g / L, drying and firing, (adsorption catalyst-
3) was obtained.
【００１９】実施例８ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）１００部、アル
ミナ５０部、シリカゾル（固形分２０％）２１５部、１
０％硝酸１１７部、水２部を磁性ポットに仕込み、実施
例１と同方法でＵＳＹとアルミナの混合スラリーを製造
した。そして、実施例１と同方法でモノリス担体上に１
５０ｇ／Ｌコートし、乾燥焼成を行なった。次に、実施
例６と同方法でＵＳＹ、アルミナ層の上に１００ｇ／Ｌ
のＰｄ／Ａｌ2 Ｏ3 触媒層をコートし、乾燥、焼成を行
なった。さらに、実施例５と同方法でＲｈ／Ａｌ2 Ｏ3
触媒層を５０ｇ／Ｌコートし、乾燥、焼成を行い、（吸
着触媒−４）を得た。Example 8 100 parts of USY (SiO 2 / Al 2 O 3 = 50), 50 parts of alumina, 215 parts of silica sol (solid content 20%), 1
117 parts of 0% nitric acid and 2 parts of water were charged into a magnetic pot, and a mixed slurry of USY and alumina was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, 1 on the monolith carrier.
It was coated with 50 g / L and dried and baked. Next, in the same manner as in Example 6, 100 g / L on USY and the alumina layer.
Pd / Al 2 O 3 catalyst layer was coated, dried and fired. Furthermore, Rh / Al 2 O 3 was prepared in the same manner as in Example 5.
A catalyst layer was coated at 50 g / L, dried and baked to obtain (adsorption catalyst-4).
【００２０】実施例９ ＺＳＭ−５（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）１００部、
アルミナ５０部、シリカゾル（固形分２０％）２１５
部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でＺＳＭ−５とアルミナの混合ス
ラリーを製造した。そして、実施例１と同方法でモノリ
ス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行い、
（吸着材−５）を得た。Example 9 100 parts of ZSM-5 (SiO 2 / Al 2 O 3 = 50),
Alumina 50 parts, silica sol (solid content 20%) 215
Part, 10% nitric acid 117 parts, and water 2 parts were charged into a porcelain pot, and a mixed slurry of ZSM-5 and alumina was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, the monolith carrier was coated with 150 g / L, dried and baked,
(Adsorbent-5) was obtained.
【００２１】実施例１０ ＺＳＭ−５（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝７００）１００
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でＺＳＭ−５とアルミナの混合ス
ラリーを製造した。そして、実施例１と同方法でモノリ
ス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行なっ
た。次に、実施例５と同方法でＺＳＭ−５、アルミナ層
の上に１００ｇ／ＬのＰｔ／ＣｅＯ2 触媒層をコート
し、乾燥、焼成を行なった。さらに、実施例５と同方法
でＰｔ／ＣｅＯ2 層の上にＲｈ／Ａｌ2 Ｏ3 触媒層を５
０ｇ／Ｌコートし、乾燥、焼成を行い、（吸着触媒−
５）を得た。Example 10 ZSM-5 (SiO 2 / Al 2 O 3 = 700) 100
Parts, alumina 50 parts, silica sol (solid content 20%) 21
5 parts, 117 parts of 10% nitric acid and 2 parts of water were charged into a porcelain pot, and a mixed slurry of ZSM-5 and alumina was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, the monolith carrier was coated with 150 g / L, dried and baked. Then, 100 g / L of Pt / CeO 2 catalyst layer was coated on ZSM-5 and alumina layer by the same method as in Example 5, dried and fired. Furthermore, in the same manner as in Example 5, 5 Rh / Al 2 O 3 catalyst layers were formed on the Pt / CeO 2 layer.
Coating with 0 g / L, drying and firing, (adsorption catalyst-
5) was obtained.
【００２２】実施例１１ ＺＳＭ−５（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝７００）１００
部、アルミナ１００部、シリカゾル（固形分２０％）２
１５部、１０％硝酸１１７部、水２部を磁器ポットに仕
込み、実施例１と同方法でＺＳＭ−５とアルミナの混合
スラリーを製造した。そして、実施例１と同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行な
った。次に、実施例６と同方法でＵＳＹ、アルミナ層の
上に１００ｇ／ＬのＰｄ／Ａｌ2 Ｏ3 触媒層をコート
し、乾燥、焼成を行なった。さらに、実施例５と同方法
でＲｈ／Ａｌ2 Ｏ3 触媒層をコートし、乾燥、焼成を行
なった。さらに、実施例５と同方法でＲｈ／Ａｌ2 Ｏ3
触媒層を５０ｇ／Ｌコートし、乾燥、焼成を行い、（吸
着触媒−６）を得た。Example 11 ZSM-5 (SiO 2 / Al 2 O 3 = 700) 100
Parts, alumina 100 parts, silica sol (solid content 20%) 2
A porcelain pot was charged with 15 parts, 117 parts of 10% nitric acid and 2 parts of water, and a mixed slurry of ZSM-5 and alumina was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, the monolith carrier was coated with 150 g / L, dried and baked. Next, in the same manner as in Example 6, 100 g / L of Pd / Al 2 O 3 catalyst layer was coated on USY and alumina layers, dried and baked. Further, a Rh / Al 2 O 3 catalyst layer was coated in the same manner as in Example 5, dried and fired. Furthermore, Rh / Al 2 O 3 was prepared in the same manner as in Example 5.
The catalyst layer was coated at 50 g / L, dried and calcined to obtain (Adsorption catalyst-6).
【００２３】実施例１２ モルデナイト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２００）１００
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でモルデナイトとアルミナの混合
スラリーを製造した。そして、実施例１と同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行な
い、（吸着材−６）を得た。Example 12 Mordenite (SiO 2 / Al 2 O 3 = 200) 100
Parts, alumina 50 parts, silica sol (solid content 20%) 21
5 parts, 117% nitric acid (117 parts) and water (2 parts) were charged into a porcelain pot, and a mixed slurry of mordenite and alumina was produced in the same manner as in Example 1. Then, a monolith carrier was coated with 150 g / L in the same manner as in Example 1, dried and fired to obtain (Adsorbent-6).
【００２４】実施例１３ モルデナイト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２００）１００
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でモルデナイトとアルミナの混合
スラリーを製造した。そして、実施例１と同方法でモノ
リス担体上に１５０ｇ／コートし、乾燥、焼成を行なっ
た。次に、実施例５と同方法でモルデナイト、アルミナ
層の上に１００ｇ／ＬのＰｔ／ＣｅＯ2 触媒層をコート
し、乾燥、焼成を行なった。さらに、実施例５と同方法
でＰｔ／ＣｅＯ2 層の上にＲｈ／Ａｌ2 Ｏ3 触媒層を５
０ｇ／Ｌコートし、乾燥、焼成を行い、（吸着触媒−
７）を得た。Example 13 Mordenite (SiO 2 / Al 2 O 3 = 200) 100
Parts, alumina 50 parts, silica sol (solid content 20%) 21
5 parts, 117% nitric acid (117 parts) and water (2 parts) were charged into a porcelain pot, and a mixed slurry of mordenite and alumina was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, the monolith carrier was coated with 150 g / coat, dried and fired. Next, in the same manner as in Example 5, a 100 g / L Pt / CeO 2 catalyst layer was coated on the mordenite and alumina layers, dried and fired. Furthermore, in the same manner as in Example 5, 5 Rh / Al 2 O 3 catalyst layers were formed on the Pt / CeO 2 layer.
Coating with 0 g / L, drying and firing, (adsorption catalyst-
7) was obtained.
【００２５】実施例１４ モルデナイト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２００）１００
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でモルデナイトとアルミナの混合
スラリーを製造した。そして、実施例１と同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行な
った。次に、実施例６と同方法でモルデナイト、アルミ
ナ層の上に１００ｇ／ＬのＰｄ／Ａｌ2 Ｏ3 触媒層をコ
ートし、乾燥、焼成を行なった。さらに、実施例５と同
方法でＲｈ／Ａｌ2 Ｏ3 触媒層を５０ｇ／Ｌコートし、
乾燥、焼成を行い、（吸着触媒−８）を得た。Example 14 Mordenite (SiO 2 / Al 2 O 3 = 200) 100
Parts, alumina 50 parts, silica sol (solid content 20%) 21
5 parts, 117% nitric acid (117 parts) and water (2 parts) were charged into a porcelain pot, and a mixed slurry of mordenite and alumina was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, the monolith carrier was coated with 150 g / L, dried and baked. Next, in the same manner as in Example 6, 100 g / L of Pd / Al 2 O 3 catalyst layer was coated on the mordenite and alumina layers, dried and fired. Further, 50 g / L of Rh / Al 2 O 3 catalyst layer was coated in the same manner as in Example 5,
It was dried and calcined to obtain (Adsorption catalyst-8).
【００２６】実施例１５ βゼオライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝１００）１００
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でβゼオライトとアルミナの混合
スラリーを製造した。そして、実施例１と同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行
い、（吸着材−７）を得た。Example 15 β zeolite (SiO 2 / Al 2 O 3 = 100) 100
Parts, alumina 50 parts, silica sol (solid content 20%) 21
5 parts, 117% nitric acid (117 parts) and water (2 parts) were charged into a porcelain pot to prepare a mixed slurry of β zeolite and alumina by the same method as in Example 1. Then, in the same manner as in Example 1, a monolith carrier was coated with 150 g / L, dried and baked to obtain (Adsorbent-7).
【００２７】実施例１６ βゼオライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝１００）１００
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でβゼオライトとアルミナの混合
スラリーを製造した。そして、実施例１と同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行な
った。次に実施例５と同方法でβゼオライト、アルミナ
層の上に１００ｇ／ＬのＰｔ／ＣｅＯ2 触媒層をコート
し、乾燥、焼成を行なった。さらに、実施例５と同方法
でＰｔ／ＣｅＯ2 層の上にＲｈ／Ａｌ2 Ｏ3 触媒層を５
０ｇ／Ｌコートし、乾燥、焼成を行い、（吸着触媒−
９）を得た。Example 16 β zeolite (SiO 2 / Al 2 O 3 = 100) 100
Parts, alumina 50 parts, silica sol (solid content 20%) 21
5 parts, 117% nitric acid (117 parts) and water (2 parts) were charged into a porcelain pot to prepare a mixed slurry of β zeolite and alumina by the same method as in Example 1. Then, in the same manner as in Example 1, the monolith carrier was coated with 150 g / L, dried and baked. Next, in the same manner as in Example 5, a 100 g / L Pt / CeO 2 catalyst layer was coated on the β-zeolite and alumina layers, dried and calcined. Furthermore, in the same manner as in Example 5, 5 Rh / Al 2 O 3 catalyst layers were formed on the Pt / CeO 2 layer.
Coating with 0 g / L, drying and firing, (adsorption catalyst-
9) was obtained.
【００２８】実施例１７ βゼオライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝１００）１００
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でβゼオライトとアルミナの混合
スラリーを製造した。そして、実施例１と同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行な
った。次に、実施例６と同方法でβゼオライト、アルミ
ナ層の上に１００ｇ／ＬのＰｄ／Ａｌ2 Ｏ3 触媒層をコ
ートし、乾燥、焼成を行なった。さらに、実施例５と同
方法でＲｈ／Ａｌ2 Ｏ3 触媒層を５０ｇ／Ｌコートし、
乾燥、焼成を行い、（吸着触媒−１０）を得た。Example 17 β zeolite (SiO 2 / Al 2 O 3 = 100) 100
Parts, alumina 50 parts, silica sol (solid content 20%) 21
5 parts, 117% nitric acid (117 parts) and water (2 parts) were charged into a porcelain pot to prepare a mixed slurry of β zeolite and alumina by the same method as in Example 1. Then, in the same manner as in Example 1, the monolith carrier was coated with 150 g / L, dried and baked. Next, in the same manner as in Example 6, 100 g / L of Pd / Al 2 O 3 catalyst layer was coated on the β-zeolite and alumina layer, dried and calcined. Further, 50 g / L of Rh / Al 2 O 3 catalyst layer was coated in the same manner as in Example 5,
It was dried and calcined to obtain (Adsorption catalyst-10).
【００２９】実施例１８ モルデナイト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２００）５０
部、ＺＳＭ−５（ＳｉＯ 2 ／Ａｌ2 Ｏ3 ＝７００）５０
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例３と同方法でモルデナイト、ＺＳＭ−５、ア
ルミナ混合スラリーを製造した。そして、同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行
い、（吸着材−８）を得た。Example 18 Mordenite (SiO 2Two/ AlTwoOThree= 200) 50
Part, ZSM-5 (SiO Two/ AlTwoOThree= 700) 50
Parts, alumina 50 parts, silica sol (solid content 20%) 21
Charge 5 parts, 117% nitric acid 117 parts, and water 2 parts into a porcelain pot
In the same manner as in Example 3, mordenite, ZSM-5,
A Lumina mixed slurry was produced. And in the same way
150g / L coating on squirrel carrier, drying and baking
(Adsorbent-8) was obtained.
【００３０】実施例１９ モルデナイト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２００）５０
部、ＺＳＭ−５（ＳｉＯ 2 ／Ａｌ2 Ｏ3 ＝７００）５０
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例３と同方法でモルデナイト、ＺＳＭ−５、ア
ルミナ混合スラリーを製造した。そして、同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行な
った。次に、実施例５と同方法でモルデナイト、ＺＳＭ
−５、アルミナ層の上に１００ｇ／ＬのＰｔ／ＣｅＯ2
触媒層をコートし、乾燥、焼成を行なった。さらに、実
施例５と同方法でＰｔ／ＣｅＯ2 層の上にＲｈ／Ａｌ2
Ｏ3 触媒層を５０ｇ／Ｌコートし、乾燥、焼成を行い、
（吸着触媒−１１）を得た。Example 19 Mordenite (SiO 2Two/ AlTwoOThree= 200) 50
Part, ZSM-5 (SiO Two/ AlTwoOThree= 700) 50
Parts, alumina 50 parts, silica sol (solid content 20%) 21
Charge 5 parts, 117% nitric acid 117 parts, and water 2 parts into a porcelain pot
In the same manner as in Example 3, mordenite, ZSM-5,
A Lumina mixed slurry was produced. And in the same way
Coat the squirrel carrier with 150g / L, and dry and bake.
Was. Next, in the same manner as in Example 5, mordenite, ZSM
-5, 100 g / L Pt / CeO on the alumina layerTwo
The catalyst layer was coated, dried and baked. Moreover, the real
Pt / CeO in the same manner as in Example 5TwoRh / Al on the layerTwo
OThreeThe catalyst layer is coated at 50 g / L, dried and baked,
(Adsorption catalyst-11) was obtained.
【００３１】実施例２０ モルデナイト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２００）５０
部、ＺＳＭ−５（ＳｉＯ 2 ／Ａｌ2 Ｏ3 ＝７００）５０
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例３と同方法でモルデナイト、ＺＳＭ−５、ア
ルミナ混合スラリーを製造した。そして、同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行な
った。次に、実施例６と同方法でモルデナイト、ＺＳＭ
−５、アルミナ層の上に１００ｇ／ＬのＰｄ／Ａｌ2 Ｏ
3 触媒層をコートし、乾燥、焼成を行なった。さらに、
実施例５と同方法でＲｈ／Ａｌ2 Ｏ3 触媒層を５０ｇ／
Ｌコートし、乾燥、焼成を行い、（吸着触媒−１２）を
得た。Example 20 Mordenite (SiOTwo/ AlTwoOThree= 200) 50
Part, ZSM-5 (SiO Two/ AlTwoOThree= 700) 50
Parts, alumina 50 parts, silica sol (solid content 20%) 21
Charge 5 parts, 117% nitric acid 117 parts, and water 2 parts into a porcelain pot
In the same manner as in Example 3, mordenite, ZSM-5,
A Lumina mixed slurry was produced. And in the same way
Coat the squirrel carrier with 150g / L, and dry and bake.
Was. Next, in the same manner as in Example 6, mordenite, ZSM
-5, 100 g / L Pd / Al on the alumina layerTwoO
ThreeThe catalyst layer was coated, dried and baked. further,
In the same manner as in Example 5, Rh / AlTwoOThree50 g / catalyst layer
L-coat, dry and bake to obtain (adsorption catalyst-12)
Obtained.
【００３２】実施例２１ βゼオライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝１００）５０
部、ＺＳＭ−５（ＳｉＯ 2 ／Ａｌ2 Ｏ3 ＝７００）５０
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でβゼオライト、ＺＳＭ−５、ア
ルミナ混合スラリーを製造した。そして、同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥し、焼成を行
なった。次に、実施例５と同方法でβゼオライト、ＺＳ
Ｍ−５、アルミナ層の上に１００ｇ／ＬのＰｔ／ＣｅＯ
2 触媒層をコートし、乾燥、焼成を行なった。さらに、
実施例５と同方法でＰｔ／ＣｅＯ2 層の上にＲｈ／Ａｌ
2 Ｏ3 触媒層を５０ｇ／Ｌコートし、乾燥、焼成を行
い、（吸着触媒−１３）を得た。Example 21 β zeolite (SiOTwo/ AlTwoOThree= 100) 50
Part, ZSM-5 (SiO Two/ AlTwoOThree= 700) 50
Parts, alumina 50 parts, silica sol (solid content 20%) 21
Charge 5 parts, 117% nitric acid 117 parts, and water 2 parts into a porcelain pot
In the same manner as in Example 1, β-zeolite, ZSM-5,
A Lumina mixed slurry was produced. And in the same way
Coat 150g / L on a squirrel carrier, dry and bake.
became. Next, in the same manner as in Example 5, β zeolite and ZS
M-5, 100 g / L Pt / CeO on the alumina layer
TwoThe catalyst layer was coated, dried and baked. further,
Pt / CeO in the same manner as in Example 5TwoRh / Al on the layer
TwoOThree50g / L coating of catalyst layer, drying and baking
(Adsorption catalyst-13) was obtained.
【００３３】実施例２２ βゼオライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝１００）５０
部、ＺＳＭ−５（ＳｉＯ 2 ／Ａｌ2 Ｏ3 ＝７００）５０
部、アルミナ５０部、シリカゾル（固形分２０％）２１
５部、１０％硝酸１１７部、水２部を磁器ポットに仕込
み、実施例１と同方法でβゼオライト、ＺＳＭ−５、ア
ルミナ混合スラリーを製造した。そして、同方法でモノ
リス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行な
った。次に、実施例６と同方法でβゼオライト、ＺＳＭ
−５、アルミナ層の上に１００ｇ／ＬのＰｄ／Ａｌ2 Ｏ
3 触媒層をコートし、乾燥、焼成を行なった。さらに、
実施例５と同方法でＲｈ／Ａｌ2 Ｏ3 触媒層を５０ｇ／
Ｌコートし、乾燥、焼成を行い、（吸着触媒−２２）を
得た。Example 22 β zeolite (SiOTwo/ AlTwoOThree= 100) 50
Part, ZSM-5 (SiO Two/ AlTwoOThree= 700) 50
Parts, alumina 50 parts, silica sol (solid content 20%) 21
Charge 5 parts, 117% nitric acid 117 parts, and water 2 parts into a porcelain pot
In the same manner as in Example 1, β-zeolite, ZSM-5,
A Lumina mixed slurry was produced. And in the same way
Coat the squirrel carrier with 150g / L, and dry and bake.
Was. Next, in the same manner as in Example 6, β-zeolite and ZSM
-5, 100 g / L Pd / Al on the alumina layerTwoO
ThreeThe catalyst layer was coated, dried and baked. further,
In the same manner as in Example 5, Rh / AlTwoOThree50 g / catalyst layer
L-coat, dry, and bake to remove (adsorption catalyst-22)
Obtained.
【００３４】実施例２３ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）３３部、ＺＳＭ
−５（ＳｉＯ2 ／Ａｌ 2 Ｏ3 ＝７００）３３部、βゼオ
ライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝１００）３３部、アル
ミナ５０部、シリカゾル（固形分２０％）２１５部、１
０％硝酸１１７部、水２部を磁器ポットに仕込み、実施
例３と同方法で混合スラリーを製造した。そして、同方
法でモノリス担体上に１５０ｇ／Ｌコートし、乾燥、焼
成を行い、（吸着材−９）を得た。Example 23 USY (SiOTwo/ AlTwoOThree= 50) 33 copies, ZSM
-5 (SiOTwo/ Al TwoOThree= 700) 33 parts, β Zeo
Light (SiOTwo/ AlTwoOThree= 100) 33 copies, al
Mina 50 parts, silica sol (solid content 20%) 215 parts, 1
Pour porcelain pot with 117 parts of 0% nitric acid and 2 parts of water
A mixed slurry was produced in the same manner as in Example 3. And the same person
Method to coat 150g / L on monolith carrier, dry and bake
(Adsorbent-9) was obtained.
【００３５】実施例２４ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）３３部、ＺＳＭ
−５（ＳｉＯ2 ／Ａｌ 2 Ｏ3 ＝７００）３３部、βゼオ
ライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝１００）３３部、アル
ミナ５０部、シリカゾル（固形分２０％）２１５部、１
０％硝酸１１７部、水２部を磁器ポットに仕込み、実施
例３と同方法で混合スラリーを製造した。そして、同方
法でモノリス担体上に１５０ｇ／Ｌコートし、乾燥し、
焼成を行なった。次に、実施例５と同方法でＺＳＭ−
５、ＵＳＹ、βゼオライト、アルミナ層の上に１００ｇ
／ＬのＰｔ／ＣｅＯ2 触媒層をコートし、乾燥、焼成を
行なった。さらに、実施例５と同方法でＰｔ／ＣｅＯ2
層の上にＲｈ／Ａｌ2 Ｏ3 触媒層を５０ｇ／Ｌコート
し、乾燥、焼成を行い、（吸着触媒−１５）を得た。Example 24 USY (SiOTwo/ AlTwoOThree= 50) 33 copies, ZSM
-5 (SiOTwo/ Al TwoOThree= 700) 33 parts, β Zeo
Light (SiOTwo/ AlTwoOThree= 100) 33 copies, al
Mina 50 parts, silica sol (solid content 20%) 215 parts, 1
Pour porcelain pot with 117 parts of 0% nitric acid and 2 parts of water
A mixed slurry was produced in the same manner as in Example 3. And the same person
Method to coat 150g / L on a monolith carrier, dry,
Firing was performed. Next, in the same manner as in Example 5, ZSM-
5, USY, β zeolite, 100g on alumina layer
/ L Pt / CeOTwoCoat the catalyst layer, and dry and calcine
Done. Furthermore, Pt / CeO was used in the same manner as in Example 5.Two
Rh / Al on the layerTwoOThree50g / L coating of catalyst layer
Then, it was dried and calcined to obtain (Adsorption catalyst-15).
【００３６】実施例２５ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）３３部、ＺＳＭ
−５（ＳｉＯ2 ／Ａｌ 2 Ｏ3 ＝７００）３３部、βゼオ
ライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝１００）３３部、アル
ミナ５０部、シリカゾル（固形分２０％）２１５部、１
０％硝酸１１７部、水２部を磁器ポットに仕込み、実施
例３と同方法で混合スラリーを製造した。そして、同方
法でモノリス担体上に１５０ｇ／Ｌコートし、乾燥、焼
成を行なった。次に、実施例６と同方法でＵＳＹ、ＺＳ
Ｍ−５、βゼオライト、アルミナ層の上に１００ｇ／Ｌ
のＰｄ／Ａｌ2 Ｏ3 触媒層をコートし、乾燥、焼成を行
なった。さらに、実施例５と同方法でＲｈ／Ａｌ2 Ｏ3
触媒層を５０ｇ／Ｌコートし、乾燥、焼成を行い、吸着
触媒−１６）を得た。Example 25 USY (SiOTwo/ AlTwoOThree= 50) 33 copies, ZSM
-5 (SiOTwo/ Al TwoOThree= 700) 33 parts, β Zeo
Light (SiOTwo/ AlTwoOThree= 100) 33 copies, al
Mina 50 parts, silica sol (solid content 20%) 215 parts, 1
Pour porcelain pot with 117 parts of 0% nitric acid and 2 parts of water
A mixed slurry was produced in the same manner as in Example 3. And the same person
Method to coat 150g / L on monolith carrier, dry and bake
Was performed. Next, in the same manner as in Example 6, USY, ZS
M-5, β zeolite, 100g / L on the alumina layer
Pd / AlTwoOThreeCoat the catalyst layer, dry and calcine
became. Further, Rh / Al was formed in the same manner as in Example 5.TwoOThree
Adsorption of 50g / L of catalyst layer, drying and baking, adsorption
Catalyst-16) was obtained.
【００３７】実施例２６ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）３３部、ＺＳＭ
−５（ＳｉＯ2 ／Ａｌ 2 Ｏ3 ＝７００）３３部、モルデ
ナイト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２００）３３部、アル
ミナ５０部、シリカゾル（固形分２０％）２１５部、１
０％硝酸１１７部、水２部を磁器ポットに仕込み、実施
例３と同方法で混合スラリーを製造した。そして、同方
法でモノリス担体上に１５０ｇ／Ｌコードし、乾燥、焼
成を行い、（吸着材−１０）を得た。Example 26 USY (SiOTwo/ AlTwoOThree= 50) 33 copies, ZSM
-5 (SiOTwo/ Al TwoOThree= 700) 33 parts, Molde
Knight (SiOTwo/ AlTwoOThree= 200) 33 copies, al
Mina 50 parts, silica sol (solid content 20%) 215 parts, 1
Pour porcelain pot with 117 parts of 0% nitric acid and 2 parts of water
A mixed slurry was produced in the same manner as in Example 3. And the same person
150g / L code on monolith carrier by the method, dry and bake
(Adsorbent-10) was obtained.
【００３８】実施例２７ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）３３部、ＺＳＭ
−５（ＳｉＯ2 ／Ａｌ 2 Ｏ3 ＝７００）、モルデナイト
（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２００）３３部、アルミナ５
０部、シリカゾル（固形分２０％）２１５部、１０％硝
酸１１７部、水２部を磁器ポットに仕込み、実施例３と
同方法で混合スラリーを製造した。そして、同方法でモ
ノリス担体上に１５０ｇ／Ｌコートし、乾燥、焼成を行
なった。次に、実施例５と同方法でＺＳＭ−５、ＵＳ
Ｙ、モルデナイト、アルミナ層の上に１００ｇ／ＬのＰ
ｔ／ＣｅＯ2 触媒層をコートし、乾燥、焼成を行なっ
た。さらに、実施例５と同方法でＰｔ／ＣｅＯ2 層の上
にＲｈ／Ａｌ2 Ｏ3 触媒層を５０ｇ／Ｌコートし、乾
燥、焼成を行い、（吸着触媒−１７）を得た。Example 27 USY (SiOTwo/ AlTwoOThree= 50) 33 copies, ZSM
-5 (SiOTwo/ Al TwoOThree= 700), mordenite
(SiOTwo/ AlTwoOThree= 200) 33 parts, 5 alumina
0 part, silica sol (solid content 20%) 215 parts, 10% glass
117 parts of acid and 2 parts of water were charged into a porcelain pot,
A mixed slurry was produced by the same method. And in the same way
Norris carrier coated at 150g / L, dried and fired
became. Then, in the same manner as in Example 5, ZSM-5, US
Y, mordenite, P of 100g / L on alumina layer
t / CeOTwoCoat the catalyst layer, dry and calcine
Was. Furthermore, Pt / CeO was used in the same manner as in Example 5.TwoAbove the layers
To Rh / AlTwoOThreeCoat the catalyst layer with 50g / L and dry.
It was dried and calcined to obtain (Adsorption catalyst-17).
【００３９】実施例２８ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）３３部、ＺＳＭ
−５（ＳｉＯ2 ／Ａｌ 2 Ｏ3 ＝７００）３３部、モルデ
ナイト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２００）３３部、アル
ミナ５０部、シリカゾル（固形分２０％）２１５部、１
０％硝酸１１７部、水２部を磁器ポットに仕込み、実施
例３と同方法で混合スラリーを製造した。そして、同方
法でモノリス担体上に１５０ｇ／Ｌコートし、乾燥、焼
成を行なった。次に、実施例６と同方法でＵＳＹ、ＺＳ
Ｍ−５、モルデナイト、アルミナ層の上に１００ｇ／Ｌ
のＰｄ／Ａｌ2 Ｏ3 触媒層をコートし、乾燥、焼成を行
なった。さらに、実施例５と同方法でＲｈ／Ａｌ2 Ｏ3
触媒層を５０ｇ／Ｌコートし、乾燥、焼成を行い、（吸
着触媒−１８）を得た。Example 28 USY (SiOTwo/ AlTwoOThree= 50) 33 copies, ZSM
-5 (SiOTwo/ Al TwoOThree= 700) 33 parts, Molde
Knight (SiOTwo/ AlTwoOThree= 200) 33 copies, al
Mina 50 parts, silica sol (solid content 20%) 215 parts, 1
Pour porcelain pot with 117 parts of 0% nitric acid and 2 parts of water
A mixed slurry was produced in the same manner as in Example 3. And the same person
Method to coat 150g / L on monolith carrier, dry and bake
Was performed. Next, in the same manner as in Example 6, USY, ZS
M-5, mordenite, 100g / L on the alumina layer
Pd / AlTwoOThreeCoat the catalyst layer, dry and calcine
became. Further, Rh / Al was formed in the same manner as in Example 5.TwoOThree
The catalyst layer is coated at 50 g / L, dried and baked, and
Thus, the deposition catalyst-18) was obtained.
【００４０】比較例１ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝５０）１００部、シリ
カゾル（固形分２０％）２１５部、１０％硝酸水１００
部、水１５部を磁器ポットに仕込み、実施例１と同方法
でウォッシュコートスラリーを製造し、同コート方法で
モノリス担体に１５０ｇ／Ｌコート、乾燥、焼成を行な
い、（吸着材−１１）を得た。Comparative Example 1 USY (SiO 2 / Al 2 O 3 = 50) 100 parts, silica sol (solid content 20%) 215 parts, 10% nitric acid water 100
Parts and 15 parts of water were charged in a porcelain pot, a washcoat slurry was produced by the same method as in Example 1, and a monolith carrier was coated with 150 g / L, dried and fired by the same coating method as (Adsorbent-11). Obtained.
【００４１】比較例２ ＵＳＹ（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝７）１００部、シリカ
ゾル（固形分２０％）２１５部、１０％硝酸水１００
部、水１５部を磁器ポットに仕込み、実施例１と同方法
でウォッシュコートスラリーを製造し、同コート方法で
モノリス担体に１５０ｇ／Ｌコート、乾燥、焼成を行な
い、（吸着材−１２）を得た。Comparative Example 2 USY (SiO 2 / Al 2 O 3 = 7) 100 parts, silica sol (solid content 20%) 215 parts, 10% nitric acid water 100
Parts and 15 parts of water were charged in a porcelain pot, a washcoat slurry was produced by the same method as in Example 1, and a monolith carrier was coated with 150 g / L, dried and baked by the same coating method as (Adsorbent-12). Obtained.
【００４２】比較例３ ＺＳＭ−５（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝２２）１００部、
シリカゾル（固形分２０％）２１５部、１０％硝酸水１
００部、水１５部を磁器ポットに仕込み、実施例１と同
方法でウォッシュコートスラリーを製造した。同コート
方法でモノリス担体に１５０ｇ／Ｌコート、乾燥、焼成
を行ない、（吸着材−１３）を得た。Comparative Example 3 100 parts of ZSM-5 (SiO 2 / Al 2 O 3 = 22),
215 parts of silica sol (solid content 20%), 10% nitric acid water 1
00 parts and 15 parts of water were charged into a porcelain pot, and a washcoat slurry was produced by the same method as in Example 1. By the same coating method, the monolith carrier was coated with 150 g / L, dried and baked to obtain (Adsorbent-13).
【００４３】試験例 実施例１〜２８および比較例１〜３の吸着材および吸着
触媒を用いて下記評価条件でＨＣ吸着・浄化特性評価を
行い、得た結果を表１に示す。尚評価に当っては図１に
示すようにエンジン１のエキゾーストマニホールド２に
プリ三元触媒3(0.5 Ｌ）としてＰｔ−Ｒｈ系触媒を配置
し、床下触媒5(1.3 Ｌ）のＰｔ−Ｒｈ系触媒の前に吸着
材または吸着触媒４（1.3 Ｌ）を装着した排ガス浄化装
置を用い、吸着材未装着の場合と性能比較を行った。評
価に当たっては、 (1) エンジン始動時に排出されるＨＣの吸着能を評価
するためAbag０〜１２５秒間のエミッション低減率を測
定した。 (2) 一時的に吸着したＨＣも吸着触媒下流の三元触媒
が活性化する前に脱離してエミッション低減効果がな
い。そこで吸着触媒による脱離抑制能および自己浄化能
を評価するためにAbag０〜５０５秒間のエミッション低
減率を測定した。 評価条件 触媒容量 1.3 Ｌ 評価車両 日産自動車（株）製、Ｖ型６気筒３０
００ｃｃエンジン 評価モード ＬＡ４−ＣＨ（Abag) エンジン始動時に排出される（触媒入口のガス中の）炭
化水素 炭素数 Ｃ２〜Ｃ３ 21.2 ％ Ｃ４〜Ｃ６ 33.0 ％ Ｃ７〜Ｃ９ 45.8 ％Test Example Using the adsorbents and adsorption catalysts of Examples 1 to 28 and Comparative Examples 1 to 3, HC adsorption / purification characteristics were evaluated under the following evaluation conditions, and the obtained results are shown in Table 1. In the evaluation, as shown in FIG. 1, a Pt-Rh system catalyst was placed as the pre-three-way catalyst 3 (0.5 L) in the exhaust manifold 2 of the engine 1, and a Pt-Rh system of the underfloor catalyst 5 (1.3 L) was arranged. Using an exhaust gas purifying apparatus equipped with an adsorbent or an adsorbent catalyst 4 (1.3 L) in front of the catalyst, the performance was compared with the case without the adsorbent. In the evaluation, (1) the emission reduction rate of Abag for 0 to 125 seconds was measured in order to evaluate the adsorption ability of HC discharged at the time of engine start. (2) HC that is temporarily adsorbed is also desorbed before the three-way catalyst downstream of the adsorption catalyst is activated, and there is no emission reduction effect. Therefore, in order to evaluate the desorption suppressing ability and the self-cleaning ability by the adsorption catalyst, the emission reduction rate in Abag 0 to 505 seconds was measured. Evaluation conditions Catalyst capacity 1.3 L Evaluation vehicle V6 cylinder 30 manufactured by Nissan Motor Co., Ltd.
00cc Engine evaluation mode LA4-CH (Abag) Hydrocarbons (in the gas at the catalyst inlet) exhausted when the engine starts C2-C3 21.2% C4-C6 33.0% C7-C9 45.8%
【００４４】[0044]
【表１】 [Table 1]
【００４５】エンジン始動時は吸着材または吸着触媒を
装着すると、ＨＣを大幅に低減できるが温度の上昇とと
もに、ゼオライトからＨＣが脱離しはじめる。そのた
め、三元触媒を表層にコートしていない触媒はAbagで比
較すると、ＨＣ低減効果はない（床下触媒が活性化する
前に脱離するため）。ただし、ゼオライト層上に触媒を
コートすると、自己浄化（脱離するＨＣを表層で浄化）
作用によりＨＣを低減することができる。When the adsorbent or the adsorbing catalyst is attached at the time of starting the engine, HC can be greatly reduced, but as the temperature rises, HC begins to desorb from the zeolite. Therefore, a catalyst that does not coat the three-way catalyst on the surface layer has no HC reduction effect when compared with Abag (because the underfloor catalyst is desorbed before activation). However, if a catalyst is coated on the zeolite layer, it will self-clean (the desorbed HC will be cleaned on the surface).
By the action, HC can be reduced.
【００４６】また同じゼオライト種同士で比較すると吸
着材１と２は吸着材１１よりもガス拡散がよくなり、吸
着率が向上しAbag０〜１２５秒間の低減率がよくなる。
ただし下流の三元触媒の活性化前に脱離するため、Abag
０〜５０５秒間で比較をすると効果はない。しかしゼオ
ライト層上に三元触媒をコートした吸着触媒３と４では
Abag０〜１２５秒間の吸着能を保ちかつ自己浄化能によ
りAbag０〜５０５でも低減効果を有する。When the same zeolite species are compared, the adsorbents 1 and 2 have better gas diffusion than the adsorbent 11, the adsorption rate is improved, and the reduction rate of Abag for 0 to 125 seconds is good.
However, since it desorbs before activation of the downstream three-way catalyst, Abag
There is no effect when comparing for 0 to 505 seconds. However, in adsorption catalysts 3 and 4 in which the three-way catalyst is coated on the zeolite layer,
Abag has 0 to 125 seconds of adsorptive capacity and has self-cleaning ability, and Abag of 0 to 505 also has a reducing effect.
【発明の効果】以上説明してきたように、本発明の吸着
材および吸着触媒は、ゼオライト層において層中にアル
ミナ粒子を混合し、小孔を形成することで吸着サイトま
でのガス拡散性が向上し、排ガス中のＨＣを効率よく吸
着することができる。As described above, the adsorbent and the adsorbent catalyst of the present invention improve the gas diffusivity to the adsorption site by mixing alumina particles in the zeolite layer to form small pores. Therefore, HC in the exhaust gas can be efficiently adsorbed.
【図１】試験例に用いた排ガス浄化装置の系統図であ
る。FIG. 1 is a system diagram of an exhaust gas purifying apparatus used in a test example.
【符号の説明】 １ エンジン ２ エキゾーストマニホールド ３ プリ三元触媒 ４ 吸着材または吸着触媒 ５ 床下触媒[Explanation of symbols] 1 engine 2 exhaust manifold 3 pre-three-way catalyst 4 adsorbent or adsorption catalyst 5 underfloor catalyst
Claims (4)
アルミナ粉末を加えてスラリーとなし、次いで該スラリ
ーをモノリス担体に塗布し、乾燥後、焼成してコート層
を形成することを特徴とする炭化水素吸着材の製造方
法。1. A hydrocarbon adsorption characterized in that silica sol, water and alumina powder are added to zeolite powder to form a slurry, and then the slurry is applied to a monolith carrier, dried and baked to form a coat layer. Method of manufacturing wood.
Ｙ、βゼオライトおよびＺＳＭ−５からなる群から選ば
れた少なくとも１種以上を用いることを特徴とする請求
項１記載の炭化水素吸着材の製造方法。2. Zeolite as mordenite, US
The method for producing a hydrocarbon adsorbent according to claim 1, wherein at least one selected from the group consisting of Y, β zeolite and ZSM-5 is used.
００であるゼオライトを用いることを特徴とする請求項
１記載の炭化水素吸着材の製造方法。3. A silica / alumina molar ratio of 50 to 20.
The method for producing a hydrocarbon adsorbent according to claim 1, wherein a zeolite of No. 00 is used.
層上に活性セリアおよび／またはアルミナを主成分とし
た粉末に触媒成分として白金、パラジウムおよびロジウ
ムからなる群から選ばれた１種以上の貴金属を含む触媒
層を設けることを特徴とする炭化水素吸着触媒の製造方
法。4. A powder comprising active ceria and / or alumina as a main component on the coat layer on the monolithic carrier according to claim 1, and at least one selected from the group consisting of platinum, palladium and rhodium as a catalyst component. A method for producing a hydrocarbon adsorption catalyst, which comprises providing a catalyst layer containing a noble metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5273779A JP2682404B2 (en) | 1993-11-01 | 1993-11-01 | Method for producing hydrocarbon adsorbent and catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5273779A JP2682404B2 (en) | 1993-11-01 | 1993-11-01 | Method for producing hydrocarbon adsorbent and catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07124467A JPH07124467A (en) | 1995-05-16 |
| JP2682404B2 true JP2682404B2 (en) | 1997-11-26 |
Family
ID=17532464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5273779A Expired - Fee Related JP2682404B2 (en) | 1993-11-01 | 1993-11-01 | Method for producing hydrocarbon adsorbent and catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2682404B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3052710B2 (en) | 1993-12-20 | 2000-06-19 | 日産自動車株式会社 | Exhaust gas purification device |
| EP0755714A3 (en) * | 1995-07-27 | 1997-03-19 | General Motors Corporation | Wide range hydrocarbon adsorber and quick lightoff catalyst |
| JP3842862B2 (en) | 1997-03-26 | 2006-11-08 | 日本碍子株式会社 | Exhaust gas purification system |
| JPH11179158A (en) * | 1997-10-15 | 1999-07-06 | Ngk Insulators Ltd | Adsorbent and adsorber for cleaning of exhaust gas of automobile containing fine hole porous body and exhaust gas cleaning system using them and method for cleaning of exhaust gas |
| JP4776151B2 (en) | 2003-05-27 | 2011-09-21 | 日産自動車株式会社 | Exhaust gas purification system |
| US8323599B2 (en) | 2010-11-22 | 2012-12-04 | Umicore Ag & Co. Kg | Three-way catalyst having an upstream multi-layer catalyst |
| US8557204B2 (en) | 2010-11-22 | 2013-10-15 | Umicore Ag & Co. Kg | Three-way catalyst having an upstream single-layer catalyst |
| JP2013091057A (en) * | 2011-10-03 | 2013-05-16 | Tosoh Corp | Palladium compound adsorbent and application thereof |
-
1993
- 1993-11-01 JP JP5273779A patent/JP2682404B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07124467A (en) | 1995-05-16 |
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