JP4905027B2 - Hydrocarbon adsorbent comprising β-type zeolite - Google Patents
Hydrocarbon adsorbent comprising β-type zeolite Download PDFInfo
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本発明は、β型ゼオライトからなる炭化水素（以下ＨＣと記載）吸着剤に関し、炭化水素の脱着開始温度、即ちＨＣ保持能力が高く、なおかつ吸着したＨＣの分解、即ちクラッキング性能の高く、さらに同等のＳｉＯ２／Ａｌ２Ｏ３比を有する従来のβ型ゼオライトに比して耐熱性の高いＨＣ吸着剤に関する。本発明のＨＣ吸着剤は、例えば自動車排ガス用のＨＣ吸着剤として用いることができる。 The present invention relates to a hydrocarbon (hereinafter referred to as HC) adsorbent composed of β-type zeolite, which has a high hydrocarbon desorption start temperature, that is, HC retention capability, and also has a high decomposition and cracking performance of adsorbed HC. The present invention relates to an HC adsorbent having high heat resistance as compared with a conventional β-type zeolite having a SiO 2 / Al 2 O 3 ratio. The HC adsorbent of the present invention can be used as, for example, an HC adsorbent for automobile exhaust gas.
β型ゼオライトは自動車等の内燃機関から排出されるＨＣを含有する排ガス中のＨＣ吸着剤として用いられている。自動車排ガスは、エンジン始動直後（冷始動、或いはコールドスタートという）に低温で炭化水素を多く含む排ガスが排出されるが、初期の排ガス温度は低いため、排ガス中の炭化水素を触媒で浄化する事が困難であり、触媒が十分に加熱されるまでＨＣ吸着剤で保持することが必要である。 β-type zeolite is used as an HC adsorbent in exhaust gas containing HC discharged from an internal combustion engine such as an automobile. Exhaust gas containing automobiles contains a lot of hydrocarbons at low temperatures immediately after the engine is started (called cold start or cold start), but since the initial exhaust gas temperature is low, hydrocarbons in the exhaust gas must be purified with a catalyst. It is difficult to hold the catalyst with the HC adsorbent until the catalyst is sufficiently heated.
これまで、β型ゼオライトによるＨＣ吸着剤としては、耐熱性向上の点からＳｉＯ２／Ａｌ２Ｏ３比（モル比）の高いもの、特にＳｉＯ２／Ａｌ２Ｏ３比が８０以上のものが提案されている。（特許文献１〜３参照）
ＳｉＯ２／Ａｌ２Ｏ３比が高いβ型ゼオライトでは耐熱性が高いが、固体酸含有量が低いため、吸着したＨＣのクラッキング性能が小さいという問題があった。そこで、クラッキング性能を要求される用途におけるＨＣ吸着剤では、ＳｉＯ２／Ａｌ２Ｏ３比が小さいものが使用されている。
So far, HC adsorbents using β-type zeolite have high SiO 2 / Al 2 O 3 ratio (molar ratio) from the viewpoint of improving heat resistance, especially those having a SiO 2 / Al 2 O 3 ratio of 80 or more. Proposed. (See Patent Documents 1 to 3)
The β-type zeolite having a high SiO 2 / Al 2 O 3 ratio has high heat resistance, but has a problem that the cracking performance of adsorbed HC is small because the solid acid content is low. Therefore, HC adsorbents for applications requiring cracking performance are those having a small SiO 2 / Al 2 O 3 ratio.
従来の低シリカ比のβ型ゼオライトによるＨＣ吸着剤では、低温でＨＣを脱着してしまい、クラッキング温度までＨＣを保持することができず、低シリカ比を選択する効果が十分に発揮されず、さらに耐熱性も低いという問題があった。 In conventional HC adsorbents with low silica ratio β-type zeolite, HC is desorbed at a low temperature, HC cannot be maintained up to the cracking temperature, and the effect of selecting a low silica ratio is not sufficiently exhibited, There was also a problem that heat resistance was low.
そのため、低シリカで、従来よりも高温までＨＣを吸着保持し、クラッキング性能が高く、なおかつ耐熱性が高いＨＣ吸着剤が求められている。 Therefore, an HC adsorbent that is low silica, adsorbs and holds HC up to a higher temperature than before, has high cracking performance, and has high heat resistance.
本発明は、ＳｉＯ２／Ａｌ２Ｏ３比が８０未満で、高温までのＨＣ吸着保持力が高く、なおかつ耐熱性の高いβ型ゼオライトからなるＨＣ吸着剤を提供することにある。 An object of the present invention is to provide an HC adsorbent composed of β-type zeolite having a SiO 2 / Al 2 O 3 ratio of less than 80, high HC adsorption holding power up to a high temperature, and high heat resistance.
本発明者らは、β型ゼオライトのＨＣの吸着特性について鋭意検討を重ねた結果、ＳｉＯ２／Ａｌ２Ｏ３比が８０未満のβ型ゼオライトからなるＨＣ吸着剤においてＨＣの脱着開始温度が１８５℃以上、特に２００℃以上であるＨＣ吸着剤を見出し、本発明を完成するに至ったものである。 As a result of intensive studies on the HC adsorption characteristics of β-type zeolite, the present inventors have found that the desorption start temperature of HC is 185 in an HC adsorbent composed of β-type zeolite having a SiO 2 / Al 2 O 3 ratio of less than 80. The inventors have found an HC adsorbent having a temperature of not lower than ° C., particularly not lower than 200 ° C., and have completed the present invention.
本発明のＨＣ吸着剤は、ＳｉＯ２／Ａｌ２Ｏ３比が８０未満のβ型ゼオライトからなり、なおかつ炭化水素の脱着温度が１８５℃以上である炭化水素吸着剤である。 The HC adsorbent of the present invention is a hydrocarbon adsorbent comprising a β-type zeolite having a SiO 2 / Al 2 O 3 ratio of less than 80 and a hydrocarbon desorption temperature of 185 ° C. or higher.
本発明のＨＣ吸着剤はβ型ゼオライトからなり、β型ゼオライトは、酸素１２員環からなる０．７６×０．６４ｎｍおよび０．５５×０．５５ｎｍの細孔が交差した３次元細孔構造を有するゼオライトである。β型ゼオライトのＸ線回折パターンは表１に示す格子面間隔ｄ（オングストローム）とその回折強度で特徴づけられる。 The HC adsorbent of the present invention is composed of β-type zeolite, which is a three-dimensional pore structure in which 0.76 × 0.64 nm and 0.55 × 0.55 nm pores composed of oxygen 12-membered rings intersect. It is a zeolite having The X-ray diffraction pattern of β-type zeolite is characterized by the lattice spacing d (angstrom) shown in Table 1 and its diffraction intensity.
本発明のＨＣ吸着剤におけるＨＣ脱着温度は、１８５℃以上、特に２００℃以上であることが好ましい。ＨＣの脱着温度が１８５℃未満では、ＨＣ吸着剤が十分に加熱する前に吸着したＨＣが脱離してしまうため、吸着したＨＣを十分にクラッキング（分解）することができない。ＨＣ脱着温度の上限は特に限定されるものではないが、本発明のＳｉＯ２／Ａｌ２Ｏ３比においては約２２０℃までである。 The HC desorption temperature in the HC adsorbent of the present invention is preferably 185 ° C. or higher, particularly 200 ° C. or higher. When the desorption temperature of HC is less than 185 ° C., HC adsorbed before the HC adsorbent is sufficiently heated is desorbed, so that the adsorbed HC cannot be sufficiently cracked (decomposed). The upper limit of the HC desorption temperature is not particularly limited, but it is up to about 220 ° C. in the SiO 2 / Al 2 O 3 ratio of the present invention.
さらに本発明のＨＣ吸着剤は、ＨＣの吸着量が２５０μｍｏｌ／ｇ以上であることが好ましい。ＨＣ脱着温度が高くても、吸着容量が少なくてはＨＣ吸着剤としては適さない。
上限は特に限定されるものではないが、本発明のＳｉＯ２／Ａｌ２Ｏ３比においては特に２８０μｍｏｌ／ｇ以上、約３３０μｍｏｌ／ｇまでである。
Further, the HC adsorbent of the present invention preferably has an HC adsorption amount of 250 μmol / g or more. Even if the HC desorption temperature is high, if the adsorption capacity is small, it is not suitable as an HC adsorbent.
The upper limit is not particularly limited, but in the SiO 2 / Al 2 O 3 ratio of the present invention, it is particularly 280 μmol / g or more and about 330 μmol / g.
ＨＣの吸着量は、便宜的に一定のＨＣ吸着条件を設定した上で、ＨＣ吸着剤からのＨＣ脱離量として定義することができる。 The amount of HC adsorbed can be defined as the amount of HC desorbed from the HC adsorbent after setting certain HC adsorption conditions for convenience.
本発明のＨＣ吸着剤に用いるβ型ゼオライトは、カチオンがＨ（プロトン）である、又はＨを含むことが好ましい。クラッキング性能を有するためには、ゼオライト中に固体酸が必要なためである。Ｈ型のβ型ゼオライトはアンモニアでイオン交換した後、通常は６００℃以下で熱処理することによって得られる。アンモニアイオン交換のβ型ゼオライトを６００℃を越える温度で熱処理した場合、ＨＣ吸着性能等が低下する。 In the β-type zeolite used in the HC adsorbent of the present invention, the cation is preferably H (proton) or contains H. This is because a solid acid is required in the zeolite in order to have cracking performance. The H-type β-type zeolite is usually obtained by heat-treating at 600 ° C. or lower after ion exchange with ammonia. When ammonia ion exchange β-type zeolite is heat-treated at a temperature exceeding 600 ° C., the HC adsorption performance and the like deteriorate.
本発明のＨＣ吸着剤は、同じＳｉＯ２／Ａｌ２Ｏ３比のβ型ゼオライトに比べて耐熱性が高いという特徴を有する。β型ゼオライトの耐熱性は、ゼオライトの結晶性（Ｘ線結晶回折）或いはＢＥＴ表面積等によって評価することができる。 The HC adsorbent of the present invention is characterized by higher heat resistance than β-type zeolite having the same SiO 2 / Al 2 O 3 ratio. The heat resistance of β-type zeolite can be evaluated by the crystallinity of the zeolite (X-ray crystal diffraction) or the BET surface area.
本発明のＨＣ吸着剤は、従来の同様なＳｉＯ２／Ａｌ２Ｏ３比のβ型ゼオライトと同一の温度での耐熱処理、特に高温での耐熱処理後の、ＸＲＤでの回折ピークの低下が小さいものである。具体的には、９００℃の熱処理で従来のβ型ゼオライトのＸＲＤの回折ピーク強度が６０％未満となるのに対して、本発明のＨＣ吸着剤では６０％以上の回折ピーク強度を維持するものである。回折ピーク強度は表１のｄ＝３．９７の回折ピークから求めることができる。上限は特に限定されるものではないが、本発明のＳｉＯ２／Ａｌ２Ｏ３比においては約８０％までである。 The HC adsorbent of the present invention has a lower diffraction peak in XRD after heat treatment at the same temperature as that of the conventional β-type zeolite having the same SiO 2 / Al 2 O 3 ratio, particularly after heat treatment at high temperature. It is a small one. Specifically, the XRD diffraction peak intensity of the conventional β-type zeolite is less than 60% by heat treatment at 900 ° C., whereas the HC adsorbent of the present invention maintains a diffraction peak intensity of 60% or more. It is. The diffraction peak intensity can be obtained from the diffraction peak at d = 3.97 in Table 1. The upper limit is not particularly limited, but is up to about 80% in the SiO 2 / Al 2 O 3 ratio of the present invention.
本発明のＨＣ吸着剤は、さらに金属及び／又は金属イオンを含有していても良い。含有させる金属及び／又は金属イオンとしては、例えばアルカリ金属、アルカリ土類金属、希土類金属、遷移金属、及び貴金属が挙げられ、それらの１種又は２種以上を含有させても良い。 The HC adsorbent of the present invention may further contain a metal and / or a metal ion. Examples of the metal and / or metal ion to be contained include alkali metals, alkaline earth metals, rare earth metals, transition metals, and noble metals, and one or more of them may be contained.
本発明のＨＣ吸着剤は、シリカ、アルミナ及び粘土鉱物等のバインダーと混合し成形して使用することもできる。粘土鉱物としては、カオリン、アタパルガイト、モンモリロナイト、ベントナイト、アロフェン、セピオライト等を挙げることができる。またコージェライト製あるいは金属製のハニカム状基材にウォッシュコートして使用することもできる。ウォッシュコートする場合、ハニカム状基材にゼオライトをコートした後に、ゼオライトを修飾する方法、予めゼオライトを修飾した後に、ハニカム状基材にコートする方法などが採用できる。 The HC adsorbent of the present invention can also be used after being mixed with a binder such as silica, alumina and clay mineral. Examples of clay minerals include kaolin, attapulgite, montmorillonite, bentonite, allophane, and sepiolite. The cordierite or metal honeycomb-like base material can be washed and used. In the case of wash coating, a method of modifying the zeolite after coating the honeycomb-shaped substrate with zeolite, a method of coating the honeycomb-shaped substrate after modifying the zeolite in advance, and the like can be employed.
本発明のＨＣ吸着剤に供するβ型ゼオライトの製造法は、以下の方法によって製造できる。
Preparation of β-type zeolite subjected to HC adsorbent of the present invention can be prepared by the methods below.
β型ゼオライトの製造法は種々の製法が報告されており、例えば特開平２−２９３０２１号他によって、ＳｉＯ２／Ａｌ２Ｏ３比が本発明の範囲のβ型ゼオライトを得ることができる。しかし、従来の方法で合成した同様のＳｉＯ２／Ａｌ２Ｏ３比のβ型ゼオライトでは、本発明のＨＣ脱着温度及び耐熱性等を満足するものとはならない。 Various production methods have been reported for the production method of β-type zeolite. For example, according to JP-A-2-293302 et al., a β-type zeolite having a SiO 2 / Al 2 O 3 ratio in the range of the present invention can be obtained. However, a similar β 2 type zeolite having a SiO 2 / Al 2 O 3 ratio synthesized by a conventional method does not satisfy the HC desorption temperature and heat resistance of the present invention.
本発明のＨＣ吸着剤として用いるβ型ゼオライトは、上述の方法他で得られたＳｉＯ２／Ａｌ２Ｏ３比が８０未満のβ型ゼオライトを７００℃以上、９００℃未満で熱処理することによって脱着温度を本発明の範囲に高めることができる。 The β-type zeolite used as the HC adsorbent of the present invention is desorbed by heat-treating the β-type zeolite having a SiO 2 / Al 2 O 3 ratio of less than 80 obtained by the above-described method and others at 700 ° C. or more and less than 900 ° C. The temperature can be increased within the scope of the present invention.
加熱温度が７００℃未満では、本発明の脱着温度とならず、特に７５０℃以上であることが好ましい。一方、９００℃を超える熱処理では、β型ゼオライトの結晶性が低下し、ＨＣ吸着性能が低くなるため、ＨＣ吸着性能を最大限に発揮するためには特に８００℃以下の温度で熱処理することが好ましい。 When the heating temperature is less than 700 ° C., the desorption temperature of the present invention is not achieved, and particularly preferably 750 ° C. or more. On the other hand, in the heat treatment exceeding 900 ° C., the crystallinity of β-type zeolite is lowered, and the HC adsorption performance is lowered. preferable.
加熱条件としては、水蒸気雰囲気であることが好ましく、例えば１０体積％程度の加湿条件が例示できる。 As heating conditions, it is preferable that it is a water vapor | steam atmosphere, for example, humidification conditions of about 10 volume% can be illustrated.
本発明のＨＣ吸着剤のカチオンはＨ（プロトン）型であることが好ましいが、通常アンモニアイオン交換したゼオライトを熱処理してＨ型にする場合、熱処理（活性化）は６００℃以下の温度で行われる。６００℃を超える温度ではゼオライトが破壊され、吸着性能が低下するためである。本発明のβ型ゼオライトは、まずＨ型に変換した後で、さらに７００℃以上で熱処理する。 The cation of the HC adsorbent of the present invention is preferably H (proton) type. However, when heat-treating an ammonia ion exchanged zeolite into H type by heat treatment, the heat treatment (activation) is performed at a temperature of 600 ° C. or lower. Is called. This is because the zeolite is destroyed at a temperature exceeding 600 ° C. and the adsorption performance is lowered. The β-type zeolite of the present invention is first heat treated at 700 ° C. or higher after first converted to H-type.
本発明のＨＣ吸着剤に供するβ型ゼオライトの熱処理方法はロータリー焼成機による焼成が例示でき、特に特別な流動状態による熱処理を必要とするものではない。 The heat treatment method of the β-type zeolite to be used for the HC adsorbent of the present invention can be exemplified by calcination with a rotary calciner, and does not particularly require heat treatment in a special fluid state.
従来、ゼオライトを熱処理によって疎水化することは知られているが、その様な疎水化は本発明のβ型ゼオライトにおいて実施した温度範囲とは異なる温度、即ち本発明の効果が得られない条件で行われているか、或いはより構造安定性の高いゼオライト種を疎水化する方法に用いられるものであった。特にβ型ゼオライトを高い耐熱性が要求される分野では、特に高シリカ比のものが用いられ、本発明の範囲の低シリカのβ型ゼオライトを上述の温度で熱処理することによりＨＣの脱着温度を高温化したものはなかった。 Conventionally, it has been known that the zeolite is hydrophobized by heat treatment, but such hydrophobization is performed at a temperature different from the temperature range performed in the β-type zeolite of the present invention, that is, under the condition where the effect of the present invention is not obtained. It has been used or used in a process for hydrophobizing zeolite species with higher structural stability. Particularly in the field where high heat resistance is required for β-type zeolite, those having a high silica ratio are used, and the desorption temperature of HC is reduced by heat-treating low-silica β-type zeolite within the scope of the present invention at the above-mentioned temperature. None were heated.
また従来、β型ゼオライトを用いたＨＣ吸着剤では、無機酸による脱アルミ処理、或いはアンモニウムイオン交換したものを熱処理によってＨ型にしたものが直接用いられており、上述した通り、これらの熱処理では通常７００℃以上で処理されることはなかった。 Conventionally, in HC adsorbents using β-type zeolite, dealuminated aluminum with inorganic acid or ammonium ion exchanged H-type by heat treatment is directly used. Usually, it was not processed at 700 ° C. or higher.
本発明のＨＣ吸着剤の使用方法は特に限定されるものではないが、例えば以下の条件が例示できる。 Although the usage method of HC adsorption agent of this invention is not specifically limited, For example, the following conditions can be illustrated.
処理ガスは、具体的には、ガソリンエンジン自動車、ディーゼルエンジン自動車等の内
燃機関の排ガスが例示される。更に上記処理ガスには、ＨＣ以外に一酸化炭素、二酸化炭
素、水素、窒素、酸素、硫黄酸化物、水等が含まれていても良い。
Specific examples of the processing gas include exhaust gas from internal combustion engines such as gasoline engine vehicles and diesel engine vehicles. Further, the processing gas may contain carbon monoxide, carbon dioxide, hydrogen, nitrogen, oxygen, sulfur oxide, water and the like in addition to HC.
処理ガス中のＨＣ濃度は特に限定されないが、メタン換算で０．００１〜１０体積％が
好ましく、より好ましくは０．００１〜５体積％である。また処理ガス中の水分濃度も特
に限定されず、０．０１〜１５体積％が例示できる。処理ガス中のＨＣ濃度、水分濃度は
時間と共に変動していても良い。
The HC concentration in the processing gas is not particularly limited, but is preferably 0.001 to 10% by volume, more preferably 0.001 to 5% by volume in terms of methane. Further, the moisture concentration in the processing gas is not particularly limited, and may be 0.01 to 15% by volume. The HC concentration and moisture concentration in the processing gas may vary with time.
更に、処理ガス中のＨＣを吸着除去する際の空間速度及び温度も特に限定されない。空
間速度：１００〜５０万ｈｒ−１、温度−３０〜２００℃であることが好ましい。
Furthermore, the space velocity and temperature when adsorbing and removing HC in the process gas are not particularly limited. Space velocity: 100 to 500,000 hr −1 , preferably temperature −30 to 200 ° C.
本発明のＨＣ吸着剤は吸着したＨＣの脱離温度が高く、なおかつＨＣ吸着量が多く、さらに従来の同等のＳｉＯ２／Ａｌ２Ｏ３比のβ型ゼオライトに比して耐熱性、クラッキング性能が高いため自動車等の排ガス浄化用吸着剤として優れている。 The HC adsorbent of the present invention has a high desorption temperature of adsorbed HC and a large amount of HC adsorption, and further has heat resistance and cracking performance as compared with conventional β-type zeolite having the same SiO 2 / Al 2 O 3 ratio. Therefore, it is excellent as an adsorbent for exhaust gas purification of automobiles.
以下に本発明を実施例で説明するが、本発明はこれらの実施例に限定されるものではな
い。
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
特開平２−２９３０２１号に開示されている方法を参照して、フッ素化合物を用いないでβ型ゼオライトを合成した。
Example 1
A β-type zeolite was synthesized without using a fluorine compound with reference to the method disclosed in JP-A-2-2933021.
珪酸ソーダ水溶液、硫酸アルミニウム水溶液を用いてれ粒状無定型アルミノ珪酸塩を得た。該無定型アルミノ珪酸塩１８９ｇ、固形水酸化ナトリウム１．４ｇ、固形水酸化カリウム３．５ｇ及びＴＥＡＯＨ２０％水溶液４８０ｇを３０分攪拌混合し、β型ゼオライトの原料とし、当該原料スラリーを１５０℃で９６時間結晶化した。結晶化後のスラリー状混合物を固液分離し、十分量の純水で洗浄し、１１０℃で乾燥した。次いで乾燥粉末を空気流通下６００℃で焼成した。粉末Ｘ線回折とＩＣＰ発光分析から、生成物はβ型ゼオライトで、ＳｉＯ２／Ａｌ２Ｏ３モル比が３６であった。 A granular amorphous aluminosilicate was obtained using a sodium silicate aqueous solution and an aluminum sulfate aqueous solution. 189 g of the amorphous aluminosilicate, 1.4 g of solid sodium hydroxide, 3.5 g of solid potassium hydroxide, and 480 g of TEAOH 20% aqueous solution were stirred and mixed for 30 minutes to obtain a raw material for β-type zeolite. Crystallized over time. The slurry mixture after crystallization was subjected to solid-liquid separation, washed with a sufficient amount of pure water, and dried at 110 ° C. The dry powder was then fired at 600 ° C. under air flow. From the powder X-ray diffraction and ICP emission analysis, the product was β-type zeolite and had a SiO 2 / Al 2 O 3 molar ratio of 36.
当該β型ゼオライトを７５０℃、水蒸気雰囲気（１０体積％）、１時間熱処理し、ＨＣ吸着剤とした。 The β-type zeolite was heat treated at 750 ° C. in a steam atmosphere (10% by volume) for 1 hour to obtain an HC adsorbent.
実施例２
ＳｉＯ２／Ａｌ２Ｏ３モル比が４０の東ソー製β型ゼオライト（商品名：ＨＳＺ−９４０ＮＨＡ）を空気流通下６００℃で焼成した。粉末Ｘ線回折とＩＣＰ発光分析から、焼成後もβ型ゼオライトであり、ＳｉＯ２／Ａｌ２Ｏ３モル比が４０であった。
Example 2
Tosoh β-type zeolite (trade name: HSZ-940NHA) having a SiO 2 / Al 2 O 3 molar ratio of 40 was calcined at 600 ° C. under air flow. From the powder X-ray diffraction and ICP emission analysis, it was β-type zeolite even after calcination, and the SiO 2 / Al 2 O 3 molar ratio was 40.
当該β型ゼオライトを７５０℃、水蒸気雰囲気（１０体積％）、１時間熱処理し、ＨＣ吸着剤とした。 The β-type zeolite was heat treated at 750 ° C. in a steam atmosphere (10% by volume) for 1 hour to obtain an HC adsorbent.
比較例１〜４
実施例１〜２のβ型ゼオライトを７５０℃で熱処理しないもの（比較例１〜２）、１０００℃で熱処理したもの（比較例３）、ＳｉＯ２／Ａｌ２Ｏ３モル比が本発明の範囲を超えるもの（比較例４）をそれぞれＨＣ吸着剤として評価した。
Comparative Examples 1-4
The β-type zeolites of Examples 1 and 2 were not heat-treated at 750 ° C. (Comparative Examples 1 and 2), heat-treated at 1000 ° C. (Comparative Example 3), and the SiO 2 / Al 2 O 3 molar ratio was within the scope of the present invention. (Comparative Example 4) exceeding the above were evaluated as HC adsorbents.
なお比較例４のβ型ゼオライトは以下のものを熱処理しないで用いた。 The β-type zeolite of Comparative Example 4 was used without heat treatment.
ＳｉＯ２／Ａｌ２Ｏ３モル比が４０の東ソー製β型ゼオライト（商品名：ＨＳＺ−９４０ＮＨＡ）を特開昭５８−２０８１３１号公報に開示されている塩酸処理を参照し、ＳｉＯ２／Ａｌ２Ｏ３モル比を高めた。β型ゼオライト２０ｇを、０．２規定の塩酸１００ｇに添加し、８０℃で２時間攪拌した。その後、固液分離、十分量の純水で洗浄し、１００℃で一晩乾燥した。粉末Ｘ線回折とＩＣＰ発光分析から、生成物はβ型ゼオライトで、ＳｉＯ２／Ａｌ２Ｏ３モル比が５３０であった。これを比較例４のＨＣ吸着剤とした。 Tosoh β-type zeolite (trade name: HSZ-940NHA) having a SiO 2 / Al 2 O 3 molar ratio of 40 is referred to the hydrochloric acid treatment disclosed in JP-A-58-208131, and SiO 2 / Al 2 The O 3 molar ratio was increased. 20 g of β-type zeolite was added to 100 g of 0.2 N hydrochloric acid and stirred at 80 ° C. for 2 hours. Thereafter, solid-liquid separation, washing with a sufficient amount of pure water, and drying at 100 ° C. overnight were performed. From the powder X-ray diffraction and ICP emission analysis, the product was β-type zeolite and had a SiO 2 / Al 2 O 3 molar ratio of 530. This was used as the HC adsorbent of Comparative Example 4.
＜吸着剤のＨＣ吸脱着特性試験＞
ＨＣ吸脱着特性を以下の方法で評価した。
<HC adsorption / desorption characteristic test of adsorbent>
HC adsorption / desorption characteristics were evaluated by the following methods.
吸着剤を各々加圧成形後、粉砕して１２〜２０メッシュに整粒した。整粒した吸着剤１ｍｌを常圧固定床流通式反応管に充填し、窒素流通下、５００℃で一時間前処理し３０℃まで冷却した。次いで、表２に示すｎ−デカンと水分を含むモデル排ガスをガス流量２０００ｍｌ／ｍｉｎで吸着剤に接触させながら、３０℃から６００℃まで１０℃／ｍｉｎの昇温速度で昇温した。 Each of the adsorbents was pressed and then pulverized and sized to 12 to 20 mesh. 1 ml of the sized adsorbent was filled into a normal pressure fixed bed flow type reaction tube, pretreated at 500 ° C. for 1 hour under nitrogen flow, and cooled to 30 ° C. Next, the model exhaust gas containing n-decane and moisture shown in Table 2 was heated from 30 ° C. to 600 ° C. at a temperature increase rate of 10 ° C./min while contacting the adsorbent at a gas flow rate of 2000 ml / min.
ＨＣの吸脱着特性は、供給濃度（２０００ｐｐｍＣ）を基準に低濃度域を吸着域、高濃度域を脱離域とみなし、吸着量は脱離領域の積分値、吸着保持力は吸着から脱離に転じる温度（脱離開始温度）で評価した。
The adsorption / desorption characteristics of HC are based on the supply concentration (2000 ppmC), with the low concentration region regarded as the adsorption region and the high concentration region as the desorption region, the adsorption amount is the integral value of the desorption region, and the adsorption retention is desorbed from the adsorption. Evaluation was made at a temperature (desorption start temperature).
実施例１〜３、及び比較例１〜３のＨＣ吸着剤のＨＣ脱離温度を表３に示す。 Table 3 shows the HC desorption temperatures of the HC adsorbents of Examples 1 to 3 and Comparative Examples 1 to 3.
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