JPH0796177A - Production of hydrocarbon adsorbent made of zeolite - Google Patents
Production of hydrocarbon adsorbent made of zeoliteInfo
- Publication number
- JPH0796177A JPH0796177A JP5243350A JP24335093A JPH0796177A JP H0796177 A JPH0796177 A JP H0796177A JP 5243350 A JP5243350 A JP 5243350A JP 24335093 A JP24335093 A JP 24335093A JP H0796177 A JPH0796177 A JP H0796177A
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- JP
- Japan
- Prior art keywords
- zeolite
- unmodified
- temperature
- heat
- adsorbent
- 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.)
- Granted
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- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は排気ガス等の浄化に用い
られるゼオライト製ＨＣ（炭化水素）吸着材の製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a zeolite HC (hydrocarbon) adsorbent used for purification of exhaust gas and the like.
【０００２】[0002]
【従来の技術】従来、この種ＨＣ吸着材の製造方法とし
ては、未改質ゼオライトに、スチーム処理と酸処理を１
サイクルとし、これを多サイクル繰返して施す方法が知
られている（例えば、特公昭５１−１５０００号公報参
照）。2. Description of the Related Art Conventionally, as a method for producing this kind of HC adsorbent, steam treatment and acid treatment are applied to unmodified zeolite.
A method is known in which a cycle is repeated and this cycle is repeated (for example, see JP-B-51-15000).
【０００３】[0003]
【発明が解決しようとする課題】従来法において多サイ
クルを必須とする理由は、スチーム処理の温度を未改質
ゼオライトが破壊されない温度、例えば５３８℃といっ
た低温に設定しているため、多サイクル繰返さないと改
質ゼオライトのＨＣ吸着能を高めることができないから
である。The reason why multiple cycles are essential in the conventional method is that the steam treatment temperature is set to a temperature at which unmodified zeolite is not destroyed, for example, 538 ° C. This is because the HC adsorption capacity of the modified zeolite cannot be increased without it.
【０００４】しかしながら、前記のように多サイクル方
式を採用すると、ＨＣ吸着材の生産性が悪く、その生産
コスト増を招く、という問題がある。However, when the multi-cycle method is adopted as described above, there is a problem that the productivity of the HC adsorbent is poor and the production cost thereof is increased.
【０００５】本発明は前記に鑑み、酸処理と水分存在下
での加熱処理をそれぞれ１回宛行うだけで、優れたＨＣ
吸着能と耐熱性を備えたゼオライト製ＨＣ吸着材を得る
ことのできる前記製造方法を提供することを目的とす
る。In view of the above, the present invention provides excellent HC by performing the acid treatment and the heat treatment in the presence of water only once.
It is an object of the present invention to provide the above-mentioned production method capable of obtaining a zeolite HC adsorbent having adsorption capacity and heat resistance.
【０００６】[0006]
【課題を解決するための手段】本発明に係るゼオライト
製ＨＣ吸着材の製造方法は、未改質ゼオライトに酸処理
を施して、その未改質ゼオライトよりも高い耐熱温度を
有する耐熱性改質ゼオライトを得る中間工程と、前記耐
熱性改質ゼオライトを、水分の存在下で、前記耐熱温度
を超えず、且つその耐熱温度近傍の温度で加熱してＨＣ
吸着能を高める最終工程とを順次行うことを特徴とす
る。Means for Solving the Problems A method for producing a zeolite HC adsorbent according to the present invention is a heat-resistant modified material having a higher heat-resistant temperature than that of unmodified zeolite, by subjecting unmodified zeolite to acid treatment. The intermediate step of obtaining zeolite and the heat-resistant modified zeolite are heated in the presence of water at a temperature which does not exceed the heat-resistant temperature and is close to the heat-resistant temperature, to thereby obtain HC
It is characterized in that a final step of increasing the adsorption ability is sequentially performed.
【０００７】[0007]
【作用】一般の未改質ゼオライトの耐熱温度、即ちその
結晶構造を破壊しない温度は７００℃程度であるが、そ
の未改質ゼオライトに中間工程で１回の酸処理を施す
と、脱Ａｌ化が発生すると共に不純物が除去されるの
で、改質ゼオライトの結晶性が向上し、また熱分解生成
物の核の発生が抑制される。これにより改質ゼオライト
の耐熱温度は１０００℃程度に上昇する。The heat resistant temperature of general unmodified zeolite, that is, the temperature at which its crystal structure is not destroyed, is about 700 ° C. However, when the unmodified zeolite is subjected to one acid treatment in the intermediate step, it is de-alloyed. And the impurities are removed, the crystallinity of the modified zeolite is improved, and the generation of nuclei of thermal decomposition products is suppressed. As a result, the heat resistant temperature of the modified zeolite rises to about 1000 ° C.
【０００８】このような改質ゼオライトの耐熱性を利用
して、最終工程では水分存在下での加熱温度を９００℃
程度に設定し得るので、この工程を１回行うだけで、改
質ゼオライトの脱Ａｌ化をさらに進行させてその疎水性
を高め、これによりＨＣ吸着能を極大化することができ
る。またこの高温下における結晶構造の破壊は回避され
るので、改質ゼオライトの耐熱性が損なわれることはな
い。By utilizing the heat resistance of such modified zeolite, the heating temperature in the presence of water is 900 ° C. in the final step.
Since it can be set to a degree, only by carrying out this step once, it is possible to further promote de-Alization of the modified zeolite and increase its hydrophobicity, thereby maximizing the HC adsorption capacity. Further, since the destruction of the crystal structure at high temperature is avoided, the heat resistance of the modified zeolite is not impaired.
【０００９】[0009]
【実施例】ゼオライト製ＨＣ吸着材は中間工程と最終工
程との二回の工程を経て製造される。Example A zeolite HC adsorbent is manufactured through two steps, an intermediate step and a final step.
【００１０】中間工程において、未改質ゼオライトとし
ては、未改質ＺＳＭ−５ゼオライト、未改質モルデナイ
ト等が用いられる。未改質ゼオライトのＳｉＯ2 ／Ａｌ
2 Ｏ 3 モル比Ｍｒは、最終工程を経て得られたＨＣ吸着
材のＨＣ吸着能に影響を与え、未改質ゼオライトとして
ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比ＭｒがＭｒ≧１００のもの
を用いると、Ｍｒ＜１００のものを用いた場合よりも、
ＨＣ吸着能を高めることができる。In the intermediate step, unmodified zeolite
Unmodified ZSM-5 zeolite, unmodified Mordenai
Etc. are used. Unmodified zeolite SiO2/ Al
2O 3The molar ratio Mr is the HC adsorption obtained through the final step.
As an unmodified zeolite that affects the HC adsorption capacity of wood
SiO2/ Al2O3Molar ratio Mr of Mr ≧ 100
Than when using Mr <100,
The HC adsorption capacity can be increased.
【００１１】酸処理では、１〜１０ＮのＨＣｌ溶液、Ｈ
ＮＯ3 溶液、Ｈ2 ＳＯ4 溶液等の酸溶液が用いられる。
その酸溶液中において未改質ゼオライトに攪拌還流処理
が施され、その際、酸溶液の温度Ｔ1 は室温≦Ｔ1 ≦１
００℃に、また処理時間ｔ1はｔ1 ≧１時間に設定され
る。In the acid treatment, 1-10N HCl solution, H
An acid solution such as NO 3 solution or H 2 SO 4 solution is used.
The unmodified zeolite is stirred and refluxed in the acid solution, and the temperature T 1 of the acid solution is room temperature ≦ T 1 ≦ 1.
The treatment time t 1 is set to 00 ° C. and t 1 ≧ 1 hour.
【００１２】最終工程において、水分存在下での加熱処
理には、スチーム処理、沸騰水処理等が適用される。In the final step, steam treatment, boiling water treatment or the like is applied to the heat treatment in the presence of water.
【００１３】スチーム処理は、水分、したがって体積比
率で１０％程度の水蒸気を含む高温雰囲気ガス下に耐熱
性改質ゼオライトを保持することによって行われる。こ
の場合の処理温度Ｔ2 はＴ2 ≧４００℃に、また処理時
間ｔ2 はｔ2 ≧５時間にそれぞれ設定される。The steam treatment is carried out by holding the heat-resistant modified zeolite in a high-temperature atmosphere gas containing water, that is, about 10% by volume of water vapor. In this case, the processing temperature T 2 is set to T 2 ≧ 400 ° C., and the processing time t 2 is set to t 2 ≧ 5 hours.
【００１４】沸騰水処理は、未改質ゼオライトに含水処
理を施し、その含水状態の未改質ゼオライトを高温下に
保持することによって行われる。この場合の処理温度Ｔ
2 はＴ2 ≧４００℃に、また処理時間ｔ2 はｔ2 ≧５時
間にそれぞれ設定される。The boiling water treatment is carried out by subjecting the unmodified zeolite to a water-containing treatment and holding the water-containing unmodified zeolite at a high temperature. Processing temperature T in this case
2 is set to T 2 ≧ 400 ° C., and the processing time t 2 is set to t 2 ≧ 5 hours.
【００１５】中間工程を経た改質ゼオライトにおいて
は、その中間工程で脱Ａｌ化が生じてはいるが、その程
度は比較的低く、したがって親水性が高い。即ち、図１
（ａ）に示すように、改質ゼオライトにおいてはＡｌの
結合手がＳｉのそれよりも少ないためＡｌはＳｉに比べ
て貧電子状態となっており、このようなＡｌに、分極が
著しく富電子状態となっているＨ2 Ｏ分子のＯ原子が結
合し易いのである。このようにＨ2 Ｏが吸着するとゼオ
ライトのＨＣ吸着能は著しく減退する。In the modified zeolite that has undergone the intermediate step, de-Alization occurs in the intermediate step, but the degree thereof is relatively low, and therefore the hydrophilicity is high. That is, FIG.
As shown in (a), in the modified zeolite, the number of Al bonds is smaller than that of Si, so that Al is in a poorer electron state than Si. The O atom of the H 2 O molecule in the state is easily bonded. When H 2 O is thus adsorbed, the HC adsorbing ability of the zeolite is significantly reduced.
【００１６】前記改質ゼオライトにスチーム処理等を施
すと、図１（ｂ）に示すようにＡｌがＨ2 Ｏと反応して
Ａｌ（ＯＨ）3 を生成し、Ａｌが改質ゼオライトから離
脱する。これにより、ＨＣ吸着材における電子状態が略
均一化されるので、その疎水性が高められ、したがって
ＨＣ吸着材はＨ2 Ｏの吸着を回避して優れたＨＣ吸着能
を発揮する。When steam treatment or the like is applied to the modified zeolite, Al reacts with H 2 O to produce Al (OH) 3 as shown in FIG. 1B, and Al is separated from the modified zeolite. . As a result, the electronic state of the HC adsorbent is made substantially uniform, so that its hydrophobicity is enhanced, and therefore the HC adsorbent avoids the adsorption of H 2 O and exhibits an excellent HC adsorbing ability.
【００１７】以下、具体例について説明する。A specific example will be described below.
【００１８】Ａ．酸処理（中間工程） （ａ）ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比ＭｒがＭｒ＝３６で
ある未改質ＺＳＭ−５ゼオライト５００ｇを、５Ｎ Ｈ
Ｃｌ溶液１０リットルを入れたセパラブルフラスコ（容
量２０リットル）に投入し、次いでそのセパラブルフラ
スコにコンデンサを付設し、その後９０℃にて２４時間
の攪拌還流処理を行った。A. Acid treatment (intermediate step) (a) SiO 2 / Al 2 O 3 molar ratio Mr = 36 unmodified ZSM-5 zeolite 500g 5N
A Cl solution was placed in a separable flask (capacity: 20 liters) containing 10 liters, and then a condenser was attached to the separable flask, and then the mixture was stirred and refluxed at 90 ° C. for 24 hours.
【００１９】（ｂ）固形分を吸引濾別して１２リットル
の純水で洗浄した。(B) The solid content was filtered by suction and washed with 12 liters of pure water.
【００２０】（ｃ）固形分に、１１０℃、２時間の乾燥
処理を施し、次いで４００℃、２時間の焼成処理を施し
た。(C) The solid content was dried at 110 ° C. for 2 hours and then baked at 400 ° C. for 2 hours.
【００２１】これにより、ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比
ＭｒがＭｒ＝４８の耐熱性改質ＺＳＭ−５ゼオライトを
得た。これを例１とする。As a result, a heat resistant modified ZSM-5 zeolite having a SiO 2 / Al 2 O 3 molar ratio Mr of 48 was obtained. This is referred to as Example 1.
【００２２】ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比Ｍｒを異にす
る二種の未改質ＺＳＭ−５ゼオライトを用いて、前記
（ａ）〜（ｃ）の作業を行い、二種の耐熱性改質ＺＳＭ
−５ゼオライトを得た。これらを例２、例３とする。Using the two types of unmodified ZSM-5 zeolite having different SiO 2 / Al 2 O 3 molar ratios Mr, the steps (a) to (c) were carried out to obtain the two types of heat resistance modification. Quality ZSM
-5 zeolite was obtained. These are referred to as Example 2 and Example 3.
【００２３】表１は、例１〜３の酸処理前、後のＳｉＯ
2 ／Ａｌ2 Ｏ3 モル比Ｍｒおよび耐熱温度を示す。Table 1 shows the SiO before and after the acid treatment of Examples 1-3.
2 / Al 2 O 3 molar ratio Mr and heat resistant temperature are shown.
【００２４】耐熱温度の測定は次のような方法で行われ
た。即ち、未改質ＺＳＭ−５ゼオライト等について、大
気中、加熱温度 ６００、７００、８００、９００、１
０００、１１００℃、各温度における加熱時間 １８時
間の条件で熱劣化テストを行い、次いで未改質ＺＳＭ−
５ゼオライト等についてＣｕ−Ｋα線による粉末Ｘ線回
折を行って熱による結晶の破壊状態を観察し、テスト後
においてもＸ線反射強度に変化がなかったときの最高加
熱温度を耐熱温度とした。The heat resistant temperature was measured by the following method. That is, for unmodified ZSM-5 zeolite and the like, heating temperatures of 600, 700, 800, 900, 1
000, 1100 ° C, heating time at each temperature 18 hours, a thermal deterioration test was performed, and then unmodified ZSM-
5 Zeolite and the like were subjected to powder X-ray diffraction using Cu-Kα rays to observe the state of crystal destruction by heat, and the maximum heating temperature when the X-ray reflection intensity did not change after the test was taken as the heat-resistant temperature.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１から明らかなように、改質ＺＳＭ−５
ゼオライトの例１〜３は優れた耐熱性を有する。As is apparent from Table 1, modified ZSM-5
Examples 1-3 of zeolite have excellent heat resistance.
【００２７】Ｂ．スチーム処理（最終工程） このスチーム処理は、改質ＺＳＭ−５ゼオライトの各例
１〜３をハニカムに担持させた状態で行われるので、先
ず、その担持法について説明する。B. Steam Treatment (Final Step) This steam treatment is performed in a state in which each of Examples 1 to 3 of modified ZSM-5 zeolite is supported on the honeycomb. First, the supporting method will be described.
【００２８】（ａ）４００ｇの例１と、２００ｇのシリ
カゾルと、５８０ｇの純水とを適量のアルミナボールと
共にボールミルにて２４時間混合しスラリを調製した。(A) 400 g of Example 1, 200 g of silica sol, and 580 g of pure water were mixed with an appropriate amount of alumina balls in a ball mill for 24 hours to prepare a slurry.
【００２９】（ｂ）直径２．５４cm（１インチ）、長さ
６０mmのハニカム（３００セル、１０．５ミル）をスラ
リ中に３０秒間浸漬し、次いでエアガンにより過剰のス
ラリをハニカムから吹飛ばして除去した。(B) A honeycomb (300 cells, 10.5 mils) having a diameter of 2.54 cm (1 inch) and a length of 60 mm was immersed in the slurry for 30 seconds, and then excess slurry was blown from the honeycomb with an air gun. Removed.
【００３０】（ｃ）スラリを担持したハニカムを１２時
間風乾し、次いでマッフル炉を用いて１００、２００、
３００、６００℃で各１時間の焼成を行った。(C) The slurry-supported honeycomb was air-dried for 12 hours, and then a muffle furnace was used for 100, 200,
Firing was performed at 300 and 600 ° C. for 1 hour each.
【００３１】（ｄ）前記（ｂ），（ｃ）の両作業を２回
繰返して、例１を５ｇ担持したハニカムを得た。(D) The above operations (b) and (c) were repeated twice to obtain a honeycomb carrying 5 g of Example 1.
【００３２】同様の方法で、例２，例３をそれぞれ５ｇ
担持した二種のハニカムを得た。In a similar manner, 5 g each of Example 2 and Example 3
Two types of supported honeycombs were obtained.
【００３３】スチーム処理に当っては、体積比率で、１
０％Ｈ2 Ｏ、１％Ｏ2 および残部Ｎ 2 からなる雰囲気ガ
スが流量１リットル／min で流通する９００℃の温度下
に、各ハニカムを２０時間保持した。これにより、耐熱
性改質ＺＳＭ−５ゼオライトの例１〜例３に対応するＨ
Ｃ吸着材の例１ａ〜例３ａを備えた三種のＨＣ浄化部材
を得た。この場合、各ハニカムにおけるＨＣ吸着材の担
持量は、耐熱性改質ＺＳＭ−５ゼオライトのそれと略同
じである。In the steam treatment, the volume ratio is 1
0% H2O, 1% O2And the balance N 2Atmosphere consisting of
At a temperature of 900 ° C where the gas flows at a flow rate of 1 liter / min.
Then, each honeycomb was held for 20 hours. This makes it heat resistant
H corresponding to Examples 1 to 3 of the property-modified ZSM-5 zeolite
Three types of HC purification members provided with C adsorbent examples 1a to 3a
Got In this case, the role of the HC adsorbent in each honeycomb
Content is almost the same as that of heat-resistant modified ZSM-5 zeolite
It is the same.
【００３４】また例１〜３にスチーム処理を施して得ら
れたＨＣ吸着材１ａ〜３ａの担持量を異にする各種ＨＣ
浄化部材を前記と同様の方法で製造した。また比較のた
め例１〜３をＨＣ吸着材とし、それらを前記同様の方法
でハニカムに担持させると共にその担持量を異にする各
種ＨＣ浄化部材を製造した。Various types of HC having different amounts of carried HC adsorbents 1a to 3a obtained by steaming Examples 1 to 3
The purification member was manufactured by the same method as described above. Further, for comparison, Examples 1 to 3 were used as HC adsorbents, and various HC purifying members were manufactured by supporting them on the honeycomb by the same method as above and different in the supported amount.
【００３５】ＨＣ吸着テストを行うため、テスト用ガス
として、体積比率で、１０％Ｈ2 Ｏ、４００ppm Ｃ3 Ｈ
6 、０．５％ＣＯ、５００ppm ＮＯ、０．１７％Ｈ2 、
１４％ＣＯ2 、０．５％Ｏ2 および残部Ｎ2 よりなるガ
スを調製した。In order to carry out the HC adsorption test, as a test gas, a volume ratio of 10% H 2 O, 400 ppm C 3 H
6 , 0.5% CO, 500ppm NO, 0.17% H 2 ,
A gas consisting of 14% CO 2 , 0.5% O 2 and the balance N 2 was prepared.
【００３６】ＨＣ吸着テストは、４５〜５５℃のテスト
用ガスを、各ＨＣ浄化部材内に流量２５０００ml／min
で、６０秒間流通させ、この間のＨＣ吸着率を測定する
ことによって行われた。In the HC adsorption test, a test gas at 45 to 55 ° C. is flown into each HC purification member at a flow rate of 25,000 ml / min.
At 60 ° C. for 60 seconds and measuring the HC adsorption rate during this period.
【００３７】図２はＨＣ吸着テスト結果を示す。図２よ
り、スチーム処理を施すことによって例１ａ〜３ａのよ
うにＨＣ吸着率が大幅に向上することが判る。FIG. 2 shows the results of the HC adsorption test. From FIG. 2, it is understood that the HC adsorption rate is significantly improved by performing the steam treatment as in Examples 1a to 3a.
【００３８】また例１ａ，２ａと例３ａとを比べると、
酸処理前におけるＳｉＯ2 ／Ａｌ2Ｏ3 モル比ＭｒがＭ
ｒ≧１００である例３ａは例１ａ，２ａよりもＨＣ吸着
率が高い。ただし、スチーム処理によるＨＣ吸着率の向
上度合は、改質ＺＳＭ−５ゼオライトの担持量５ｇにお
いて、酸処理後のＳｉＯ2 ／Ａｌ2 Ｏ3 モル比Ｍｒが小
さい例１，１ａおよび例２，２ａの方が例３，３ａに比
べて高く、例１，１ａおよび例２，２ａにおいて約１．
８倍、例３において約１．２倍である。Comparing Examples 1a and 2a with Example 3a,
Before the acid treatment, the SiO 2 / Al 2 O 3 molar ratio Mr is M
Example 3a in which r ≧ 100 has a higher HC adsorption rate than Examples 1a and 2a. However, the degree of improvement of the HC adsorption rate by the steam treatment is as follows: Examples 1 and 1a and Examples 2 and 2a in which the SiO 2 / Al 2 O 3 molar ratio Mr after acid treatment is small when the amount of the modified ZSM-5 zeolite carried is 5 g. Is higher than in Examples 3 and 3a, and is about 1. in Examples 1 and 1a and Examples 2 and 2a.
8 times, about 1.2 times in Example 3.
【００３９】図３は、例１ａ，３ａに関するスチーム処
理温度とＨＣ吸着率との関係を示す。この場合、スチー
ム処理における保持時間は３時間に設定された。FIG. 3 shows the relationship between the steam treatment temperature and the HC adsorption rate for Examples 1a and 3a. In this case, the holding time in the steam treatment was set to 3 hours.
【００４０】図３より、例１ａ，３ａにおいて温度上昇
に伴いＨＣ吸着率が向上し、また例３ａの方が例１ａに
比べてＨＣ吸着能が高いことが判る。From FIG. 3, it can be seen that in Examples 1a and 3a, the HC adsorption rate is improved as the temperature rises, and that Example 3a has a higher HC adsorption capacity than Example 1a.
【００４１】[0041]
【発明の効果】本発明によれば、優れたＨＣ吸着能と耐
熱性を有するゼオライト製ＨＣ吸着材を、二工程のみ行
うことによって容易に量産することができる。According to the present invention, a zeolite HC adsorbent having excellent HC adsorbing ability and heat resistance can be easily mass-produced by performing only two steps.
【図１】（ａ）は、耐熱性改質ゼオライトの水分吸着反
応説明図、（ｂ）はスチーム処理における耐熱性改質ゼ
オライトの脱Ａｌ反応説明図である。FIG. 1 (a) is a diagram for explaining a moisture adsorption reaction of a heat-resistant modified zeolite, and FIG. 1 (b) is a diagram for explaining an Al removal reaction of a heat-resistant modified zeolite in a steam treatment.
【図２】ＨＣ吸着材の担持量とＨＣ吸着率との関係を示
すグラフである。FIG. 2 is a graph showing the relationship between the amount of HC adsorbent carried and the HC adsorption rate.
【図３】スチーム処理温度とＨＣ吸着率との関係を示す
グラフである。FIG. 3 is a graph showing a relationship between a steam treatment temperature and an HC adsorption rate.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年１２月１４日[Submission date] December 14, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】沸騰水処理は、耐熱性改質ゼオライトに含
水処理を施し、その含水状態の改質ゼオライトを高温下
に保持することによって行われる。この場合の処理温度
Ｔ2はＴ2 ≧４００℃に、また処理時間ｔ2 はｔ2 ≧５
時間にそれぞれ設定される。The boiling water treatment is carried out by subjecting the heat-resistant modified zeolite to a water-containing treatment and keeping the water-containing modified zeolite at a high temperature. In this case, the processing temperature T 2 is T 2 ≧ 400 ° C., and the processing time t 2 is t 2 ≧ 5.
Each time is set.
フロントページの続き (72)発明者 清水 治彦 埼玉県和光市中央１丁目４番１号 株式会 社本田技術研究所内Front Page Continuation (72) Inventor Haruhiko Shimizu 1-4-1 Chuo, Wako, Saitama Prefecture
Claims (3)
の未改質ゼオライトよりも高い耐熱温度を有する耐熱性
改質ゼオライトを得る中間工程と、前記耐熱性改質ゼオ
ライトを、水分の存在下で、前記耐熱温度を超えず、且
つその耐熱温度近傍の温度で加熱してＨＣ吸着能を高め
る最終工程とを順次行うことを特徴とする、ゼオライト
製ＨＣ吸着材の製造方法。1. An intermediate step of subjecting an unmodified zeolite to an acid treatment to obtain a heat resistant modified zeolite having a heat resistant temperature higher than that of the unmodified zeolite, and the heat resistant modified zeolite in the presence of water. A method for producing a zeolite-made HC adsorbent, which comprises successively performing a final step of increasing the HC adsorbing ability by heating at a temperature close to the upper temperature limit and not exceeding the upper temperature limit below.
／Ａｌ2 Ｏ3 モル比ＭｒがＭｒ≧１００の未改質ゼオラ
イトを用いる、請求項１記載のゼオライト製ＨＣ吸着材
の製造方法。2. The unmodified zeolite is SiO 2
The method for producing a zeolite-made HC adsorbent according to claim 1, wherein an unmodified zeolite having a molar ratio Mr / Al 2 O 3 Mr of Mr ≧ 100 is used.
ＳＭ−５ゼオライトを用いる、請求項１または２記載の
ゼオライト製ＨＣ吸着材の製造方法。3. The unmodified Z is used as the unmodified zeolite.
The method for producing a zeolite HC adsorbent according to claim 1, wherein SM-5 zeolite is used.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5243350A JP3052035B2 (en) | 1993-09-29 | 1993-09-29 | Method for producing zeolite HC adsorbent |
| CA 2132902 CA2132902A1 (en) | 1993-09-27 | 1994-09-26 | Highly active zsm-5 zeolite and process for producing the same |
| DE1994630562 DE69430562T2 (en) | 1993-09-27 | 1994-09-27 | Catalytic converter compositions with modified ZSM-5 zeolites, their use and methods for the preparation thereof |
| EP94115193A EP0645185B1 (en) | 1993-09-27 | 1994-09-27 | Exhaust gas control catalyst compositions comprising modified ZSM-5 zeolites, their use and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5243350A JP3052035B2 (en) | 1993-09-29 | 1993-09-29 | Method for producing zeolite HC adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0796177A true JPH0796177A (en) | 1995-04-11 |
| JP3052035B2 JP3052035B2 (en) | 2000-06-12 |
Family
ID=17102528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5243350A Expired - Fee Related JP3052035B2 (en) | 1993-09-27 | 1993-09-29 | Method for producing zeolite HC adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3052035B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7112550B2 (en) | 2002-01-24 | 2006-09-26 | Nissan Motor Co., Ltd. | Exhaust gas purifying catalyst |
| US7981834B2 (en) | 2006-03-16 | 2011-07-19 | Ict Co., Ltd. | Adsorbent for hydrocarbons, catalyst for exhaust gas purification and method for exhaust gas purification |
| WO2014002482A1 (en) | 2012-06-25 | 2014-01-03 | パナソニック株式会社 | Carbon dioxide adsorbent |
-
1993
- 1993-09-29 JP JP5243350A patent/JP3052035B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7112550B2 (en) | 2002-01-24 | 2006-09-26 | Nissan Motor Co., Ltd. | Exhaust gas purifying catalyst |
| US7981834B2 (en) | 2006-03-16 | 2011-07-19 | Ict Co., Ltd. | Adsorbent for hydrocarbons, catalyst for exhaust gas purification and method for exhaust gas purification |
| WO2014002482A1 (en) | 2012-06-25 | 2014-01-03 | パナソニック株式会社 | Carbon dioxide adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3052035B2 (en) | 2000-06-12 |
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