JP3208637B2 - NOx adsorbent and method for producing the same - Google Patents
NOx adsorbent and method for producing the sameInfo
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- JP3208637B2 JP3208637B2 JP00718095A JP718095A JP3208637B2 JP 3208637 B2 JP3208637 B2 JP 3208637B2 JP 00718095 A JP00718095 A JP 00718095A JP 718095 A JP718095 A JP 718095A JP 3208637 B2 JP3208637 B2 JP 3208637B2
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- titania
- nox
- carrier
- adsorbent
- nox adsorbent
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Description
【０００１】[0001]
【産業上の利用分野】本発明は道路トンネル換気ガスな
ど、多量の湿分と数ppm の低濃度窒素酸化物（ＮＯｘ）
を含有するガスよりＮＯｘを効率的に吸着除去するＮＯ
ｘ吸着剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a large amount of moisture and a low concentration of nitrogen oxides (NOx) of several ppm such as road tunnel ventilation gas.
NO to efficiently adsorb and remove NOx from gas containing
x Adsorbent.
【０００２】[0002]
【従来の技術と問題点】アナターゼ型のチタニアにＲ
ｕ、Ｃｅなどの酸化物を担持し焼成して得られたＮＯｘ
吸着剤、或いは担体としてゼオライト、シリカアルミナ
を用いこれに同じくＲｕ、Ｃｅなどの酸化物を担持し焼
成して得られたＮＯｘ吸着剤等が知られている。2. Description of the Related Art Anatase-type titania has R
NOx obtained by carrying and sintering oxides such as u and Ce
There is known a NOx adsorbent or the like obtained by using zeolite or silica alumina as an adsorbent or a carrier, supporting an oxide such as Ru, Ce or the like, and calcining the same.
【０００３】チタニアを担体として用いた吸着剤は耐熱
性に難点があり、たとえば空気中４００℃の加熱でＮＯ
ｘ吸着性能は急激に低下する。また３００℃の加熱でも
徐々にではあるがＮＯｘ吸着性能は低下し、吸着剤の再
生に２５０℃前後の加熱が必要であることを考えると実
用上問題となる。An adsorbent using titania as a carrier has a problem in heat resistance. For example, NO.
x Adsorption performance drops sharply. In addition, NOx adsorption performance gradually decreases even with heating at 300 ° C., and this poses a practical problem in view of the fact that heating at about 250 ° C. is required for regeneration of the adsorbent.
【０００４】一方、シリカアルミナ、ゼオライト等のＡ
ｌ−Ｓｉ系複合酸化物を担体として用いた吸着剤は、十
分な耐熱性を有し４００℃程度の加熱でもＮＯｘ吸着性
能の低下は認められない。しかし、これは耐酸性に劣
り、ＮＯｘの吸着・脱着を繰り返し行うことにより吸着
性能が低下する。On the other hand, A such as silica alumina and zeolite
An adsorbent using an l-Si-based composite oxide as a carrier has sufficient heat resistance, and does not show a decrease in NOx adsorption performance even when heated at about 400 ° C. However, this is inferior in acid resistance, and the adsorption performance is reduced by repeatedly adsorbing and desorbing NOx.
【０００５】また、耐酸性が高いとされている高シリカ
ゼオライトは、担体細孔径が５遙以下と非常に小さく、
Ｒｕ、Ｃｅなどの化合物を含浸担持する際に細孔が閉塞
され、充分なＮＯｘ吸着性能が得られないという問題を
有する。On the other hand, high silica zeolites, which are said to have high acid resistance, have a very small carrier pore diameter of 5 or less,
When impregnating and supporting a compound such as Ru or Ce, pores are closed and there is a problem that sufficient NOx adsorption performance cannot be obtained.
【０００６】本発明は、上記の点に鑑み、耐熱性に優
れ、かつ耐酸性に問題がなく、もって高い吸着性能を発
揮できるＮＯｘ吸着剤を提供することを目的とする。In view of the above, an object of the present invention is to provide a NOx adsorbent which is excellent in heat resistance, has no problem in acid resistance, and can exhibit high adsorption performance.
【０００７】[0007]
【課題を解決するための手段】本発明によるＮＯｘ吸着
剤は、チタニア担体に吸着成分が担持されているＮＯｘ
吸着剤において、該担体が、非晶質チタニアにＭｎ化合
物を添加し焼成して得られたＭｎ−Ｔｉ系表面改質チタ
ニア担体であり、該吸着成分がＲｕおよび／またはＣｅ
の酸化物であることを特徴とするものである。The NOx adsorbent according to the present invention is a NOx adsorbent in which an adsorbed component is supported on a titania carrier.
In the adsorbent, the carrier is a Mn-Ti-based surface-modified titania carrier obtained by adding a Mn compound to amorphous titania and calcining, and the adsorption component is Ru and / or Ce.
Characterized in that it is an oxide of
【０００８】上記ＮＯｘ吸着剤において、非晶質チタニ
アは、例えば、硝酸塩加水分解法で得られたチタニアコ
ロイド溶液を乾燥することにより得られる。非晶質チタ
ニアは、例えば、不燃性繊維プレフォーム体にチタニア
コロイド溶液を含浸させ、これを乾燥して得られた板状
物であり得る。In the above-mentioned NOx adsorbent, amorphous titania is obtained, for example, by drying a titania colloid solution obtained by a nitrate hydrolysis method. The amorphous titania may be, for example, a plate-like material obtained by impregnating a non-combustible fiber preform with a titania colloid solution and drying the same.
【０００９】また、該担体は、非晶質チタニアにＭｎ化
合物、および／または、Ｃｕ、Ｆｅ、ＮｉおよびＳｎよ
り選ばれた少なくとも１種の第２金属化合物を添加し焼
成して得られた金属−Ｔｉ系表面改質チタニア担体であ
ってもよい。The carrier is obtained by adding an Mn compound and / or at least one second metal compound selected from Cu, Fe, Ni and Sn to amorphous titania and calcining the same. -A Ti-based surface-modified titania carrier may be used.
【００１０】本発明によるＮＯｘ吸着剤を製造するに
は、例えば、硝酸マンガン水溶液を非晶質チタニアに含
浸させ焼成して、Ｍｎ−Ｔｉ系表面改質チタニア担体を
得、この担体にＲｕおよび／またはＣｅの酸化物を担持
する方法が好ましい。この方法で用いる非晶質チタニア
は、やはり、不燃性繊維プレフォーム体にチタニアコロ
イド溶液を含浸させ、これを乾燥して得られた板状物で
あり得る。In order to produce the NOx adsorbent according to the present invention, for example, an aqueous solution of manganese nitrate is impregnated in amorphous titania and calcined to obtain a Mn-Ti-based surface-modified titania carrier, and Ru and / or Alternatively, a method of supporting Ce oxide is preferable. The amorphous titania used in this method may also be a plate-like material obtained by impregnating a non-combustible fiber preform with a titania colloid solution and drying it.
【００１１】硝酸マンガン水溶液を非晶質チタニアに含
浸させるには、例えば、硝酸マンガンの０．２〜５．０
mol ／l 水溶液、より好ましくは硝酸マンガンの０．５
〜１．５mol ／l 水溶液に非晶質チタニアを浸漬し、つ
いで好ましくは２５０〜４８０℃、より好ましくは４０
０〜４５０℃で焼成する。In order to impregnate the amorphous titania with the aqueous solution of manganese nitrate, for example, 0.2 to 5.0 of manganese nitrate is impregnated.
mol / l aqueous solution, more preferably 0.5% of manganese nitrate
Amorphous titania is immersed in an aqueous solution of 1.5 to 1.5 mol / l, preferably 250 to 480 ° C, more preferably 40 to 480 ° C.
Bake at 0-450 ° C.
【００１２】[0012]
【作用】吸着成分としてＲｕおよび／またはＣｅの酸化
物を用いたＮＯｘ吸着剤の耐熱性は、 担体の固体酸酸性点にＲｕイオンまたはＲｕ錯イオン
を吸着担持させ、 比較的低温の焼成を行い、 残存する酸性点をＣｅイオンまたはＣｅ錯イオンで覆
い、および さらに過剰のＣｅをＲｕ周辺に配置・焼成する ことで向上できる。この時、担体固体酸の酸強度が強い
と、より高い耐熱性が得られる。The heat resistance of a NOx adsorbent using an oxide of Ru and / or Ce as an adsorbing component is determined by adsorbing and supporting Ru ions or Ru complex ions at the solid acid acid point of the carrier and performing calcination at a relatively low temperature. It can be improved by covering the remaining acidic points with Ce ions or Ce complex ions, and arranging and firing excess Ce around Ru. At this time, when the acid strength of the carrier solid acid is high, higher heat resistance can be obtained.
【００１３】強い固体酸担体として知られるＡｌ−Ｓｉ
系複合酸化物は前述のように高い耐熱性を有している。
しかしながら、これは耐酸性に劣り吸着剤使用時のＮＯ
ｘ吸着・脱着の繰り返しにより、固体酸性の発現要因で
あるＳｉ骨格中のＡｌ成分が硝酸塩化または亜硝酸塩化
と熱分解を繰り返して骨格から外れるので、酸性点が消
失し、その結果、吸着剤の耐熱性が失われ加熱再生時に
性能が低下する現象が顕著に現れる。Al-Si known as a strong solid acid carrier
The system composite oxide has high heat resistance as described above.
However, this is inferior in acid resistance to NO
x By repeated adsorption and desorption, the Al component in the Si skeleton, which is a factor of the solid acidity, is repeatedly decomposed from the skeleton by repeating nitric acid or nitrite and thermal decomposition, so that the acidic point disappears. As a result, the adsorbent Phenomena in which the heat resistance is lost and the performance is degraded during heating and regeneration.
【００１４】これを防止するには強い固体酸性を示し、
かつ耐酸性が高い担体を使用する必要がある。In order to prevent this, it shows strong solid acidity,
It is necessary to use a carrier having high acid resistance.
【００１５】そこで、非晶質チタニアにＭｎ塩を添加し
焼成した表面改質チタニア担体を使用し、これに吸着成
分としてＲｕおよび／またはＣｅの酸化物を担持させ、
ＮＯｘ吸着剤を製造した。このＮＯｘ吸着剤は、高い耐
熱性を示し、かつＮＯｘ吸着・脱着によっても吸着性能
が全く低下しないものである。Therefore, a surface-modified titania support obtained by adding a Mn salt to amorphous titania and calcining is used, and an oxide of Ru and / or Ce is carried on the support as an adsorbing component.
A NOx adsorbent was produced. This NOx adsorbent has high heat resistance, and its adsorption performance does not decrease at all even by NOx adsorption / desorption.
【００１６】[0016]
【実施例】以下、ＮＯｘ吸着剤の製造法および得られた
吸着剤の特性について具体的に説明する。EXAMPLES Hereinafter, a method for producing a NOx adsorbent and characteristics of the obtained adsorbent will be specifically described.
【００１７】実施例１ 硝酸塩加水分解法で得られたチタニアコロイド溶液（固
形分３２重量％）を０．５ｍｍ厚さのセラミックスペー
パーに含浸保持させ、同ペーパーを１１０℃で乾燥し、
非晶質チタニアを１５８ｇ／ｍ2 保持した板状物を得
た。これを１．０mol ／l の硝酸マンガン水溶液に６分
間浸漬し、ついで１１０℃で乾燥した。この操作によ
り、１ｇのＴｉＯ2 当たり１．１mmolのＭｎが添加され
た。この板状物を３００℃で１時間、さらに４００℃で
３時間、空気流通下で焼成し、表面改質板状チタニア担
体を得た。Example 1 A titania colloid solution (solid content 32% by weight) obtained by a nitrate hydrolysis method was impregnated and held in a ceramic paper having a thickness of 0.5 mm, and the paper was dried at 110 ° C.
A plate-like material holding 158 g / m 2 of amorphous titania was obtained. This was immersed in a 1.0 mol / l manganese nitrate aqueous solution for 6 minutes, and then dried at 110 ° C. This operation, Mn of TiO 2 per 1.1mmol of 1g was added. The plate-like material was fired at 300 ° C. for 1 hour and further at 400 ° C. for 3 hours under air flow to obtain a surface-modified plate-like titania carrier.
【００１８】この担体は１ｇのＴｉＯ2 当たり９１ｍ2
の比表面積を有していた。[0018] The carrier 91m TiO 2 per 1g 2
Specific surface area.
【００１９】この板状担体をＲｕとして１４ｇ／l のＲ
ｕＣｌ3 水溶液（ｐＨ＝０．９２）に６分間浸漬し、１
１０℃で乾燥後、さらに２３０℃で１時間焼成した。This plate-like carrier is defined as Ru at 14 g / l of R.
dipped in uCl 3 aqueous solution (pH = 0.92) for 6 minutes,
After drying at 10 ° C., it was further baked at 230 ° C. for 1 hour.
【００２０】次にＣｅとして２５０ｇ／l のＣｅ（ＮＯ
3 ）3 水溶液に上記板状担体を１２分間浸漬し、３５０
℃で３時間焼成した。以上の操作により１ｇのＴｉＯ2
当たり０．１６mmolのＲｕならびに２．０mmolのＣｅが
担持されたＮＯｘ吸着剤が得られた。この吸着剤の比表
面積は１ｇのＴｉＯ2 当たり７７ｍ2 であった。Next, as Ce, 250 g / l of Ce (NO
3 ) Immerse the plate-like carrier in 3 aqueous solution for 12 minutes,
Calcination was performed at 3 ° C. for 3 hours. By the above operation, 1 g of TiO 2
A NOx adsorbent loaded with 0.16 mmol of Ru and 2.0 mmol of Ce was obtained. The specific surface area of this adsorbent was 77 m 2 per 1 g of TiO 2 .
【００２１】これを試料Ａとする。This is designated as Sample A.
【００２２】実施例２〜５ 硝酸マンガン水溶液のＭｎ濃度をそれぞれ０．５mol ／
l 、１．０mol ／l 、１．５mol ／l および２．０mol
／l とし、その他は実施例１と同様の操作を行ってＮＯ
ｘ吸着剤を得た。これらを、各々、試料Ｂ、Ｃ、Ｄおよ
びＥとする。Examples 2 to 5 The manganese nitrate aqueous solution had an Mn concentration of 0.5 mol /
l, 1.0 mol / l, 1.5 mol / l and 2.0 mol
/ L, and performing the same operations as in Example 1
x adsorbent was obtained. These are designated as Samples B, C, D and E, respectively.
【００２３】比較例１ 実施例１と同様にして得た非晶質チタニア保持板状物
を、Ｍｎを添加せず、実施例１と同様の条件で焼成した
点を除いて、実施例１と同様にしてＮＯｘ吸着剤を得
た。これを試料Ｆとする。Comparative Example 1 An amorphous titania holding plate obtained in the same manner as in Example 1 was fired under the same conditions as in Example 1 without adding Mn. Similarly, a NOx adsorbent was obtained. This is designated as Sample F.
【００２４】比較例２ シリカアルミナ／（Ａｌ／Ｓｉ＝３／７）のコロイド溶
液（固形分２１重量％）に、実施例１で用いたのと同じ
セラミックペーパーを浸漬しついで乾燥し、シリカアル
ミナを１１０ｇ／ｍ2 保持した板状物を得た。Comparative Example 2 The same ceramic paper as used in Example 1 was immersed in a colloidal solution of silica-alumina / (Al / Si = 3/7) (solid content: 21% by weight), and then dried. Was obtained at 110 g / m 2 .
【００２５】これを１mmol／l の塩化アンモン水溶液で
９０℃で５時間処理し、アルカリ分を除去した後、５０
０℃で５時間焼成し、シリカアルミナ系板状担体を得
た。これに実施例１と同様の処理を施してＲｕおよびＣ
ｅを担持させ、板状ＮＯｘ吸着剤を得た。これを試料Ｇ
とする。This was treated with a 1 mmol / l aqueous ammonium chloride solution at 90 ° C. for 5 hours to remove alkali components.
It was calcined at 0 ° C. for 5 hours to obtain a silica-alumina-based plate-like carrier. This is subjected to the same processing as in Example 1 to obtain Ru and C
e was carried to obtain a plate-like NOx adsorbent. This is sample G
And
【００２６】性能試験 こうして調製した試料Ａ〜Ｇの組成、比表面積、１００
ppm ＮＯを含む空気（室温、相対湿度７０％）雰囲気中
でのＮＯｘ飽和吸着量、試料を更に空気中４００℃で１
２時間または２４時間焼成した後のＮＯｘ飽和吸着量を
測定した。この測定結果を表１に示す。 Performance Test The composition, specific surface area, 100
ppm NOx saturated adsorption in air containing NO (room temperature, 70% relative humidity)
The NOx saturated adsorption amount after firing for 2 hours or 24 hours was measured. Table 1 shows the measurement results.
【００２７】[0027]
【表１】 上記表１から下記のことが分かる。Ｍｎ転化量を変化さ
せてもＲｕおよびＣｅ担持量には大きな変化は認められ
ない。初期ＮＯｘ飽和吸着量はＲｕおよびＣｅの担持量
によってほぼ定まるので、試料Ａ〜Ｅで大きな変化は認
められない。しかしＭｎ無添加の試料Ｆでは他と比べ初
期ＮＯｘ飽和吸着量が明確に低い。このことより、Ｃｅ
担持後の焼成で既に有る程度熱劣化が進行していること
が伺える。[Table 1] The following can be seen from Table 1 above. Even if the Mn conversion amount is changed, no significant change is observed in the Ru and Ce supported amounts. Since the initial NOx saturated adsorption amount is substantially determined by the supported amounts of Ru and Ce, no significant change is observed in Samples A to E. However, Sample F without Mn had a clearly lower initial NOx saturation adsorption amount than the others. From this, Ce
It can be seen that the thermal degradation has already progressed to some extent in the firing after the loading.
【００２８】４００℃での加熱による性能変化は試料Ｆ
で非常に激しかった。Ａ〜Ｅの各試料の相違はＭｎ添加
量の差によって発現する強い固体酸の酸量の差として理
解できる。即ち、加熱後のＮＯｘ吸着性能は殆ど強い酸
性点へ吸着されたＲｕ量によって定まると考えられ、試
料ＢではＭｎ添加量が少なく酸量がＲｕ担持量に対し充
分でなく、試料Ａ、Ｃ、Ｄ、Ｅでは担持Ｒｕのほとんど
が酸点に吸着されていると考えられる。The performance change due to heating at 400 ° C.
It was very intense. The difference between the samples A to E can be understood as the difference in the acid amount of the strong solid acid which is expressed by the difference in the amount of Mn added. That is, it is considered that the NOx adsorption performance after heating is determined by the amount of Ru adsorbed to almost strong acidic sites. In Sample B, the amount of added Mn was small and the acid amount was not sufficient for the amount of Ru supported, and Samples A, C, In D and E, it is considered that most of the supported Ru is adsorbed to the acid sites.
【００２９】試料ＥではＭｎ添加が過剰であり、比表面
積の低下、ＲｕおよびＣｅ担持量の低下が認められ、全
体として低めの性能が示されている。In sample E, the addition of Mn was excessive, and a decrease in the specific surface area and a decrease in the supported amounts of Ru and Ce were observed, indicating a lower performance as a whole.
【００３０】試料Ｇでは非常に高い耐熱性が認められる
が、Ｍｎ添加担体と比べペーパーの担体保持量が低いの
で、初期性能が低く示されている。Sample G shows extremely high heat resistance, but the initial performance is low because the amount of paper retained on the paper is lower than that of the Mn-added carrier.
【００３１】ＮＯｘ吸着・脱着の繰り返し試験 次に試料ＡならびにＦ、Ｇについて、下記の方法でＮＯ
ｘ吸着・脱着の繰り返し試験を行なった。この結果を図
１に示す。 Repeated test of NOx adsorption / desorption Next, samples A, F, and G were tested for NOx by the following method.
A repeated test of x adsorption / desorption was performed. The result is shown in FIG.
【００３２】板状吸着剤を吸着管（３０×３０ｍｍ角
型）に充填し、ＮＯを４．５ppm 含む室温の空気（相対
湿度７０％）を同管に流し、流通開始からの時間と出口
ＮＯｘ濃度の関係を測定した。空気流通を２１時間で清
浄空気（相対湿度７０％）に切り替え、同時に吸着管を
加熱し２６０℃で１時間保持し、吸着剤を再生した。こ
の操作を繰り返し、ＮＯｘ吸着性能の変化をみた。A plate-shaped adsorbent is filled in an adsorption tube (30 × 30 mm square type), room temperature air containing 4.5 ppm of NO (70% relative humidity) is passed through the tube, and the time from the start of distribution and the NOx at the outlet are measured. The concentration relationship was measured. The air flow was switched to clean air (70% relative humidity) in 21 hours, and at the same time, the adsorption tube was heated and maintained at 260 ° C. for 1 hour to regenerate the adsorbent. This operation was repeated to observe the change in the NOx adsorption performance.
【００３３】[0033]
【式１】 上記式より脱硝率を求めた。この結果を図１に示す。(Equation 1) The denitration rate was determined from the above equation. The result is shown in FIG.
【００３４】図１から明らかなように、試料ＡはＮＯｘ
吸着・脱着の繰り返しによっては、殆ど性能低下を示さ
ないが、試料Ｆ、Ｇは繰り返し開始当初激しくその後は
徐々に性能が低下した。特に耐熱性の高い試料Ｇの性能
低下が激しかった。As is clear from FIG. 1, the sample A was NOx
Although the performance was hardly reduced by repeated adsorption / desorption, the performance of Samples F and G was severe at the beginning of the repetition and then gradually decreased. In particular, the performance of Sample G having high heat resistance was significantly reduced.
【００３５】[0035]
【発明の効果】本発明によるＮＯｘ吸着剤は、以上の通
り構成されているので、高い耐熱性および耐酸性を示
し、かつＮＯｘ吸着・脱着によっても吸着性能が全く低
下しないものである。Since the NOx adsorbent according to the present invention is constituted as described above, it exhibits high heat resistance and acid resistance, and its adsorption performance does not decrease at all even by NOx adsorption / desorption.
【図１】ＮＯｘ吸着・脱着の繰り返し回数と、脱硝率の
関係を示すグラフである。FIG. 1 is a graph showing the relationship between the number of repetitions of NOx adsorption / desorption and the denitration rate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 福寿 厚 大阪市此花区西九条５丁目３番28号 日 立造船株式会社内 (56)参考文献 特開 平７−204468（ＪＰ，Ａ) 特開 平７−88363（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 20/00 - 20/34 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Atsushi Fukuju 5-3-28 Nishikujo, Konohana-ku, Osaka-shi Inside Tachibana Shipbuilding Co., Ltd. (56) References JP-A-7-204468 (JP, A) Hei 7-88363 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) B01J 20/00-20/34
Claims (4)
るＮＯｘ吸着剤において、該担体が、非晶質チタニアに
Ｍｎ化合物を添加し焼成して得られたＭｎ−Ｔｉ系表面
改質チタニア担体であり、該吸着成分がＲｕおよび／ま
たはＣｅの酸化物であることを特徴とするＮＯｘ吸着
剤。1. A NOx adsorbent in which an adsorption component is carried on a titania carrier, wherein the carrier is a Mn-Ti-based surface-modified titania carrier obtained by adding a Mn compound to amorphous titania and calcining the same. A NOx adsorbent, wherein the adsorbent is an oxide of Ru and / or Ce.
ーム体にチタニアコロイド溶液を含浸させ、これを乾燥
して得られた板状物であることを特徴とする請求項１記
載のＮＯｘ吸着剤。2. The NOx adsorbent according to claim 1, wherein the amorphous titania is a plate-like material obtained by impregnating a non-combustible fiber preform with a titania colloid solution and drying it. Agent.
物、および／または、Ｃｕ、Ｆｅ、ＮｉおよびＳｎより
選ばれた少なくとも１種の第２金属化合物を添加し焼成
して得られた金属−Ｔｉ系表面改質チタニア担体である
ことを特徴とする請求項１記載のＮＯｘ吸着剤。3. A metal obtained by adding an Mn compound and / or at least one second metal compound selected from Cu, Fe, Ni and Sn to amorphous titania and calcining the carrier. The NOx adsorbent according to claim 1, wherein the NOx adsorbent is a Ti-based surface-modified titania carrier.
含浸させ焼成して、Ｍｎ−Ｔｉ系表面改質チタニア担体
を得、この担体にＲｕおよび／またはＣｅの酸化物を担
持することを特徴とするＮＯｘ吸着剤の製造法。4. An aqueous manganese nitrate solution is impregnated into amorphous titania and calcined to obtain a Mn-Ti surface-modified titania support, and Ru and / or Ce oxide is supported on the support. For producing a NOx adsorbent.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00718095A JP3208637B2 (en) | 1995-01-20 | 1995-01-20 | NOx adsorbent and method for producing the same |
| TW085100297A TW412438B (en) | 1995-01-20 | 1996-01-11 | Nox adsorbent |
| DK96100643T DK0722763T3 (en) | 1995-01-20 | 1996-01-17 | NOx adsorbents |
| EP96100643A EP0722763B1 (en) | 1995-01-20 | 1996-01-17 | NOx adsorbents |
| DE69615228T DE69615228T2 (en) | 1995-01-20 | 1996-01-17 | Adsorbent for nitrogen oxides |
| AT96100643T ATE205741T1 (en) | 1995-01-20 | 1996-01-17 | ADSORBANT FOR NITROGEN OXIDES |
| KR1019960000975A KR100194483B1 (en) | 1995-01-20 | 1996-01-18 | NOx Adsorbent |
| CN96100689A CN1063353C (en) | 1995-01-20 | 1996-01-19 | NOX adsorbent |
| CA002167661A CA2167661C (en) | 1995-01-20 | 1996-01-19 | Nox adsorbent comprising mn-ti system surface-reformed titania carrier |
| US08/588,882 US5840649A (en) | 1995-01-20 | 1996-01-19 | NOx adsorbents |
| SG1996008942A SG47119A1 (en) | 1995-01-20 | 1996-04-15 | Nox adsorbents |
| KR1019980043111A KR100196207B1 (en) | 1995-01-20 | 1998-10-15 | Nox absorbents |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00718095A JP3208637B2 (en) | 1995-01-20 | 1995-01-20 | NOx adsorbent and method for producing the same |
| SG1996008942A SG47119A1 (en) | 1995-01-20 | 1996-04-15 | Nox adsorbents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08192045A JPH08192045A (en) | 1996-07-30 |
| JP3208637B2 true JP3208637B2 (en) | 2001-09-17 |
Family
ID=26341442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00718095A Expired - Fee Related JP3208637B2 (en) | 1995-01-20 | 1995-01-20 | NOx adsorbent and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3208637B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180038531A (en) * | 2015-08-14 | 2018-04-16 | 바스프 코포레이션 | Methods for making and using adsorbents and adsorbents |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3924322B2 (en) * | 1995-09-26 | 2007-06-06 | 株式会社 神戸製鋼所 | Hazardous gas removal agent |
| CN114700088B (en) * | 2022-03-23 | 2024-04-12 | 天津水泥工业设计研究院有限公司 | Medium-low temperature denitration catalyst prepared by recycling fly ash, and preparation method and application thereof |
-
1995
- 1995-01-20 JP JP00718095A patent/JP3208637B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180038531A (en) * | 2015-08-14 | 2018-04-16 | 바스프 코포레이션 | Methods for making and using adsorbents and adsorbents |
| KR102602701B1 (en) | 2015-08-14 | 2023-11-15 | 바스프 코포레이션 | Adsorbents and their preparation and use methods |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08192045A (en) | 1996-07-30 |
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