JPH08150324A - Method for catalytically reducing nitrogen oxide - Google Patents
Method for catalytically reducing nitrogen oxideInfo
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- JPH08150324A JPH08150324A JP3043006A JP4300691A JPH08150324A JP H08150324 A JPH08150324 A JP H08150324A JP 3043006 A JP3043006 A JP 3043006A JP 4300691 A JP4300691 A JP 4300691A JP H08150324 A JPH08150324 A JP H08150324A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は窒素酸化物の接触還元方
法に係わり、詳しくは工場、自動車などから排出される
排気ガスの中に含まれる有害な窒素酸化物を特定の還元
剤により選択的に効率良く接触還元する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for catalytic reduction of nitrogen oxides, and more specifically, it can selectively remove harmful nitrogen oxides contained in exhaust gas emitted from factories, automobiles, etc. by a specific reducing agent. The present invention relates to a method for efficient catalytic reduction.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
排気ガス中に含まれる窒素酸化物は、該窒素酸化物を
酸化した後、アルカリに吸収させる方法、ＮＨ3 、Ｈ
2 、ＣＯ等の還元剤を用いて窒素に変える方法などによ
って除去されてきた。2. Description of the Related Art Conventionally, the problems to be solved by the invention
Nitrogen oxides contained in the exhaust gas after oxidizing the nitrogen oxide, a method of absorbing the alkali, NH 3, H
2 , it has been removed by a method of changing to nitrogen using a reducing agent such as CO.
【０００３】しかしながら、の方法による場合は、公
害防止のためのアルカリの排液処理が必要となり、また
の方法において還元剤としてＮＨ3 等のアルカリ剤を
用いる場合においては、これが排気ガス中のＳＯｘと反
応して塩類を生成し、この塩類が触媒の還元活性を低下
させてしまうという問題があった。また、のＨ2 、Ｃ
Ｏを還元剤として用いる場合は、これらが低濃度に存在
するＮＯX よりも高濃度に存在するＯ2 と優先的に反応
してしまうため、ＮＯX を低減するためには多量の還元
剤を必要とするという問題があった。However, in the case of the method (1), it is necessary to perform drainage treatment of alkali for preventing pollution, and in the case of using an alkali agent such as NH 3 as a reducing agent in the method (2), this is SOx in exhaust gas. However, there is a problem in that the salt reacts with the salt to form a salt, and the salt reduces the reducing activity of the catalyst. Also, H 2 , C
When O is used as a reducing agent, these react preferentially with O 2 present in a high concentration rather than NO X present in a low concentration. Therefore, in order to reduce NO X , a large amount of reducing agent should be used. There was a problem of needing it.
【０００４】上記およびの方法以外に、還元剤を
用いることなく窒素酸化物を触媒により直接分解する方
法が提案されているが、触媒の窒素酸化物分解活性が低
いため、実用に供し得ないという問題があった。In addition to the above methods and methods, a method of directly decomposing nitrogen oxides with a catalyst without using a reducing agent has been proposed, but it is not practically applicable because the catalyst has a low activity of decomposing nitrogen oxides. There was a problem.
【０００５】本発明は以上の事情に鑑みてなされたもの
であって、その目的とするところは、酸素共存下におい
て、排気ガス中の窒素酸化物を効率的に除去する方法を
提供するにある。The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for efficiently removing nitrogen oxides in exhaust gas in the coexistence of oxygen. .
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
の本発明に係る窒素酸化物の接触還元方法は、排気ガス
中に還元剤としてアルコール類を添加し、この還元剤を
触媒と接触させることにより、排気ガス中の窒素酸化物
を還元除去することを特徴とする。In order to achieve the above object, the method for catalytic reduction of nitrogen oxides according to the present invention comprises adding alcohols as a reducing agent to exhaust gas and bringing the reducing agent into contact with a catalyst. Thus, the nitrogen oxide in the exhaust gas is reduced and removed.
【０００７】本発明におけるアルコール類としては、脂
肪族系アルコール、芳香族系アルコールなど、特に制限
されない。好適なアルコール類としては、エタノール、
プロパノール、イソプロパノール、ｎ−ブチルアルコー
ル、イソブチルアルコール、ｔ−−ブチルアルコール、
アリルアルコール等の常温では液体であって、反応温度
では気体である低級アルコールが挙げられる。輸送、貯
蔵、取扱が容易だからである。The alcohols in the present invention are not particularly limited, such as aliphatic alcohols and aromatic alcohols. Suitable alcohols include ethanol,
Propanol, isopropanol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol,
Lower alcohols such as allyl alcohol which are liquid at room temperature and gaseous at the reaction temperature are mentioned. This is because they are easy to transport, store and handle.
【０００８】アルコール類の好適な添加量は、使用する
アルコール類の種類によって異なるが、排気ガス中に含
有される窒素酸化物に対して０．１〜１０倍（モル比）
の量が好適であり、１〜５倍の量がより好適である。
０．１倍未満であると充分な触媒活性を得ることができ
ず、また１０倍を越えると未反応のアルコールまたは部
分酸化生成物の排出量が多くなるためこれらを処理する
ための後処理が必要となるので、ともに好ましくない。
本発明における触媒としては、次の（１）〜(11)に示す
ものが例示される。The suitable addition amount of alcohols varies depending on the kind of alcohols used, but is 0.1 to 10 times (molar ratio) with respect to nitrogen oxides contained in the exhaust gas.
Is preferable, and an amount of 1 to 5 times is more preferable.
If it is less than 0.1 times, sufficient catalytic activity cannot be obtained, and if it exceeds 10 times, the amount of unreacted alcohol or partial oxidation product is increased, so post-treatment for treating them is required. Both are not preferable because they are required.
Examples of the catalyst in the present invention include those shown in the following (1) to (11).
【０００９】（１） 下記組成式で表されるゼオライト
中のイオンＭの一部または全部を、Ｔｉ4+、Ｚｒ4+およ
びＳｎ4+からなる群より選ばれた金属イオンでイオン交
換してなるゼオライトに、Ｒｕ、Ｒｈ、Ａｇ、Ｐｄおよ
びＰｔからなる群より選ばれた少なくとも一種の金属お
よび／またはその金属酸化物を担持させてなる窒素酸化
物接触還元用触媒。 ＭA [(ＡｌＯ2)X （ＳｉＯ2)Y ] ・ＺＨ2 Ｏ 〔式中、イオンＭはアルカリ金属イオン、アルカリ土類
金属イオンまたは水素イオン、ｎＡ＝Ｘ（ｎ：イオンＭ
の価数）、Ｙ／Ｘ≧５である。〕(1) A part or all of the ions M in the zeolite represented by the following composition formula are ion-exchanged with a metal ion selected from the group consisting of Ti 4+ , Zr 4+ and Sn 4+. A catalyst for catalytic reduction of nitrogen oxides, which comprises supporting at least one metal selected from the group consisting of Ru, Rh, Ag, Pd, and Pt and / or a metal oxide thereof on the following zeolite. M A [(AlO 2 ) X (SiO 2 ) Y ] .ZH 2 O [In the formula, the ion M is an alkali metal ion, an alkaline earth metal ion or a hydrogen ion, nA = X (n: ion M
Valence of Y) and Y / X ≧ 5. ]
【００１０】（２） 下記組成式で表されるゼオライト
または該ゼオライト中のイオンＭの一部または全部を、
Ｔｉ4+、Ｚｒ4+およびＳｎ4+からなる群より選ばれた金
属イオンでイオン交換してなるゼオライトの細孔内に、
ＴｉＯ2 、ＺｒＯ2 およびＳｎＯ2 からなる群より選ば
れた少なくとも一種の金属酸化物を担持させてなるゼオ
ライトに、Ｒｕ、Ｒｈ、Ａｇ、ＰｄおよびＰｔからなる
群より選ばれた少なくとも一種の金属および／またはそ
の金属酸化物を担持させてなる窒素酸化物接触還元用触
媒。 ＭA [(ＡｌＯ2)X （ＳｉＯ2)Y ] ・ＺＨ2 Ｏ 〔式中、Ｍはアルカリ金属イオン、アルカリ土類金属イ
オンおよび水素イオンからなる群より選ばれたイオン、
ｎＡ＝Ｘ（ｎ：イオンＭの価数）、Ｙ／Ｘ≧５であ
る。〕(2) The zeolite represented by the following composition formula or a part or all of the ion M in the zeolite,
In the pores of the zeolite formed by ion exchange with a metal ion selected from the group consisting of Ti 4+ , Zr 4+ and Sn 4+ ,
At least one metal selected from the group consisting of Ru, Rh, Ag, Pd, and Pt is added to a zeolite supporting at least one metal oxide selected from the group consisting of TiO 2 , ZrO 2, and SnO 2. / Or a catalyst for catalytic reduction of nitrogen oxides, which carries the metal oxide thereof. M A [(AlO 2 ) X (SiO 2 ) Y ] .ZH 2 O [In the formula, M is an ion selected from the group consisting of alkali metal ions, alkaline earth metal ions and hydrogen ions,
nA = X (n: valence of the ion M), Y / X ≧ 5. ]
【００１１】（３） ＴｉＯ2 と、Ａｌ2 Ｏ3 、ＳｉＯ
2 、ＺｒＯ2 からなる群より選ばれた少なくとも一種の
金属酸化物と、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｐｔからなる
群より選ばれた少なくとも一種の金属および／またはそ
の金属酸化物とからなる窒素酸化物接触還元用触媒。(3) TiO 2 , Al 2 O 3 and SiO
Nitrogen consisting of at least one metal oxide selected from the group consisting of 2 , and ZrO 2, and at least one metal selected from the group consisting of Ru, Rh, Pd, Ag, and Pt and / or its metal oxide. Oxide catalytic reduction catalyst.
【００１２】（４） ＴｉＯ2 に、Ｐｄ、Ｒｕ、Ｒｈ、
ＡｇおよびＰｔからなる群より選ばれた少なくとも一種
の金属および／またはその金属酸化物を担持させてなる
窒素酸化物接触還元用触媒。(4) TiO 2 with Pd, Ru, Rh,
A catalyst for catalytic reduction of nitrogen oxides, which carries at least one metal selected from the group consisting of Ag and Pt and / or a metal oxide thereof.
【００１３】（５） ＴｉＯ2 、Ａｌ2 Ｏ3 、ＺｒＯ2
およびＳｉＯ2 からなる群より選ばれた少なくとも一種
の金属酸化物と、希土類の酸化物と、Ｒｕ、Ｒｈ、Ｐ
ｄ、ＡｇおよびＰｔからなる群より選ばれた少なくとも
一種の金属および／またはその金属酸化物とからなる窒
素酸化物接触還元用触媒。(5) TiO 2 , Al 2 O 3 , ZrO 2
And at least one metal oxide selected from the group consisting of SiO 2 and a rare earth oxide, Ru, Rh, P
A catalyst for catalytic reduction of nitrogen oxides comprising at least one metal selected from the group consisting of d, Ag and Pt and / or its metal oxide.
【００１４】（６） 下記一般式で表されるペロブスカ
イト型複合酸化物からなる窒素酸化物接触還元用触媒。 Ｌａx Ｓｒ(1-X) ＢY Ｂ'(1-Y) Ｏ3 〔式中、ＢはＭｎまたはＣｏ；Ｂ'はＣｏ、Ｆｅ、Ｎ
ｉ、ＣｕまたはＣｒ；０≦Ｘ≦１、０≦Ｙ≦１であ
る。〕(6) A catalyst for catalytic reduction of nitrogen oxides comprising a perovskite type complex oxide represented by the following general formula. La x Sr (1-X) B Y B '(1-Y) O 3 wherein, B is Mn or Co; B' is Co, Fe, N
i, Cu or Cr; 0 ≦ X ≦ 1, 0 ≦ Y ≦ 1. ]
【００１５】（７） 下記一般式で表されるペロブスカ
イト型複合酸化物に、Ｐｔ、Ｒｈ、Ｐｄ、Ｒｕ、および
Ａｇからなる群より選ばれた少なくとも一種の金属およ
び／またはその金属酸化物を担持させてなる窒素酸化物
接触還元用触媒。 Ｌａx Ｓｒ(1-X) ＢY Ｂ'(1-Y) Ｏ3 〔式中、ＢはＭｎまたはＣｏ；Ｂ'はＣｏ、Ｆｅ、Ｎ
ｉ、ＣｕまたはＣｒ；０≦Ｘ≦１、０≦Ｙ≦１であ
る。〕(7) At least one metal selected from the group consisting of Pt, Rh, Pd, Ru, and Ag and / or its metal oxide is supported on the perovskite type composite oxide represented by the following general formula. A catalyst for catalytic reduction of nitrogen oxides. La x Sr (1-X) B Y B '(1-Y) O 3 wherein, B is Mn or Co; B' is Co, Fe, N
i, Cu or Cr; 0 ≦ X ≦ 1, 0 ≦ Y ≦ 1. ]
【００１６】（８） 下記組成式で表されるゼオライト
中のイオンＭの一部または全部を、Ｔｉ4+、Ｚｒ4+およ
びＳｎ4+からなる群より選ばれた金属イオンでイオン交
換してなるゼオライトに、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、ＭｏおよびＷからなる群
より選ばれた少なくとも一種の金属の酸化物を担持させ
てなる窒素酸化物接触還元用触媒。 ＭA [(ＡｌＯ2)X （ＳｉＯ2)Y ] ・ＺＨ2 Ｏ 〔式中、イオンＭはアルカリ金属イオン、アルカリ土類
金属イオンまたは水素イオン、ｎＡ＝Ｘ（ｎ：イオンＭ
の価数）、Ｙ／Ｘ≧５である。〕(8) Part or all of the ions M in the zeolite represented by the following composition formula are ion-exchanged with a metal ion selected from the group consisting of Ti 4+ , Zr 4+ and Sn 4+. , Zeolite, V, Cr, Mn, Fe, C
A catalyst for catalytic reduction of nitrogen oxides, which carries an oxide of at least one metal selected from the group consisting of o, Ni, Cu, Zn, Nb, Mo and W. M A [(AlO 2 ) X (SiO 2 ) Y ] .ZH 2 O [In the formula, the ion M is an alkali metal ion, an alkaline earth metal ion or a hydrogen ion, nA = X (n: ion M
Valence of Y) and Y / X ≧ 5. ]
【００１７】（９） 下記組成式で表されるゼオライト
または該ゼオライト中のイオンＭの一部または全部を、
Ｔｉ4+、Ｚｒ4+およびＳｎ4+からなる群より選ばれた金
属イオンでイオン交換してなるゼオライトに、Ｔｉ
Ｏ2 、ＺｒＯ2 およびＳｎＯ2 からなる群より選ばれた
少なくとも一種の金属酸化物を担持させてなるゼオライ
トに、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚ
ｎ、Ｎｂ、ＭｏおよびＷからなる群より選ばれた少なく
とも一種の金属の酸化物を担持させてなる窒素酸化物接
触還元用触媒。 ＭA [(ＡｌＯ2)X （ＳｉＯ2)Y ] ・ＺＨ2 Ｏ 〔式中、Ｍはアルカリ金属イオン、アルカリ土類金属イ
オンおよび水素イオンからなる群より選ばれたイオン、
ｎＡ＝Ｘ（ｎ：イオンＭの価数）、Ｙ／Ｘ≧５であ
る。〕(9) The zeolite represented by the following composition formula or a part or all of the ions M in the zeolite are
Zeolite formed by ion exchange with a metal ion selected from the group consisting of Ti 4+ , Zr 4+ and Sn 4+ is added to Ti
V, Cr, Mn, Fe, Co, Ni, Cu, Z are added to a zeolite supporting at least one metal oxide selected from the group consisting of O 2 , ZrO 2 and SnO 2.
A catalyst for catalytic reduction of nitrogen oxides, which carries an oxide of at least one metal selected from the group consisting of n, Nb, Mo and W. M A [(AlO 2 ) X (SiO 2 ) Y ] .ZH 2 O [In the formula, M is an ion selected from the group consisting of alkali metal ions, alkaline earth metal ions and hydrogen ions,
nA = X (n: valence of the ion M), Y / X ≧ 5. ]
【００１８】（１０） ＴｉＯ2 と、Ａｌ2 Ｏ3 、Ｓｉ
Ｏ2 、ＺｒＯ2 からなる群より選ばれた少なくとも一種
の金属酸化物と、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、
Ｃｕ、Ｚｎ、Ｎｂ、ＭｏおよびＷからなる群より選ばれ
た少なくとも一種の金属の酸化物とからなる窒素酸化物
接触還元用触媒。(10) TiO 2 , Al 2 O 3 and Si
At least one metal oxide selected from the group consisting of O 2 and ZrO 2 , and V, Cr, Mn, Fe, Co, Ni,
A catalyst for catalytic reduction of nitrogen oxides, which comprises an oxide of at least one metal selected from the group consisting of Cu, Zn, Nb, Mo and W.
【００１９】（１１） 下記組成式で表されるゼオライ
ト中のアルカリ金属イオンＭの一部または全部を、アル
カリ土類金属イオンでイオン交換してなるゼオライト
に、Ｍｎ、Ｆｅ、Ｃｏ、ＮｉおよびＣｕからなる群より
選ばれた少なくとも一種の金属の酸化物を担持させてな
る窒素酸化物接触還元用触媒。 ＭX [(ＡｌＯ2)X （ＳｉＯ2)Y ] ・ＺＨ2 Ｏ(11) Mn, Fe, Co, Ni and Cu are added to a zeolite obtained by ion-exchanging a part or all of alkali metal ions M in the zeolite represented by the following composition formula with alkaline earth metal ions. A catalyst for catalytic reduction of nitrogen oxides, which carries an oxide of at least one metal selected from the group consisting of: M X [(AlO 2 ) X (SiO 2 ) Y ] .ZH 2 O
【００２０】本発明方法において、窒素酸化物接触還元
用触媒が窒素酸化物に対して良好な還元活性を示す好適
な還元温度は、使用するアルコール類および触媒の種類
により異なるが通常１００〜８００°Ｃである。この温
度領域においては、５００〜５００００程度の空間速度
（ＳＶ）で排気ガスを通流させることが好ましい。より
好適な使用温度領域は３００〜６００°Ｃである。In the method of the present invention, the suitable reduction temperature at which the catalyst for catalytic reduction of nitrogen oxides exhibits good reduction activity for nitrogen oxides varies depending on the alcohols and the type of catalyst used, but is usually 100 to 800 °. It is C. In this temperature range, it is preferable to let the exhaust gas flow at a space velocity (SV) of about 500 to 50,000. A more preferable operating temperature range is 300 to 600 ° C.
【００２１】[0021]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
のではなく、その要旨を変更しない範囲において適宜変
更して実施することが可能なものである。 （１）触媒の調製EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples, and various modifications may be made without departing from the scope of the invention. Is possible. (1) Preparation of catalyst
【００２２】（製造例１）組成式：ＮａX 〔 (ＡｌＯ2)
X ・（ＳｉＯ2 ）Y 〕・ＺＨ2 Ｏで表されるナトリウム
型モルデナイトの市販品（日本化学社製、商品名「ＮＭ
−１００Ｐ」、Ｙ／Ｘ＝８）１００ｇを０．０２５モル
／リットルのＴｉＣｌ4 水溶液１リットルに浸漬し、２
４時間攪拌してＮａをＴｉでイオン交換した後、ろ別、
水洗してゼオライトのケーキを得た。次いで、このケー
キを乾燥した後、６５０°Ｃで４時間焼成した。得られ
たゼオライト中のＴｉの量はＴｉＯ2 として０．４重量
％であった。このゼオライトを、Ｐｔ担持後のゼオライ
ト中のＰｔの重量分率が１重量％になる量のＰｔを含有
するＨ2 ＰｔＣｌ6 の水溶液１リットルに浸漬し、攪拌
しながら理論量の１．２倍のヒドラジンを加えてＨ2 Ｐ
ｔＣｌ6 を還元した後、ろ別、水洗、乾燥してＰｔを担
持した触媒１を得た。(Production Example 1) Compositional formula: Na X [(AlO 2 ).
X. (SiO 2 ) Y ] .ZH 2 O A commercial product of sodium-type mordenite (manufactured by Nippon Kagaku Co., Ltd., trade name “NM
-100P ", Y / X = 8) 100 g was immersed in 1 liter of 0.025 mol / liter TiCl 4 aqueous solution, and 2
After stirring for 4 hours to ion exchange Na with Ti, filtration was performed,
It was washed with water to obtain a cake of zeolite. Then, after drying this cake, it baked at 650 degreeC for 4 hours. The amount of Ti in the obtained zeolite was 0.4% by weight as TiO 2 . This zeolite was immersed in 1 liter of an aqueous solution of H 2 PtCl 6 containing Pt in an amount such that the weight fraction of Pt in the zeolite after supporting Pt was 1% by weight, and 1.2 times the theoretical amount with stirring. H 2 P by adding hydrazine
After reducing tCl 6 , it was filtered, washed with water, and dried to obtain a Pt-supported catalyst 1.
【００２３】（製造例２）組成式：ＨX 〔 (ＡｌＯ2)X
・（ＳｉＯ2 ）Y 〕・ＺＨ2 Ｏで表される水素型モルデ
ナイトの市販品（日本化学社製、商品名「ＨＭ−１００
Ｐ」、Ｙ／Ｘ＝１２）１００ｇを０．０２５モル／リッ
トルのＺｒＯＣｌ2 水溶液１リットルに浸漬し、２４時
間攪拌してＮａをＺｒでイオン交換した後、過剰のＺｒ
をアンモニア水で中和してＺｒＯ2 として２重量％担持
させた。次いで、このケーキを乾燥した後、６５０°Ｃ
で４時間焼成した。このゼオライトを、Ｐｄ担持後のゼ
オライト中のＰｄの重量分率が１重量％になる量のＰｄ
を含有するＰｄＣｌ2 の水溶液１リットルに浸漬し、攪
拌しながら理論量の１．２倍のヒドラジンを加えてＰｄ
Ｃｌ2 を還元した後、ろ別、水洗、乾燥してＰｄを担持
した触媒２を得た。(Production Example 2) Compositional formula: H X [(AlO 2 ) X
· (SiO 2) Y] · ZH 2 hydrogen form mordenite represented by O of commercially available (Nippon Chemical Co., Ltd., trade name "HM-100
P ", Y / X = 12) 100 g was immersed in 1 liter of 0.025 mol / liter ZrOCl 2 aqueous solution and stirred for 24 hours to ion exchange Na with Zr.
Was neutralized with aqueous ammonia to support 2% by weight of ZrO 2 . Then, after drying this cake, 650 ° C
It was baked for 4 hours. This zeolite is mixed with Pd in such an amount that the weight fraction of Pd in the zeolite after supporting Pd is 1% by weight.
It is immersed in 1 liter of an aqueous solution of PdCl 2 containing Pd, and 1.2 times the theoretical amount of hydrazine is added with stirring to add PdCl 2.
After reducing Cl 2 , it was filtered, washed with water and dried to obtain a Pd-supported catalyst 2.
【００２４】（製造例３）製造例１においてＴｉＣｌ4
に代えてＳｎＣｌ4 を用いたこと以外は製造例１と同様
にして触媒３を得た。(Production Example 3) In Production Example 1, TiCl 4
A catalyst 3 was obtained in the same manner as in Production Example 1 except that SnCl 4 was used instead of.
【００２５】（製造例４）製造例２においてＺｒＯＣｌ
2 に代えてＴｉＯＳＯ4 を用いたこと以外は製造例２と
同様にして触媒４を得た。Production Example 4 ZrOCl in Production Example 2
A catalyst 4 was obtained in the same manner as in Production Example 2 except that TiOSO 4 was used instead of 2 .
【００２６】（製造例５）製造例１においてＨ2 ＰｔＣ
ｌ6 水溶液に代えてＲｕＣｌ4 、５Ｈ2 Ｏの水溶液を用
いたこと以外は製造例１と同様にして触媒５を得た。Production Example 5 H 2 PtC in Production Example 1
A catalyst 5 was obtained in the same manner as in Production Example 1, except that an aqueous solution of RuCl 4 , 5H 2 O was used instead of the aqueous solution of 16 .
【００２７】（製造例６）硫酸チタン、硝酸アルミニウ
ムを各々酸化物基準で９０ｇ、９ｇ秤量し、これを１リ
ットルのイオン交換水に溶解した。この水溶液中に、充
分攪拌を行いながら、アンモニアを吹き込みｐＨ７．０
となるまで添加し中和反応を終了した（中和時間１時
間）。その後、３０分間熟成した後、ろ過、水洗し、１
００°Ｃにて１８時間乾燥した後、５００°Ｃにて３時
間焼成した。この焼成物をＲｈ担持後の触媒中のＲｈの
重量分率が０．５重量％になる量のＲｈを含有するＲｈ
Ｃｌ3・３Ｈ2 Ｏの水溶液１リットルに浸漬し、攪拌し
ながら理論量の１．２倍の水素化ホウ酸ナトリウムを加
えてＲｈＣｌ3 を還元した後、ろ別、水洗、乾燥してＲ
ｈを担持した触媒６を得た。(Production Example 6) 90 g and 9 g of titanium sulfate and aluminum nitrate, respectively, were weighed on the basis of oxides and dissolved in 1 liter of ion-exchanged water. Ammonia was blown into this aqueous solution with sufficient stirring to bring the pH to 7.0.
The neutralization reaction was completed by adding until the reaction time reached (neutralization time 1 hour). Then, after aging for 30 minutes, filtration, washing with water, 1
After drying at 00 ° C for 18 hours, it was baked at 500 ° C for 3 hours. This calcined product contains Rh in an amount such that the weight fraction of Rh in the catalyst after supporting Rh is 0.5% by weight.
Immerse in 1 liter of an aqueous solution of Cl 3 .3H 2 O, add 1.2 times the stoichiometric amount of sodium borohydride to reduce RhCl 3 with stirring, then filter, wash with water and dry R
A catalyst 6 carrying h was obtained.
【００２８】（製造例７）硝酸アルミニウムおよびオキ
シ塩化ジルコニウムを各々酸化物基準で５０ｇ、５０ｇ
秤量し、これを１リットルのイオン交換水に溶解した。
この水溶液中に、充分攪拌を行いながらアンモニアを吹
き込みｐＨ７．０として中和反応を終了した（中和時間
１時間）。その後、３０分間熟成した後、ろ過、水洗
し、１００°Ｃにて１８時間乾燥した後、６００°Ｃに
て３時間焼成した。この焼成物５０ｇとＴｉＯ2 ５０ｇ
をＡｇ担持後の触媒中のＡｇの重量分率が２重量％にな
る量のＡｇを含有するＡｇＮＯ3 の水溶液１リットルに
浸漬し、攪拌しながら理論量の１．２倍ヒドラジンを加
えてＡｇＮＯ3 を還元した後、ろ別、水洗、乾燥してＡ
ｇを担持した触媒７を得た。(Production Example 7) Aluminum nitrate and zirconium oxychloride were added in amounts of 50 g and 50 g, respectively, based on the oxide.
It was weighed and dissolved in 1 liter of ion-exchanged water.
Ammonia was blown into this aqueous solution with sufficient stirring to adjust the pH to 7.0 to complete the neutralization reaction (neutralization time 1 hour). Then, the mixture was aged for 30 minutes, filtered, washed with water, dried at 100 ° C for 18 hours, and then baked at 600 ° C for 3 hours. 50g of this baked product and 50g of TiO 2
Was immersed in 1 liter of an aqueous solution of AgNO 3 containing Ag in an amount such that the weight fraction of Ag in the catalyst after supporting Ag was 2% by weight, and 1.2 times the theoretical amount of hydrazine was added with stirring to add AgNO 3. After reducing 3 , A is separated by filtration, washed with water and dried.
A catalyst 7 carrying g was obtained.
【００２９】（製造例８）日産化学社製スノーテックス
Ｏとメタチタン酸ゾル（メタチタン酸を硝酸により解膠
したもの）とを酸化物換算で各々５０ｇ、５０ｇ秤量
し、充分混合した後、１００°Ｃにて１８時間乾燥し、
次いで７００°Ｃにて３時間焼成した。この焼成物をＰ
ｄ担持後の重量分率が１重量％になる量のＰｄを含有す
るＰｄＣｌ2の水溶液１リットルに浸漬し、攪拌しなが
ら理論量の１．２倍のヒドラジンを加えてＰｄＣｌ2 を
還元した後、ろ別、水洗、乾燥してＰｄを担持した触媒
８を得た。(Production Example 8) Snowtex O (manufactured by Nissan Chemical Industries, Ltd.) and metatitanic acid sol (metatitanic acid deflocculated with nitric acid) were weighed in amounts of 50 g and 50 g, respectively, in terms of oxide, and after thorough mixing, 100 ° Dried at C for 18 hours,
Then, it was baked at 700 ° C. for 3 hours. This baked product is P
After dipped in 1 liter of an aqueous solution of PdCl 2 containing Pd in an amount such that the weight fraction after loading d is 1% by weight, 1.2 times the theoretical amount of hydrazine was added with stirring to reduce PdCl 2. The catalyst 8 carrying Pd was obtained by filtering, washing with water and drying.
【００３０】（製造例９）５００ｇ／リットルのチタニ
ル硫酸（ＴｉＯＳＯ4 ）を、オートクレーブ内で、１２
０°Ｃにて１時間加熱加水分解してメタチタン酸を生成
せしめ、これを濾過し、イオン交換水にて充分に洗浄
し、１００°Ｃにて１８時間乾燥し、さらに５００°Ｃ
にて３時間焼成して、硫酸根を８．５％含有する比表面
積１１４ｍ2／ｇのアナターゼ型酸化チタンを得た。こ
の酸化チタンを、Ｐｔ担持後の触媒中のＰｔの重量分率
が１重量％になる量のＰｔを含有するＨ2 ＰｔＣｌ6 の
水溶液１リットルに浸漬し、攪拌しながら理論量の１．
２倍のヒドラジンを加えてＨ2 ＰｔＣｌ6 を還元した
後、ろ別、水洗、乾燥してＰｔを担持した触媒９を得
た。(Production Example 9) 500 g / l of titanyl sulfuric acid (TiOSO 4 ) was added to the autoclave in an amount of 12
It is hydrolyzed by heating at 0 ° C for 1 hour to produce metatitanic acid, which is filtered, thoroughly washed with ion-exchanged water, dried at 100 ° C for 18 hours, and further 500 ° C.
By firing for 3 hours, anatase type titanium oxide containing 8.5% of sulfate group and having a specific surface area of 114 m 2 / g was obtained. This titanium oxide was immersed in 1 liter of an aqueous solution of H 2 PtCl 6 containing Pt in an amount such that the weight fraction of Pt in the catalyst after supporting Pt was 1% by weight, and the theoretical amount of 1.
After adding 2 times hydrazine to reduce H 2 PtCl 6 , it was filtered, washed with water, and dried to obtain Pt-supported catalyst 9.
【００３１】（製造例１０）５００ｇ／リットルのチタ
ニル硫酸（ＴｉＯＳＯ4 ）を、アンモニア水で常温で中
和し、これを濾過し、イオン交換水で充分に洗浄し、１
００°Ｃにて１８時間乾燥し、さらに５００°Ｃにて３
時間焼成して、硫酸根を０．２１％含有する比表面積８
５ｍ2 ／ｇのアナターゼ型酸化チタンを得た。この酸化
チタンを、Ｒｈ担持後の触媒中のＲｈの重量分率が３重
量％になる量のＲｈを含有するＲｈＣｌ3 の水溶液１リ
ットルに浸漬し、攪拌しながら理論量の１．２倍のヒド
ラジンを加えてＲｈＣｌ3 を還元した後、ろ別、水洗、
乾燥してＲｈを担持した触媒１０を得た。(Production Example 10) 500 g / liter of titanyl sulfuric acid (TiOSO 4 ) was neutralized with aqueous ammonia at room temperature, filtered, and thoroughly washed with ion-exchanged water.
Dry at 00 ° C for 18 hours and then at 500 ° C for 3 hours
Specific surface area containing 0.21% of sulfate radical after firing for 8 hours
5 m 2 / g of anatase type titanium oxide was obtained. This titanium oxide was immersed in 1 liter of an aqueous solution of RhCl 3 containing Rh in an amount such that the weight fraction of Rh in the catalyst after supporting Rh was 3% by weight, and 1.2 times the theoretical amount with stirring. After adding hydrazine to reduce RhCl 3 , it is filtered, washed with water,
After drying, a catalyst 10 supporting Rh was obtained.
【００３２】（製造例１１）ビーカーに、ＣｅＯ2 換算
で１ｇとなる量の硝酸セリウムを秤量して入れ、これに
水１リットルおよびＴｉＯ2 １００ｇを加えて、充分に
攪拌混合して水溶液とした。次いで、この水溶液に、ア
ンモニアを沈澱剤として加えて沈澱物を生成させ、該沈
澱物をろ別、水洗、乾燥した後、５００°Ｃにて３時間
焼成して焼成物を得た。このようにして得た焼成物５０
ｇを、担持後のＰｄの重量分率が１重量％となる量のＰ
ｄＣｌ2 水溶液１リットルに入れて、充分に攪拌混合し
た後、理論量の１．２倍のヒドラジンを還元剤として加
えてＰｄＣｌ2 を還元した後、ろ別、水洗、乾燥してＰ
ｄを担持した触媒１１を得た。(Production Example 11) 1 g of cerium nitrate in terms of CeO 2 was weighed and put in a beaker, 1 liter of water and 100 g of TiO 2 were added, and the mixture was sufficiently stirred and mixed to obtain an aqueous solution. . Next, ammonia was added to this aqueous solution as a precipitating agent to form a precipitate, which was filtered, washed with water, dried, and then calcined at 500 ° C for 3 hours to obtain a calcined product. Fired product 50 thus obtained
g of Pd in an amount such that the weight fraction of Pd after loading becomes 1% by weight.
Put in 1 liter of dCl 2 aqueous solution, stir and mix thoroughly, add 1.2 times the theoretical amount of hydrazine as a reducing agent to reduce PdCl 2 , and then filter, wash and dry P
A catalyst 11 carrying d was obtained.
【００３３】（製造例１２）ビーカーに、Ｔｂ4 Ｏ7 換
算で５ｇとなる量の硝酸テレビウムを秤量して入れ、こ
れに水１リットルおよびＳｉＯ2 １００ｇを加えて、充
分に攪拌混合して水溶液とした。次いで、この水溶液
に、アンモニアを沈澱剤として加えて沈澱物を生成さ
せ、該沈澱物をろ別、水洗、乾燥した後、５００°Ｃに
て３時間焼成して焼成物を得た。このようにして得た焼
成物５０ｇを、担持後のＲｕの重量分率が３重量％とな
る量のＲｕＣｌ3 水溶液１リットルに入れて、充分に攪
拌混合した後、理論量の１．２倍のヒドラジンを還元剤
として加えてＲｕＣｌ3 を還元した後、ろ別、水洗、乾
燥してＲｕを担持した触媒１２を得た。(Production Example 12) A beaker was weighed with terbium nitrate in an amount of 5 g in terms of Tb 4 O 7 , 1 liter of water and 100 g of SiO 2 were added thereto, and the mixture was sufficiently stirred and mixed to prepare an aqueous solution. And Next, ammonia was added to this aqueous solution as a precipitating agent to form a precipitate, which was filtered, washed with water, dried, and then calcined at 500 ° C for 3 hours to obtain a calcined product. 50 g of the calcined material thus obtained was placed in 1 liter of an aqueous RuCl 3 solution in an amount such that the weight fraction of Ru after loading was 3% by weight, and sufficiently stirred and mixed, and then 1.2 times the theoretical amount. Was added as a reducing agent to reduce RuCl 3 and then filtered, washed with water and dried to obtain a catalyst 12 carrying Ru.
【００３４】（製造例１３）Ｓｍ2 Ｏ3 １０ｇとＡｌ2
Ｏ3 １００ｇを乳鉢で充分に混合した後、５００°Ｃに
て３時間焼成して焼成物を得た。このようにして得た焼
成物５０ｇを、担持後のＰｔの重量分率が０．５重量％
となる量のＨ2 ＰｔＣｌ6 水溶液１リットルに入れて、
充分に攪拌混合した後、理論量の１．２倍のヒドラジン
を還元剤として加えてＨ2 ＰｔＣｌ6 を還元した後、ろ
別、水洗、乾燥して触媒１３を得た。(Production Example 13) 10 g of Sm 2 O 3 and Al 2
After thoroughly mixing 100 g of O 3 in a mortar, the product was baked at 500 ° C. for 3 hours to obtain a baked product. The weight fraction of Pt after supporting 50 g of the fired product thus obtained was 0.5% by weight.
In 1 liter of H 2 PtCl 6 aqueous solution
After thoroughly stirring and mixing, 1.2 times the theoretical amount of hydrazine was added as a reducing agent to reduce H 2 PtCl 6 , followed by filtration, washing with water and drying to obtain a catalyst 13.
【００３５】（製造例１４）ビーカーに、Ｐｒ6 Ｏ11換
算で５ｇとなる量の硝酸プラセオジムとＺｒＯ2 換算で
１００ｇとなる量の酸塩化ジルコニウムを秤量して入
れ、これに水１リットルを加え充分に攪拌混合して水溶
液とした。次いで、この水溶液に、アンモニアを沈澱剤
として加えて沈澱させ、該沈澱物をろ別、水洗、乾燥し
た後、５００°Ｃにて３時間焼成して焼成物を得た。こ
のようにして得た焼成物５０ｇを、担持後のＡｇの重量
分率が１０重量％となる量のＡｇＮＯ3 水溶液１リット
ルに入れて、充分に攪拌混合した後、理論量の１．２倍
のヒドラジンを還元剤として加えてＡｇＮＯ3 を還元し
た後、ろ別、水洗、乾燥して触媒１４を得た。(Production Example 14) Praseodymium nitrate in an amount of 5 g in terms of Pr 6 O 11 and zirconium oxychloride in an amount of 100 in terms of ZrO 2 were weighed into a beaker, and 1 liter of water was added thereto. The mixture was thoroughly mixed with stirring to give an aqueous solution. Next, ammonia was added to this aqueous solution as a precipitant to cause precipitation, and the precipitate was filtered, washed with water, dried, and then calcined at 500 ° C. for 3 hours to obtain a calcined product. 50 g of the calcined material thus obtained was placed in 1 liter of an aqueous AgNO 3 solution in an amount such that the weight fraction of Ag after loading was 10% by weight, and sufficiently stirred and mixed, and then 1.2 times the theoretical amount. Was added as a reducing agent to reduce AgNO 3 , and then filtered, washed with water and dried to obtain a catalyst 14.
【００３６】（製造例１５）ＳｉＯ2 ５０ｇとＡｌ2 Ｏ
3 ５０ｇを乳鉢で充分に混合した後、７００°Ｃで３時
間焼成して焼成物を得た。この焼成物を、硝酸ネオジウ
ム水溶液に１０分間浸漬した後過剰の水分を取り除いて
乾燥した。この操作を担持後のＮｄ2 Ｏ3 の重量分率が
５重量％になるまで繰り返した後、５００°Ｃで３時間
焼成した。この焼成物５０ｇを、担持後のＲｈの重量分
率が２重量％となるＲｈＣｌ3 水溶液１リットルに入れ
て、充分に攪拌混合した後、理論量の１．２倍のヒドラ
ジンを還元剤として加えてＲｈＣｌ3 を還元した後、ろ
別、水洗、乾燥して触媒１５を得た。(Production Example 15) 50 g of SiO 2 and Al 2 O
After thorough mixing the 3 50 g in a mortar to obtain a calcined product was fired for 3 hours at 700 ° C. The fired product was immersed in an aqueous solution of neodymium nitrate for 10 minutes, and then excess water was removed to dry the product. This operation was repeated until the weight fraction of Nd 2 O 3 after loading reached 5% by weight, and then firing was carried out at 500 ° C. for 3 hours. 50 g of the calcined product was placed in 1 liter of an aqueous solution of RhCl 3 having a weight fraction of Rh after loading of 2% by weight, thoroughly mixed with stirring, and 1.2 times the theoretical amount of hydrazine was added as a reducing agent. Then, RhCl 3 was reduced to obtain a catalyst 15 by filtration, washing with water and drying.
【００３７】（製造例１６）ビーカーに、Ｌａ（ＮＯ3)
3 ・６Ｈ2 Ｏを６９．３ｇ、Ｓｒ（ＮＯ3)2 を５０．８
ｇ、Ｍｎ（ＮＯ3)2 ・６Ｈ2 Ｏを９１．９ｇ、Ｆｅ（Ｎ
Ｏ3)3 ・９Ｈ2 Ｏを３２．３ｇおよび水を１リットル入
れて攪拌し、水溶液とした。この水溶液中のＬａ、Ｓ
ｒ、Ｍｎ、Ｆｅの原子比は、４：６：８：２である。こ
の溶液に、沈澱剤として２５０ｇ／リットルの炭酸ナト
リウム水溶液を溶液のｐＨが８になるまで添加して沈澱
物を生成させた。生成した沈澱物を充分に水洗した後、
１１０°Ｃにて乾燥し、次いで８００°Ｃにて３時間焼
成して触媒１６を得た。(Production Example 16) La (NO 3 ) was added to a beaker.
3 · 6H 2 O and 69.3 g, Sr a (NO 3) 2 50.8
g, Mn (NO 3) 2 · 6H 2 O and 91.9 g, Fe (N
O 3) 3 · 9H 2 O-placed 32.3g and 1 liter of water with stirring, into an aqueous solution. La and S in this aqueous solution
The atomic ratio of r, Mn, and Fe is 4: 6: 8: 2. A 250 g / liter aqueous solution of sodium carbonate as a precipitant was added to this solution until the pH of the solution reached 8, thereby forming a precipitate. After thoroughly washing the formed precipitate with water,
It was dried at 110 ° C and then calcined at 800 ° C for 3 hours to obtain a catalyst 16.
【００３８】（製造例１７）ビーカーに、Ｌａ（ＮＯ3)
3 ・６Ｈ2 Ｏを１２９．９ｇ、Ｓｒ（ＮＯ3)2 を４２．
３ｇ、Ｃｏ（ＮＯ3)2 ・６Ｈ2 Ｏを１１６．４ｇ、Ｍｎ
（ＮＯ3)2 ・６Ｈ2Ｏを２８．７ｇおよび水を１リット
ル入れて攪拌し、水溶液とした。この水溶液をＺｒＯ2
粉に含浸させた後、余剰の水溶液を取り除き乾燥した。
この操作を３回繰り返した後、８００°Ｃで３時間焼成
して触媒１７を得た。(Production Example 17) La (NO 3 ) was added to a beaker.
3 · 6H 2 O and 129.9 g, Sr a (NO 3) 2 42.
3g, Co (NO 3) 2 · 6H 2 O and 116.4 g, Mn
(NO 3) the 2 · 6H 2 O and stirred into 1 liter of 28.7g and water, and an aqueous solution. This aqueous solution was added to ZrO 2
After impregnating the powder, the excess aqueous solution was removed and dried.
After repeating this operation 3 times, it baked at 800 degreeC for 3 hours, and the catalyst 17 was obtained.
【００３９】（製造例１８）ビーカーに、Ｌａ（ＮＯ3)
3 ・６Ｈ2 Ｏを１４．７ｇ、Ｓｒ（ＮＯ3)2 を１．８
ｇ、Ｃｏ（ＮＯ3)2 ・６Ｈ2 Ｏを１２．４ｇおよび水を
１リットル入れて攪拌し、水溶液とした。この水溶液中
のＬａ、Ｓｒ、Ｃｏの原子比は、８：２：１０である。
次いで、この溶液中に、ＴｉＯ2 粉１００ｇを混合した
後、沈澱剤として２５０ｇ／リットルの炭酸ナトリウム
水溶液を溶液のｐＨが８になるまで添加して、沈澱物を
生成させた。生成した沈澱物を充分に水洗した後、１１
０°Ｃで乾燥し、８００°Ｃで３時間焼成した。得られ
た焼成物をＲｈ担持後の触媒中のＲｈの重量分率が１重
量％とになる量のＲｈを含有するＲｈＣｌ3 水溶液に浸
漬し、攪拌しながら理論量の１．２倍のヒドラジンを加
えてＲｈＣｌ3 を還元した後、ろ別、水洗、乾燥してＲ
ｈを担持した触媒１８を得た。(Production Example 18) La (NO 3 ) was added to a beaker.
3 · 6H 2 O and 14.7 g, Sr a (NO 3) 2 1.8
g, 12.4 g of Co (NO 3 ) 2 .6H 2 O and 1 liter of water were added and stirred to obtain an aqueous solution. The atomic ratio of La, Sr, and Co in this aqueous solution is 8: 2: 10.
Next, 100 g of TiO 2 powder was mixed into this solution, and then 250 g / liter of an aqueous sodium carbonate solution was added as a precipitating agent until the pH of the solution reached 8, thereby forming a precipitate. After washing the formed precipitate thoroughly with water, 11
It was dried at 0 ° C and calcined at 800 ° C for 3 hours. The obtained calcined product was immersed in an RhCl 3 aqueous solution containing Rh in an amount such that the weight fraction of Rh in the catalyst after supporting Rh was 1% by weight, and 1.2 times the theoretical amount of hydrazine while stirring. Is added to reduce RhCl 3 , then filtered, washed with water and dried to obtain RhCl 3.
A catalyst 18 carrying h was obtained.
【００４０】（製造例１９）製造例１で得たゼオライト
５０ｇを１５．２ｇ／リットルの硝酸銅 (II) 水溶液５
００ミリリットルに入れて充分に攪拌混合した後、これ
に水酸化ナトリウム水溶液を液のｐＨが８になるまで加
えて沈澱物を生成させた。この沈澱物をろ別、水洗、乾
燥した後５００°Ｃで３時間焼成して触媒１９を得た。(Production Example 19) 50 g of the zeolite obtained in Production Example 1 was mixed with an aqueous solution of 15.2 g / liter of copper (II) nitrate 5
The mixture was placed in 00 ml and sufficiently stirred and mixed, and an aqueous sodium hydroxide solution was added thereto until the pH of the solution reached 8, to form a precipitate. The precipitate was filtered, washed with water, dried and then calcined at 500 ° C. for 3 hours to obtain a catalyst 19.
【００４１】（製造例２０）製造例２で得たゼオライト
５０ｇを１８．２ｇ／リットルの硝酸コバルト水溶液５
００ミリリットルに入れて充分に攪拌した後、製造例１
９と同様にして触媒２０を得た。(Production Example 20) 50 g of the zeolite obtained in Production Example 2 was mixed with an aqueous solution of cobalt nitrate 5 at 18.2 g / liter.
After putting in 00 ml and stirring sufficiently, Production Example 1
A catalyst 20 was obtained in the same manner as in 9.
【００４２】（製造例２１）製造例３で得たゼオライト
５０ｇを１８．２ｇ／リットルの硝酸マンガン水溶液５
００ミリリットルに入れて充分に攪拌した後、製造例１
９と同様にして触媒２１を得た。(Production Example 21) 50 g of the zeolite obtained in Production Example 3 was mixed with an aqueous solution of manganese nitrate 5 at 18.2 g / liter.
After putting in 00 ml and stirring sufficiently, Production Example 1
A catalyst 21 was obtained in the same manner as in 9.
【００４３】（製造例２２）製造例４で得たゼオライト
５０ｇをＶ2０5換算で１４２ｇ／リットルのシュウ酸バ
ナジルを含有する水溶液に浸漬し、過剰の水溶液を取り
除いた後、乾燥し、次いで５００°Ｃで３時間焼成して
触媒２２を得た。[0043] After the (preparation 22) was dipped zeolite 50g obtained in Production Example 4 in an aqueous solution containing vanadyl oxalate of 142g / liter V 2 0 5 in terms to remove excess solution, dried, then The catalyst 22 was obtained by calcining at 500 ° C. for 3 hours.
【００４４】（製造例２３）製造例１で得たゼオライト
５０ｇをＭｏＯ3 換算で１４２ｇ／リットルのモリブデ
ン酸アンモニウム水溶液に浸漬し、その後、製造例２２
と同様にして触媒２３を得た。(Production Example 23) 50 g of the zeolite obtained in Production Example 1 was immersed in an aqueous ammonium molybdate solution of 142 g / liter in terms of MoO 3 , and then Production Example 22.
A catalyst 23 was obtained in the same manner as in.
【００４５】（製造例２４）製造例６で得た焼成物５０
ｇを１５．７ｇ／リットルの硝酸銅(II)水溶液５００ミ
リリットルに入れて充分に攪拌混合した後、これに水酸
化ナトリウム水溶液を液のｐＨが８になるまで加えて沈
澱物を生成させた。この沈澱物をろ別、水洗、乾燥した
後５００°Ｃで３時間焼成して触媒２４を得た。(Production Example 24) Fired product 50 obtained in Production Example 6
g was added to 500 ml of a 15.7 g / liter copper (II) nitrate aqueous solution and mixed thoroughly with stirring, and then an aqueous sodium hydroxide solution was added to this to form a precipitate. The precipitate was filtered, washed with water, dried and then calcined at 500 ° C. for 3 hours to obtain a catalyst 24.
【００４６】（製造例２５）製造例２４において硝酸銅
に代えて３６．６ｇ／リットルの硝酸亜鉛水溶液を用い
たこと以外は製造例２４と同様にして触媒２５を得た。Production Example 25 A catalyst 25 was obtained in the same manner as in Production Example 24 except that 36.6 g / liter zinc nitrate aqueous solution was used instead of copper nitrate in Production Example 24.
【００４７】（製造例２６）製造例７で得た焼成物５０
ｇを５．１ｇ／リットルの硝酸鉄(III) 水溶液５００ミ
リリットルに入れて充分に攪拌混合した後、これに水酸
化ナトリウム水溶液を液のｐＨが８になるまで加えて沈
澱物を生成させた。次いで、この沈澱物をろ別、水洗、
乾燥した後５００°Ｃで３時間焼成して触媒２６を得
た。(Production Example 26) Fired product 50 obtained in Production Example 7
g was added to 500 ml of a 5.1 g / liter iron (III) nitrate aqueous solution and thoroughly mixed by stirring, and then an aqueous sodium hydroxide solution was added to this to form a precipitate. Then, the precipitate is filtered off, washed with water,
After drying, it was calcined at 500 ° C. for 3 hours to obtain a catalyst 26.
【００４８】（実施例２７）実施例２６において硝酸鉄
(III) に代えて３９．５ｇ／リットルの硝酸クロム水溶
液を用いたこと以外は実施例２６と同様にして触媒２７
を得た。(Example 27) Iron nitrate in Example 26
A catalyst 27 was prepared in the same manner as in Example 26 except that 39.5 g / liter of an aqueous chromium nitrate solution was used instead of (III).
I got
【００４９】（製造例２８）製造例８で得た焼成物５０
ｇを３９．０ｇ／リットルの硝酸ニッケル水溶液５００
ミリリットルに入れて充分に攪拌混合した後、これに水
酸化ナトリウム水溶液を液のｐＨが８になるまで加えて
沈澱物を生成させた。この沈澱物をろ別、水洗、乾燥し
た後５００°Ｃで３時間焼成して触媒２８を得た。(Production Example 28) Fired product 50 obtained in Production Example 8
500 g of nickel nitrate aqueous solution of 39.0 g / liter
The mixture was placed in a milliliter and sufficiently stirred and mixed, and then an aqueous sodium hydroxide solution was added thereto until the pH of the liquid became 8, to form a precipitate. The precipitate was filtered, washed with water, dried and then calcined at 500 ° C. for 3 hours to obtain a catalyst 28.
【００５０】（製造例２９）製造例２８において硝酸ニ
ッケルに代えて２０．２ｇ／リットルのシュウ酸ニオブ
水溶液を用いたこと以外は製造例２８と同様にして触媒
２９を得た。Production Example 29 A catalyst 29 was obtained in the same manner as in Production Example 28 except that 20.2 g / liter of niobium oxalate aqueous solution was used in place of nickel nitrate in Production Example 28.
【００５１】（製造例３０）ナトリウム型モルデナイト
の市販品（日本化学社製、商品名「ＮＭ−１００Ｐ」）
１００ｇを０．０５モル／リットルのＣａＣｌ2 水溶液
１リットルに浸漬し、２４時間攪拌してＮａイオンをＣ
ａイオンにイオン交換した後、ろ別、水洗してゼオライ
トのケーキを得た。次いでこのケーキを乾燥した後、６
５０°Ｃで４時間焼成した。イオン交換率は７０％であ
った。このゼオライト５０ｇを１５．２ｇ／リットルの
硝酸銅(II)水溶液５００ミリリットルに入れて、充分に
攪拌混合した後、これに水酸化ナトリウム水溶液を液の
ｐＨが８になるまで加えて沈澱物を生成せしめ、次いで
この沈澱物を５００°Ｃで３時間焼成して、触媒３０を
得た。(Production Example 30) Commercially available sodium mordenite (manufactured by Nippon Kagaku Co., Ltd., trade name "NM-100P")
100 g was immersed in 1 liter of 0.05 mol / liter CaCl 2 aqueous solution and stirred for 24 hours to remove Na ions
After ion-exchanged to a-ion, it was filtered and washed with water to obtain a cake of zeolite. Then the cake is dried and then 6
It was baked at 50 ° C for 4 hours. The ion exchange rate was 70%. 50 g of this zeolite was added to 500 ml of a 15.2 g / liter copper (II) nitrate aqueous solution, and after sufficiently stirring and mixing, an aqueous sodium hydroxide solution was added to this to form a precipitate by adjusting the pH of the solution to 8. Then, the precipitate was calcined at 500 ° C. for 3 hours to obtain catalyst 30.
【００５２】（製造例３１）カリウム型Ａ型ゼオライト
の市販品（日本化学社製、商品名「ＫＡ−１００Ｐ」）
１００ｇを０．０５モル／リットルのＭｇＣｌ2 水溶液
１リットルに浸漬し、２４時間攪拌してＫイオンをＭｇ
イオンにイオン交換した後、ろ別、水洗してゼオライト
のケーキを得た。次いでこのケーキを乾燥した後、６５
０°Ｃで４時間焼成した。イオン交換率は６４％であっ
た。このゼオライト５０ｇを１８．２ｇ／リットルの硝
酸コバルト水溶液５００ミリリットルに入れて、充分に
攪拌混合した後、これに水酸化ナトリウム水溶液を液の
ｐＨが８になるまで加えて沈澱物を生成させ、この沈澱
物を５００°Ｃで３時間焼成して、触媒３１を得た。(Production Example 31) Commercial product of potassium-type A zeolite (manufactured by Nippon Kagaku Co., Ltd., trade name "KA-100P")
100 g was immersed in 1 liter of 0.05 mol / liter MgCl 2 aqueous solution and stirred for 24 hours to remove K ions from Mg.
After ion exchange with ions, it was filtered and washed with water to obtain a cake of zeolite. Then after drying the cake, 65
Baking at 0 ° C for 4 hours. The ion exchange rate was 64%. 50 g of this zeolite was put in 500 ml of an aqueous 18.2 g / liter cobalt nitrate solution, and after thoroughly stirring and mixing, an aqueous sodium hydroxide solution was added to this to form a precipitate, and a precipitate was formed. The precipitate was calcined at 500 ° C. for 3 hours to obtain a catalyst 31.
【００５３】（製造例３２）ナトリウム型Ｘ型ゼオライ
トの市販品（日本化学社製、商品名「ＮＸ−１００
Ｐ」）１００ｇを０．０５モル／リットルのＳｒＣｌ2
水溶液１リットルに浸漬し、２４時間攪拌してＮａイオ
ンをＳｒイオンにイオン交換した後、ろ別、水洗してゼ
オライトのケーキを得た。次いで、このケーキを乾燥し
た後、６５０°Ｃで４時間焼成した。イオン交換率は７
５％であった。 このゼオライト５０ｇを３９．０ｇ／
リットルの硝酸ニッケル水溶液５００ミリリットルに入
れて、充分に攪拌混合した後、これに水酸化ナトリウム
水溶液を液のｐＨが８になるまで加えて沈澱物を生成さ
せた。 次いで、この沈澱物を５００°Ｃで３時間焼成
して、触媒３２を得た。(Production Example 32) Commercially available sodium-type X-type zeolite (manufactured by Nippon Kagaku Co., Ltd., trade name "NX-100")
P ") 100 g with 0.05 mol / l of SrCl 2
It was immersed in 1 liter of an aqueous solution and stirred for 24 hours to exchange Na ions with Sr ions, then filtered and washed with water to obtain a zeolite cake. Then, after drying this cake, it baked at 650 degreeC for 4 hours. Ion exchange rate is 7
5%. 50 g of this zeolite is 39.0 g /
It was put in 500 ml of a nickel nitrate aqueous solution and sufficiently stirred and mixed, and then a sodium hydroxide aqueous solution was added thereto until a pH of the solution reached 8, to form a precipitate. Then, the precipitate was calcined at 500 ° C. for 3 hours to obtain a catalyst 32.
【００５４】（製造例３３）ビーカーにＡｌ（ＮＯ3)3
・９Ｈ2 Ｏ を３．１３ｇおよび水を１００ミリリット
ル入れ、マグネチックスターラーで攪拌して溶解しなが
ら、臭化テトラプロピルアンモニウム７．９８ｇと、シ
リカゾル水溶液（ＳｉＯ2 ：３１重量％、Ｎａ2 Ｏ：
０．４重量％、Ａｌ2 Ｏ3 ：０．０３重量％を含有する
水溶液）６０ｇとを加えた。次いで、この溶液に、水酸
化ナトリウム３．１２ｇを４０ミリリットルの水に溶解
した水酸化ナトリウム水溶液を攪拌しながら徐々に加え
た。この混合液をオートクレーブに仕込み、１６０°Ｃ
で７２時間、攪拌を加えて結晶化させた。この生成物を
固液分離した後、固形物を水洗、乾燥してＺＳＭ−５ゼ
オライトを得た。このＺＳＭ−５ゼオライトを、０．０
５モル／リットルのＢａＣｌ2 水溶液に入れて、２４時
間攪拌して、ＮａイオンをＢａイオンでイオン交換した
後、ろ別、水洗、乾燥し、次いで６５０°Ｃで４時間焼
成した。このゼオライト５０ｇを２５．３ｇ／リットル
の硝酸鉄(III) 水溶液５００ミリリットルに入れて、充
分に攪拌混合した後、これに水酸化ナトリウム水溶液を
液のｐＨが８になるまで加えて沈澱物を生成せしめ、次
いでこの沈澱物を５００°Ｃで３時間焼成して、触媒３
３を得た。(Production Example 33) Al (NO 3 ) 3 was added to a beaker.
3.13 g of 9H 2 O and 100 ml of water were put, and while stirring and dissolving with a magnetic stirrer, 7.98 g of tetrapropylammonium bromide and a silica sol aqueous solution (SiO 2 : 31% by weight, Na 2 O:
60 g of an aqueous solution containing 0.4% by weight and Al 2 O 3 : 0.03% by weight). Then, to this solution, an aqueous sodium hydroxide solution in which 3.12 g of sodium hydroxide was dissolved in 40 ml of water was gradually added while stirring. This mixed solution was charged into an autoclave at 160 ° C.
It was crystallized by stirring for 72 hours. After solid-liquid separation of this product, the solid was washed with water and dried to obtain ZSM-5 zeolite. This ZSM-5 zeolite was
The mixture was placed in a 5 mol / liter BaCl 2 aqueous solution, stirred for 24 hours, ion-exchanged for Na ions with Ba ions, filtered, washed with water, dried, and then calcined at 650 ° C. for 4 hours. 50 g of this zeolite was added to 500 ml of a 25.3 g / liter aqueous solution of iron (III) nitrate, thoroughly mixed with stirring, and an aqueous solution of sodium hydroxide was added to this to form a precipitate. Then, the precipitate was calcined at 500 ° C. for 3 hours to obtain the catalyst 3
3 was obtained.
【００５５】（製造例３４）製造例３０において硝酸銅
(II)水溶液に代えて３６．４ｇ／リットルの硝酸マンガ
ンを用いたこと以外は製造例３０と同様にして触媒３４
を得た。Production Example 34 Copper nitrate in Production Example 30
(II) A catalyst 34 was produced in the same manner as in Production Example 30 except that 36.4 g / liter of manganese nitrate was used instead of the aqueous solution.
I got
【００５６】（製造例３５）ビーカーにＡｌ（ＮＯ3)3
・９Ｈ2 Ｏ を３．１３ｇおよび水を１００ミリリット
ル入れ、マグネチックスターラーで攪拌して溶解しなが
ら、臭化テトラプロピルアンモニウム７．９８ｇと、シ
リカゾル水溶液（ＳｉＯ2 ：３１重量％、Ｎａ2 Ｏ：
０．４重量％、Ａｌ2 Ｏ3 ：０．０３重量％を含有する
水溶液）６０ｇとを加えた。次いで、この溶液に、水酸
化ナトリウム３．１２ｇを４０ミリリットルの水に溶解
した水酸化ナトリウム水溶液を攪拌しながら徐々に加え
た。この混合液をオートクレーブに仕込み、１６０°Ｃ
で７２時間、攪拌を加えて結晶化させた。この生成物を
固液分離した後、固形物を水洗、乾燥してＺＳＭ−５ゼ
オライト（ＳｉＯ2 ／Ａｌ2 Ｏ3 ＝７０）を得た。この
ＺＳＭ−５ゼオライトを、０．０５モル／リットルの酢
酸銅の水溶液に入れて、２４時間攪拌した後、遠心分離
した。上記操作を合計３回繰り返し行った後、純水で５
回水洗し、次いで１１０°Ｃで約１２時間乾燥して触媒
３５を得た。(Production Example 35) Al (NO 3 ) 3 was added to a beaker.
3.13 g of 9H 2 O and 100 ml of water were put, and while stirring and dissolving with a magnetic stirrer, 7.98 g of tetrapropylammonium bromide and a silica sol aqueous solution (SiO 2 : 31% by weight, Na 2 O:
60 g of an aqueous solution containing 0.4% by weight and Al 2 O 3 : 0.03% by weight). Then, to this solution, an aqueous sodium hydroxide solution in which 3.12 g of sodium hydroxide was dissolved in 40 ml of water was gradually added while stirring. This mixed solution was charged into an autoclave at 160 ° C.
It was crystallized by stirring for 72 hours. After the product to solid-liquid separation to obtain water washing the solids, dried ZSM-5 zeolite (SiO 2 / Al 2 O 3 = 70). This ZSM-5 zeolite was put in an aqueous solution of 0.05 mol / liter of copper acetate, stirred for 24 hours, and then centrifuged. After repeating the above operation 3 times in total,
It was washed with water twice and then dried at 110 ° C. for about 12 hours to obtain a catalyst 35.
【００５７】（製造例３６）Ａｌ2 Ｏ3 １００ｇをＰｔ
担持後の触媒中のＰｔの重量分率が１重量％となるよう
に調製したＨ2 ＰｔＣｌ6 水溶液中に浸漬し、過剰の水
分を取り除いた後、１１０°Ｃにて乾燥して触媒３６を
得た。(Production Example 36) 100 g of Al 2 O 3 was added to Pt.
The catalyst 36 was immersed in an H 2 PtCl 6 aqueous solution prepared so that the weight fraction of Pt in the loaded catalyst was 1% by weight, and after removing excess water, the catalyst 36 was dried at 110 ° C. Obtained.
【００５８】（２）実施例１〜３４ 製造例１〜３４で得た触媒１〜３４について、下記の条
件で、ガス中の窒素酸化物の接触還元を行い、このとき
の窒素酸化物のＮ2 への転換率を、ガスクロマトグラフ
法によりＮ2 を定量して算出した。 （試験条件） (1)ガス組成 ＮＯ １容量％ Ｏ2 １０容量％ 還元剤 １容量％ Ｈｅ 残部 (2)空間速度 １０００ １／Ｈｒ (3)反応温度 ３００°Ｃ、４００°Ｃ、５００°Ｃ
または６００°Ｃ 結果を表１および２に示す。(2) Examples 1 to 34 Catalysts 1 to 34 obtained in Production Examples 1 to 34 were subjected to catalytic reduction of nitrogen oxides in gas under the following conditions. the conversion to 2, was calculated by quantifying the N 2 by gas chromatography. (Test conditions) (1) Gas composition NO 1% by volume O 2 10% by volume Reducing agent 1% by volume He balance (2) Space velocity 1000 1 / Hr (3) Reaction temperature 300 ° C, 400 ° C, 500 ° C
Or 600 ° C results are shown in Tables 1 and 2.
【００５９】[0059]
【表１】 [Table 1]
【００６０】[0060]
【表２】 （３）比較例１〜３[Table 2] (3) Comparative Examples 1 to 3
【００６１】（比較例１）製造例３５で得た触媒３５を
用いて下記の試験条件により窒素酸化物含有ガスの窒素
酸化物接触分解を行い、窒素酸化物のＮ2 への転換率を
ガスクロマトグラフ法によりＮ2 を定量して算出した。 （試験条件） (1)ガス組成 ＮＯ １容量％ Ｏ2 １０容量％ Ｈｅ 残部 (2)空間速度 １０００ １／Ｈｒ (3)反応温度 ３００°Ｃ、４００°Ｃ、５００°Ｃ
または６００°Ｃ(Comparative Example 1) Using the catalyst 35 obtained in Production Example 35, catalytic decomposition of nitrogen oxide-containing gas with nitrogen oxide was carried out under the following test conditions, and the conversion rate of nitrogen oxide to N 2 was measured by gas chromatography. N 2 was quantified and calculated by the Tograph method. (Test conditions) (1) Gas composition NO 1% by volume O 2 10% by volume He balance (2) Space velocity 1000 1 / Hr (3) Reaction temperature 300 ° C, 400 ° C, 500 ° C
Or 600 ° C
【００６２】（比較例２）製造例３６で得た触媒３６を
用いて下記の試験条件により窒素酸化物含有ガスの窒素
酸化物接触還元を行い、窒素酸化物のＮ2 への転換率を
ガスクロマトグラフ法によりＮ2 を定量して算出した。 （試験条件） (1)ガス組成 ＮＯ １容量％ ＣＯ １容量％ Ｏ2 １０容量％ Ｈｅ 残部 (2)空間速度 １０００ １／Ｈｒ (3)反応温度 ３００°Ｃ、４００°Ｃ、５００°Ｃ
または６００°ＣComparative Example 2 Using the catalyst 36 obtained in Production Example 36, the nitrogen oxide-containing gas was subjected to catalytic reduction with nitrogen oxide under the following test conditions, and the conversion rate of nitrogen oxide to N 2 was measured by gas chromatography. N 2 was quantified and calculated by the Tograph method. (Test conditions) (1) Gas composition NO 1% by volume CO 1% by volume O 2 10% by volume He balance (2) Space velocity 1000 1 / Hr (3) Reaction temperature 300 ° C, 400 ° C, 500 ° C
Or 600 ° C
【００６３】（比較例３）比較例２の試験条件において
ＣＯの代わりにＨ2 １容量％使用したこと以外は比較例
２と同様にして試験を行った。比較例１〜３の結果を表
３に示す。Comparative Example 3 A test was conducted in the same manner as in Comparative Example 2 except that H 2 1% by volume was used instead of CO under the test conditions of Comparative Example 2. The results of Comparative Examples 1 to 3 are shown in Table 3.
【００６４】[0064]
【表３】 表１〜３より、本発明に係るアルコール類を還元剤とし
て使用する方法（実施例１〜３４）は、還元剤を使用す
ることなく触媒により直接分解する方法（比較例１）
や、還元剤としてＣＯやＨ2 を使用する方法（比較例２
および３）に比べて、窒素酸化物のＮ2 への転換率が極
めて高いことが分かる。[Table 3] From Tables 1 to 3, the method of using alcohols according to the present invention as a reducing agent (Examples 1 to 34) is a method of directly decomposing with a catalyst without using a reducing agent (Comparative Example 1).
Alternatively, a method of using CO or H 2 as a reducing agent (Comparative Example 2
It can be seen that the conversion rate of nitrogen oxides into N 2 is extremely high as compared with 3) and 3).
【００６５】[0065]
【発明の効果】以上、詳細に説明したように、本発明に
係るアルコール類を還元剤として使用する窒素酸化物の
接触還元方法は、排気ガス中の窒素酸化物を効率良く接
触還元することができるなど、本発明は優れた特有の効
果を奏する。As described above in detail, the method for catalytic reduction of nitrogen oxides using alcohols as a reducing agent according to the present invention can efficiently catalytically reduce nitrogen oxides in exhaust gas. That is, the present invention has excellent unique effects.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｄ 53/86 ＺＡＢ Ｂ０１Ｊ 23/42 ＺＡＢ Ａ 23/44 ＺＡＢ Ａ 23/46 ＺＡＢ Ａ ３１１ Ａ 23/50 ＺＡＢ Ａ 23/63 ＺＡＢ 23/84 ＺＡＢ Ａ 23/889 23/89 ＺＡＢ Ａ 29/14 ＺＡＢ Ａ 29/18 ＺＡＢ Ａ 29/22 ＺＡＢ Ａ 29/24 ＺＡＢ Ａ 29/26 ＺＡＢ Ａ 29/46 ＺＡＢ Ａ 29/76 ＺＡＢ Ａ Ｂ０１Ｄ 53/34 １２９ Ｂ 53/36 ＺＡＢ １０２ Ｃ １０２ Ｈ Ｂ０１Ｊ 23/56 ＺＡＢ Ａ ３０１ Ａ 23/84 ３１１ Ａ (72)発明者 仲辻 忠夫 大阪府堺市戎島町５丁１番地 堺化学工業 株式会社内 (72)発明者 清水 宏益 大阪府堺市戎島町５丁１番地 堺化学工業 株式会社内 (72)発明者 菅沼 藤夫 埼玉県北葛飾郡庄和町新宿新田228−16 (72)発明者 田畑 光紀 埼玉県幸手市権現堂1134−２ (72)発明者 浜田 秀昭 茨城県つくば市東１−１ 工業技術院化学 技術研究所内 (72)発明者 伊藤 建彦 茨城県つくば市東１−１ 工業技術院化学 技術研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location B01D 53/86 ZAB B01J 23/42 ZAB A 23/44 ZAB A 23/46 ZAB A 311 A 23 / 50 ZAB A 23/63 ZAB 23/84 ZAB A 23/889 23/89 ZAB A 29/14 ZAB A 29/18 ZAB A 29/22 ZAB A 29/24 ZAB A 29/26 ZAB A 29/46 ZAB A 29/76 ZAB A B01D 53/34 129 B 53/36 ZAB 102 C 102 H B01J 23/56 ZAB A 301 A 23/84 311 A (72) Inventor Tadao Nakatsuji 5-1, Kisoshima-cho, Sakai-shi, Osaka Sakai Chemical Industry Co., Ltd. (72) Inventor Hiromitsu Shimizu 5-1, Ebishima-cho, Sakai City, Osaka Prefecture Sakai Chemical Industry Co., Ltd. (72) Inventor Fujio Suganuma Showa, Kita Katsushika-gun, Saitama Prefecture Town Shinjuku Nitta 228-16 (72) Inventor Mitsunori Tabata 1134-2, Gongen-do, Satte City, Saitama Prefecture (72) Hideaki Hamada 1-1, East, Tsukuba City, Ibaraki Prefecture (72) Inventor, Ito Takehiko 1-1 East, Tsukuba, Ibaraki Prefectural Institute of Chemical Technology, Institute of Chemical Technology
Claims (1)
還元剤により選択的に接触還元する方法において、前記
還元剤としてアルコール類を用いることを特徴とする窒
素酸化物の接触還元方法。1. A catalytic reduction method for nitrogen oxides, wherein alcohols are used as the reducing agent in a method for selectively catalytically reducing nitrogen oxides in exhaust gas with a reducing agent in the presence of a catalyst. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3043006A JPH08150324A (en) | 1991-02-14 | 1991-02-14 | Method for catalytically reducing nitrogen oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3043006A JPH08150324A (en) | 1991-02-14 | 1991-02-14 | Method for catalytically reducing nitrogen oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08150324A true JPH08150324A (en) | 1996-06-11 |
Family
ID=12651908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3043006A Pending JPH08150324A (en) | 1991-02-14 | 1991-02-14 | Method for catalytically reducing nitrogen oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08150324A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005254217A (en) * | 2004-03-15 | 2005-09-22 | National Institute Of Advanced Industrial & Technology | Nitrogen oxide removing catalyst |
| JP2008161812A (en) * | 2006-12-28 | 2008-07-17 | Asahi Kasei Corp | CATALYST FOR PURIFYING NOx OF AUTOMOTIVE EXHAUST GAS AND METHOD FOR TREATING NOx OF EXHAUST GAS |
| GB2455181A (en) * | 2007-11-29 | 2009-06-03 | Gen Electric | Methods and systems for reducing the emissions from combustion gases |
| WO2014087910A1 (en) * | 2012-12-03 | 2014-06-12 | 日立造船株式会社 | Catalyst for combustion exhaust gas purification and denitration purification method using this catalyst |
| US9492814B2 (en) | 2013-04-08 | 2016-11-15 | Saudi Basic Industries Corporation | Catalyst for conversion of propylene to product comprising a carboxylic acid moiety |
| JP2017192940A (en) * | 2017-07-21 | 2017-10-26 | 三菱重工業株式会社 | Catalyst for exhaust gas treatment, exhaust gas treatment device and manufacturing method of catalyst for exhaust gas treatment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5812047A (en) * | 1981-07-15 | 1983-01-24 | Hitachi Ltd | File transfer system |
| JPH02233124A (en) * | 1989-03-03 | 1990-09-14 | Hitachi Zosen Corp | Removal of nitrogen oxide |
-
1991
- 1991-02-14 JP JP3043006A patent/JPH08150324A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5812047A (en) * | 1981-07-15 | 1983-01-24 | Hitachi Ltd | File transfer system |
| JPH02233124A (en) * | 1989-03-03 | 1990-09-14 | Hitachi Zosen Corp | Removal of nitrogen oxide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005254217A (en) * | 2004-03-15 | 2005-09-22 | National Institute Of Advanced Industrial & Technology | Nitrogen oxide removing catalyst |
| JP2008161812A (en) * | 2006-12-28 | 2008-07-17 | Asahi Kasei Corp | CATALYST FOR PURIFYING NOx OF AUTOMOTIVE EXHAUST GAS AND METHOD FOR TREATING NOx OF EXHAUST GAS |
| GB2455181A (en) * | 2007-11-29 | 2009-06-03 | Gen Electric | Methods and systems for reducing the emissions from combustion gases |
| WO2014087910A1 (en) * | 2012-12-03 | 2014-06-12 | 日立造船株式会社 | Catalyst for combustion exhaust gas purification and denitration purification method using this catalyst |
| US9492814B2 (en) | 2013-04-08 | 2016-11-15 | Saudi Basic Industries Corporation | Catalyst for conversion of propylene to product comprising a carboxylic acid moiety |
| JP2017192940A (en) * | 2017-07-21 | 2017-10-26 | 三菱重工業株式会社 | Catalyst for exhaust gas treatment, exhaust gas treatment device and manufacturing method of catalyst for exhaust gas treatment |
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