JP2003071298A - COMPOSITE MATERIAL, PRODUCTION METHOD THEREFOR, CATALYST, PRODUCTION METHOD THEREFOR, NOx SORPTION METHOD, AND NOx SORPTIVE REDUCTION METHOD - Google Patents
COMPOSITE MATERIAL, PRODUCTION METHOD THEREFOR, CATALYST, PRODUCTION METHOD THEREFOR, NOx SORPTION METHOD, AND NOx SORPTIVE REDUCTION METHODInfo
- Publication number
- JP2003071298A JP2003071298A JP2001269155A JP2001269155A JP2003071298A JP 2003071298 A JP2003071298 A JP 2003071298A JP 2001269155 A JP2001269155 A JP 2001269155A JP 2001269155 A JP2001269155 A JP 2001269155A JP 2003071298 A JP2003071298 A JP 2003071298A
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- Japan
- Prior art keywords
- catalyst
- compound
- composite material
- nox
- group
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、複合材料及びその
製造方法、複合材料及びその製造方法、触媒及びその製
造方法、並びにＮＯｘ吸蔵方法及びＮＯｘ吸蔵還元方法
に関するものである。TECHNICAL FIELD The present invention relates to a composite material and a method for manufacturing the same, a composite material and a method for manufacturing the same, a catalyst and a method for manufacturing the same, and a NOx storage method and a NOx storage reduction method.
【０００２】[0002]
【従来の技術】自動車などの排ガスには有害な窒素酸化
物（ＮＯｘ）が含まれており、これを浄化するためにＮ
Ｏｘの吸蔵及び／又は還元が可能な材料を触媒（ＮＯｘ
吸蔵還元型触媒）として利用することが従来より行われ
ている。ＮＯｘを吸蔵することが可能な材料としては例
えばバリウム化合物が知られており、バリウム化合物を
単独もしくは貴金属触媒と共に担体に担持させたものが
触媒として用いられている。このような触媒は、例え
ば、バリウム、アルミニウムアルコキシド及び貴金属塩
を含む溶液（アルコール溶液又はグリコール溶液）を触
媒担体の触媒担持層に担持させ反応させることにより得
ることができる（特開平５−１６８９４８号公報参
照）。2. Description of the Related Art Exhaust gas from automobiles contains harmful nitrogen oxides (NOx).
A material that can store and / or reduce Ox is used as a catalyst (NOx
It has been conventionally used as an occlusion reduction type catalyst). As a material capable of occluding NOx, for example, a barium compound is known, and a barium compound alone or with a noble metal catalyst supported on a carrier is used as a catalyst. Such a catalyst can be obtained, for example, by allowing a solution (alcohol solution or glycol solution) containing barium, aluminum alkoxide and a noble metal salt to be carried on a catalyst-supporting layer of a catalyst carrier and reacting (JP-A-5-168948). See the bulletin).
【０００３】自動車の排ガスには、上記のＮＯｘ以外
に、燃料中に含まれている硫黄（Ｓ）が燃焼して生じた
酸化硫黄（ＳＯ2）も含まれている。このＳＯ2は排ガス
中で酸化され更に水蒸気と反応することにより硫酸とな
り、これが触媒中のバリウム化合物と反応して亜硫酸バ
リウムや硫酸バリウムを生じるため、バリウム化合物の
ＮＯｘの吸蔵及び／又は還元作用が阻害される（硫黄被
毒劣化）。Exhaust gas from automobiles contains, in addition to NOx, sulfur oxide (SO 2 ) produced by combustion of sulfur (S) contained in fuel. This SO 2 is oxidized in the exhaust gas and further reacts with water vapor to become sulfuric acid, which reacts with the barium compound in the catalyst to produce barium sulfite or barium sulfate, so that the barium compound has a NOx occlusion and / or reduction effect. Inhibited (Sulfur poisoning deterioration).
【０００４】この硫黄被毒劣化を低減させるために、例
えば、バリウム化合物をチタニアと混合し加熱すること
で固溶体を形成させ、貴金属触媒と共に担体に担持させ
て、これをＮＯｘ吸蔵還元型触媒として用いることが提
案されている（特開平７−１３６５１４号公報参照）。In order to reduce the deterioration due to sulfur poisoning, for example, a barium compound is mixed with titania and heated to form a solid solution, which is supported on a carrier together with a noble metal catalyst and used as a NOx storage reduction catalyst. It has been proposed (see Japanese Patent Laid-Open No. 7-136514).
【０００５】また、国際公開公報９９／３３５６０号公
報には、ルチル型チタニアを含む担体と、アルカリ金
属、アルカリ土類金属及び希土類金属から選ばれる少な
くとも一種よりなり該担体に担持されたＮＯｘ吸蔵材
と、該担体に担持された貴金属と、を含んでなる排気ガ
ス浄化用触媒が開示されている。Further, in WO 99/33560, a NOx storage material comprising a carrier containing rutile type titania and at least one selected from an alkali metal, an alkaline earth metal and a rare earth metal and supported on the carrier. And an exhaust gas purifying catalyst containing a noble metal supported on the carrier.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記従
来の吸蔵材及び触媒は、チタニア粉末と、バリウム化合
物等のＮＯｘ吸蔵材との固溶により得られたものである
ため、形成される複合酸化物はチタニア粉末の表面の一
部のみであり、また、微細な複合酸化物とすることが困
難であった。このために、ＮＯｘ吸蔵性能やＮＯｘ吸蔵
還元性能を高くすることができないという問題があっ
た。また、かかる吸蔵材及び触媒においては、硫黄被毒
を受けた際に形成される硫黄化合物が粗大であるため、
被毒前の状態に回復しにくく、高い硫黄被毒耐久性を得
ることができないという問題もあった。However, since the above-mentioned conventional storage materials and catalysts are those obtained by solid solution of titania powder and NOx storage materials such as barium compounds, the complex oxide formed. Was only a part of the surface of the titania powder, and it was difficult to form a fine composite oxide. Therefore, there is a problem that the NOx occlusion performance and the NOx occlusion reduction performance cannot be improved. Further, in such storage material and catalyst, since the sulfur compound formed when sulfur poisoning is coarse,
There is also a problem that it is difficult to recover the state before poisoning, and high durability against sulfur poisoning cannot be obtained.
【０００７】本発明は、上記従来技術の有する課題に鑑
みてなされたものであり、自動車の排ガス等に含まれる
ＮＯｘの吸蔵性能の優れた複合材料及びその製造方法を
提供することを目的とする。また、ＮＯｘ吸蔵還元性能
が十分に高く、硫黄被毒を受けた場合であっても高いＮ
Ｏｘ吸蔵性能を発揮する触媒及びその製造方法を提供す
ることを目的とする。更に、かかる複合材料を用いたＮ
Ｏｘ吸蔵方法、並びにかかる触媒を用いたＮＯｘ吸蔵還
元方法を提供することを目的とする。The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to provide a composite material having an excellent occlusion performance of NOx contained in an exhaust gas of an automobile and a method for producing the same. . In addition, the NOx occlusion reduction performance is sufficiently high, and even if sulfur poisoning occurs, high N
An object of the present invention is to provide a catalyst exhibiting Ox storage performance and a method for producing the same. Furthermore, N using such a composite material
An object is to provide an Ox storage method and a NOx storage reduction method using such a catalyst.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意研究を重ねた結果、アルカリ金属、ア
ルカリ土類金属及び／又は希土類金属を含有する化合物
と、第３族元素、第４族元素及び／又は繊維金属元素を
含有する化合物とを用いて複合材料を製造する場合、あ
るいは更に貴金属を用いて触媒を製造する場合に、これ
らの化合物を含有する溶液に多座配位子を有する化合物
を添加し、その溶液を用いて複合材料又は触媒を調製す
ることによって、得られる複合材料及び触媒が、ＮＯｘ
吸蔵性能又はＮＯｘ吸蔵還元性能に優れると共に、十分
に高い硫黄被毒耐久性を示すことを見出し、本発明を完
成するに至った。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a compound containing an alkali metal, an alkaline earth metal and / or a rare earth metal, and a Group 3 element. In the case of producing a composite material using a compound containing a Group 4 element and / or a fiber metal element, or in the case of producing a catalyst using a noble metal, a polydentate compound is added to a solution containing these compounds. By adding a compound having a ligand and using the solution to prepare a composite material or a catalyst, the obtained composite material and catalyst are NOx.
The inventors have found that the present invention is excellent in storage performance or NOx storage reduction performance and exhibits sufficiently high sulfur poisoning durability, and has completed the present invention.
【０００９】すなわち、本発明の複合材料の製造方法
は、アルカリ金属、アルカリ土類金属及び希土類金属か
らなる群より選ばれる少なくとも１種を含有する第１の
化合物と、第３族元素、第４族元素及び遷移金属元素か
らなる群より選ばれる少なくとも１種を含有する第２の
化合物と、多座配位子を有する第３の化合物とを含有す
る溶液をゲル化させる工程と、得られたゲルを焼成して
複合材料を得る工程とを含むことを特徴とするものであ
る。That is, the method for producing a composite material according to the present invention comprises a first compound containing at least one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, a group 3 element and a group 4 element. A step of gelling a solution containing a second compound containing at least one selected from the group consisting of group elements and transition metal elements and a third compound having a polydentate ligand, And a step of firing the gel to obtain a composite material.
【００１０】また、本発明の複合材料は、上記本発明の
複合材料の製造方法により得られたことを特徴とするも
のである。Further, the composite material of the present invention is characterized by being obtained by the above-mentioned method for producing the composite material of the present invention.
【００１１】また、本発明のＮＯｘ吸蔵方法は、上記本
発明の複合材料にＮＯｘを接触させて、該複合材料にＮ
Ｏｘを吸蔵させることを特徴とするものである。Further, in the NOx storage method of the present invention, NOx is brought into contact with the composite material of the present invention, and NOx is contacted with the composite material.
It is characterized in that it occludes Ox.
【００１２】本発明によれば、上記第１、第２及び第３
の化合物を含む溶液をゲル化させ、又は担体に接触させ
て含有成分を担持させた後、これを焼成することによっ
て、第１の化合物に含まれるアルカリ金属、アルカリ土
類金属及び／又は希土類金属と、第２の化合物に含まれ
る第３族元素、第４族元素及び／又は遷移金属元素とが
微細に且つ均一に複合化されるので、十分に高いＮＯｘ
吸蔵性能を有する複合材料を得ることができる。従っ
て、本発明の複合材料にＮＯｘを接触させることによっ
て、該複合材料に十分な量のＮＯｘを効率よく且つ確実
に吸蔵させることができる。According to the present invention, the above-mentioned first, second and third
The solution containing the compound of (1) is gelled, or the content of the component is supported by bringing it into contact with a carrier and then calcined to give an alkali metal, an alkaline earth metal and / or a rare earth metal contained in the first compound. And a Group 3 element, a Group 4 element and / or a transition metal element contained in the second compound are finely and uniformly compounded, so that the NOx is sufficiently high.
A composite material having storage performance can be obtained. Therefore, by bringing NOx into contact with the composite material of the present invention, a sufficient amount of NOx can be efficiently and surely stored in the composite material.
【００１３】また、本発明の触媒の第１の製造方法は、
上記本発明の複合材料に貴金属を含有する溶液を接触さ
せて、該複合材料に該貴金属を担持させる工程と、前記
貴金属を担持した前記複合材料を焼成して触媒を得る工
程とを含むことを特徴とするものである。The first method for producing the catalyst of the present invention is
A step of bringing a solution containing a noble metal into contact with the composite material of the present invention to support the noble metal on the composite material; and a step of firing the composite material carrying the noble metal to obtain a catalyst. It is a feature.
【００１４】また、本発明の触媒の第２の製造方法は、
アルカリ金属、アルカリ土類金属及び希土類金属からな
る群より選ばれる少なくとも１種を含有する第１の化合
物と、第３族元素、第４族元素及び遷移金属元素からな
る群より選ばれる少なくとも１種を含有する第２の化合
物と、多座配位子を有する第３の化合物とを含有する溶
液を担体と接触させて、該担体に該第１、第２及び第３
の化合物を担持させる工程と、貴金属を含有する溶液を
前記担体に接触させて、該担体に該貴金属を担持する工
程と前記第１、第２及び第３の化合物並びに前記貴金属
を担持した前記担体を焼成して触媒を得る工程とを含む
ことを特徴とするものである。The second method for producing the catalyst of the present invention is
A first compound containing at least one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, and at least one selected from the group consisting of Group 3 elements, Group 4 elements and transition metal elements A solution containing a second compound containing a polydentate ligand and a solution containing a third compound having a polydentate ligand is contacted with a carrier, and the carrier is charged with the first, second and third compounds.
The step of supporting the compound, the step of bringing a solution containing a noble metal into contact with the carrier to support the noble metal on the carrier, and the first, second and third compounds and the carrier supporting the noble metal. To obtain a catalyst.
【００１５】また、本発明の触媒は、上記第１又は第２
の製造方法により得られたことを特徴とするものであ
る。Further, the catalyst of the present invention is the above-mentioned first or second
It is obtained by the manufacturing method of.
【００１６】また、本発明のＮＯｘ吸蔵還元方法は、上
記本発明の触媒をＮＯｘと接触させて、該触媒にＮＯｘ
を吸蔵させて還元することを特徴とするものである。Further, in the NOx occlusion reduction method of the present invention, the catalyst of the present invention is brought into contact with NOx, and NOx is applied to the catalyst.
It is characterized by occluding and reducing.
【００１７】このように本発明では、触媒担体として本
発明の複合材料もしくはその所定の成分（第１の化合物
及び第２の化合物）を担持させた担体を用いるに際し、
その調製工程において当該所定の成分を含有する溶液に
多座配位子を有する第３の化合物を更に含有させること
によって、その含有成分が十分に微細化且つ複合化され
るので、この担体に貴金属を更に担持させた触媒におい
ては、十分に高いＮＯｘ吸蔵還元性能が発揮され、更
に、優れた硫黄被毒耐久性も得ることができる。従っ
て、本発明の触媒をＮＯｘと接触させることによって、
当該触媒に十分な量のＮＯｘを吸蔵させてこれを効率よ
く且つ確実に還元することができる。As described above, in the present invention, when the carrier supporting the composite material of the present invention or the predetermined components thereof (the first compound and the second compound) is used as the catalyst carrier,
In the preparation step, by further adding a third compound having a polydentate ligand to the solution containing the predetermined component, the contained component is sufficiently miniaturized and complexed. In the catalyst further supporting NO, a sufficiently high NOx occlusion reduction performance is exhibited, and further, excellent sulfur poisoning durability can be obtained. Therefore, by contacting the catalyst of the present invention with NOx,
The catalyst can occlude a sufficient amount of NOx and efficiently and reliably reduce it.
【００１８】本発明においては、前記第１の化合物がバ
リウムを含有する化合物であることが好ましく、また、
前記第２の化合物がチタンを含有する化合物であること
が好ましい。これにより、ＮＯｘ吸蔵性能又はＮＯｘ吸
蔵還元性能と、硫黄被毒耐久性との双方がより高められ
る傾向にある。In the present invention, the first compound is preferably a barium-containing compound, and
It is preferable that the second compound is a compound containing titanium. Thereby, both the NOx occlusion performance or NOx occlusion reduction performance and the sulfur poisoning durability tend to be further enhanced.
【００１９】また、本発明においては、前記第３の化合
物がクエン酸であることが好ましい。これにより、複合
材料又は触媒に含まれる第１の化合物及び第２の化合物
をより微細化且つ複合化することができ、ＮＯｘ吸蔵性
能又はＮＯｘ吸蔵還元性能と、硫黄被毒耐久性との双方
がより高められる傾向にある。Further, in the present invention, the third compound is preferably citric acid. As a result, the first compound and the second compound contained in the composite material or the catalyst can be made finer and composite, and both NOx storage performance or NOx storage reduction performance and sulfur poisoning durability can be obtained. It tends to be higher.
【００２０】[0020]
【発明の実施の形態】以下、本発明の好適な実施形態に
ついて詳細に説明する。本発明の複合材料の製造方法
は、アルカリ金属、アルカリ土類金属及び希土類金属か
らなる群より選ばれる少なくとも１種を含有する第１の
化合物と、第３族元素、第４族元素及び遷移金属元素か
らなる群より選ばれる少なくとも１種を含有する第２の
化合物と、多座配位子を有する第３の化合物とを含有す
る溶液をゲル化させる工程と、得られたゲルを焼成して
複合材料を得る工程とを含むことを特徴とするものであ
る。BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described in detail below. The method for producing a composite material according to the present invention comprises a first compound containing at least one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, a group 3 element, a group 4 element and a transition metal. A step of gelling a solution containing a second compound containing at least one selected from the group consisting of elements and a third compound having a polydentate ligand, and calcining the obtained gel And a step of obtaining a composite material.
【００２１】第１の化合物が含有するアルカリ金属とし
てはリチウム、ナトリウム、カリウム、セシウム等が挙
げられ、アルカリ土類金属としてはバリウム、マグネシ
ウム、カルシウム、ストロンチウム等が挙げられ、希土
類金属としてはスカンジウム、イットリウム、ランタ
ン、セリウム、プラセオジウム、ネオジム等が挙げられ
るが、これらの中でもバリウムを含有する化合物（硝酸
バリウム、酢酸バリウム等）が好ましい。なお、第１の
化合物は、上記のアルカリ金属、アルカリ土類金属又は
希土類金属のうちの１種のみを含有するものであっても
よく、２種以上を含有するものであってもよい。The alkali metal contained in the first compound includes lithium, sodium, potassium, cesium and the like, the alkaline earth metal includes barium, magnesium, calcium, strontium and the like, and the rare earth metal includes scandium, Examples thereof include yttrium, lanthanum, cerium, praseodymium and neodymium, and of these, compounds containing barium (barium nitrate, barium acetate, etc.) are preferable. The first compound may contain only one kind of the above-mentioned alkali metal, alkaline earth metal or rare earth metal, or may contain two kinds or more.
【００２２】第２の化合物が含有する第３族元素として
はアルミニウム、ケイ素、リン等が挙げられ、第４族元
素としてはチタン、ジルコニウム等が挙げられ、遷移金
属元素としては、バナジウム、クロム、マンガン、鉄、
コバルト、ニッケル、銅、亜鉛等が挙げられるが、これ
らの中でもチタンを含有する化合物（チタンイソプロポ
キシド等）が好ましい。なお、第２の化合物は、上記の
第３族元素、第４族元素又は遷移金属元素のうちの１種
のみを含有するものであってもよく、２種以上を含有す
るものであってもよい。The Group 3 elements contained in the second compound include aluminum, silicon, phosphorus, etc., the Group 4 elements include titanium, zirconium, etc., and the transition metal elements include vanadium, chromium, Manganese, iron,
Examples thereof include cobalt, nickel, copper, zinc and the like, and of these, a compound containing titanium (titanium isopropoxide or the like) is preferable. The second compound may contain only one kind of the above Group 3 element, Group 4 element or transition metal element, or may contain two or more kinds thereof. Good.
【００２３】第３の化合物が有する多座配位子とは、２
個以上の配位基で配位し得るものをいう。第３の化合物
としては、クエン酸、シュウ酸等の多価カルボン酸類、
グリコール、ピナコール等のジオール類等が挙げられる
が、これらの中でもクエン酸が好ましい。なお、第３の
化合物は、１種を単独で用いてもよく、２種以上を組み
合わせて用いてもよい。The polydentate ligand contained in the third compound is 2
It means one that can be coordinated with more than one coordination group. As the third compound, polyvalent carboxylic acids such as citric acid and oxalic acid,
Examples include diols such as glycol and pinacol, and among these, citric acid is preferable. The third compound may be used alone or in combination of two or more.
【００２４】上記第１、第２及び第３の化合物を所定の
溶媒（好ましくは水、より好ましくはイオン交換水）に
溶解させて、その溶液のゲル化が行われる。なお、ゲル
化の際には、予め第１、第２及び第３の化合物を含有す
る溶液を調製し、所定の温度下で当該溶液を撹拌するこ
とによってゲル化を行ってもよいが、上記化合物のうち
の１種（例えば第１の化合物）を含有する溶液を他の２
種（例えば第２及び第３の化合物）を含有する溶液に滴
下しながら撹拌すると、反応がより均一となるので好ま
しい。なお、当該溶液をゲル化させるときの温度は、２
０〜８０℃であることが好ましい。The above-mentioned first, second and third compounds are dissolved in a predetermined solvent (preferably water, more preferably ion-exchanged water) to gel the solution. At the time of gelation, a solution containing the first, second, and third compounds may be prepared in advance, and the gelation may be performed by stirring the solution at a predetermined temperature. A solution containing one of the compounds (eg, the first compound) is replaced with another solution
It is preferable to stir the solution containing the seed (for example, the second and third compounds) while adding it dropwise, because the reaction becomes more uniform. The temperature at which the solution is gelled is 2
It is preferably 0 to 80 ° C.
【００２５】また、当該溶液中の各化合物の含有量は、
溶媒１０００ｍＬに対して、アルカリ金属とアルカリ土
類金属と希土類金属との総和が０．１〜０．５ｍｏｌ、
第３族元素と第４族元素と遷移金属元素との総和が０．
１〜０．５ｍｏｌ、多座配位子が０．３〜１．５ｍｏｌ
となるように設定されることが好ましい。各化合物の配
合量がそれぞれ前記上限値を超えると、溶液濃度が高す
ぎて反応が均一に起こりにくくなる傾向にある。また、
各化合物の配合量がそれぞれ前記下限値未満であると、
溶液濃度が希薄すぎて製造効率が低下する傾向にある。The content of each compound in the solution is
The total sum of alkali metal, alkaline earth metal, and rare earth metal is 0.1 to 0.5 mol per 1000 mL of the solvent,
The sum of the group 3 element, the group 4 element, and the transition metal element is 0.
1-0.5 mol, 0.3-1.5 mol of polydentate ligand
It is preferable to set so that When the compounding amount of each compound exceeds the upper limit value, the solution concentration tends to be too high and the reaction tends to be difficult to uniformly occur. Also,
When the compounding amount of each compound is less than the lower limit value,
Since the solution concentration is too dilute, the production efficiency tends to decrease.
【００２６】このゲルを焼成することによって、第１の
化合物に含まれる成分（アルカリ金属、アルカリ土類金
属、希土類金属）と第２の化合物に含まれる成分（第３
族元素、第４族元素、遷移金属元素）とが十分に微細に
且つ均一に複合化した本発明の複合材料が得られる。例
えば、第１の化合物としてチタンイソプロポキシド、第
２の化合物として酢酸バリウムを用いた場合には、チタ
ンとバリウムとの複合化によりこれらの複合酸化物が得
られる。By calcining this gel, the components contained in the first compound (alkali metal, alkaline earth metal, rare earth metal) and the components contained in the second compound (third component).
It is possible to obtain the composite material of the present invention in which the group element, the group 4 element, and the transition metal element) are sufficiently finely and uniformly compounded. For example, when titanium isopropoxide is used as the first compound and barium acetate is used as the second compound, a composite oxide of titanium and barium can be obtained.
【００２７】焼成の条件は特に制限されないが、例えば
空気中で、好ましくは３００〜１０００℃、より好まし
くは３５０〜７００℃に加熱することによってゲルを焼
成することができる。また、加熱時間は加熱温度により
異なるが、例えば１〜３時間とすることができる。The firing conditions are not particularly limited, but the gel can be fired, for example, by heating in air, preferably at 300 to 1000 ° C, more preferably 350 to 700 ° C. The heating time may vary depending on the heating temperature, but may be, for example, 1 to 3 hours.
【００２８】このようにして得られる本発明の複合材料
は、十分に高いＮＯｘ吸蔵性能を有するものであり、当
該複合材料にＮＯｘを接触させることによって十分な量
のＮＯｘを効率よく吸蔵することができる。より具体的
には、本発明の複合材料を自動車等の排ガスと接触させ
ることによって、当該排ガス中のＮＯｘが例えばＢａ
（ＮＯ3）2を含む化合物として複合材料中に吸蔵される
ので、ＮＯｘが除去されて排ガスが浄化される。また、
本発明の複合材料は、硫黄被毒耐久性にも優れており、
自動車等の排ガスのように酸化硫黄を含有するガスを浄
化する場合であっても、硫黄被毒劣化を生じることな
く、長期にわたって十分に高いＮＯｘ吸蔵性能を得るこ
とができる。なお、本発明の複合材料の形状は特に制限
されず、粉末状、ペレット状、ハニカム状等の形状で用
いることができる。The thus obtained composite material of the present invention has a sufficiently high NOx storage performance, and it is possible to store a sufficient amount of NOx efficiently by bringing NOx into contact with the composite material. it can. More specifically, when the composite material of the present invention is brought into contact with exhaust gas from an automobile or the like, NOx in the exhaust gas is, for example, Ba.
Since it is stored in the composite material as a compound containing (NO 3 ) 2 , NOx is removed and exhaust gas is purified. Also,
The composite material of the present invention is also excellent in durability against sulfur poisoning,
Even when purifying a gas containing sulfur oxide, such as exhaust gas from an automobile or the like, it is possible to obtain a sufficiently high NOx storage performance for a long period of time without causing sulfur poisoning deterioration. The shape of the composite material of the present invention is not particularly limited, and it can be used in the shape of powder, pellet, honeycomb or the like.
【００２９】次に、本発明の触媒の製造方法について説
明する。本発明の触媒の第１の製造方法は、上記の製造
方法によって得られる本発明の複合材料に貴金属を含有
する溶液を接触させて、該複合材料に該貴金属を担持さ
せる工程と、前記貴金属を担持した前記複合材料を焼成
して触媒を得る工程とを含むことを特徴とするものであ
る。Next, the method for producing the catalyst of the present invention will be described. A first method for producing a catalyst of the present invention comprises the steps of bringing a solution containing a noble metal into contact with the composite material of the present invention obtained by the above-mentioned production method, and supporting the noble metal on the composite material. And a step of calcining the supported composite material to obtain a catalyst.
【００３０】本発明の複合材料に担持される貴金属とし
ては、具体的には、白金（Ｐｔ）、ルテニウム（Ｒ
ｕ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、イリジ
ウム（Ｉｒ）等が挙げられ、これらの１種を単独で用い
てもよく、２種以上を組み合わせて用いてもよい。Specific examples of the noble metal supported on the composite material of the present invention include platinum (Pt) and ruthenium (R).
u), rhodium (Rh), palladium (Pd), iridium (Ir), and the like, and one of these may be used alone, or two or more thereof may be used in combination.
【００３１】複合材料への貴金属の担持は、貴金属を含
有する溶液を用い、含浸法や選択吸着法等により行うこ
とができる。貴金属を含有する溶液は、当該貴金属及び
／又は貴金属前駆体を所定の溶媒（好ましくは水、より
好ましくはイオン交換水）に溶解させたものであること
が好ましく、当該貴金属前駆体としては、例えば、白金
のハロゲン化物、白金の硝酸塩、白金アセチルアセトナ
ート等が挙げられる。貴金属の担持量は、触媒全量を基
準として好ましくは０．２〜５重量％である。The noble metal can be supported on the composite material by using a solution containing the noble metal by an impregnation method or a selective adsorption method. The solution containing the noble metal is preferably a solution of the noble metal and / or the noble metal precursor in a predetermined solvent (preferably water, more preferably ion-exchanged water). Examples of the noble metal precursor include: , Platinum halides, platinum nitrates, platinum acetylacetonate, and the like. The amount of the noble metal supported is preferably 0.2 to 5% by weight based on the total amount of the catalyst.
【００３２】このようにして貴金属が担持された複合材
料を焼成して本発明の触媒が得られる。焼成の条件につ
いては特に制限されず、例えば本発明の複合材料の製造
方法の説明において例示された焼成条件が挙げられる。
また、当該触媒の焼成は還元性雰囲気下で行ってもよ
い。さらに、かかる焼成の後に、アルカリ金属等を担持
し、焼成してもよい。In this way, the catalyst of the present invention is obtained by firing the composite material carrying the noble metal. The firing conditions are not particularly limited, and examples thereof include the firing conditions exemplified in the description of the method for producing the composite material of the present invention.
The catalyst may be calcined in a reducing atmosphere. Further, after such firing, an alkali metal or the like may be supported and fired.
【００３３】次に、本発明の触媒の第２の製造方法につ
いて説明する。本発明の触媒の第２の製造方法は、アル
カリ金属、アルカリ土類金属及び希土類金属からなる群
より選ばれる少なくとも１種を含有する第１の化合物
と、第３族元素、第４族元素及び遷移金属元素からなる
群より選ばれる少なくとも１種を含有する第２の化合物
と、多座配位子を有する第３の化合物とを含有する溶液
を担体と接触させて、該担体に該第１、第２及び第３の
化合物を担持させる工程と、貴金属を含有する溶液を前
記担体に接触させて、該担体に該貴金属を担持する工程
と前記第１、第２及び第３の化合物並びに前記貴金属を
担持した前記担体を焼成して触媒を得る工程とを含むこ
とを特徴とするものである。Next, the second method for producing the catalyst of the present invention will be described. A second method for producing a catalyst of the present invention is a first compound containing at least one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, a Group 3 element, a Group 4 element and A solution containing a second compound containing at least one selected from the group consisting of transition metal elements and a third compound having a polydentate ligand is brought into contact with a carrier to give the first compound to the carrier. A step of supporting the second and third compounds, a step of bringing a solution containing a noble metal into contact with the carrier to support the noble metal on the carrier, the first, second and third compounds, and the step of And a step of obtaining the catalyst by firing the carrier supporting the noble metal.
【００３４】第２の製造方法において用いられる担体と
しては、アルミナ、シリカ、ジルコニア、チタニア、セ
リア、マグネシア又はこれらの混合物もしくは複合酸化
物が挙げられ、これらのうちの１種を単独で用いてもよ
く、２種以上を組み合わせて用いてもよい。Examples of the carrier used in the second production method include alumina, silica, zirconia, titania, ceria, magnesia, or a mixture or complex oxide thereof, and one of these may be used alone. Of course, two or more kinds may be used in combination.
【００３５】担体への第１、第２及び第３の化合物の担
持は、これらの化合物を含有する溶液を用い、含浸法や
選択吸着法等により行うことができる。かかる溶液とし
ては、第１、第２及び第３の化合物を所定の溶媒（好ま
しくは水、より好ましくはイオン交換水）に溶解させた
ものが好ましく、各化合物の含有量は、担体１００ｇに
対して、アルカリ金属とアルカリ土類金属と希土類金属
との総和が０．０２〜０．２ｍｏｌ、第３族元素と第４
族元素と遷移金属元素との総和が０．０２〜０．２ｍｏ
ｌ、多座配位子が０．０６〜０．６ｍｏｌとなるように
設定されることが好ましい。The loading of the first, second and third compounds on the carrier can be carried out by a solution containing these compounds by an impregnation method or a selective adsorption method. As such a solution, it is preferable to dissolve the first, second and third compounds in a predetermined solvent (preferably water, more preferably ion-exchanged water), and the content of each compound is 100 g of the carrier. And the total sum of alkali metal, alkaline earth metal and rare earth metal is 0.02 to 0.2 mol, Group 3 element and Group 4
The total sum of the group element and the transition metal element is 0.02 to 0.2 mo
1 and the polydentate ligand is preferably set to 0.06 to 0.6 mol.
【００３６】また、担体への貴金属の担持は、貴金属を
含有する溶液を用い、含浸法や選択吸着法等により行う
ことができる。かかる溶液としては、本発明の触媒の第
１の製造方法において例示された貴金属を含有する溶液
を用いることができる。The supporting of the noble metal on the carrier can be carried out by the impregnation method or the selective adsorption method using a solution containing the noble metal. As such a solution, the solution containing the noble metal exemplified in the first method for producing a catalyst of the present invention can be used.
【００３７】なお、当該第２の製造方法においては、担
体への第１、第２及び第３の化合物の担持工程と、担体
への貴金属の担持工程との順序は特に制限されない。す
なわち、第１、第２及び第３の化合物が担持された担体
に貴金属を担持させてもよく、貴金属が担持された担体
に第１、第２及び第３の化合物を担持させてもよい。In the second manufacturing method, the order of the step of supporting the first, second and third compounds on the carrier and the step of supporting the noble metal on the carrier is not particularly limited. That is, the noble metal may be carried on the carrier carrying the first, second and third compounds, and the first, second and third compounds may be carried on the carrier carrying the noble metal.
【００３８】このようにして第１、第２及び第３の化合
物並びに貴金属が担持された担体を焼成することによっ
て、本発明の触媒が得られる。焼成の条件については特
に制限されず、上記第１の製造方法における焼成と同様
にして行うことができる。In this way, the catalyst of the present invention can be obtained by calcining the carrier carrying the first, second and third compounds and the noble metal. The firing conditions are not particularly limited, and the firing can be performed in the same manner as the firing in the first manufacturing method.
【００３９】なお、第１、第２及び第３の化合物、並び
に貴金属の担持を行った後、アルカリ金属等を更に担持
し、焼成してもよい。これにより、ＮＯｘ吸蔵還元性能
を更に高めることができる。アルカリ金属等の担持は、
これらを含有する溶液を用い、含浸法や選択吸着法等に
より行うことができる上記第１又は第２の製造方法によ
り得られる本発明の触媒は、十分に高いＮＯｘ吸蔵還元
性能を有するものであり、当該触媒にＮＯｘを接触させ
ることによって十分な量のＮＯｘを効率よく吸蔵還元す
ることができる。より具体的には、本発明の触媒を自動
車等の排ガスと接触させることによって、当該排ガス中
に含まれるＮＯｘが例えばＢａ（ＮＯ3）2を含む化合物
として触媒中に吸蔵され、更には窒素（Ｎ2）に還元さ
れて放出されるので、ＮＯｘが無害化されて排ガスが浄
化される。また、本発明の触媒は、硫黄被毒耐久性にも
優れており、自動車等の排ガスのように酸化硫黄を含有
するガスを浄化する場合であっても、硫黄被毒劣化を生
じることなく、長期にわたって十分に高いＮＯｘ吸蔵還
元性能を得ることができる。なお、本発明の触媒の形状
は特に制限されず、粉末状、ペレット状、ハニカム状等
の形状で用いることができる。After loading the first, second and third compounds and the noble metal, an alkali metal or the like may be further loaded and baked. Thereby, the NOx occlusion reduction performance can be further improved. Loading of alkali metals, etc.
The catalyst of the present invention obtained by the above-mentioned first or second production method which can be carried out by an impregnation method or a selective adsorption method using a solution containing these has a sufficiently high NOx storage reduction performance. By contacting NOx with the catalyst, a sufficient amount of NOx can be efficiently occluded and reduced. More specifically, by contacting the catalyst of the present invention with exhaust gas from an automobile or the like, NOx contained in the exhaust gas is occluded in the catalyst as a compound containing, for example, Ba (NO 3 ) 2 , and further nitrogen ( Since it is reduced to N 2 ) and released, NOx is rendered harmless and exhaust gas is purified. Further, the catalyst of the present invention is also excellent in sulfur poisoning durability, even when purifying a gas containing sulfur oxide such as exhaust gas of automobiles, etc., without causing sulfur poisoning deterioration, It is possible to obtain a sufficiently high NOx occlusion reduction performance over a long period of time. The shape of the catalyst of the present invention is not particularly limited, and it can be used in the form of powder, pellet, honeycomb or the like.
【００４０】[0040]
【実施例】以下、実施例及び比較例に基づいて本発明を
更に具体的に説明するが、本発明は以下の実施例に何ら
限定されるものではない。実施例１
（複合材料の調製）チタンイソプロポキシド７３．７ｇ
及びクエン酸４４２ｇを７５℃のイオン交換水６００ｍ
Ｌに溶解して溶液Ａを調製した。一方、酢酸バリウム６
６．２ｇをイオン交換水１００ｍＬに溶解して溶液Ｂを
調製した。次に、撹拌下、溶液Ｂを溶液Ａに滴下し、大
気中、３００℃で３時間加熱して水分を蒸発させた。こ
のようにして得られたゲルを大気中、６５０℃で３時間
焼成してバリウムとチタンとを含む複合材料を得た。EXAMPLES The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to the following examples. Example 1 (Preparation of composite material) 73.7 g of titanium isopropoxide
And 442g citric acid 600m ion-exchanged water at 75 ° C
Solution A was prepared by dissolving in L. On the other hand, barium acetate 6
Solution B was prepared by dissolving 6.2 g in 100 mL of ion-exchanged water. Next, the solution B was added dropwise to the solution A under stirring and heated in the air at 300 ° C. for 3 hours to evaporate the water content. The gel thus obtained was calcined in the air at 650 ° C. for 3 hours to obtain a composite material containing barium and titanium.
【００４１】（触媒の調製）上記の複合材料１０ｇを、
白金Ｐソルト（白金の硝酸塩）水溶液に含浸し、白金の
硝酸塩を担持させた。このとき、ＢａＴｉＯ3に換算し
た複合材料１ｍｏｌに対して、白金の担持量が１ｇとな
るようにした。この担持物を大気中、３００℃で３時間
焼成してＮＯｘ吸蔵還元型触媒を得た。(Preparation of catalyst) 10 g of the above composite material was
An aqueous solution of platinum P salt (nitrate of platinum) was impregnated to support the nitrate of platinum. At this time, the amount of platinum supported was set to 1 g per 1 mol of the composite material converted to BaTiO 3 . This supported material was calcined in air at 300 ° C. for 3 hours to obtain a NOx occlusion reduction type catalyst.
【００４２】比較例１
硝酸バリウム４６ｇ及び四塩化チタン１６ｗｔ％水溶液
２０４ｇをイオン交換水２０００ｍＬに投入し撹拌して
分散液を得た。これとは別に重炭酸アンモニウム１７．
５ｇ及びアンモニア水（３０％水溶液）２５０ｇをイオ
ン交換水５００ｍＬに溶解して沈殿剤とした。分散液中
にこの沈殿剤を全量投入し、共沈により生じた沈殿を濾
過して共沈物を得た。この共沈物を大気中、６５０℃で
３時間焼成して、バリウムとチタンとを含む複合材料を
得た。 Comparative Example 1 46 g of barium nitrate and 204 g of a 16 wt% aqueous solution of titanium tetrachloride were added to 2000 mL of ion-exchanged water and stirred to obtain a dispersion liquid. Separately from this, ammonium bicarbonate 17.
5 g and 250 g of ammonia water (30% aqueous solution) were dissolved in 500 mL of ion-exchanged water to obtain a precipitant. The whole amount of this precipitant was added to the dispersion, and the precipitate generated by coprecipitation was filtered to obtain a coprecipitate. This coprecipitate was calcined in the air at 650 ° C. for 3 hours to obtain a composite material containing barium and titanium.
【００４３】この複合材料１０ｇを、白金Ｐソルト（白
金の硝酸塩）水溶液に含浸し、白金の硝酸塩を担持させ
た。このとき、ＢａＴｉＯ3に換算した複合材料１ｍｏ
ｌに対して、白金の担持量が１ｇとなるようにした。こ
の担持物を大気中、３００℃で３時間してＮＯｘ吸蔵還
元型触媒を得た。10 g of this composite material was impregnated with an aqueous solution of platinum P salt (platinum nitrate) to support platinum nitrate. At this time, 1mo of the composite material converted to BaTiO 3
The amount of platinum supported was 1 g per 1 l. This supported material was kept in the air at 300 ° C. for 3 hours to obtain a NOx occlusion reduction type catalyst.
【００４４】（ＮＯｘ吸蔵性能評価試験１）実施例１及
び比較例１のＮＯｘ吸蔵還元型触媒を、加圧成型器によ
り圧紛した後で粉砕し、３００〜７００μｍのペレット
とした。このペレットに対して、表１に示す硫黄被毒ガ
スをＳ／Ｂａのモル比が約２となる流量を６００℃で流
通させた後、表２に示す回復処理ガスを７００℃で５分
間流通させた。このように硫黄被毒及び再生を行ったペ
レット０．５ｇを用いて、表３に示すＮＯｘ吸蔵評価条
件で、測定温度３００℃、４００℃及び５００℃におけ
るＲＳＮＯｘ吸蔵量（リッチスパイク後のＮＯｘ吸蔵
量）を測定した。測定結果を図１に示す。(NOx occlusion performance evaluation test 1) The NOx occlusion reduction type catalysts of Example 1 and Comparative Example 1 were pressed by a pressure molding machine and then pulverized to give pellets of 300 to 700 µm. The sulfur poisoning gas shown in Table 1 was passed through the pellets at a flow rate of 600 ° C. at which the S / Ba molar ratio was about 2, and then the recovery treatment gas shown in Table 2 was passed at 700 ° C. for 5 minutes. It was Using 0.5 g of the pellets thus subjected to sulfur poisoning and regeneration, under the NOx storage evaluation conditions shown in Table 3, the RSNOx storage amount at the measurement temperatures of 300 ° C, 400 ° C and 500 ° C (NOx storage after rich spike) Amount) was measured. The measurement results are shown in FIG.
【表１】 [Table 1]
【表２】 [Table 2]
【表３】
図１に示したように、実施例１のＮＯｘ吸蔵還元型触媒
は、いずれの測定温度においても比較例のＮＯｘ吸蔵還
元型触媒に比べて高いＮＯｘ吸蔵性能を示した。[Table 3] As shown in FIG. 1, the NOx occlusion reduction catalyst of Example 1 exhibited higher NOx occlusion performance than the NOx occlusion reduction catalyst of Comparative Example at any measurement temperature.
【００４５】実施例２
（白金の担持）アルミナ１００ｇ、チタニア−ジルコニ
ア複合酸化物（Ｔｉ／Ｚｒのモル比：２／３）１００
ｇ、ロジウム０．５ｇを担持したジルコニア５０ｇ、並
びにセリア−ジルコニア複合酸化物（Ｃｅ／Ｚｒのモル
比：５／１）２０ｇをアルミナバインダを用いてスラリ
ー化して混合し、３５ｃｃテストピースハニカムに触媒
１Ｌ当たり２７０ｇとなるようにコートし、５００℃で
１時間焼成して触媒担体コートを得た。この触媒担体コ
ートをジニトロジアンミン白金溶液に含浸し、白金の担
持量が触媒１Ｌ当たり２ｇとなるように担持し、大気
中、３００℃で３時間焼成して白金担持触媒を得た。 Example 2 (supporting platinum) 100 g of alumina, 100 titania-zirconia composite oxide (Ti / Zr molar ratio: 2/3) 100
g, 50 g of zirconia supporting 0.5 g of rhodium, and 20 g of ceria-zirconia composite oxide (molar ratio of Ce / Zr: 5/1) were slurried with an alumina binder and mixed to form a catalyst on a 35 cc test piece honeycomb. It was coated so that it would be 270 g per liter, and was baked at 500 ° C. for 1 hour to obtain a catalyst carrier coat. This catalyst carrier coat was impregnated with a dinitrodiammine platinum solution, and the catalyst was supported so that the amount of platinum supported was 2 g per 1 L of the catalyst, and the platinum-supported catalyst was obtained by firing at 300 ° C. for 3 hours in the air.
【００４６】（バリウム−チタン複合酸化物の担持）実
施例１と同様にして溶液Ａ及び溶液Ｂを調製し、溶液Ａ
を０℃に冷却してこれに溶液Ｂを滴下して混合溶液を調
製した。この混合溶液を上記の白金担持触媒に吸収させ
た後、大気中、３００℃で３時間焼成してバリウム−チ
タン複合酸化物の担持を行った。バリウム−チタン複合
酸化物の担持量は、ＢａＴｉＯ3に換算して触媒１Ｌ当
たり０．２ｍｏｌとした。(Supporting Barium-Titanium Composite Oxide) Solution A and solution B were prepared in the same manner as in Example 1, and solution A was prepared.
Was cooled to 0 ° C., and the solution B was added dropwise thereto to prepare a mixed solution. After this mixed solution was absorbed by the above platinum-supported catalyst, it was calcined in air at 300 ° C. for 3 hours to support the barium-titanium composite oxide. The supported amount of barium-titanium composite oxide was 0.2 mol per 1 L of catalyst in terms of BaTiO 3 .
【００４７】（カリウム及びリチウムの担持）更に、白
金及びバリウム−チタン複合酸化物が担持された触媒
に、酢酸カリウム及び酢酸リチウムを含有する水溶液を
吸収させた後、大気中、３００℃で３時間焼成してＮＯ
ｘ吸蔵還元型触媒を得た。カリウムの担持量は触媒１Ｌ
当たり０．１５ｍｏｌ、リチウムの担持量は触媒１Ｌ当
たり０．１ｍｏｌとした。(Support of potassium and lithium) Further, after a platinum- and barium-titanium composite oxide-supported catalyst was made to absorb an aqueous solution containing potassium acetate and lithium acetate, the catalyst was supported in the atmosphere at 300 ° C. for 3 hours. NO after firing
x storage reduction catalyst was obtained. The amount of potassium supported is 1 L of catalyst
0.15 mol per 1 L, and the amount of lithium supported was 0.1 mol per 1 L of the catalyst.
【００４８】実施例３
（バリウム−チタン複合酸化物の担持）実施例２と同様
にして調製した触媒担体コートに、溶液Ａと溶液Ｂとの
混合溶液を吸収させた後、大気中、３００℃で３時間焼
成してバリウム−チタン複合酸化物担持触媒を得た。バ
リウム−チタン複合酸化物の担持量がＢａＴｉＯ3に換
算して触媒１Ｌ当たり０．２ｍｏｌとした。 Example 3 (Supporting Barium-Titanium Composite Oxide) A catalyst carrier coat prepared in the same manner as in Example 2 was allowed to absorb a mixed solution of solution A and solution B, and then, at 300 ° C. in the atmosphere. It was calcined for 3 hours to obtain a barium-titanium composite oxide-supported catalyst. The supported amount of barium-titanium composite oxide was converted to BaTiO 3 and was 0.2 mol per 1 L of the catalyst.
【００４９】（白金の担持）上記のバリウム−チタン複
合酸化物担持触媒に、ジニトロジアンミン白金溶液に含
浸し、白金の担持量が触媒１Ｌ当たり２ｇとなるように
担持し、大気中、３００℃で３時間焼成した。(Supporting Platinum) The above barium-titanium composite oxide-supported catalyst was impregnated with a dinitrodiammine platinum solution and supported so that the supported amount of platinum was 2 g per 1 L of the catalyst, and the temperature was 300 ° C. in the atmosphere. Baked for 3 hours.
【００５０】（カリウム及びリチウムの担持）更に、実
施例２と同様にして、白金及びバリウム−チタン複合酸
化物が担持された触媒に、酢酸カリウム及び酢酸リチウ
ムを含有する水溶液を吸収させた後、大気中、３００℃
で３時間焼成してＮＯｘ吸蔵還元型触媒を得た。カリウ
ムの担持量は触媒１Ｌ当たり０．１５ｍｏｌ、リチウム
の担持量は触媒１Ｌ当たり０．１ｍｏｌとした。(Support of potassium and lithium) Further, in the same manner as in Example 2, after the platinum- and barium-titanium composite oxide-supported catalyst was made to absorb the aqueous solution containing potassium acetate and lithium acetate, 300 ° C in air
It was calcined for 3 hours to obtain a NOx occlusion reduction type catalyst. The amount of potassium carried was 0.15 mol per liter of catalyst, and the amount of lithium carried was 0.1 mol per liter of catalyst.
【００５１】比較例２
実施例２と同様にして得られた白金担持触媒に、酢酸バ
リウム、酢酸カリウム及び酢酸リチウムを含有する水溶
液を吸収させた後、大気中、３００℃で３時間加熱して
触媒を得た。バリウムの担持量は触媒１Ｌ当たり０．２
ｍｏｌ、カリウムの担持量は触媒１Ｌ当たり０，１５ｍ
ｏｌ、リチウムの担持量は触媒１Ｌ当たり０．１ｍｏｌ
とした。 Comparative Example 2 A platinum-supported catalyst obtained in the same manner as in Example 2 was allowed to absorb an aqueous solution containing barium acetate, potassium acetate and lithium acetate, and then heated in air at 300 ° C. for 3 hours. A catalyst was obtained. The supported amount of barium is 0.2 per 1 L of catalyst
The amount of mol and potassium supported is 0.15 m per 1 L of catalyst
The amount of ol and lithium supported is 0.1 mol per liter of catalyst
And
【００５２】（ＮＯｘ吸蔵性能評価試験２）実施例２、
３及び比較例２のＮＯｘ吸蔵還元型触媒（いずれも円筒
状のハニカム型触媒）をそれぞれガラス円筒に充填し、
表４に示す硫黄被毒ガスを、Ｓ／（Ｂａ＋Ｋ／２＋Ｌｉ
／２）のモル比が１．２５となる流量で、リーン１１０
秒、リッチ１０秒を繰り返して流通させた。このように
して硫黄被毒耐久処理が行われた触媒に、表５に示すＮ
Ｏｘ含有ガスを、２５０℃、３００℃、４００℃、５０
０℃、６００℃の各温度で流通させ、触媒を通過した後
のガス中に含まれるＮＯｘ濃度を測定した。(NOx occlusion performance evaluation test 2) Example 2,
3 and the NOx occlusion reduction type catalysts of Comparative Example 2 (both are cylindrical honeycomb type catalysts) were filled in glass cylinders,
The sulfur poisoning gas shown in Table 4 was added to S / (Ba + K / 2 + Li
At a flow rate such that the molar ratio of / 2) becomes 1.25, lean 110
Seconds and rich 10 seconds were repeatedly distributed. The catalysts that have been subjected to the sulfur poisoning endurance treatment in this way are provided with N shown in Table 5.
Ox-containing gas, 250 ℃, 300 ℃, 400 ℃, 50
The NOx concentration contained in the gas after passing through the catalyst was measured by allowing the mixture to flow at each temperature of 0 ° C and 600 ° C.
【表４】 [Table 4]
【表５】
図２は各測定におけるＮＯｘ濃度（Ａ）と時間（ｔ）と
の相関を概念的に示すグラフである。図２中、時間ｔ＝
０〜ｔ1において、触媒に流入したＮＯｘの総量（Ａ＋
Ｂ）に対して、排出されない、すなわち吸蔵されたＮＯ
ｘ量（Ａ）が９５％となるときの時間ｔ1を測定し、ｔ
＝０〜ｔ1におけるＮＯｘ濃度の減少量の積算値（図２
中の面積Ａ）を９５％ＮＯｘ吸蔵量として、各触媒のＮ
Ｏｘ吸蔵性能を評価した。評価結果を図３に示す。[Table 5] FIG. 2 is a graph conceptually showing the correlation between the NOx concentration (A) and the time (t) in each measurement. In FIG. 2, time t =
At 0 to t 1 , the total amount of NOx (A +
In contrast to B), NO is not emitted, that is, NO is stored
The time t 1 when the x amount (A) reaches 95% is measured and t
= 0 to t 1 integrated value of the reduction amount of NOx concentration (see FIG. 2
The area A) is defined as 95% NOx storage amount, and N of each catalyst is
The Ox storage performance was evaluated. The evaluation result is shown in FIG.
【００５３】図３に示したように、実施例２、３のＮＯ
ｘ吸蔵還元型触媒は、いずれの温度においても比較例２
のＮＯｘ吸蔵還元型触媒に比べて高いＮＯｘ吸蔵性能を
示した。As shown in FIG. 3, NO in Examples 2 and 3
The x storage-reduction type catalyst was used in Comparative Example 2 at any temperature.
The NOx occlusion reduction type catalyst exhibited higher NOx occlusion performance.
【００５４】[0054]
【発明の効果】以上説明した通り、本発明によれば、自
動車の排ガス等に含まれるＮＯｘの吸蔵性能の優れた複
合材料及びその製造方法が提供される。また、ＮＯｘ吸
蔵還元性能が十分に高く、硫黄被毒を受けた場合であっ
ても高いＮＯｘ吸蔵性能を発揮する触媒及びその製造方
法が提供される。更に、かかる複合材料を用いたＮＯｘ
吸蔵方法、並びにかかる触媒を用いたＮＯｘ吸蔵還元方
法が提供される。As described above, according to the present invention, there is provided a composite material having an excellent occlusion performance of NOx contained in the exhaust gas of an automobile and the like, and a method for producing the same. Further, there is provided a catalyst having sufficiently high NOx storage reduction performance and exhibiting high NOx storage performance even when it is subjected to sulfur poisoning, and a manufacturing method thereof. Furthermore, NOx using such a composite material
An occlusion method and a NOx occlusion reduction method using such a catalyst are provided.
【図１】実施例１及び比較例１で得られたＮＯｘ吸蔵還
元型触媒のＲＳＮＯｘ吸蔵量を示すグラフである。FIG. 1 is a graph showing RSNOx storage amounts of NOx storage-reduction catalysts obtained in Example 1 and Comparative Example 1.
【図２】ＮＯｘ吸蔵性能試験２におけるＮＯｘ濃度と時
間との相関を概念的に示すグラフである。FIG. 2 is a graph conceptually showing the correlation between NOx concentration and time in NOx occlusion performance test 2.
【図３】実施例２、３及び比較例２で得られたＮＯｘ吸
蔵還元型触媒の９５％ＮＯｘ吸蔵量を示すグラフであ
る。3 is a graph showing the 95% NOx storage amount of the NOx storage reduction catalysts obtained in Examples 2 and 3 and Comparative Example 2. FIG.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｆ０１Ｎ 3/10 Ｂ０１Ｄ 53/36 １０２Ｂ (72)発明者 高橋 直樹 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 Ｆターム(参考） 3G091 AB06 BA14 BA39 GB02Y GB03Y GB04Y GB05W 4D048 AA06 AB02 BA01Y BA02Y BA03Y BA06Y BA07X BA08X BA14X BA15X BA16Y BA18Y BA19X BA23Y BA25Y BA28Y BA30X BA31Y BA32Y BA33Y BA35Y BA36Y BA37Y BA38Y BA41Y BA42X BA44Y BB01 BC01 EA04 4G069 AA03 AA08 BA01A BA01B BA02A BA04A BA04B BA05B BA21C BB02A BB02B BB04A BB06A BB06B BC01A BC02A BC03A BC03B BC04A BC04B BC06A BC08A BC09A BC10A BC12A BC13A BC13B BC16A BC29A BC32A BC35A BC38A BC39A BC40A BC42A BC43A BC43B BC44A BC49A BC50A BC50B BC51A BC51B BC54A BC58A BC62A BC66A BC67A BC68A BC69A BC75B BD05A BD07A BE08C CA02 CA03 CA08 CA13 ED07 FA01 FA02 FB09 FB14 FB19 FB30 FC04─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI Theme Coat (reference) F01N 3/10 B01D 53/36 102B (72) Inventor Naoki Takahashi Nagakute-cho, Aichi-gun, Aichi Prefecture 41 Address 1 Toyota Central Research Laboratory F-term (reference) 3G091 AB06 BA14 BA39 GB02Y GB03Y GB04Y GB05W 4D048 AA06 AB02 BA01Y BA02Y BA03Y BA06Y BA07X BA08X BA14X BA15X BA16Y BA18Y BA38Y BA42YBA32 BA36Y BA32YBA30 BA32Y BA30X BA31Y BA44Y BB01 BC01 EA04 4G069 AA03 AA08 BA01A BA01B BA02A BA04A BA04B BA05B BA21C BB02A BB02B BB04A BB06A BB06B BC01A BC02A BC03A BC03B BC04A BC04B BC06A BC08A BC09A BC10A BC12A BC13A BC13B BC16A BC29A BC32A BC35A BC38A BC39A BC40A BC42A BC43A BC43B BC44A BC49A BC50A BC50B BC51A BC51B BC54A BC58A BC62A BC66A BC67A BC68A BC69A BC75B BD05 A BD07A BE08C CA02 CA03 CA08 CA13 ED07 FA01 FA02 FB09 FB14 FB19 FB30 FC04
Claims (13)
土類金属からなる群より選ばれる少なくとも１種を含有
する第１の化合物と、第３族元素、第４族元素及び遷移
金属元素からなる群より選ばれる少なくとも１種を含有
する第２の化合物と、多座配位子を有する第３の化合物
とを含有する溶液をゲル化させる工程と、得られたゲル
を焼成して複合材料を得る工程とを含むことを特徴とす
る複合材料の製造方法。1. A first compound containing at least one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, and a group consisting of Group 3 elements, Group 4 elements and transition metal elements. A step of gelling a solution containing a second compound containing at least one selected and a third compound having a polydentate ligand, and a step of firing the obtained gel to obtain a composite material A method of manufacturing a composite material, comprising:
合物であることを特徴とする、請求項１に記載の複合材
料の製造方法。2. The method for producing a composite material according to claim 1, wherein the second compound is a compound containing titanium.
化合物であることを特徴とする、請求項１又は２に記載
の複合材料の製造方法。3. The method for producing a composite material according to claim 1, wherein the first compound is a barium-containing compound.
を特徴とする、請求項１〜３のうちのいずれか一項に記
載の複合材料の製造方法。4. The method for producing a composite material according to claim 1, wherein the third compound is citric acid.
載の製造方法で得られたことを特徴とする複合材料。5. A composite material obtained by the manufacturing method according to any one of claims 1 to 4.
触させて、該複合材料にＮＯｘを吸蔵させることを特徴
とするＮＯｘ吸蔵方法。6. A NOx storage method, wherein NOx is stored in the composite material by bringing NOx into contact with the composite material according to claim 5.
有する溶液を接触させて、該複合材料に該貴金属を担持
させる工程と、前記貴金属を担持した前記複合材料を焼
成して触媒を得る工程とを含むことを特徴とする触媒の
製造方法。7. A step of bringing a solution containing a noble metal into contact with the composite material according to claim 5 to support the noble metal on the composite material, and calcining the composite material carrying the noble metal to form a catalyst. And a step of obtaining the catalyst.
土類金属からなる群より選ばれる少なくとも１種を含有
する第１の化合物と、第３族元素、第４族元素及び遷移
金属元素からなる群より選ばれる少なくとも１種を含有
する第２の化合物と、多座配位子を有する第３の化合物
とを含有する溶液を担体と接触させて、該担体に該第
１、第２及び第３の化合物を担持させる工程と、貴金属
を含有する溶液を前記担体に接触させて、該担体に該貴
金属を担持する工程と前記第１、第２及び第３の化合物
並びに前記貴金属を担持した前記担体を焼成して触媒を
得る工程とを含むことを特徴とする触媒の製造方法。8. A first compound containing at least one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, and a group consisting of Group 3 elements, Group 4 elements and transition metal elements. A solution containing a second compound containing at least one selected from the above and a third compound having a polydentate ligand is brought into contact with a carrier to allow the carrier to contain the first, second and third compounds. A step of supporting a compound; a step of bringing a solution containing a noble metal into contact with the carrier to carry the noble metal on the carrier; and a step of carrying the first, second and third compounds and the noble metal. And a step of obtaining the catalyst by calcination.
合物であることを特徴とする、請求項８に記載の触媒の
製造方法。9. The method for producing a catalyst according to claim 8, wherein the second compound is a compound containing titanium.
る化合物であることを特徴とする、請求項８又は９に記
載の触媒の製造方法。10. The method for producing a catalyst according to claim 8, wherein the first compound is a barium-containing compound.
とを特徴とする、請求項８〜１０のうちのいずれか一項
に記載の触媒の製造方法。11. The method for producing a catalyst according to claim 8, wherein the third compound is citric acid.
に記載の製造方法によって得られたことを特徴とする触
媒。12. A catalyst obtained by the method according to any one of claims 7 to 11.
触させて、該触媒にＮＯｘを吸蔵させて還元することを
特徴とするＮＯｘ吸蔵還元方法。13. A NOx occlusion reduction method characterized by bringing the catalyst according to claim 12 into contact with NOx to cause the catalyst to occlude and reduce NOx.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060147A (en) * | 2003-08-08 | 2005-03-10 | Toyota Central Res & Dev Lab Inc | AQUEOUS SOLUTION OF COMPOUND OXIDE PRECURSOR AND METHOD FOR CARRYING NOx OCCLUSION MATERIAL |
| JP2006175299A (en) * | 2004-12-20 | 2006-07-06 | Toyota Central Res & Dev Lab Inc | Nox occlusion material, its carrying method and nox occlusion reduction type catalyst |
| JP2008012501A (en) * | 2006-07-10 | 2008-01-24 | Toyota Motor Corp | METHOD FOR CARRYING NOx OCCLUSION MATERIAL |
| JP2008137886A (en) * | 2006-11-08 | 2008-06-19 | Toyota Central R&D Labs Inc | Oxide composite precursor aqueous solution, method of manufacturing oxide composite, oxide composite, exhaust cleaning catalyst provided with the oxide composite, and method of cleaning exhaust using the exhaust cleaning catalyst |
| JP2008178811A (en) * | 2007-01-25 | 2008-08-07 | Toyota Central R&D Labs Inc | Aqueous solution of composite particle precursor and method for manufacturing composite particle using the same |
| WO2013128261A3 (en) * | 2012-03-02 | 2013-12-27 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas control apparatus, exhaust gas control method and exhaust gas purification catalyst |
| JP2019210260A (en) * | 2018-06-08 | 2019-12-12 | 株式会社豊田中央研究所 | Methane production apparatus, control method of methane production apparatus, and methane production method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060147A (en) * | 2003-08-08 | 2005-03-10 | Toyota Central Res & Dev Lab Inc | AQUEOUS SOLUTION OF COMPOUND OXIDE PRECURSOR AND METHOD FOR CARRYING NOx OCCLUSION MATERIAL |
| JP4599817B2 (en) * | 2003-08-08 | 2010-12-15 | 株式会社豊田中央研究所 | Method for supporting NOx storage material |
| JP2006175299A (en) * | 2004-12-20 | 2006-07-06 | Toyota Central Res & Dev Lab Inc | Nox occlusion material, its carrying method and nox occlusion reduction type catalyst |
| JP4534749B2 (en) * | 2004-12-20 | 2010-09-01 | 株式会社豊田中央研究所 | NOx storage material, method for supporting the same, and NOx storage reduction catalyst |
| JP2008012501A (en) * | 2006-07-10 | 2008-01-24 | Toyota Motor Corp | METHOD FOR CARRYING NOx OCCLUSION MATERIAL |
| JP2008137886A (en) * | 2006-11-08 | 2008-06-19 | Toyota Central R&D Labs Inc | Oxide composite precursor aqueous solution, method of manufacturing oxide composite, oxide composite, exhaust cleaning catalyst provided with the oxide composite, and method of cleaning exhaust using the exhaust cleaning catalyst |
| JP2008178811A (en) * | 2007-01-25 | 2008-08-07 | Toyota Central R&D Labs Inc | Aqueous solution of composite particle precursor and method for manufacturing composite particle using the same |
| WO2013128261A3 (en) * | 2012-03-02 | 2013-12-27 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas control apparatus, exhaust gas control method and exhaust gas purification catalyst |
| JP2019210260A (en) * | 2018-06-08 | 2019-12-12 | 株式会社豊田中央研究所 | Methane production apparatus, control method of methane production apparatus, and methane production method |
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