JPH04265155A - Catalyst for purification of exhaust gas - Google Patents
Catalyst for purification of exhaust gasInfo
- Publication number
- JPH04265155A JPH04265155A JP3023445A JP2344591A JPH04265155A JP H04265155 A JPH04265155 A JP H04265155A JP 3023445 A JP3023445 A JP 3023445A JP 2344591 A JP2344591 A JP 2344591A JP H04265155 A JPH04265155 A JP H04265155A
- Authority
- JP
- Japan
- Prior art keywords
- cat
- alumina
- layer
- cerium
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000000746 purification Methods 0.000 title description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 124
- 229910052751 metal Inorganic materials 0.000 claims abstract description 85
- 239000002184 metal Substances 0.000 claims abstract description 85
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 21
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- 229910052684 Cerium Inorganic materials 0.000 claims description 24
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000010948 rhodium Substances 0.000 claims description 23
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 239000010410 layer Substances 0.000 abstract description 98
- 239000011888 foil Substances 0.000 abstract description 36
- 229930195733 hydrocarbon Natural products 0.000 abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 8
- 239000011247 coating layer Substances 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 238000004299 exfoliation Methods 0.000 abstract 1
- 230000000452 restraining effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 40
- 238000000576 coating method Methods 0.000 description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
- 229910052746 lanthanum Inorganic materials 0.000 description 28
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 26
- 229910052791 calcium Inorganic materials 0.000 description 26
- 239000011575 calcium Substances 0.000 description 26
- 239000002002 slurry Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 19
- 229910052759 nickel Inorganic materials 0.000 description 16
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 229910052726 zirconium Inorganic materials 0.000 description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 13
- 229910052700 potassium Inorganic materials 0.000 description 13
- 239000011591 potassium Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- 229910052788 barium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 4
- 239000001639 calcium acetate Substances 0.000 description 4
- 235000011092 calcium acetate Nutrition 0.000 description 4
- 229960005147 calcium acetate Drugs 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- -1 rare earth compounds Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、排気ガス浄化用触媒に
関するものである。更に詳しくは、金属製ハニカム担体
触媒を使用する自動車等の内燃機関からの排気ガス中に
含まれる有害成分である炭化水素（ＨＣ）、一酸化炭素
（ＣＯ）および窒素酸化物（ＮＯＸ ）を浄化し、かつ
金属製ハニカム担体の基材である金属箔の伸びを抑制す
る排気ガス浄化用触媒に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for purifying exhaust gas. More specifically, a metal honeycomb carrier catalyst is used to purify harmful components such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOX) contained in exhaust gas from internal combustion engines such as automobiles. The present invention also relates to an exhaust gas purifying catalyst that suppresses the elongation of metal foil, which is the base material of a metal honeycomb carrier.
【０００２】0002
【従来の技術】従来、自動車のような内燃機関から排出
される排気ガスの浄化用触媒は、多数提案されており、
現在では、炭化水素（ＨＣ）、一酸化炭素（ＣＯ）およ
び窒素酸化物（ＮＯＸ ）を同時に浄化する三元触媒が
主流になっている。[Prior Art] Conventionally, many catalysts for purifying exhaust gas emitted from internal combustion engines such as automobiles have been proposed.
Currently, three-way catalysts that simultaneously purify hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOX) have become mainstream.
【０００３】上記の三元触媒は、アルミナ、アルミナー
シリカ、シリカ等の耐火性無機酸化物粉体に、白金（Ｐ
ｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）等の触媒
成分を単独あるいは組み合わせて分散担持してなる触媒
組成物をコージェライトや金属製等のハニカム担体に被
覆せしめてなるものや、コージェライトや金属製等のハ
ニカム担体にアルミナ、アルミナーシリカ、シリカ等の
耐火性無機酸化物を被覆した後、該担体を、白金（Ｐｔ
）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）等の触媒成
分を単独あるいは組み合わせてなる水溶液に浸漬せしめ
てなるものが一般的である。[0003] The above three-way catalyst is a refractory inorganic oxide powder such as alumina, alumina-silica, or silica, and platinum (P).
t), catalyst components such as palladium (Pd), rhodium (Rh), etc., singly or in combination, are coated on a honeycomb carrier made of cordierite or metal, etc.; After coating a honeycomb carrier made of metal or the like with a refractory inorganic oxide such as alumina, alumina-silica, or silica, the carrier is coated with platinum (Pt).
), palladium (Pd), rhodium (Rh), and other catalyst components, either alone or in combination, are immersed in an aqueous solution.
【０００４】さらに、触媒成分の白金（Ｐｔ）、パラジ
ウム（Ｐｄ）、ロジウム（Ｒｈ）等に該触媒成分の触媒
作用を促進させたり、安定化させるためセリウム、ラン
タン等の希土類化合物、ニッケル、鉄等の第ＶＩＩＩ族
化合物、アルカリ金属化合物、アルカリ土類化合物など
から選ばれたものが、助触媒成分として触媒組成物に添
加されている。Furthermore, rare earth compounds such as cerium, lanthanum, nickel, iron, etc. are added to the catalyst components such as platinum (Pt), palladium (Pd), and rhodium (Rh) to promote or stabilize the catalytic action of the catalyst components. A compound selected from Group VIII compounds, alkali metal compounds, alkaline earth compounds, etc., is added to the catalyst composition as a cocatalyst component.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、このよ
うな触媒のうち金属製のハニカム担体は、高温時の金属
製担体とアルミナ等の耐火性無機酸化物との熱膨張の違
いなどにより、金属製のハニカム担体の基材である金属
箔上の耐火性無機酸化物が剥離し、触媒性能が低下する
という問題点があった。[Problems to be Solved by the Invention] However, among such catalysts, the metal honeycomb carrier is difficult to use due to the difference in thermal expansion between the metal carrier and the refractory inorganic oxide such as alumina at high temperatures. There was a problem in that the refractory inorganic oxide on the metal foil, which is the base material of the honeycomb carrier, peeled off and the catalyst performance deteriorated.
【０００６】本発明の目的は、高温時に金属箔の伸びを
抑制し、金属箔上の耐火性無機酸化物の剥離がなく、炭
化水素（ＨＣ）、一酸化炭素（ＣＯ）および窒素酸化物
（ＮＯＸ ）を同時に浄化する三元触媒を提供するもの
である。The object of the present invention is to suppress the elongation of metal foil at high temperatures, prevent the peeling of refractory inorganic oxides on the metal foil, and prevent the removal of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides ( This provides a three-way catalyst that simultaneously purifies NOx).
【０００７】[0007]
【課題を解決するための手段】本発明の排ガス浄化用触
媒は、金属製ハニカム担体基材に二層以上のアルミナ層
を形成し、該アルミナ層中に、セリウムと、白金、パラ
ジウム、ロジウムの一種以上を含有する触媒に於いて、
金属製ハニカム担体基材と接触する一層目がセリウムを
含まないことを特徴とする排ガス浄化用触媒である。[Means for Solving the Problems] The exhaust gas purifying catalyst of the present invention has two or more alumina layers formed on a metal honeycomb carrier base material, and contains cerium, platinum, palladium, and rhodium in the alumina layer. In catalysts containing one or more types of
This is an exhaust gas purifying catalyst characterized in that the first layer in contact with a metal honeycomb carrier base material does not contain cerium.
【０００８】金属製ハニカム担体基材と接触する一層目
のアルミナ層のコート量は、１０〜１２０ｇ／ｌ−ｃａ
ｔであることが好ましい。また一層目のアルミナコート
層中に、カリウム、カルシウム、ストロンチウム、バリ
ウム等アルカリ金属およびアルカリ土類金属から選ばれ
た一種以上の金属を添加することにより、基材とアルミ
ナ層との密着性を向上させることができる。該金属の添
加量を０．２ｍｏｌ／ｌ−ｃａｔまでにすることが好ま
しい。０．２ｍｏｌ／ｌ−ｃａｔを越えて添加しても効
果が少ない。[0008] The coating amount of the first alumina layer in contact with the metal honeycomb carrier base material is 10 to 120 g/l-ca.
It is preferable that it is t. In addition, by adding one or more metals selected from alkali metals and alkaline earth metals such as potassium, calcium, strontium, and barium to the first alumina coating layer, the adhesion between the base material and the alumina layer is improved. can be done. It is preferable that the amount of the metal added is 0.2 mol/l-cat or less. Even if it is added in excess of 0.2 mol/l-cat, there is little effect.
【０００９】更に、金属製ハニカム担体基材と接触する
一層目のアルミナ層中に、触媒作用の促進安定化のため
にランタン、ニッケル、鉄、ジルコニウムから選ばれた
一種以上を添加しても差支えない。Furthermore, it is acceptable to add one or more selected from lanthanum, nickel, iron, and zirconium to the first alumina layer in contact with the metal honeycomb carrier base material in order to promote and stabilize the catalytic action. do not have.
【００１０】0010
【作用】箔の伸びを抑制するメカニズムは明らかでない
が、金属製ハニカム担体基材と接触する一層目のアルミ
ナ層にセリウムが含まれていないため、金属箔の伸びが
抑制されると思われる。また、金属製ハニカム担体基材
と接触する一層目のアルミナ中にカリウム、カルシウム
、ストロンチウム、バリウム等アルカリ金属およびアル
カリ土類金属から選ばれた一種以上を含む層でコートす
ることにより、金属製ハニカム担体基材の箔とアルミナ
のコート層の密着性を向上させ、箔の伸びを抑える事が
できると思われる。[Operation] Although the mechanism for suppressing the elongation of the foil is not clear, it is thought that the elongation of the metal foil is suppressed because the first alumina layer that contacts the metal honeycomb carrier base material does not contain cerium. In addition, by coating the first layer of alumina in contact with the metal honeycomb carrier base material with a layer containing one or more selected from alkali metals and alkaline earth metals such as potassium, calcium, strontium, and barium, metal honeycomb It is thought that it is possible to improve the adhesion between the foil of the carrier base material and the alumina coating layer, and to suppress the elongation of the foil.
【００１１】[0011]
【実施例】以下に、本発明の実施例について説明する。 実施例１[Examples] Examples of the present invention will be described below. Example 1
【００１２】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるメタルハニカム担体に使
用する平板の金属箔に、γ−アルミナ粉末とアルミナ水
和物と水からなるスラリーをコート後、乾燥した。次に
、アルミナコートした担体にセリウム−ジルコニウムの
複合酸化物粉末と炭酸ランタン粉末とγ−アルミナ粉末
とアルミナ水和物と水からなるスラリーをコート、乾燥
後、６５０℃で１時間焼成して金属箔の一層目にアルミ
ナ層、二層目にセリウム−ジルコニウム、ランタンを含
有するアルミナ層を形成した。（コートＡ）[0012] γ-alumina powder, alumina hydrate, and water are added to the flat metal foil used for the metal honeycomb carrier, which is made by stacking a metal flat plate and a corrugated plate and winding them multiple times to form a core part. After coating with a slurry consisting of, it was dried. Next, the alumina-coated carrier was coated with a slurry consisting of cerium-zirconium composite oxide powder, lanthanum carbonate powder, γ-alumina powder, alumina hydrate, and water, and after drying, it was fired at 650°C for 1 hour to form a metal An alumina layer was formed as the first layer of the foil, and an alumina layer containing cerium-zirconium and lanthanum was formed as the second layer. (Coat A)
【００１３
】金属製の平板と波板とを重ね、これを多重に巻回しコ
ア部を形成してなるφ８０×１０５Ｌ（５２８ｃｃ）の
メタルハニカム担体に上記平板にコートした方法で一層
目にアルミナコート量６０ｇ／ｌ−ｃａｔ、二層目にア
ルミナコート量６０ｇ／ｌ−ｃａｔ、セリウム０．２５
ｍｏｌ／ｌ−ｃａｔ、ジルコニウム０．０５ｍｏｌ／ｌ
−ｃａｔ、ランタン０．１ｍｏｌ／ｌ−ｃａｔを含有す
るアルミナ層を形成した。0013
] A metal honeycomb carrier with a diameter of 80 x 105 L (528 cc), which is made by stacking a metal flat plate and a corrugated plate and winding them multiple times to form a core part, was coated with the above flat plate, and the amount of alumina coated in the first layer was 60 g. /l-cat, second layer alumina coating amount 60g/l-cat, cerium 0.25
mol/l-cat, zirconium 0.05mol/l
-cat, and an alumina layer containing 0.1 mol/l-cat of lanthanum was formed.
【００１４】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒１を得た。
実施例２The carrier thus obtained was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 1. Example 2
【００１５】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるメタルハニカム担体に使
用する平板の金属箔に、γ−アルミナ粉末とアルミナ水
和物と水からなるスラリーをコート後、乾燥した。次に
、該担体を酢酸カリウム溶液に含漬して、カリウムを担
持した。[0015] γ-alumina powder, alumina hydrate, and water are added to the flat metal foil used for the metal honeycomb carrier, which is made by stacking a metal flat plate and a corrugated plate and winding them multiple times to form a core part. After coating with a slurry consisting of, it was dried. Next, the carrier was immersed in a potassium acetate solution to support potassium.
【００１６】次に、カリウムを担持した担体に、セリウ
ム−ジルコニウムの複合酸化物粉末、炭酸ランタン粉末
とγ−アルミナ粉末とアルミナ水和物と水からなるスラ
リーをコート、乾燥後、６５０℃で１時間焼成して金属
箔の一層目にカリウム、二層目にセリウム−ジルコニウ
ム、ランタンを含有するアルミナ層を形成した。（コー
トＢ）Next, the carrier carrying potassium was coated with a slurry consisting of cerium-zirconium composite oxide powder, lanthanum carbonate powder, γ-alumina powder, alumina hydrate, and water, and after drying, it was heated at 650°C for 1 hour. The metal foil was fired for a period of time to form an alumina layer containing potassium in the first layer and cerium-zirconium and lanthanum in the second layer. (Court B)
【００１７】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるφ８０×１０５Ｌ（５２
８ｃｃ）のメタルハニカム担体に上記平板にコートした
方法で一層目にアルミナコート量６０ｇ／ｌ−ｃａｔ、
カリウム０．０５ｍｏｌ／ｌ−ｃａｔ、二層目にアルミ
ナコート量６０ｇ／ｌ−ｃａｔ、セリウム０．２５ｍｏ
ｌ／ｌ−ｃａｔ、ジルコニウム０．０５ｍｏｌ／ｌ−ｃ
ａｔ、ランタン０．１ｍｏｌ／ｌ−ｃａｔを含有するア
ルミナ層を形成した。[0017] φ80×105L (52
The first layer was coated with alumina in an amount of 60 g/l-cat on a metal honeycomb carrier of 8 cc) using the above flat plate coating method.
Potassium 0.05mol/l-cat, second layer alumina coating amount 60g/l-cat, cerium 0.25mo
l/l-cat, zirconium 0.05mol/l-c
At, an alumina layer containing 0.1 mol/l-cat of lanthanum was formed.
【００１８】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒２を得た。
実施例３The carrier obtained in this way was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 2. Example 3
【００１９】実施例１と同様のメタルハニカム担体の平
板の金属箔に、γ−アルミナ粉末とアルミナ水和物と水
からなるスラリーをコート後、乾燥した。次に、該担体
を酢酸カルシウム溶液に含浸して、カルシウムを担持し
た。A flat metal foil of the same metal honeycomb carrier as in Example 1 was coated with a slurry consisting of γ-alumina powder, alumina hydrate, and water, and then dried. Next, the carrier was impregnated with a calcium acetate solution to support calcium.
【００２０】次に、カルシウムを担持した担体に、セリ
ウム−ジルコニウムの複合酸化物粉末、炭酸ランタン粉
末、酸化ニッケル粉末、γ−アルミナ粉末とアルミナ水
和物および水からなるスラリーをコート、乾燥後、６５
０℃で１時間焼成して金属箔の一層目にカルシウム、二
層目にセリウム−ジルコニウム、ランタン、ニッケルを
含有するアルミナ層を形成した。（コートＣ）Next, the carrier supporting calcium was coated with a slurry consisting of cerium-zirconium composite oxide powder, lanthanum carbonate powder, nickel oxide powder, γ-alumina powder, alumina hydrate, and water, and after drying, 65
By firing at 0° C. for 1 hour, the first layer of the metal foil was formed with calcium, and the second layer was formed with an alumina layer containing cerium-zirconium, lanthanum, and nickel. (Court C)
【００２
１】金属製の平板と波板とを重ね、これを多重に巻回し
コア部を形成してなるφ８０×１０５Ｌ（５２８ｃｃ）
のメタルハニカム担体に上記平板にコートした方法で一
層目にアルミナコート量６０ｇ／ｌ−ｃａｔ、カルシウ
ム０．０５ｍｏｌ／ｌ−ｃａｔを、二層目にアルミナコ
ート量６０ｇ／ｌ−ｃａｔ、セリウム０．２５ｍｏｌ／
ｌ−ｃａｔ、ジルコニウム０．０５ｍｏｌ／ｌ−ｃａｔ
、ランタン０．１ｍｏｌ／ｌ−ｃａｔ、ニッケル０．０
５ｍｏｌ／ｌ−ｃａｔを含有するアルミナ層を形成した
。002
1] φ80 x 105L (528cc) made by stacking a metal flat plate and a corrugated plate and winding them multiple times to form a core part.
The above flat plate was coated on a metal honeycomb carrier.The first layer was coated with alumina of 60 g/l-cat and calcium 0.05 mol/l-cat, and the second layer was coated with alumina of 60 g/l-cat and cerium 0. 25mol/
l-cat, zirconium 0.05 mol/l-cat
, lanthanum 0.1mol/l-cat, nickel 0.0
An alumina layer containing 5 mol/l-cat was formed.
【００２２】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒３を得た。
実施例４The carrier thus obtained was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 3. Example 4
【００２３】実施例１と同様のメタルハニカム担体の平
板の金属箔に、γ−アルミナ粉末とアルミナ水和物と水
からなるスラリーをコート後、乾燥した。次に、該担体
を硝酸ストロンチウム溶液に含浸して、ストロンチウム
を担持した。A flat metal foil of the same metal honeycomb carrier as in Example 1 was coated with a slurry consisting of γ-alumina powder, alumina hydrate, and water, and then dried. Next, the carrier was impregnated with a strontium nitrate solution to support strontium.
【００２４】次に、ストロンチウムを担持した担体にセ
リウム−ジルコニウムの複合酸化物粉末、炭酸ランタン
粉末、酸化鉄粉末、γ−アルミナ粉末とアルミナ水和物
および水からなるスラリーをコート、乾燥後、６５０℃
で１時間焼成して金属箔の一層目にストロンチウム、二
層目にセリウム−ジルコニウム、ランタン、鉄を含有す
るアルミナ層を形成した。（コートＤ）Next, the carrier supporting strontium was coated with a slurry consisting of cerium-zirconium composite oxide powder, lanthanum carbonate powder, iron oxide powder, γ-alumina powder, alumina hydrate, and water, and after drying, ℃
The metal foil was fired for 1 hour to form a first layer of strontium and a second layer of alumina containing cerium-zirconium, lanthanum, and iron. (Court D)
【００２５】金
属製の平板と波板とを重ね、これを多重に巻回しコア部
を形成してなるφ８０×１０５Ｌ（５２８ｃｃ）のメタ
ルハニカム担体に上記平板にコートした方法で一層目に
アルミナコート量６０ｇ／ｌ−ｃａｔ、ストロンチウム
０．０５ｍｏｌ／ｌ−ｃａｔ、二層目にアルミナコート
量６０ｇ／ｌ−ｃａｔ、セリウム０．２５ｍｏｌ／ｌ−
ｃａｔ、ジルコニウム０．０５ｍｏｌ／ｌ−ｃａｔ、ラ
ンタン０．１ｍｏｌ／ｌ−ｃａｔ、鉄０．０５ｍｏｌ／
ｌ−ｃａｔを含有するアルミナ層を形成した。 この
ようにして得た担体を、ジニトロジアンミン白金溶液と
硝酸ロジウム溶液に含漬し、白金、ロジウムをそれぞれ
１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ−ｃａｔ担持して
触媒４を得た。
実施例５[0025] A metal honeycomb carrier with a diameter of 80 x 105 L (528 cc), which is made by stacking a metal flat plate and a corrugated plate and winding them multiple times to form a core part, is coated with alumina as the first layer by the method of coating the flat plate. Amount 60g/l-cat, strontium 0.05mol/l-cat, second layer alumina coating amount 60g/l-cat, cerium 0.25mol/l-
cat, zirconium 0.05 mol/l-cat, lanthanum 0.1 mol/l-cat, iron 0.05 mol/l-cat
An alumina layer containing l-cat was formed. The support thus obtained was immersed in a dinitrodiammine platinum solution and a rhodium nitrate solution to support platinum and rhodium at 1.2 g/l-cat and 0.2 g/l-cat, respectively, to obtain catalyst 4. . Example 5
【００２６】実施例１と同様のメタルハニカム担体の平
板の金属箔に、γ−アルミナ粉末とアルミナ水和物およ
び水からなるスラリーをコート後、乾燥した。次に、該
担体を硝酸バリウム溶液に含漬して、バリウムを担持し
た。A flat metal foil of the same metal honeycomb carrier as in Example 1 was coated with a slurry consisting of γ-alumina powder, alumina hydrate, and water, and then dried. Next, the carrier was immersed in a barium nitrate solution to support barium.
【００２７】次に、バリウムを担持した担体にセリウム
−ジルコニウムの複合酸化物粉末、炭酸ランタン粉末、
酸化鉄粉末、γ−アルミナ粉末とアルミナ水和物および
水からなるスラリーをコート、乾燥後、６５０℃で１時
間焼成して金属箔の一層目にバリウム、二層目にセリウ
ム−ジルコニウム、ランタン、鉄を含有するアルミナ層
を形成した。（コートＥ）Next, cerium-zirconium composite oxide powder, lanthanum carbonate powder,
A slurry consisting of iron oxide powder, γ-alumina powder, alumina hydrate, and water is coated, dried, and fired at 650°C for 1 hour to form barium on the first layer of the metal foil, cerium-zirconium, lanthanum, and lanthanum on the second layer. An alumina layer containing iron was formed. (Court E)
【００２８】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるφ８０×１０５Ｌ（５２
８ｃｃ）のメタルハニカム担体に上記平板にコートした
方法で一層目にアルミナコート量６０ｇ／ｌ−ｃａｔ、
バリウム０．０５ｍｏｌ／ｌ−ｃａｔを、二層目にアル
ミナコート層６０ｇ／ｌ−ｃａｔ、セリウム０．２５ｍ
ｏｌ／ｌ−ｃａｔ、ジルコニウム０．０５ｍｏｌ／ｌ−
ｃａｔ、ランタン０．１ｍｏｌ／ｌ−ｃａｔ、鉄０．０
５ｍｏｌ／ｌ−ｃａｔを含有するアルミナ層を形成した
。[0028] φ80×105L (52
The first layer was coated with alumina in an amount of 60 g/l-cat on a metal honeycomb carrier of 8 cc) using the above flat plate coating method.
Barium 0.05mol/l-cat, second layer alumina coat layer 60g/l-cat, cerium 0.25m
ol/l-cat, zirconium 0.05mol/l-
cat, lanthanum 0.1mol/l-cat, iron 0.0
An alumina layer containing 5 mol/l-cat was formed.
【００２９】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒５を得た。
実施例６The carrier obtained in this way was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 5. Example 6
【００３０】実施例１と同様のメタルハニカム担体の平
板の金属箔に、α−アルミナ粉末とアルミナ水和物およ
び水からなるスラリーをコート後、乾燥した。次に、該
担体を酢酸カリウムと酢酸カルシウム溶液に含漬して、
カリウムとカルシウムを担持した。A flat metal foil of a metal honeycomb carrier similar to that in Example 1 was coated with a slurry consisting of α-alumina powder, alumina hydrate, and water, and then dried. Next, the carrier is immersed in a potassium acetate and calcium acetate solution,
Loaded with potassium and calcium.
【００３１】次に、カリウムとカルシウムを担持した担
体に炭酸セリウム粉末と炭酸ランタン粉末とγ−アルミ
ナ粉末とアルミナ水和物および水からなるスラリーをコ
ート、乾燥後、６５０℃で１時間焼成して金属箔の一層
目にカリウム、カルシウム、二層目にセリウム、ランタ
ンを含有するアルミナ層を形成した。（コートＦ）Next, the carrier supporting potassium and calcium was coated with a slurry consisting of cerium carbonate powder, lanthanum carbonate powder, γ-alumina powder, alumina hydrate, and water, and after drying, it was calcined at 650°C for 1 hour. An alumina layer containing potassium and calcium was formed in the first layer of the metal foil, and an alumina layer containing cerium and lanthanum was formed in the second layer. (Court F)
【０
０３２】金属製の平板と波板とを重ね、これを多重に巻
回しコア部を形成してなるφ８０×１０５Ｌ（５２８ｃ
ｃ）のメタルハニカム担体に上記平板にコートした方法
で一層目にアルミナコート量６０ｇ／ｌ−ｃａｔ、カリ
ウム０．０５ｍｏｌ／ｌ−ｃａｔ、カルシウム０．０５
ｍｏｌ／ｌ−ｃａｔを、二層目にアルミナコート量６０
ｇ／ｌ−ｃａｔ、セリウム０．２５ｍｏｌ／ｌ−ｃａｔ
、ランタン０．１ｍｏｌ／ｌ−ｃａｔを含有するアルミ
ナ層を形成した。0
032] φ80×105L (528c
In the method of coating the above flat plate on the metal honeycomb carrier of c), the first layer was coated with alumina in an amount of 60 g/l-cat, potassium 0.05 mol/l-cat, and calcium 0.05.
mol/l-cat, alumina coating amount 60 in the second layer
g/l-cat, cerium 0.25mol/l-cat
, an alumina layer containing 0.1 mol/l-cat of lanthanum was formed.
【００３３】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒６を得た。
実施例７The carrier thus obtained was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 6. Example 7
【００３４】実施例１と同様のメタルハニカム担体の平
板の金属箔を、酢酸カリウムと酢酸カルシウム溶液と界
面活性剤を含有する溶液に含浸して、カリウムとカルシ
ウムを付着した。A flat metal foil of the same metal honeycomb carrier as in Example 1 was impregnated with a solution containing potassium acetate, a calcium acetate solution, and a surfactant to adhere potassium and calcium.
【００３５】次に、カリウムとカルシウムを付着した担
体にセリウム−ジルコニウムの複合酸化物粉末、炭酸ラ
ンタン粉末、酸化ニッケル粉末、γ−アルミナ粉末とア
ルミナ水和物および水からなるスラリーをコート、乾燥
後、６５０℃で１時間焼成して金属箔の一層目にバリウ
ム、二層目にセリウム−ジルコニウム、ランタン、ニッ
ケルを含有するアルミナ層を形成した。（コートＧ）Next, a slurry consisting of cerium-zirconium composite oxide powder, lanthanum carbonate powder, nickel oxide powder, γ-alumina powder, alumina hydrate, and water was coated on the carrier to which potassium and calcium had been attached, and after drying. The metal foil was fired at 650° C. for 1 hour to form barium in the first layer of the metal foil, and an alumina layer containing cerium-zirconium, lanthanum, and nickel in the second layer. (Court G)
【
００３６】金属製の平板と波板とを重ね、これを多重に
巻回しコア部を形成してなるφ８０×１０５Ｌ（５２８
ｃｃ）のメタルハニカム担体に上記平板にコートした方
法で一層目にアルミナコート量６０ｇ／ｌ−ｃａｔ、カ
リウム０．０５ｍｏｌ／ｌ−ｃａｔ、カルシウム０．０
５ｍｏｌ／ｌ−ｃａｔを、二層目にアルミナコート量６
０ｇ／ｌ−ｃａｔ、セリウム０．２５ｍｏｌ／ｌ−ｃａ
ｔ、ジルコニウム０．０５ｍｏｌ／ｌ−ｃａｔ、ランタ
ン０．１ｍｏｌ／ｌ−ｃａｔ、ニッケル０．０５ｍｏｌ
／ｌ−ｃａｔを含有するアルミナ層を形成した。[
[0036] A metal flat plate and a corrugated plate are stacked and wound in multiple layers to form a core part.
cc) metal honeycomb carrier was coated with the above flat plate, and the first layer was coated with alumina in an amount of 60 g/l-cat, potassium 0.05 mol/l-cat, and calcium 0.0.
5 mol/l-cat, alumina coating amount 6 in the second layer
0g/l-cat, cerium 0.25mol/l-ca
t, zirconium 0.05 mol/l-cat, lanthanum 0.1 mol/l-cat, nickel 0.05 mol
An alumina layer containing /l-cat was formed.
【００３７】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒７を得た。
実施例８The carrier thus obtained was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 7. Example 8
【００３８】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるφ８０×１０５Ｌ（５２
８ｃｃ）のメタルハニカム担体に実施例３と同様な方法
で一層目にカルシウム、二層目にセリウム−ジルコニウ
ム、ランタン、ニッケルを含有するアルミナ層を形成し
た。[0038] φ80×105L (52
An alumina layer containing calcium in the first layer and cerium-zirconium, lanthanum, and nickel was formed in the second layer on a 8 cc) metal honeycomb carrier in the same manner as in Example 3.
【００３９】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸パラジウムと硝酸ロジウム溶液に
含浸し、白金、パラジウム、ロジウムをそれぞれ０．４
ｇ／ｌ−ｃａｔ、０．８ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒８を得た。
実施例９The carrier thus obtained was impregnated with a dinitrodiammine platinum solution, palladium nitrate, and rhodium nitrate solution, and platinum, palladium, and rhodium were each added to a concentration of 0.4
g/l-cat, 0.8g/l-cat, 0.2g/l
-cat was supported to obtain catalyst 8. Example 9
【００４０】実施例３の一層目のアルミナコート量を２
０ｇ／ｌ−ｃａｔ、二層目のアルミナコート量を８０ｇ
／ｌ−ｃａｔにした以外は、実施例３と同様に行い触媒
９を得た。
実施例１０[0040] The amount of alumina coating in the first layer of Example 3 was 2
0g/l-cat, second layer alumina coating amount 80g
Catalyst 9 was obtained in the same manner as in Example 3 except that /l-cat was used. Example 10
【００４１】実施例３の一層目のアルミナコート量を４
０ｇ／ｌ−ｃａｔ、二層目のアルミナコート量を８０ｇ
／ｌ−ｃａｔにした以外は、実施例３と同様に行い触媒
１０を得た。
実施例１１[0041] The amount of alumina coating for the first layer in Example 3 was 4.
0g/l-cat, second layer alumina coating amount 80g
Catalyst 10 was obtained in the same manner as in Example 3 except that the catalyst was changed to /l-cat. Example 11
【００４２】実施例３の一層目のアルミナコート量を８
０ｇ／ｌ−ｃａｔ、二層目のアルミナコート量を６０ｇ
／ｌ−ｃａｔにした以外は、実施例３と同様に行い触媒
１１を得た。
実施例１２[0042] The amount of alumina coating in the first layer of Example 3 was 8
0g/l-cat, second layer alumina coating amount 60g
Catalyst 11 was obtained in the same manner as in Example 3 except that the catalyst was changed to /l-cat. Example 12
【００４３】実施例３の一層目のアルミナコート量を１
００ｇ／ｌ−ｃａｔ、二層目のアルミナコート量を６０
ｇ／ｌ−ｃａｔにした以外は、実施例３と同様に行い触
媒１２を得た。
実施例１３実施例３のカルシウムの担持量を０．１ｍｏ
ｌ／ｌ−ｃａｔにした以外は、実施例３と同様に行い触
媒１３を得た。
実施例１４実施例３のカルシウムの担持量を０．１５ｍ
ｏｌ／ｌ−ｃａｔにした以外は、実施例３と同様に行い
触媒１４を得た。
実施例１５実施例３のカルシウムの担持量を０．２ｍｏ
ｌ／ｌ−ｃａｔにした以外は、実施例３と同様に行い触
媒１５を得た。
実施例１６[0043] The amount of alumina coating for the first layer in Example 3 was 1
00g/l-cat, second layer alumina coating amount 60
Catalyst 12 was obtained in the same manner as in Example 3 except that g/l-cat was used. Example 13 The amount of calcium supported in Example 3 was 0.1 mo.
Catalyst 13 was obtained in the same manner as in Example 3 except that 1/1-cat was used. Example 14 The amount of calcium supported in Example 3 was 0.15 m
Catalyst 14 was obtained in the same manner as in Example 3 except that ol/l-cat was used. Example 15 The amount of calcium supported in Example 3 was 0.2 mo.
Catalyst 15 was obtained in the same manner as in Example 3 except that 1/1-cat was used. Example 16
【００４４】実施例３の二層目に酸化カルシウム粉末を
加えたスラリーをコートした以外は、実施例３と同様に
行い、一層目にアルミナコート層６０ｇ／ｌ−ｃａｔ、
カルシウム０．０５ｍｏｌ／ｌ−ｃａｔを、二層目にア
ルミナコート量６０ｇ／ｌ−ｃａｔ、セリウム０．２５
ｍｏｌ／ｌ−ｃａｔ、ジルコニウム０．０５ｍｏｌ／ｌ
−ｃａｔ、ランタン０．１ｍｏｌ／ｌ−ｃａｔ、ニッケ
ル０．０５ｍｏｌ／ｌ−ｃａｔ、カルシウム０．０５ｍ
ｏｌ／ｌ−ｃａｔを含有するアルミナ層を形成した。The same procedure as in Example 3 was carried out except that the second layer of Example 3 was coated with a slurry containing calcium oxide powder, and the first layer was coated with an alumina coating layer of 60 g/l-cat.
Calcium 0.05mol/l-cat, second layer alumina coating amount 60g/l-cat, cerium 0.25
mol/l-cat, zirconium 0.05mol/l
-cat, lanthanum 0.1mol/l-cat, nickel 0.05mol/l-cat, calcium 0.05m
An alumina layer containing ol/l-cat was formed.
【００４５】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒１６を得た。
実施例１７The carrier thus obtained was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 16. Example 17
【００４６】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるメタルハニカム担体に使
用する平板の金属箔に、γ−アルミナ粉末と炭酸ランタ
ン粉末、アルミナ水和物および水からなるスラリーをコ
ート後、乾燥した。[0046] γ-alumina powder, lanthanum carbonate powder, and alumina water are added to the flat metal foil used for the metal honeycomb carrier, which is made by stacking a metal flat plate and a corrugated plate and winding them multiple times to form a core part. After coating with a slurry consisting of hydroxide and water, it was dried.
【００４７】次に、ランタンを含有したアルミナコート
担体にセリウム−ジルコニウムの複合酸化物粉末、酸化
ニッケル粉末、γ−アルミナ粉末とアルミナ水和物およ
び水からなるスラリーをコート、乾燥後、６５０℃で１
時間焼成して金属箔の一層目にランタン、二層目にセリ
ウム−ジルコニウム、ニッケルを含有するアルミナ層を
形成した。（コートＨ）Next, a slurry consisting of cerium-zirconium composite oxide powder, nickel oxide powder, γ-alumina powder, alumina hydrate, and water was coated on an alumina-coated carrier containing lanthanum, and after drying, the slurry was heated at 650°C. 1
The metal foil was fired for a time to form a lanthanum layer in the first layer and an alumina layer containing cerium-zirconium and nickel in the second layer. (Court H)
【００４８】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるφ８０×１０５Ｌ（５２
８ｃｃ）のメタルハニカム担体に上記平板にコートした
方法で一層目にアルミナコート量６０ｇ／ｌ−ｃａｔ、
ランタン０．０５ｍｏｌ／ｌ−ｃａｔを、二層目にアル
ミナコート量６０ｇ／ｌ−ｃａｔ、セリウム０．２５ｍ
ｏｌ／ｌ−ｃａｔ、ジルコニウム０．０５ｍｏｌ／ｌ−
ｃａｔ、ニッケル０．０５ｍｏｌ／ｌ−ｃａｔを含有す
るアルミナ層を形成した。[0048] φ80×105L (52
The first layer was coated with alumina in an amount of 60 g/l-cat on a metal honeycomb carrier of 8 cc) using the above flat plate coating method.
Lanthanum 0.05mol/l-cat, second layer coated with alumina 60g/l-cat, cerium 0.25m
ol/l-cat, zirconium 0.05mol/l-
An alumina layer containing 0.05 mol/l-cat of nickel and 0.05 mol/l-cat of nickel was formed.
【００４９】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒１７を得た。
実施例１８The carrier obtained in this way was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 17. Example 18
【００５０】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるメタルハニカム担体に使
用する平板の金属箔に、γ−アルミナ粉末と酸化ジルコ
ニウム粉末、アルミナ水和物および水からなるスラリー
をコート後、乾燥した。[0050] γ-alumina powder, zirconium oxide powder, and alumina water are added to the flat metal foil used for the metal honeycomb carrier, which is made by stacking a metal flat plate and a corrugated plate and winding them multiple times to form a core part. After coating with a slurry consisting of hydroxide and water, it was dried.
【００５１】次に、ジルコニウムを含有したアルミナコ
ート担体にセリウム−ジルコニウムの複合酸化物粉末、
酸化ニッケル粉末、γ−アルミナ粉末とアルミナ水和物
および水からなるスラリーをコート、乾燥後、６５０℃
で１時間焼成して金属箔の一層目にジルコニウム、二層
目にセリウム−ジルコニウム、ニッケルを含有するアル
ミナ層を形成した。（コートＩ）Next, cerium-zirconium composite oxide powder,
Coat with a slurry consisting of nickel oxide powder, γ-alumina powder, alumina hydrate, and water, and dry at 650°C.
The metal foil was fired for 1 hour to form a first layer of zirconium and a second layer of alumina containing cerium-zirconium and nickel. (Court I)
【００５２】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるφ８０×１０５Ｌ（５２
８ｃｃ）のメタルハニカム担体に上記平板にコートした
方法で一層目にアルミナコート量６０ｇ／ｌ−ｃａｔ、
ジルコニウム０．０５ｍｏｌ／ｌ−ｃａｔを、二層目に
アルミナコート量６０ｇ／ｌ−ｃａｔ、セリウム０．２
５ｍｏｌ／ｌ−ｃａｔ、ジルコニウム０．０５ｍｏｌ／
ｌ−ｃａｔ、ニッケル０．０５ｍｏｌ／ｌ−ｃａｔを含
有するアルミナ層を形成した。[0052] φ80×105L (52
The first layer was coated with alumina in an amount of 60 g/l-cat on a metal honeycomb carrier of 8 cc) using the above flat plate coating method.
Zirconium 0.05mol/l-cat, second layer alumina coating amount 60g/l-cat, cerium 0.2
5mol/l-cat, zirconium 0.05mol/
An alumina layer containing 1-cat and 0.05 mol/1-cat of nickel was formed.
【００５３】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒１８を得た。
比較例１The carrier thus obtained was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 18. Comparative example 1
【００５４】実施例１と同様のメタルハニカム担体の平
板の金属箔に、γ−アルミナ粉末とアルミナ水和物と水
からなるスラリーをコートし、硝酸セリウム溶液を担持
、乾燥後、６５０℃で１時間焼成して金属箔にセリウム
を含有するアルミナ層を形成した。（コートＪ）[0054] A flat metal foil of a metal honeycomb carrier similar to that in Example 1 was coated with a slurry consisting of γ-alumina powder, alumina hydrate, and water, and a cerium nitrate solution was supported. After drying, the slurry was heated at 650°C for 1 hour. An alumina layer containing cerium was formed on the metal foil by firing for a period of time. (Court J)
【００
５５】金属製の平板と波板とを重ね、これを多重に巻回
しコア部を形成してなるφ８０×１０５Ｌ（５２８ｃｃ
）のメタルハニカム担体に上記平板にコートした方法で
アルミナ層を１２０ｇ／ｌ−ｃａｔコート後、硝酸セリ
ウム溶液に含浸し、セリウムを０．２５ｍｏｌ／ｌ−ｃ
ａｔ担持した。00
55] φ80×105L (528cc
) was coated with an alumina layer of 120 g/l-cat using the above flat plate coating method, and then impregnated with a cerium nitrate solution to add 0.25 mol/l-c of cerium.
It carried at.
【００５６】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒１９を得た。
比較例２The carrier thus obtained was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 19. Comparative example 2
【００５７】実施例１と同様のメタルハニカム担体の平
板の金属箔に、炭酸セリウム粉末と炭酸ランタン粉末と
γ−アルミナ粉末とアルミナ水和物と水からなるスラリ
ーをコート、乾燥後、６５０℃で１時間焼成して金属箔
にセリウム、ランタンを含有するアルミナ層を形成した
。（コートＫ）[0057] A flat metal foil of a metal honeycomb carrier similar to that in Example 1 was coated with a slurry consisting of cerium carbonate powder, lanthanum carbonate powder, γ-alumina powder, alumina hydrate, and water, and after drying, it was heated at 650°C. After firing for 1 hour, an alumina layer containing cerium and lanthanum was formed on the metal foil. (Court K)
【００５８】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるφ８０×１０５Ｌ（５２
８ｃｃ）のメタルハニカム担体に上記平板にコートした
方法でアルミナコート量１２０ｇ／ｌ−ｃａｔ、セリウ
ム０．２５ｍｏｌ／ｌ−ｃａｔ、ランタン０．１ｍｏｌ
／ｌ−ｃａｔを含有するアルミナ層を形成した。[0058] φ80×105L (52
The amount of alumina coated was 120 g/l-cat, cerium 0.25 mol/l-cat, and lanthanum 0.1 mol by the method of coating the flat plate on a metal honeycomb carrier of 8 cc).
An alumina layer containing /l-cat was formed.
【００５９】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒２０を得た。
比較例３The carrier thus obtained was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
A catalyst 20 was obtained by supporting -cat. Comparative example 3
【００６０】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるφ８０×１０５Ｌ（５２
８ｃｃ）のメタルハニカム担体に比較例２と同様の方法
でアルミナコート量１２０ｇ／ｌ−ｃａｔ、セリウム０
．２５ｍｏｌ／ｌ−ｃａｔ、ランタン０．１ｍｏｌ／ｌ
−ｃａｔを含有するアルミナ層を形成した。[0060] φ80×105L (52
Alumina coating amount of 120 g/l-cat and cerium 0
．． 25mol/l-cat, lanthanum 0.1mol/l
An alumina layer containing -cat was formed.
【００６１】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸パラジウムと硝酸ロジウム溶液に
含浸し、白金、パラジウム、ロジウムをそれぞれ０．４
ｇ／ｌ−ｃａｔ、０．８ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒２１を得た。
比較例４The carrier thus obtained was impregnated with a dinitrodiammine platinum solution, palladium nitrate, and rhodium nitrate solution, and platinum, palladium, and rhodium were each added to a concentration of 0.4
g/l-cat, 0.8g/l-cat, 0.2g/l
-cat was supported to obtain catalyst 21. Comparative example 4
【００６２】実施例１と同様のメタルハニカム担体の平
板の金属箔に、γ−アルミナ粉末とアルミナ水和物と水
からなるスラリーをコート後、乾燥した。次に、該担体
を酢酸カルシウム溶液に含浸して、カルシウムを担持し
た。A flat metal foil of a metal honeycomb carrier similar to that in Example 1 was coated with a slurry consisting of γ-alumina powder, alumina hydrate, and water, and then dried. Next, the carrier was impregnated with a calcium acetate solution to support calcium.
【００６３】次に、カルシウムを担持した担体に、セリ
ウム−ジルコニウムの複合酸化物粉末、炭酸ランタン粉
末、酸化ニッケル粉末、γ−アルミナ粉末とアルミナ水
和物および水からなるスラリーをコート、乾燥後、６５
０℃で１時間焼成して金属箔の一層目にカルシウム、二
層目にセリウム−ジルコニウム、ランタン、ニッケルを
含有するアルミナ層を形成した。Next, the carrier supporting calcium was coated with a slurry consisting of cerium-zirconium composite oxide powder, lanthanum carbonate powder, nickel oxide powder, γ-alumina powder, alumina hydrate, and water, and after drying, 65
By firing at 0° C. for 1 hour, the first layer of the metal foil was formed with calcium, and the second layer was formed with an alumina layer containing cerium-zirconium, lanthanum, and nickel.
【００６４】金属製の平板と波板とを重ね、これを多重
に巻回しコア部を形成してなるφ８０×１０５Ｌ（５２
８ｃｃ）のメタルハニカム担体に上記平板にコートした
方法で一層目にアルミナコート量６０ｇ／ｌ−ｃａｔ、
カルシウム０．２５ｍｏｌ／ｌ−ｃａｔ、ジルコニウム
０．０５ｍｏｌ／ｌ−ｃａｔ、ランタン０．１ｍｏｌ／
ｌ−ｃａｔ、ニッケル０．０５ｍｏｌ／ｌ−ｃａｔを含
有するアルミナ層を形成した。[0064] φ80×105L (52
The first layer was coated with alumina in an amount of 60 g/l-cat on a metal honeycomb carrier of 8 cc) using the above flat plate coating method.
Calcium 0.25mol/l-cat, zirconium 0.05mol/l-cat, lanthanum 0.1mol/
An alumina layer containing 1-cat and 0.05 mol/1-cat of nickel was formed.
【００６５】このようにして得た担体を、ジニトロジア
ンミン白金溶液と硝酸ロジウム溶液に含浸し、白金、ロ
ジウムをそれぞれ１．２ｇ／ｌ−ｃａｔ、０．２ｇ／ｌ
−ｃａｔ担持して触媒２２を得た。The carrier thus obtained was impregnated with a dinitrodiammine platinum solution and a rhodium nitrate solution, and platinum and rhodium were added at 1.2 g/l-cat and 0.2 g/l, respectively.
-cat was supported to obtain catalyst 22.
【００６６】実施例１乃至実施例７および実施例１７、
１８と比較例１、２で得られたコートＡ乃至コートＫの
平板を電気炉で空気中１，１００℃、５０時間曝した後
、平板の伸び率を測定した結果を第１表に示す。Examples 1 to 7 and Example 17,
Table 1 shows the results of measuring the elongation rate of the flat plates after exposing the flat plates of Coats A to K obtained in Comparative Examples 1 and 2 in an electric furnace at 1,100° C. for 50 hours.
【００６７】また、実施例１乃至実施例１８と比較例１
乃至比較例４で得られた触媒を４，０００ｃｃのエンジ
ンに取り付け、Ａ／Ｆ＝１４．６（ストイキ）、入ガス
温度９００℃の条件で５０時間耐久した。[0067] Also, Examples 1 to 18 and Comparative Example 1
The catalysts obtained in Comparative Examples 4 to 4 were installed in a 4,000 cc engine and endured for 50 hours under conditions of A/F = 14.6 (stoichiometric) and an inlet gas temperature of 900°C.
【００６８】評価は、２０００ｃｃのエンジンでＡ／Ｆ
＝１４．６（ストイキ）、入ガス温度４６０℃の条件で
行った。実施例１乃至実施例１８と比較例１乃至比較例
４で得られた触媒１乃至触媒２２の各々の割合及び評価
結果を第２〜４表に示す。[0068] The evaluation is A/F with a 2000cc engine.
= 14.6 (stoichiometric) and the gas input temperature was 460°C. Tables 2 to 4 show the respective ratios and evaluation results of catalysts 1 to 22 obtained in Examples 1 to 18 and Comparative Examples 1 to 4.
【００６９】第１表では、本発明の実施例１〜７で形成
されるセリウムを第一層に含まないコートＡ〜Ｉの伸び
率は、いずれも１％台と低いのに対して、比較例１、２
で形成されるコートＬ、Ｋの伸び率は５％を越える高い
ものとなっている。Table 1 shows that the elongation rates of coats A to I, which do not contain cerium in the first layer, formed in Examples 1 to 7 of the present invention are all as low as 1%. Examples 1 and 2
The elongation rates of coats L and K formed by the above method are as high as over 5%.
【００７０】また第２〜４表に示されるように、本発明
の実施例による触媒１〜１８は比較例に比べいずれも、
ＨＣ、ＣＯ、ＮＯＸ の浄化率が高い。第一層のアルミ
ナ層のコート量については、比較例がいずれも１００ｇ
を越えるのに対して、本発明の実施例は１００ｇ以内で
ある。さらに金属製ハニカム担体基材と接触する一層目
のアルミナコート層中には、いずれもアルカリ金属およ
びアルカリ土類金属の一種以上がコートされている。ま
たその添加量については、比較例４の触媒２２における
０．２５ｍｏｌ／ｌ−ｃａｔのカルシウム添加に比べ、
実施例３の触媒３、実施例９〜１５における０．０５ｍ
ｏｌ／ｌ−ｃａｔ〜０．２ｍｏｌ／ｌ−ｃａｔのカルシ
ウム添加の場合の方が浄化性能が優れていることがわか
る。従って金属製ハニカム担体基材と接触する一層目の
アルミナコート層中に添加するアルカリ金属およびアル
カリ土類金属の添加量は０．２ｍｏｌ／ｌ−ｃａｔを越
えないのが望ましい。Furthermore, as shown in Tables 2 to 4, catalysts 1 to 18 according to the examples of the present invention all had the following properties compared to the comparative examples:
High purification rate of HC, CO, and NOX. The coating amount of the first alumina layer was 100g in both comparative examples.
In contrast, in the embodiments of the present invention, the weight is within 100 g. Furthermore, the first alumina coating layer in contact with the metal honeycomb carrier base material is coated with one or more of alkali metals and alkaline earth metals. Regarding the amount of calcium added, compared to the addition of 0.25 mol/l-cat of calcium in catalyst 22 of Comparative Example 4,
Catalyst 3 in Example 3, 0.05 m in Examples 9 to 15
It can be seen that the purification performance is better when calcium is added in an amount of 0.2 mol/l-cat to 0.2 mol/l-cat. Therefore, it is desirable that the amount of alkali metals and alkaline earth metals added to the first alumina coat layer that contacts the metal honeycomb carrier base material does not exceed 0.2 mol/l-cat.
【００７１】そして実施例１７、１８より明らかなよう
に、金属製ハニカム担体基材と接触する一層目のアルミ
ナ層中に、触媒作用の促進安定化のためにランタン、ニ
ッケル、鉄、ジルコニウムから選ばれた一種以上を添加
しても差支えないことがわかる。As is clear from Examples 17 and 18, the first alumina layer in contact with the metal honeycomb carrier base material contained lanthanum, nickel, iron, and zirconium in order to promote and stabilize the catalytic action. It can be seen that there is no problem in adding one or more of the following.
【００７２】[0072]
【発明の効果】第１表乃至第４表から明らかなように金
属製ハニカム担体基材と接触する一層目にセリウムを含
有しない本発明品は、従来品と比べ金属製箔の伸びが少
なく、触媒性能が優れていることが判る。Effects of the Invention As is clear from Tables 1 to 4, the product of the present invention, which does not contain cerium in the first layer that contacts the metal honeycomb carrier base material, has less elongation of the metal foil than conventional products. It can be seen that the catalyst performance is excellent.
【００７３】[0073]
【表１】[Table 1]
【００７４】[0074]
【表２】[Table 2]
【００７５】[0075]
【表３】[Table 3]
【００７６】[0076]
【表４】[Table 4]
Claims (1)
アルミナ層を形成し、該アルミナ層中に、セリウムと、
白金、パラジウム、ロジウムの一種以上を含有する触媒
において、金属製ハニカム担体基材と接触する一層目が
セリウムを含まないことを特徴とする排ガス浄化用触媒
。Claim 1: Two or more alumina layers are formed on a metal honeycomb carrier base material, and in the alumina layer, cerium and
A catalyst for purifying exhaust gas containing one or more of platinum, palladium, and rhodium, characterized in that the first layer in contact with a metal honeycomb carrier substrate does not contain cerium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02344591A JP3247956B2 (en) | 1991-02-18 | 1991-02-18 | Exhaust gas purification catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02344591A JP3247956B2 (en) | 1991-02-18 | 1991-02-18 | Exhaust gas purification catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04265155A true JPH04265155A (en) | 1992-09-21 |
| JP3247956B2 JP3247956B2 (en) | 2002-01-21 |
Family
ID=12110703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02344591A Expired - Fee Related JP3247956B2 (en) | 1991-02-18 | 1991-02-18 | Exhaust gas purification catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3247956B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6165935A (en) * | 1995-06-07 | 2000-12-26 | Asec Manufacturing General Partnership | Palladium catalyst washcoat supports for improved methane oxidation in natural gas automotive emission catalysts |
| JP2002306964A (en) * | 2001-04-16 | 2002-10-22 | Ict:Kk | Catalyst |
| JP2005161311A (en) * | 1993-06-25 | 2005-06-23 | Engelhard Corp | Layered catalyst composite |
| JP2007289811A (en) * | 2006-04-21 | 2007-11-08 | Toyota Motor Corp | Manufacturing method of alkaline earth metal carrying exhaust gas purifying catalyst |
| JP2008018374A (en) * | 2006-07-14 | 2008-01-31 | Honda Motor Co Ltd | Catalyst and apparatus for cleaning exhaust gas |
| US9278336B2 (en) | 2011-11-28 | 2016-03-08 | Hyundai Motor Company | SCR on diesel particular filter and method for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6339633A (en) * | 1986-08-01 | 1988-02-20 | Nissan Motor Co Ltd | Catalyst for cleaning exhaust gas |
| JPS63258648A (en) * | 1987-04-15 | 1988-10-26 | Mazda Motor Corp | Catalyst for purifying exhaust gas |
| JPH01242149A (en) * | 1988-03-24 | 1989-09-27 | Toyota Motor Corp | Catalyst for purification of exhaust gas |
-
1991
- 1991-02-18 JP JP02344591A patent/JP3247956B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6339633A (en) * | 1986-08-01 | 1988-02-20 | Nissan Motor Co Ltd | Catalyst for cleaning exhaust gas |
| JPS63258648A (en) * | 1987-04-15 | 1988-10-26 | Mazda Motor Corp | Catalyst for purifying exhaust gas |
| JPH01242149A (en) * | 1988-03-24 | 1989-09-27 | Toyota Motor Corp | Catalyst for purification of exhaust gas |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005161311A (en) * | 1993-06-25 | 2005-06-23 | Engelhard Corp | Layered catalyst composite |
| US6165935A (en) * | 1995-06-07 | 2000-12-26 | Asec Manufacturing General Partnership | Palladium catalyst washcoat supports for improved methane oxidation in natural gas automotive emission catalysts |
| JP2002306964A (en) * | 2001-04-16 | 2002-10-22 | Ict:Kk | Catalyst |
| JP2007289811A (en) * | 2006-04-21 | 2007-11-08 | Toyota Motor Corp | Manufacturing method of alkaline earth metal carrying exhaust gas purifying catalyst |
| JP4697028B2 (en) * | 2006-04-21 | 2011-06-08 | トヨタ自動車株式会社 | Process for producing alkaline earth metal-supported exhaust gas purification catalyst |
| JP2008018374A (en) * | 2006-07-14 | 2008-01-31 | Honda Motor Co Ltd | Catalyst and apparatus for cleaning exhaust gas |
| US9278336B2 (en) | 2011-11-28 | 2016-03-08 | Hyundai Motor Company | SCR on diesel particular filter and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3247956B2 (en) | 2002-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS63162043A (en) | Catalyst for cleaning exhaust gas | |
| JP7255459B2 (en) | Exhaust gas purification catalyst | |
| JPS59127649A (en) | Catalyst for purifying exhaust gas | |
| JPH11276907A (en) | Catalyst for purifying exhaust gas and its production | |
| JPH04265155A (en) | Catalyst for purification of exhaust gas | |
| JP2001070791A (en) | Exhaust gas cleaning catalyst | |
| JPH05184926A (en) | Catalyst for purifying exhaust gas | |
| JP2001062295A (en) | Exhaust gas cleaning catalyst | |
| JPS63267804A (en) | Oxidizing catalyst for high temperature service | |
| JPH10165817A (en) | Catalyst for cleaning of exhaust gas | |
| JPH07171392A (en) | Catalyst for exhaust gas purification | |
| JPH10249199A (en) | Catalyst for purifying exhaust gas | |
| JPH0472577B2 (en) | ||
| JP2022135562A (en) | Exhaust-purifying catalyst | |
| EP1457249B1 (en) | Exhaust-gas purifying catalyst | |
| JP2001104785A (en) | Catalyst for purifying exhaust gas | |
| JPH02119939A (en) | Exhaust gas purification catalyst | |
| JP2823251B2 (en) | Exhaust gas purifying catalyst and method for producing exhaust gas purifying catalyst | |
| JPH0427433A (en) | High-temperature combustion catalyst and its production | |
| US11801492B2 (en) | Exhaust gas purification catalyst | |
| JPH0573461B2 (en) | ||
| JPS62254845A (en) | Production of monolithic catalyst carrier for purifying exhaust gas | |
| JPS62125855A (en) | Exhaust gas purifying catalyst | |
| JPH10244154A (en) | Multilayered catalyst for treatment of exhaust gas from diesel engine and its production | |
| JPH10174878A (en) | Catalyst for cleaning of exhaust gas from diesel engine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |