JPH03109941A - Catalyst for purifying exhaust gas - Google Patents
Catalyst for purifying exhaust gasInfo
- Publication number
- JPH03109941A JPH03109941A JP1246421A JP24642189A JPH03109941A JP H03109941 A JPH03109941 A JP H03109941A JP 1246421 A JP1246421 A JP 1246421A JP 24642189 A JP24642189 A JP 24642189A JP H03109941 A JPH03109941 A JP H03109941A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- cerium oxide
- activated alumina
- alcohol
- catalyst layer
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 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 85
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 83
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 23
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 41
- 239000010948 rhodium Substances 0.000 claims description 21
- 238000000746 purification Methods 0.000 claims description 15
- 239000000446 fuel Substances 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003502 gasoline Substances 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 25
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 6
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract 2
- 239000002002 slurry Substances 0.000 description 69
- 239000000843 powder Substances 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 239000007864 aqueous solution Substances 0.000 description 34
- 150000003839 salts Chemical class 0.000 description 22
- 239000010410 layer Substances 0.000 description 20
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 11
- 238000010298 pulverizing process Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 229910018967 Pt—Rh Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 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 2
- 238000001354 calcination Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 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 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical compound [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HLVXFWDLRHCZEI-UHFFFAOYSA-N chromotropic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 HLVXFWDLRHCZEI-UHFFFAOYSA-N 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、アルコールを含有する燃料を用いる内燃機関
の排ガス中に含まれる有害物質を浄化する触媒に関する
。詳しくは、アルコールを含有する燃料を用いる内燃機
関の排ガス中の未燃アルコール、−酸化炭素（Ｇｏ＞、
炭化水素（ＨＣ）およびアルデヒド類を酸化し、同時に
発生する窒素酸化物（ＮＯｘ＞を還元し、かつ、これら
の浄化能が低温域から優れた触媒に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a catalyst for purifying harmful substances contained in the exhaust gas of an internal combustion engine using fuel containing alcohol. In detail, unburned alcohol, -carbon oxide (Go>,
The present invention relates to a catalyst that oxidizes hydrocarbons (HC) and aldehydes, simultaneously reduces generated nitrogen oxides (NOx), and has excellent purifying ability from low temperatures.
〈従来の技術〉
自動車等の内燃機関に使用される燃料としては、ガソリ
ンが用いられてきた。しかし、排ガス等の問題、燃料の
供給の問題により、近年ガソリンに替え、クリーンな燃
料であるメタノールを主成分とした燃料、たとえば１０
０％メタノール、メタノールにガソリンを５０＝５０で
加えた燃料またはメタノールにガソリンを８５：１５で
加えた燃料等の混合燃料の使用が検討されている。<Prior Art> Gasoline has been used as a fuel for internal combustion engines such as automobiles. However, due to problems such as exhaust gas and fuel supply, in recent years gasoline has been replaced with fuels mainly composed of methanol, which is a clean fuel, such as 10
The use of mixed fuels such as 0% methanol, methanol and gasoline at a ratio of 50:50, or methanol and gasoline at a ratio of 85:15 are being considered.
これらの燃料を使用した場合、内燃機関から発生する排
ガスには、通常のガソリンを燃料とした場合に比べ未燃
アルコールおよびアルデヒド類等種々の成分が含まれ、
これらの排ガス成分が新たな問題となっている。When these fuels are used, the exhaust gas generated from the internal combustion engine contains various components such as unburned alcohol and aldehydes compared to when normal gasoline is used as fuel.
These exhaust gas components have become a new problem.
これらの排ガスの浄化方法として、ガソリン燃料用の触
媒として一般的に用いられる三元性能を有する触媒を使
用した場合、）−ＩＣ，ＣＯおよびＮＯｘの浄化はでき
るが、低温域でのアルデヒド類および未燃焼アルコール
等を浄化することができないという欠点がある。As a method for purifying these exhaust gases, if a catalyst with three-way performance, which is commonly used as a catalyst for gasoline fuel, is used, it is possible to purify )-IC, CO, and NOx, but aldehydes and The disadvantage is that unburned alcohol and the like cannot be purified.
一方、メタノール、エタノールを燃料とした内燃機関の
排ガス浄化方法として、γ−アルミナに銀およびパラジ
ウムを担持した触媒（特開昭６２１２９１２５号）、ラ
ンタンおよびネオジウムを含有するアルミナにパラジウ
ムを担持した触媒（特開昭５８−７９５５４号）等が提
案されているが、いずれの触媒においても、未燃メタノ
ール等には有効なものであるが、ＨＣ，ＣｏおよびＮＯ
ｘの浄化に関しては、はとんど効果がみられないもので
ある。On the other hand, as exhaust gas purification methods for internal combustion engines using methanol and ethanol as fuel, there are catalysts in which silver and palladium are supported on γ-alumina (Japanese Patent Application Laid-open No. 62129125), catalysts in which palladium is supported on alumina containing lanthanum and neodymium ( JP-A No. 58-79554), etc. have been proposed, but all of these catalysts are effective against unburned methanol, etc., but they are effective against HC, Co, and NO.
Regarding the purification of x, there is hardly any effect.
〈発明が解決しようとする課題〉
したがって、ＨＣｌＣｏおよびＮＯｘを同時に除去し、
さらに低温域から未燃アルコールおよびアルデヒド類を
浄化できる触媒を提案する目的で、本発明はなされたも
のである。<Problem to be solved by the invention> Therefore, HClCo and NOx are removed simultaneously,
Furthermore, the present invention was made for the purpose of proposing a catalyst that can purify unburned alcohol and aldehydes from a low temperature range.
く課題を解決するための手段〉
本発明者らは、上記の課題に対処するために鋭意研究の
結果、モノリス担体上にアルコールおよび／またはアル
デヒド浄化能を有する触媒層を設け、さらに該触媒層上
に三元性能を有する触媒層を設けたことを特徴とするア
ルコール燃料またはアルコールガソリン混合燃料を用い
る内燃機関排出ガスの浄化用触媒を見い比すことにより
本発明を完成するに至ったのである。Means for Solving the Problems In order to solve the above problems, the present inventors, as a result of intensive research, provided a catalyst layer having an ability to purify alcohol and/or aldehyde on a monolithic carrier, and The present invention was completed by comparing a catalyst for purifying exhaust gas from an internal combustion engine using alcohol fuel or alcohol-gasoline mixed fuel, which is characterized by having a catalyst layer having three-way performance provided thereon. be.
本発明にかかるモノリス担体は、一般的に排ガス浄化用
触媒担体に用いられるものであればよく、特に、金属性
またはセラミック性のハニカムモノリス担体が好ましい
。The monolithic carrier according to the present invention may be one that is generally used as a catalyst carrier for exhaust gas purification, and a metallic or ceramic honeycomb monolithic carrier is particularly preferred.
アルコールおよび／またはアルデヒド浄化能を有する触
媒層には、通常メタノール、一般的なアルデヒド類を完
全酸化しうる触媒組成物であれば良く、例えば鉄（Ｆｅ
）、ニッケル＜Ｎ ｉ ） 、コバルト（ＣＯ）、白金
（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）、ア
ルカリ金属、アルカリ土類金（ＡＵ）、銀（Ａｏ＞、銅
（Ｃｕ）、ペロブスカイト（例えばランタン・コバルト
複合酸化物等）等の触媒組成物を単独あるいは、多孔質
担体（例えば、アルミナ、シリカ、ジルコニア等）に担
持して用いることができる。For the catalyst layer having alcohol and/or aldehyde purification ability, any catalyst composition that can completely oxidize methanol and general aldehydes may be used, for example, iron (Fe
), nickel <N i ), cobalt (CO), platinum (Pt), palladium (Pd), rhodium (Rh), alkali metals, alkaline earth gold (AU), silver (Ao>, copper (Cu), perovskite) A catalyst composition such as (for example, lanthanum-cobalt composite oxide, etc.) can be used alone or supported on a porous carrier (for example, alumina, silica, zirconia, etc.).
これらの触媒組成物のうち、好ましくはパラジウム、白
金および銀からなる群から選ばれる少なくとも１種の金
属と、酸化セリウム、活性アルミナおよび希土類を含有
した活性アルミナからなる群から選ばれる少なくとも１
種の酸化物とを含有してなる触媒組成物であり、さらに
好ましくはパラジウムおよび／または白金と、銀並びに
酸化セリウム、活性アルミナおよび希土類を含有した活
性アルミナからなる群から選ばれる少なくとも１種の酸
化物とを含有してなる触媒組成物である。Among these catalyst compositions, preferably at least one metal selected from the group consisting of palladium, platinum, and silver, and at least one metal selected from the group consisting of cerium oxide, activated alumina, and activated alumina containing rare earth elements.
A catalyst composition comprising a species oxide, more preferably palladium and/or platinum, and at least one species selected from the group consisting of silver and cerium oxide, activated alumina and rare earth-containing activated alumina. This is a catalyst composition containing an oxide.
三元性能を有する触媒層には一般的な三元性能を有する
触媒組成物であれば良く、好ましくはパラジウムおよび
／または白金と、ロジウムと、活性アルミナと、酸化セ
リウムを含有する触媒組成物である。The catalyst layer having three-way performance may be a catalyst composition having general three-way performance, preferably a catalyst composition containing palladium and/or platinum, rhodium, activated alumina, and cerium oxide. be.
また、活性アルミナに希土類、アルカリ金属、アルカリ
土類金属を含有して用いることもできる。Furthermore, activated alumina may contain rare earth metals, alkali metals, and alkaline earth metals.
本発明による触媒は、モノリス担体の内層として、アル
デヒド類およびアルコール浄化性能を有する異種又は同
一の触媒組成物を少なくとも１層以上被覆し、次いで三
元性能を有する異種又は同一の触媒組成物を少なくとも
１層以上被覆されてなる。In the catalyst of the present invention, a monolithic carrier is coated with at least one layer of different or the same catalyst composition having aldehyde and alcohol purification performance as an inner layer, and then at least one layer of different or the same catalyst composition having ternary performance is coated. It is coated with one or more layers.
これらアルデヒドおよび／またはアルコール浄化性能を
有する触媒組成物と三元性能を有する触媒組成物の層は
明確に分離され、両層の組成物を混合、または内層の組
成物と外層の組成物を逆に被覆することでは、本発明に
よる効果は得ることができないものである。The layers of the catalyst composition with aldehyde and/or alcohol purification performance and the catalyst composition with ternary performance are clearly separated, and the compositions of both layers can be mixed, or the compositions of the inner layer and the outer layer can be reversed. However, the effects of the present invention cannot be obtained by coating the surface of the substrate.
以下に、本発明にかかる触媒の製造方法の具体的実施態
様として、アルデヒド類および／またはアルコール浄化
性能を有する触媒組成物（以下「アルコール用触媒」と
する）として、パラジウム、銀および酸化セリウム、ざ
らに活性アルミナを用い、また三元性能を有する触媒組
成物（以下「三元触媒」とする）として、白金、ロジウ
ム、酸化セリウムおよび活性アルミナを用いた場合につ
いて、以下に例示するが、本発明の趣旨に反しない限り
、これらの方法に限定されるものではない。Below, as a specific embodiment of the method for producing a catalyst according to the present invention, a catalyst composition having aldehyde and/or alcohol purification performance (hereinafter referred to as "alcohol catalyst") includes palladium, silver and cerium oxide, Examples are given below of cases in which activated alumina is used, and platinum, rhodium, cerium oxide, and activated alumina are used as a catalyst composition having three-way performance (hereinafter referred to as a "three-way catalyst"). The method is not limited to these methods unless it goes against the spirit of the invention.
（１）Ｐｄの水溶性塩の水溶液と八９の水溶性塩の水溶
液を混合し、これに酸化セリウム粉体を加え、充分混ぜ
合せた後、乾燥、焼成し、Ｐｄへｇ担持酸化セリウム粉
体を調製した。このえられた粉体をボールミルで湿式粉
砕することにより水性スラリーを調製し、このスラリー
にモノリス担体を浸し、次いで余分なスラリーを吹きは
らい、乾燥、焼成し、Ｐｄ−ＡＣＩ担持酸化セリウムを
被覆した担体（アルコール触媒）を得た。(1) Mix an aqueous solution of a water-soluble salt of Pd and an aqueous solution of a water-soluble salt of 89, add cerium oxide powder to this, mix thoroughly, dry and bake, and transfer g-supported cerium oxide powder to Pd. body was prepared. The obtained powder was wet-pulverized in a ball mill to prepare an aqueous slurry, and the monolithic carrier was immersed in this slurry, and then the excess slurry was blown off, dried, and fired to coat Pd-ACI-supported cerium oxide. A carrier (alcohol catalyst) was obtained.
次に、Ｐｔの水溶性塩の水溶液とＲｈの水溶性塩の水溶
液を混合し、これに活性アルミナ粉体を加え、充分混ぜ
合せ、乾燥、焼成し、ＰｔＲｈ担持アルミナ粉体を調製
した。この粉体と酸化セリウムをボールミルで湿式粉砕
することによりスラリーを調製し、このスラリーにＰｄ
−Ａｇ担持酸化セリウムを被覆した担体を浸し、次いで
余分なスラリーを吹きはらった後、乾燥、焼成し、外層
に三元触媒を被覆することにより完成触媒を得た。Next, an aqueous solution of a water-soluble salt of Pt and an aqueous solution of a water-soluble salt of Rh were mixed, and activated alumina powder was added thereto, thoroughly mixed, dried, and fired to prepare a PtRh-supported alumina powder. A slurry was prepared by wet-pulverizing this powder and cerium oxide in a ball mill, and this slurry was mixed with Pd.
The carrier coated with -Ag-supported cerium oxide was immersed, the excess slurry was blown off, the slurry was dried and fired, and the outer layer was coated with a three-way catalyst to obtain a finished catalyst.
（２）Ｐｄの水溶性塩の水溶液に酸化［リウムを加え混
合した後、乾燥、焼成し、Ｐｄ−酸化セリウム粉体を調
製した。得られた粉体をボールミ０
ルで湿式粉砕することにより、水性スラリーを調製し、
このスラリーにモノリス担体を浸し、余分なスラリーを
吹きはらい、乾燥、焼成し、Ｐｄ−酸化セリＴクムを被
覆した担体を得た。この担体をＡｃｔの水溶性塩の水溶
液に浸漬し、余分の水溶液を吹きはらい、乾燥、焼成し
、ＰｄＡＣＩ−酸化セリウムを被覆した担体（アルコー
ル用触媒）を得た。(2) After adding and mixing [rium oxide] to an aqueous solution of a water-soluble salt of Pd, the mixture was dried and fired to prepare a Pd-cerium oxide powder. The obtained powder was wet-milled using a ball mill to prepare an aqueous slurry.
A monolithic carrier was immersed in this slurry, excess slurry was blown off, dried, and fired to obtain a carrier coated with Pd-seri oxide T cum. This carrier was immersed in an aqueous solution of a water-soluble salt of Act, the excess aqueous solution was blown off, dried and fired to obtain a PdACI-cerium oxide coated carrier (alcohol catalyst).
次に、ｐｔの水溶性塩の水溶液とＲｈの水溶性塩の水溶
液を混合し、これに活性アルミナを加え混合した後、乾
燥、焼成し、Ｐｔ−Ｒｈ担持アルミナ粉体を調製した。Next, an aqueous solution of a water-soluble salt of PT and an aqueous solution of a water-soluble salt of Rh were mixed, and activated alumina was added thereto and mixed, followed by drying and firing to prepare a Pt-Rh supported alumina powder.
この粉体と酸化セリウムをボールミルで湿式粉砕するこ
とによりスラリーを調製し、該スラリーにｐｔｊ−ＡＣ
＋酸化セリウムを被覆した担体を浸し、余分なスラリー
を吹きはらい、乾燥、焼成し、外層に三元触媒を被覆す
ることにより完成触媒を得た。A slurry was prepared by wet-pulverizing this powder and cerium oxide in a ball mill, and ptj-AC was added to the slurry.
+ The carrier coated with cerium oxide was immersed, excess slurry was blown off, dried and fired, and the outer layer was coated with a three-way catalyst to obtain a completed catalyst.
（３）酸化セリウム粉体をボールミルで湿式粉砕するこ
とにより水性スラリーを調製し、このスラリーにモノリ
ス担体を浸し、余分なスラリーを１
吹きはらい、乾燥、焼成し、酸化セリウムを被覆した担
体を得た。次にＰｄの水溶性塩の水溶液とＡＣＩの水溶
性塩の水溶液を混合し、混合溶液に上記酸化セリウム被
覆担体を浸漬し、余分の水溶液を吹きはらい、乾燥、焼
成し、Ｐ’ｄＡＱ−酸化セリウムを被覆した担体くアル
コール用触媒）を得た。(3) Prepare an aqueous slurry by wet-pulverizing cerium oxide powder in a ball mill, immerse a monolithic carrier in this slurry, blow off excess slurry, dry, and sinter to obtain a cerium oxide-coated carrier. Ta. Next, an aqueous solution of a water-soluble salt of Pd and an aqueous solution of a water-soluble salt of ACI are mixed, the above-mentioned cerium oxide-coated carrier is immersed in the mixed solution, the excess aqueous solution is blown off, and the P'dAQ-oxidized A cerium-coated carrier (alcohol catalyst) was obtained.
次にＰ ｔの水溶性塩の水溶液とＲｈの水溶性塩の水溶
液を混合し、これに活性アルミナを加え混合し、乾燥、
焼成し、Ｐｔ−Ｒｈ担持アルミナ粉体を調製する。この
粉体と酸化セリウムをボールミルで湿式粉砕することに
よりスラリーを調製し、このスラリーを上記のｐｄ−／
’１−酸化セリウムを被覆した担体を浸し、余分なスラ
リーを吹きはらい、乾燥し焼成し、三元触媒を被覆する
ことにより完成触媒を得た。Next, an aqueous solution of a water-soluble salt of Pt and an aqueous solution of a water-soluble salt of Rh are mixed, activated alumina is added thereto, mixed, dried,
Calcinate to prepare Pt-Rh supported alumina powder. A slurry was prepared by wet-pulverizing this powder and cerium oxide in a ball mill, and this slurry was mixed with the above pd-/
The carrier coated with '1-cerium oxide was immersed, excess slurry was blown off, dried and calcined, and a three-way catalyst was coated to obtain a finished catalyst.
（４）Ｐｄの水溶性塩の水溶液と△ｑの水溶性塩の水溶
液を混合し、これに酸化セリウムを加え混合し、乾燥、
焼成し、ｐｄ−Ａｃｔ担持酸化セリウム粉体を調製した
。この粉体をボールミルで２
湿式乾燥することにより水性スラリーを調製し、このス
ラリーにモノリス担体を浸し、余分なスラリーを吹きは
らい、乾燥し焼成し、ＰｄＡＣＩ−酸化セリウムを被覆
した担体（アルコール用触媒）を得た。(4) Mix the aqueous solution of the water-soluble salt of Pd and the aqueous solution of the water-soluble salt of △q, add cerium oxide to this, mix, dry,
By firing, a pd-Act-supported cerium oxide powder was prepared. An aqueous slurry was prepared by wet-drying this powder in a ball mill for 2 hours, a monolithic support was immersed in this slurry, excess slurry was blown off, dried and calcined, and a PdACI-cerium oxide coated support (alcohol catalyst) was prepared. ) was obtained.
次にｐｔの水溶性塩の水溶液に活性アルミナを加え混合
し、乾燥、焼成し、Ｐｔ担持アルミナ粉体を調製した。Next, activated alumina was added to an aqueous solution of a water-soluble salt of PT, mixed, dried, and fired to prepare a Pt-supported alumina powder.
この粉体と酸化セリウムをボールミルで湿式粉砕するこ
とにより水性スラリーを調製し、このスラリーにＰｄ−
Ａｑ担持酸化セリウムを被覆した担体を浸し、余分なス
ラリーを吹きはらい、乾燥、焼成し、Ｐｄ−Ａｑ担持酸
化セリウムにＰｔ−活性アルミナー酸化セリウムを被覆
した担体を得た。さらにＲｈの水溶性塩の水溶液を活性
アルミナに含浸担持し、乾燥、焼成し、Ｒｈ担持アルミ
ナ粉体を調製した。この粉体をボールミルで湿式粉砕す
ることにより、水性スラリーを調製し、このスラリーに
ｐｄ−ＡＱ担持酸化セリウムにｐｔ−活性アルミナー酸
化セリウムを追加被覆した担体３
を浸し、余分なスラリーを吹きはらい乾燥、焼成するこ
とにより完成触媒を得た（三元触媒が２層に被覆された
もの）。An aqueous slurry was prepared by wet-pulverizing this powder and cerium oxide in a ball mill, and this slurry was mixed with Pd-
The carrier coated with Aq-supported cerium oxide was immersed, excess slurry was blown off, dried, and fired to obtain a carrier in which Pd-Aq-supported cerium oxide was coated with Pt-activated alumina cerium oxide. Furthermore, an aqueous solution of a water-soluble salt of Rh was impregnated and supported on activated alumina, dried, and fired to prepare Rh-supported alumina powder. This powder is wet-milled in a ball mill to prepare an aqueous slurry, and the carrier 3, which is an additional coating of PT-activated alumina cerium oxide on PD-AQ-supported cerium oxide, is immersed in this slurry, and the excess slurry is blown off and dried. A completed catalyst was obtained by calcination (three-way catalyst coated in two layers).
（５）Ｐｄの水溶性塩の水溶液とＡｃｔの水溶性塩の水
溶液を混合し、これに酸化セリウムを加え混合し、乾燥
、焼成し、Ｐ（ｊ−ＡＱ担持酸化セリウム粉体を調製し
た。この粉体をボールミルで湿式粉砕することにより水
性スラリーを調製し、このスラリーにモノリス担体を浸
し、余分なスラリーを吹きはらい、乾燥、焼成し、Ｐｄ
−ＡＱ担持酸化セリウムを塗布した担体（アルコール用
触媒）を得た。(5) An aqueous solution of a water-soluble salt of Pd and an aqueous solution of a water-soluble salt of Act were mixed, cerium oxide was added thereto, mixed, dried, and fired to prepare P(j-AQ-supported cerium oxide powder). An aqueous slurry is prepared by wet-pulverizing this powder in a ball mill, a monolithic carrier is immersed in this slurry, excess slurry is blown off, the Pd is
A carrier (alcohol catalyst) coated with -AQ-supported cerium oxide was obtained.
次に、Ｐｄの水溶性塩の水溶液とＡｃｔの水溶性塩の水
溶液を混合し、これに活性アルミナを加え混合し、乾燥
、焼成し、Ｐｄ−ＡＣＩ担持アルミナ粉体を調製した。Next, an aqueous solution of a water-soluble salt of Pd and an aqueous solution of a water-soluble salt of Act were mixed, activated alumina was added thereto, mixed, dried, and fired to prepare a Pd-ACI-supported alumina powder.
この粉体をボールミルで湿式粉砕することにより水性ス
ラリーを調製し、このスラリーにｐｄ−ＡＱ担持酸化セ
リウムを被覆した担体を浸し、余分なスラリーを吹きは
らい、乾燥、焼成し、Ｐｄ−ＡＱ担持酸化４
セリウムにＰｄ−Ａｃｔ担持活性アルミナを追加被覆し
た担体を得た（アルコール用触媒が２層被覆されたもの
）。An aqueous slurry is prepared by wet-pulverizing this powder in a ball mill, and a carrier coated with pd-AQ-supported cerium oxide is immersed in this slurry, excess slurry is blown off, dried, calcined, and Pd-AQ-supported cerium oxide is immersed in the slurry. 4 A carrier was obtained in which cerium was additionally coated with Pd-Act-supported activated alumina (coated with two layers of alcohol catalyst).
次に、ｐｔの水溶性塩の水溶液とＲｈの水溶性塩の水溶
液を混合し、これに活性アルミナを加え混合し、乾燥、
焼成し、Ｐｔ−Ｒｈ担持アルミナ粉体を調製した。この
粉体ど酸化セリウムをボールミルで湿式粉砕することに
よりスラリーを調製し、該スラリーにｐｄ−ＡＱ担持酸
化セリウムにｐｄ−ＡＣＩ担持活性アルミナを被覆した
担体を浸し、余分なスラリーを吹きはらい、乾燥、焼成
し、三元触媒を被覆することにより完成触媒を得た。Next, an aqueous solution of a water-soluble salt of PT and an aqueous solution of a water-soluble salt of Rh are mixed, activated alumina is added thereto, mixed, dried,
This was fired to prepare Pt-Rh supported alumina powder. A slurry is prepared by wet-pulverizing this powdered cerium oxide in a ball mill, and a carrier in which pd-AQ-supported cerium oxide is coated with pd-ACI-supported activated alumina is immersed in the slurry, excess slurry is blown away, and the slurry is dried. A finished catalyst was obtained by calcination and coating with a three-way catalyst.
〈発明の効果〉
本発明の排気ガス浄化用触媒の製造方法は、モノリス担
体表面に形成する触媒コーティング層が少なくとも２層
以上の触媒組成の異なるコーティング層からなり、少な
くとも１層以上のアルデヒドおよび／またはアルコール
浄化性能を有する触５
媒コーティング層が内層にあり、少なくとも１層以上の
三元性能を有する触媒コーティング層が外層にある構成
としたものである。この触媒は、アルデヒド浄化性能を
有する触媒組成物と三元性能を有する触媒組成物とを分
離し、互いの触媒が活性に悪影響を与えないようにし、
また三元性能を有する触媒コーティング層を外層にする
ことによって、Ｃｏ、ＨＣ，ＮＯｘのガス拡散が律速に
ならないようにすることによりＣｏ、ＨＣＳＮ。<Effects of the Invention> In the method for producing an exhaust gas purification catalyst of the present invention, the catalyst coating layer formed on the surface of the monolithic carrier is composed of at least two coating layers having different catalyst compositions, and at least one layer of aldehyde and/or Alternatively, a catalyst coating layer having alcohol purification performance is provided as an inner layer, and at least one catalyst coating layer having ternary performance is provided as an outer layer. This catalyst separates a catalyst composition having aldehyde purification performance and a catalyst composition having three-way performance, so that the catalysts do not adversely affect the activity of each other,
In addition, by using a catalyst coating layer with ternary performance as the outer layer, the gas diffusion of Co, HC, and NOx is prevented from becoming rate-determining.
Ｘを除去と同時に低温域から未燃メタノールおよびアル
デヒド類を浄化できるものである。It can remove X and simultaneously purify unburned methanol and aldehydes from a low temperature range.
く実 施 例〉
以下、実施例および比較例にて本発明の詳細な説明して
いくが、本発明はこれらに限定さるものではない。EXAMPLES The present invention will be described in detail below using Examples and Comparative Examples, but the present invention is not limited thereto.
実施例 １
市販のコージェライト質ハニカム担体（日本碍子製、以
下「ハニカム担体」という）を用いて触６
媒を調製した。用いたハニカム担体は、横断面が１イン
チ平方当り約４００個のガス流通セルを右する２４Ｈφ
、長さ１２０ｓＬの円柱状のもので５４−の体積を有す
るものを用い１ζ。パラジウム（Ｐｄ）として１．５０
を含有する硝酸パラジウム水溶液と銀（ＡＣＩ）として
１５０を含有する硝酸銀水溶液を混合し、これと酸化セ
リウム（市販品）１５０ｑを混合し、１５０°Ｃで２時
間乾燥した後、空気中５００°Ｃで１時間焼成した。こ
のＰｄ−Ａｑ担持酸化セリウム粉体（Ａ）をボールミル
で湿式粉砕することにより、コーティング用水性スラリ
ーを調製した。このコーティング用水性スラリーに前記
モノリス担体を浸漬し、取り出した後、セル内の過剰ス
ラリーを空気でブローして、全てのセルの目詰りを除去
した。Example 1 A catalyst was prepared using a commercially available cordierite honeycomb carrier (manufactured by Nippon Insulators, hereinafter referred to as "honeycomb carrier"). The honeycomb carrier used had a cross section of 24Hφ with approximately 400 gas flow cells per square inch.
, 1ζ using a cylindrical one with a length of 120 sL and a volume of 54-. 1.50 as palladium (Pd)
A palladium nitrate aqueous solution containing 150 as silver (ACI) was mixed with a silver nitrate aqueous solution containing 150 as silver (ACI), and this was mixed with 150q of cerium oxide (commercial product), dried at 150°C for 2 hours, and then heated at 500°C in air. Baked for 1 hour. An aqueous slurry for coating was prepared by wet-pulverizing this Pd-Aq-supported cerium oxide powder (A) in a ball mill. After the monolithic carrier was immersed in this aqueous coating slurry and taken out, the excess slurry in the cells was blown out with air to remove clogging from all cells.
次いで、１５０℃で２時間乾燥し、５００°Ｃで１時間
焼成して、ｐｄ−ＡＣＩ担持酸化セリウムを被覆した担
体（Ｂ）が得られた。Next, it was dried at 150°C for 2 hours and calcined at 500°C for 1 hour to obtain a carrier (B) coated with pd-ACI-supported cerium oxide.
次に、白金（Ｐｔ）１．５ｇを含有するジニトロジアン
ミン白金の硝酸水溶液とロジウム（Ｒｈ）７
０．３ｇを含有する硝酸ロジウム水溶液を混合し、この
水溶液と比表面積１００ｍ２／ｑの活性アルミナ１００
ｇを混合し、充分に乾燥した後、空気中４００℃で２時
間焼成して、Ｐｔ−Ｒｈ含有アルミナ（Ｃ）を調製した
。このＰｌ、Ｒｈ含有アルミナと市販の酸化セリウム粉
体５Ｃ１とをボールミルで湿式粉砕することによりコー
ティング用水性スラリーを調製した。このコーティング
用水性スラリーに該ｐ（ＩＡｇ担持酸化セリウムを被覆
した担体を浸漬し、取り出した後、セル内の過剰スラリ
ーを空気でブローして、全てのセルの目詰りを除去した
。次いで、１５０℃で２時間乾燥して触媒（ａ）を得た
。Next, a nitric acid aqueous solution of dinitrodiammine platinum containing 1.5 g of platinum (Pt) and a rhodium nitrate aqueous solution containing 0.3 g of rhodium (Rh) 7 were mixed, and this aqueous solution and activated alumina 100 with a specific surface area of 100 m2/q were mixed.
After thoroughly drying, Pt-Rh-containing alumina (C) was prepared by baking in air at 400°C for 2 hours. An aqueous slurry for coating was prepared by wet-pulverizing this Pl- and Rh-containing alumina and commercially available cerium oxide powder 5C1 in a ball mill. The carrier coated with the p(IAg-supported cerium oxide) was immersed in this aqueous slurry for coating, and after being taken out, the excess slurry in the cells was blown with air to remove clogging from all the cells. The catalyst (a) was obtained by drying at ℃ for 2 hours.
この触媒は１１当り、Ｐｄ１．Ｏｑ、Ａｇ１０ｇ、酸化
セリウム１３３．３ｑ、活性アルミナ６６．７ ａ、Ｐ
ｔ１．ＯｇおよびＲｈＯ，２Ｃ］が担持されていた。This catalyst has Pd1. Oq, Ag10g, cerium oxide 133.3q, activated alumina 66.7a, P
t1. Og and RhO, 2C] were supported.
実施例 ２
実施例１のＰｄ−Ａ ａ担持酸化セリウム粉体（八）に
おいてパラジウム（Ｐｄ）として１．５ｇを８
用いる代りに白金（Ｐｔ）として１，５Ｑを含有するジ
ニトロジアミン白金の水溶液を用いる以外は同様の方法
で、Ｐｔ−ＡＱ担持酸化セリウムを被覆した担体を得た
。Example 2 Instead of using 1.5 g of palladium (Pd) in the Pd-A a-supported cerium oxide powder (8) of Example 1, an aqueous solution of dinitrodiamine platinum containing 1,5Q as platinum (Pt) was used. A carrier coated with Pt-AQ-supported cerium oxide was obtained in the same manner except for the use of Pt-AQ-supported cerium oxide.
次に、実施例１と同様の操作を行ってＰＩ、Ｒｈ担持ア
ルミナ（Ｃ）を調製し、このＰｔ−Ｒｈ担持粉体１００
ｏと実施例１で用いた酸化セリウム５Ｃ１とをボールミ
ルで湿式粉砕し、水性スラリーを調製した。該スラリー
にＰｔ−ＡＣｔ担持酸化セリウムを被覆した担体を浸漬
し、以下実施例１と同様の操作を行って触媒（ｂ）を得
た。Next, the same operation as in Example 1 was carried out to prepare PI and Rh-supported alumina (C), and this Pt-Rh-supported powder 100
o and the cerium oxide 5C1 used in Example 1 were wet-milled in a ball mill to prepare an aqueous slurry. A carrier coated with Pt-ACt-supported cerium oxide was immersed in the slurry, and the same operations as in Example 1 were performed to obtain a catalyst (b).
Ｌ、（７）触媒は１１当り、Ｐｔ２．Ｏｑ、Ａｇ１Ｏｃ
＋、酸化セリウム１３３．３（Ｊ、活性アルミナ６６．
７ｇ、Ｐ ｔ １．ＯａおよびＲｈ０．２ＣＩが担持さ
れていた。L, (7) catalyst per 11, Pt2. Oq, Ag1Oc
+, cerium oxide 133.3 (J, activated alumina 66.
7g, Pt1. Oa and Rh0.2CI were supported.
実施例 ３
実施例１のＰｔ−Ｒｈ担持アルミナ（Ｃ）においてＰｔ
として１．５ｇを用いる代りに、Ｐｄとして１．５９を
含有する硝酸パラジウムの水溶液を用いる以外は同様の
方法でＰｄ−Ｒｈ担持アルミナを ９
調製した。Example 3 Pt in the Pt-Rh supported alumina (C) of Example 1
Pd-Rh supported alumina was prepared in a similar manner except that instead of using 1.5 g of Pd, an aqueous solution of palladium nitrate containing 1.59 Pd was used.
このＰｄ−Ｒｈ担持アルミナ１００ｇと実施例１で用い
た酸化セリウム５０ｏとをボールミルで湿式粉砕し、水
性スラリーを調製した。該スラリーに実施例１と同様の
操作を行って得たＰｄ−Ａｑ担持酸化セリウムを被覆し
た担体（Ｂ）を浸漬し、以下実施例１と同様の操作を行
って触媒（Ｃ）を得た。100 g of this Pd-Rh supported alumina and 50 o of cerium oxide used in Example 1 were wet-pulverized in a ball mill to prepare an aqueous slurry. A carrier (B) coated with Pd-Aq-supported cerium oxide obtained by performing the same operation as in Example 1 was immersed in the slurry, and a catalyst (C) was obtained by performing the same operation as in Example 1. .
コノ触媒Ｌｔ１ｊ２当り、Ｐｄ１．Ｏｏ、ＡＯ１０Ｃ］
、活性アルミナ１００ｇ、酸化セリウム１３３．３Ｑ、
Ｐｔ１゜ＯｑおよびＰｈ０．２ｇが担持されていた。Per Kono catalyst Lt1j2, Pd1. Oo, AO10C]
, activated alumina 100g, cerium oxide 133.3Q,
1°Oq of Pt and 0.2g of Ph were supported.
実施例 ４
Ｐｔ１．５ｇを含有するジニトロジアンミン白金の硝酸
水溶液と実施例１で用いた活性アルミナ１００ｇを混合
し、充分乾燥した後、空気中４００℃で２時間焼成して
、ｐｔ担持アルミナを調製した。Example 4 A nitric acid aqueous solution of dinitrodiammine platinum containing 1.5 g of Pt was mixed with 100 g of the activated alumina used in Example 1, thoroughly dried, and then calcined in air at 400°C for 2 hours to prepare PT-supported alumina. did.
このＰｔ担持アルミナと実施例１で用いた酸化セリウム
５０ｇとをボールミルで湿式乾燥し、水０
性スラリーを調製した。該スラリーに実施例１と同様の
操作を行って得たｐｃｉ−Ａｏ担持酸化セリウムを被覆
した担体（Ｂ）を浸漬し、以下実施例１と同様の操作を
行ってｐｄ−ＡＱ担持酸化セリウムの上にｐｔ−活性ア
ルミナ担持酸化セリウムを被覆した担体が得られた。This Pt-supported alumina and 50 g of cerium oxide used in Example 1 were wet-dried in a ball mill to prepare a water-free slurry. The carrier (B) coated with pci-Ao-supported cerium oxide obtained by performing the same operation as in Example 1 was immersed in the slurry, and then the same operation as in Example 1 was performed to obtain pd-AQ-supported cerium oxide. A support was obtained on which cerium oxide supported on pt-activated alumina was coated.
次に、Ｒｈ０．３ＣＩを含有する硝酸ロジウム水溶液と
実施例１で用いた活性アルミナ６６．７０を混合し、充
分乾燥した後空気中４００°Ｃで２時間焼成して、Ｒｈ
担持アルミナをＩＩした。このＲｈ含有アルミナをボー
ルミルで湿式粉砕し、水性スラリーを調製した。該スラ
リーにＰｃｊ−Ａｇ担持酸化セリウムの上にｐｔ担持活
性アルミナ−酸化セリウムを被覆した担体を浸漬し、以
下実施例１と同様の操作を行って触媒（ｄ）を得た。Next, the rhodium nitrate aqueous solution containing Rh0.3CI and the activated alumina 66.70 used in Example 1 were mixed, thoroughly dried, and then calcined in air at 400°C for 2 hours.
Supported alumina was used as II. This Rh-containing alumina was wet-pulverized in a ball mill to prepare an aqueous slurry. A carrier in which Pcj-Ag-supported cerium oxide was coated with PT-supported activated alumina-cerium oxide was immersed in the slurry, and the same operations as in Example 1 were carried out to obtain a catalyst (d).
この触媒は１１当り、ＰｄＬＯＱ、 ＡｇＩ ＯＱ。This catalyst has 11 per cent, PdLOQ, AgI OQ.
酸化セリウム１３３．３ｇ、活性アルミナ１１６．７０
、Ｐｔ１．ＯＣｌ、Ｒｈ ０．２ ＣＩが担持されてい
た。Cerium oxide 133.3g, activated alumina 116.70g
, Pt1. OCl and Rh 0.2 CI were supported.
１
実施例 ５
実施例１のＰｄ−Ａｇ担持酸化セリウム粉体（＾）にお
いて、酸化セリウム１５０Ｑを用いる代りに実施例１で
用いた活性アルミナ１５０ｇを用いる以外は同様の方法
でＰｄ−Ａｃｔ担持活性アルミナ粉体（Ｄ）を調製した
。1 Example 5 In the Pd-Ag-supported cerium oxide powder (^) of Example 1, Pd-Ac supported activity was obtained in the same manner except that 150 g of activated alumina used in Example 1 was used instead of cerium oxide 150Q. Alumina powder (D) was prepared.
この粉体をボールミルで湿式粉砕し、水性スラリーを調
製した。該スラリーにアルミニウム含有フェライト系ク
ロムスチールからなる渦巻状金属モノリス担体を浸漬し
、実施例１と同様の操作を行ってＰｄ−Ａｑ担持アルミ
ナを被覆した担体が得られた。This powder was wet-milled using a ball mill to prepare an aqueous slurry. A spiral metal monolithic support made of aluminum-containing ferritic chromium steel was immersed in the slurry, and the same operation as in Example 1 was performed to obtain a support coated with Pd-Aq-supported alumina.
次に、実施例１と同様の方法で１ｑたＰｔ、Ｒｈ含有ア
ルミナ（ＣＭＯＯＣＩと実施例１で用いた酸化セリウム
５０ｇとをボールミルで湿式粉砕し、水性スラリーを調
製した。該スラリーに該ＰｄＡＱ担持アルミナを被覆し
た担体を浸漬し、以下実施例１と同様の操作を行って触
媒（ｅ）を得た。Next, in the same manner as in Example 1, 1 q of Pt and Rh-containing alumina (CMOOCI) and 50 g of cerium oxide used in Example 1 were wet-pulverized in a ball mill to prepare an aqueous slurry. A carrier coated with alumina was immersed, and the same operations as in Example 1 were performed to obtain a catalyst (e).
コノ触媒は１１当り、Ｐｄ１．ＯＱ、Ａｑｌｏｑ。Kono catalyst is 11 per cent, Pd1. OQ, Aqloq.
活性アルミナ１６６．７ＣＩ、酸化セリウム３３．３Ｃ
Ｉ、２
ｐｔｌ、ＯｃＩ、Ｒｈ０．２Ｃ］が担持されていた。Activated alumina 166.7CI, cerium oxide 33.3C
I, 2ptl, OcI, Rh0.2C] were carried.
実施例 ６
実施例５のｐ（ｊ−Ａｇ担持活性アルミナ粉体（Ｄ）に
おいて、ｐｄｉ、ｓｑを用いない以外は同様の方法でＡ
ｃｔ担持活性アルミナ粉体を調製した。Example 6 A was prepared in the same manner as in Example 5 except that pdi and sq were not used in the p(j-Ag-supported activated alumina powder (D)).
A ct-supported activated alumina powder was prepared.
この粉体をボールミルで湿式粉砕し、水性スラリーを調
製した。該スラリーに実流例１と同様の操作を行ってＡ
ｃｔ担持アルミナを被覆した担体が得られた。次に実施
例１と同様の方法で得たＰｔＲｈ担持アルミナ（Ｃ）１
００ＣＩと実施例１で用いた酸化セリウム５０ＣＪとを
ボールミルで湿式粉砕し、水性スラリーを調製した。該
スラリーに該ＡＯ−アルミナを被覆した担体と浸漬し、
以下実施例１と同様の操作を行って触媒ｍを得た。This powder was wet-milled using a ball mill to prepare an aqueous slurry. The slurry was subjected to the same operation as in Actual Flow Example 1 to obtain A.
A support coated with ct-supported alumina was obtained. Next, PtRh-supported alumina (C) 1 obtained in the same manner as in Example 1
00CI and cerium oxide 50CJ used in Example 1 were wet-pulverized in a ball mill to prepare an aqueous slurry. immersing the AO-alumina-coated carrier in the slurry;
Thereafter, the same operation as in Example 1 was performed to obtain catalyst m.
この触媒は１１当り、Ａｏ１０ｃ＋、活性アルミナ１６
６．７０．酸化セリウム３３．３Ｃ１、Ｐｔ１．Ｏａ、
Ｒｈ０．２ｇが担持されていた。This catalyst is 11 per cent, Ao10c+, activated alumina 16
6.70. Cerium oxide 33.3C1, Pt1. Oa,
0.2 g of Rh was supported.
３
実施例 ７
硝酸ランタン［Ｌａ （ＮＯ３）３ ・６Ｈ２０］６．
５１Ｑと硝酸ネオジウム［Ｎｂ （ＮＯ３）ａ６Ｈ２０
］２．７４ｇを純水２００ ｃｃに溶液したものを実施
例１で用いた活性アルミナ１５０ｇと混合し、１５０℃
で２時間乾燥した後、空気中７００℃で２時間焼成した
。この粉体にＰｄ１．５Ｑを含有する硝酸パラジウム水
溶液と混合し、１５０℃で２時間乾燥した後、空気中５
００℃で１時間焼成し、Ｐｄ−ランタン−ネオジウム担
持アルミナを調製した。このＰｄ−ランタン−ネオジウ
ム担持アルミナをボールミルで湿式粉砕し、水性スラリ
ーを調製した。該スラリーに実施例１で用いたモノリス
担体を浸漬し、以下実施例１と同様の操作を行ってＰｄ
−ランタン−ネオジウム担持アルミナを被覆した担体が
得られた。次に、実施例１と同様の方法で得たＰｔ−Ｒ
ｈ担持アルミナ（Ｃ）１０Ｃ１と実施例１で用いた酸化
セリウム５０Ｃ１とをボールミルで湿式粉砕し、水性ス
ラリーを調製した。該スラリーに該Ｐｄ−ランタン４
ネオジウム担持アルミナを被覆した担体を浸漬し、以下
実施例１と同様の操作を行って触媒（ｇ）を得た。3 Example 7 Lanthanum nitrate [La (NO3)3 ・6H20]6.
51Q and neodymium nitrate [Nb (NO3)a6H20
]2.74g in 200cc of pure water was mixed with 150g of activated alumina used in Example 1, and heated at 150°C.
After drying for 2 hours, it was fired in air at 700°C for 2 hours. This powder was mixed with a palladium nitrate aqueous solution containing Pd1.5Q, dried at 150°C for 2 hours, and then
The mixture was fired at 00° C. for 1 hour to prepare Pd-lanthanum-neodymium-supported alumina. This Pd-lanthanum-neodymium-supported alumina was wet-pulverized in a ball mill to prepare an aqueous slurry. The monolithic support used in Example 1 was immersed in the slurry, and the same operation as in Example 1 was performed to obtain Pd.
A support coated with -lanthanum-neodymium supported alumina was obtained. Next, Pt-R obtained in the same manner as in Example 1
h-supported alumina (C) 10C1 and cerium oxide 50C1 used in Example 1 were wet-pulverized in a ball mill to prepare an aqueous slurry. A carrier coated with the Pd-lanthanum 4 neodymium-supported alumina was immersed in the slurry, and the same operation as in Example 1 was carried out to obtain a catalyst (g).
こ（Ｄ触媒は１．１２当り、Ｐｄ１．Ｏｇ、Ｎｄ２０３
１．０５ＱＳＬａ２０３２．４５Ｑ、活性アルミナ１６
６、７ ｇ、酸化セリウム３３．３ｇが担持されていた
。(D catalyst per 1.12, Pd1.Og, Nd203
1.05QSLa2032.45Q, activated alumina 16
6.7 g of cerium oxide and 33.3 g of cerium oxide were supported.
比較例 １
実施例１と同様の方法で得たＰｔ−Ｒｈ担持アルミナ（
Ｃ）１０Ｃ１と、実施例１で用いた酸化セリウム５０ｇ
とをボールミルで湿式粉砕し、水性スラリーを調製した
。該スラリーに実施例１ど同様の操作を行ってＰｔ、Ｒ
ｈ−アルミナ担持酸化セリウムを被覆した担体が得られ
た。次に、実施例１と同様の方法で得たｐｄ−Ａｇ担持
酸化セリウム粉体（Ａ）１５００をボールミルで湿式粉
砕し、水性スラリーを調製した。該スラリーにｐｔ−Ｒ
ｈ−アルミナ担持酸化セリウムを被覆した担体を浸漬し
、実施例１と同様の操作を行って触媒５
（ｈ）を得た。Comparative Example 1 Pt-Rh supported alumina (obtained in the same manner as in Example 1)
C) 10C1 and 50g of cerium oxide used in Example 1
was wet-milled using a ball mill to prepare an aqueous slurry. The slurry was subjected to the same operation as in Example 1 to obtain Pt, R.
A carrier coated with cerium oxide supported on h-alumina was obtained. Next, pd-Ag supported cerium oxide powder (A) 1500 obtained in the same manner as in Example 1 was wet-pulverized in a ball mill to prepare an aqueous slurry. Add pt-R to the slurry
A carrier coated with cerium oxide supported on h-alumina was immersed, and the same operation as in Example 1 was performed to obtain catalyst 5 (h).
この触媒は１ｊ！当り、Ｐｄ１．ＯＣ］、ＡＣｌｌｏｇ
、活性アルミナ６６．、７ Ｑ 、酸化セリウム１３３
．．３ｇ、Ｐｔ１．Ｏｑ、Ｒｈ０．２ＣＩが担持されて
いた。This catalyst is 1j! Hit, Pd1. OC], ACllog
, activated alumina66. , 7 Q, cerium oxide 133
．． ．． 3g, Pt1. Oq, Rh0.2CI was supported.
比較例 ２
実施例１と同様の方法で得たＰｄ−Ａｇ担持酸化セリウ
ム粉体（Ａ）１５０ｃ＋と、実施例１と同様の方法で得
たＰｔ−Ｒｈ担持アルミナ（Ｃ）１００ｑと実施例１で
用いた酸化セリウム５０ｇとをボールミルで湿式粉砕し
、水性スラリーを調製した。Comparative Example 2 Pd-Ag-supported cerium oxide powder (A) 150c+ obtained by the same method as Example 1, Pt-Rh-supported alumina (C) 100q obtained by the same method as Example 1, and Example 1 50 g of the cerium oxide used in the above was wet-pulverized in a ball mill to prepare an aqueous slurry.
該スラリーに実施例１で用いたモノリス担体を浸漬し、
以下実施例１と同様の操作を行って触媒１）を得た。The monolithic carrier used in Example 1 was immersed in the slurry,
Thereafter, the same operation as in Example 1 was performed to obtain catalyst 1).
この触媒は１．ｉ２当り、Ｐｄ１．ＯＯｌＡｇｌｏｇ、
酸化セリウム１３３．３ＣＩ、活性アルミナ６６．７（
１１、Ｐｔ１．ＯＣ］、Ｒｈ０．２０が担持されていた
。This catalyst is 1. per i2, Pd1. OOlAglog,
Cerium oxide 133.3 CI, activated alumina 66.7 (
11, Pt1. OC], Rh0.20 was supported.
実施例 ８ 実施例１〜７、比較例１〜２で調製した触媒６ （ａ）〜（ｉ）について触媒性能テストを行った。Example 8 Catalyst 6 prepared in Examples 1-7 and Comparative Examples 1-2 Catalyst performance tests were conducted for (a) to (i).
２５．５ ｔｔｖｎφＸ ３００ ｒｔｖｎ Ｌのステ
ンレス製反応管に触媒を充填後、−酸化炭素０．５容量
％、酸素０．６５容量％、ＨＣ成分としてプロピレン４
３０ｐｐｍ 、−酸化窒素５ＱＱｐｐｍ、二酸化炭素１
４．５容量％、水２０容量％、メタノール（Ｍ ｅ Ｏ
Ｈ）１３００ｐｐｍ、ホルムアルデヒド’＋ｏｏｐｐｍ
、残り窒素金含有するＳ、Ｖ、２５，０００Ｈｒ−１の
条件で導入し、触媒入口温度を１５０°Ｃから４００℃
まで変化させ、触媒（ａ）〜（１）について触媒性能の
評価を行った。After filling a stainless steel reaction tube of 25.5 ttvnφ
30ppm, -nitrogen oxide 5QQppm, carbon dioxide 1
4.5% by volume, 20% by volume of water, methanol (M e O
H) 1300ppm, formaldehyde'+ooppm
, S and V containing remaining nitrogen and gold were introduced under the conditions of 25,000 Hr-1, and the catalyst inlet temperature was changed from 150°C to 400°C.
The catalyst performance was evaluated for catalysts (a) to (1).
メタノールの分析はＦＩＤガスクロマトグラフィーを用
い、ホルムアルデヒド（ＨＣＨＯ）の分析はクロモトロ
ープ酸を用いた比色分析で行った。Methanol was analyzed using FID gas chromatography, and formaldehyde (HCHO) was analyzed by colorimetric analysis using chromotropic acid.
また、プロピレンの分析は、ＨＣ分析計を用いて行い、
そのプロピレンａ度は全ＨＣの値からメタノールの値を
引いた値より求めた。In addition, propylene analysis was performed using an HC analyzer.
The propylene a degree was determined by subtracting the methanol value from the total HC value.
ＣＯは、赤外分析計により、Ｎｏは、化学発光分析によ
り濃度を測定した。The concentration of CO was measured by an infrared analyzer, and the concentration of No was measured by chemiluminescence analysis.
ＣＯ、Ｎｏ、ＨＣ，ＭｅＯＨおよびＨＣＨＯの評価結果
を表１に示し、表中の値は、ＣＯ，Ｎｏ１ＨＣ，ＭｅＯ
）−１については、各々の浄化率が５０％になる温度を
、ＨＣＨＯについては、触媒入口温度１５０°Ｃでの浄
化率を示した。The evaluation results for CO, No. 1HC, MeOH and HCHO are shown in Table 1, and the values in the table are CO, No.1HC, MeO
)-1, the temperature at which each purification rate becomes 50% is shown, and for HCHO, the purification rate at a catalyst inlet temperature of 150°C is shown.
８ ２つ 手続主甫正書（自艶） 平成に年夕月ｋｚ日8 two Procedural Master Fu Seisho (Seishin) Heisei year, evening moon kz day
Claims (10)
デヒド浄化能を有する触媒層を設け、さらに該触媒層上
に三元性能を有する触媒層を設けたことを特徴とするア
ルコール燃料またはアルコール−ガソリン混合燃料を用
いる内燃機関排出ガスの浄化用触媒。(1) Alcohol fuel or alcohol-gasoline mixed fuel characterized by providing a catalyst layer having alcohol and/or aldehyde purification ability on a monolithic carrier, and further providing a catalyst layer having three-way performance on the catalyst layer. A catalyst for purifying internal combustion engine exhaust gas.
する触媒層が複層である請求項（１）記載の触媒。(2) The catalyst according to claim (1), wherein the catalyst layer having alcohol and/or aldehyde purifying ability is multi-layered.
）記載の触媒。(3) Claim (1) wherein the catalyst layer having three-way performance is a multi-layered catalyst layer.
) described catalyst.
する触媒層が複層で、かつ三元性能を有する触媒層が複
層である請求項（１）記載の触媒。(4) The catalyst according to claim (1), wherein the catalyst layer having alcohol and/or aldehyde purifying ability is multilayered, and the catalyst layer having three-way performance is multilayered.
する触媒層が、パラジウム、白金および銀からなる群か
ら選ばれる少なくとも１種の金属と、酸化セリウム、活
性アルミナおよび希土類を含有した活性アルミナからな
る群から選ばれる少なくとも１種の酸化物とを含有して
なる請求項（１）、（２）または（４）記載の触媒。(5) The catalyst layer having alcohol and/or aldehyde purifying ability is selected from the group consisting of at least one metal selected from the group consisting of palladium, platinum, and silver, and activated alumina containing cerium oxide, activated alumina, and rare earth elements. The catalyst according to claim 1, comprising at least one selected oxide.
する触媒層が、パラジウムおよび／または白金と、銀並
びに酸化セリウム、活性アルミナおよび希土類を含有し
た活性アルミナからなる群から選ばれる少なくとも１種
の 酸化物とを含有してなる請求項（１）、（２）、（４）
または（５）記載の触媒。(6) The catalyst layer having alcohol and/or aldehyde purification ability is made of at least one oxide selected from the group consisting of palladium and/or platinum, silver, and activated alumina containing cerium oxide, activated alumina, and rare earth elements. Claims (1), (2), (4) containing
Or the catalyst described in (5).
たは白金と、ロジウム、活性アルミナおよび酸化セリウ
ムを含有する請求項（１）、（３）または（４）記載の
触媒。(7) The catalyst according to claim (1), (3) or (4), wherein the catalyst layer having ternary performance contains palladium and/or platinum, rhodium, activated alumina and cerium oxide.
する触媒層が、パラジウム、白金および銀からなる群か
ら選ばれる少なくとも１種の金属と、酸化セリウム、活
性アルミナおよび希土類を含有した活性アルミナからな
る群から選ばれる少なくとも１種の酸化物とを含有し、
三元性能を有する触媒層がパラジウムおよび／または白
金と、ロジウム、活性アルミナおよび酸化セリウムを含
有する請求項（１）または（４）記載の触媒。(8) The catalyst layer having alcohol and/or aldehyde purifying ability is selected from the group consisting of at least one metal selected from the group consisting of palladium, platinum, and silver, and activated alumina containing cerium oxide, activated alumina, and rare earth elements. and at least one selected oxide,
The catalyst according to claim 1 or 4, wherein the catalyst layer having ternary performance contains palladium and/or platinum, rhodium, activated alumina, and cerium oxide.
する触媒層が、パラジウムおよび／または白金と、銀並
びに酸化セリウム、活性アルミナおよび希土類を含有し
た活性アルミナからなる群から選ばれる少なくとも１種
の酸化物を含有し、三元性能を有する触媒層が、パラジ
ウムおよび／または白金と、ロジウム、活性アルミナお
よび酸化セリウムを含有する請求項（１）または（４）
記載の触媒。(9) The catalyst layer having alcohol and/or aldehyde purification ability contains at least one oxide selected from the group consisting of palladium and/or platinum, silver, and activated alumina containing cerium oxide, activated alumina, and rare earth elements. Claim (1) or (4), wherein the catalyst layer containing ternary performance contains palladium and/or platinum, rhodium, activated alumina, and cerium oxide.
Catalysts as described.
あるハニカムモノリス担体である請求項（１）記載の触
媒。(10) The catalyst according to claim (1), wherein the monolithic carrier is a metallic or ceramic honeycomb monolithic carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1246421A JPH03109941A (en) | 1989-09-25 | 1989-09-25 | Catalyst for purifying exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1246421A JPH03109941A (en) | 1989-09-25 | 1989-09-25 | Catalyst for purifying exhaust gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03109941A true JPH03109941A (en) | 1991-05-09 |
Family
ID=17148230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1246421A Pending JPH03109941A (en) | 1989-09-25 | 1989-09-25 | Catalyst for purifying exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03109941A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU677534B2 (en) * | 1994-12-16 | 1997-04-24 | Toyota Jidosha Kabushiki Kaisha | Catalyst for exhaust gases |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50145381A (en) * | 1974-05-14 | 1975-11-21 | ||
| JPS57105240A (en) * | 1980-12-24 | 1982-06-30 | Mitsui Toatsu Chem Inc | Exhaust gas purifying catalyst and preparation thereof |
| JPS637845A (en) * | 1986-06-30 | 1988-01-13 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for purifying exhaust gas from internal combustion engine using alcohol as fuel |
-
1989
- 1989-09-25 JP JP1246421A patent/JPH03109941A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50145381A (en) * | 1974-05-14 | 1975-11-21 | ||
| JPS57105240A (en) * | 1980-12-24 | 1982-06-30 | Mitsui Toatsu Chem Inc | Exhaust gas purifying catalyst and preparation thereof |
| JPS637845A (en) * | 1986-06-30 | 1988-01-13 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for purifying exhaust gas from internal combustion engine using alcohol as fuel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU677534B2 (en) * | 1994-12-16 | 1997-04-24 | Toyota Jidosha Kabushiki Kaisha | Catalyst for exhaust gases |
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