JPS63178848A - Catalyst for purifying exhaust gas - Google Patents
Catalyst for purifying exhaust gasInfo
- Publication number
- JPS63178848A JPS63178848A JP62009110A JP911087A JPS63178848A JP S63178848 A JPS63178848 A JP S63178848A JP 62009110 A JP62009110 A JP 62009110A JP 911087 A JP911087 A JP 911087A JP S63178848 A JPS63178848 A JP S63178848A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zirconia
- exhaust gas
- weight
- average particle
- 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 74
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000002245 particle Substances 0.000 claims abstract description 32
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 20
- 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 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 40
- 239000010948 rhodium Substances 0.000 claims description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 29
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000011164 primary particle Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002002 slurry Substances 0.000 abstract description 7
- 238000000151 deposition Methods 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 description 20
- 239000007789 gas Substances 0.000 description 14
- 239000011247 coating layer Substances 0.000 description 12
- 238000011068 loading method Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010970 precious metal Substances 0.000 description 8
- 238000004453 electron probe microanalysis Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 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 5
- 230000032683 aging Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 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 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 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 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 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 2
- 239000006255 coating slurry Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［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。詳
しく述べると、本発明は、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）、
−酸化炭素（Ｇｏ）および窒素酸化物（ＮＯＸ ＞を同
時に除去する排気ガス浄化用触媒に関するものであり、
特に、高温酸化雰囲気のような厳しい条件下で使用され
ても優れた耐久性を有し、かつ上記有害成分に対し、低
温での高い浄化性能を有する排気ガス浄化用触媒に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a catalyst for purifying exhaust gas. Specifically, the present invention deals with hydrocarbons (HC), which are harmful components contained in exhaust gas from internal combustion engines such as automobiles,
- relates to an exhaust gas purification catalyst that simultaneously removes carbon oxides (Go) and nitrogen oxides (NOX);
In particular, the present invention relates to an exhaust gas purifying catalyst that has excellent durability even when used under severe conditions such as high-temperature oxidizing atmospheres, and has high purification performance at low temperatures against the above-mentioned harmful components.
［従来の技術］
従来、排気ガス浄化用触媒においては、使用量が微量に
限定された貴金属を有効に使用するため、例えば、高表
面積の活性アルミナ等に貴金属を出来るだけ高分散に担
持する努力がなされてきた。[Prior art] Conventionally, in exhaust gas purification catalysts, in order to effectively use precious metals whose usage was limited to trace amounts, efforts were made to support precious metals as highly dispersed as possible, for example, on activated alumina with a high surface area. has been done.
しかしながら貴金属を高分散に担持した触媒は、初期活
性は高いが、高温酸化雰囲気のような厳しい条件に曝さ
れると、貴金属の粒子成長や貴金属と担体物質との反応
が起こりやすく、貴金属が高分散に担持されているが故
に却って活性劣化が大きいという問題があった。However, although catalysts with highly dispersed noble metals have high initial activity, when exposed to harsh conditions such as high-temperature oxidizing atmospheres, noble metal particles are likely to grow and reactions between noble metals and the support material occur, resulting in noble metals becoming highly active. Since it is supported in a dispersion, there is a problem in that the deterioration of activity is rather large.
そして、ジルコニアは、本分野においては、触媒の比表
面積等の物性の安定を目的として主として担持基材に添
加して使用されることが多い。貴金属の担持基材として
使用した例としては、特公昭５７−２９２１５号および
特開昭５７−１５３７３７号公報において、アルミナお
よびジルコニアを含有する被覆層を担体に形成せしめた
後に貴金属を担持する方法が提案されている。しかし、
これらの方法では、大部分の貴金属が実質的にはアルミ
ナに高分散されるため、上記したのと同様な原因による
活性劣化が起こる。In this field, zirconia is often used mainly by being added to a supporting base material for the purpose of stabilizing the physical properties such as the specific surface area of the catalyst. As an example of use as a substrate for supporting noble metals, Japanese Patent Publication No. 57-29215 and Japanese Patent Application Laid-open No. 57-153737 disclose a method in which a coating layer containing alumina and zirconia is formed on a carrier and then noble metals are supported. Proposed. but,
In these methods, since most of the noble metals are substantially highly dispersed in alumina, activity deterioration occurs due to the same causes as described above.
米国特許第４２３３１８９号明細書では、ジルコニアの
被覆層を担体に形成せしめた後に、ジルコニアに対して
低い担持率のロジウムを担持する触媒が開示されている
が、本発明に開示する貴金属を高い担持率で担持した少
量のジルコニアを他の多量の耐火性無機酸化物に分散さ
せた触媒と比較して、触媒の耐久性能が大幅に劣るもの
であった。U.S. Pat. No. 4,233,189 discloses a catalyst that supports rhodium at a low loading rate on zirconia after forming a coating layer of zirconia on a carrier, but the catalyst disclosed in the present invention supports a high loading of noble metal. The durability of the catalyst was significantly inferior to that of a catalyst in which a small amount of zirconia supported at a high concentration was dispersed in a large amount of other refractory inorganic oxide.
１問題点を解決するための手段］
本発明者らは鋭意研究の結果、使用量が微量に限定され
るべき貴金属は、多量の高表面積の耐火性無機酸化物に
低い担持率で担持し、出来るだけ貴金属の分散度を高め
るべきとする従来の知見とは全く逆に貴金属を物性を特
定された少量のジルコニアに高い担持率で担持せしめて
なる貴金属含有ジルコニアを、その平均粒径０．１〜２
０μの比較的大きい凝集粒子に調整し、これを触媒コー
ティング層に分散させることにより触媒の耐久性能が飛
躍的に向上することを見出し、本発明を完成するに至っ
たのである。[Means for Solving Problem 1] As a result of intensive research, the present inventors have found that noble metals whose usage should be limited to a trace amount are supported at a low loading rate on a large amount of refractory inorganic oxide with a high surface area. Quite contrary to the conventional knowledge that the degree of dispersion of precious metals should be increased as much as possible, precious metal-containing zirconia is made by supporting a small amount of zirconia with specified physical properties at a high loading rate, and its average particle size is 0.1. ~2
They discovered that the durability of the catalyst could be dramatically improved by adjusting the agglomerated particles to a relatively large size of 0μ and dispersing them in the catalyst coating layer, leading to the completion of the present invention.
さらに、本発明者らは、白金および／またはパラジウム
とロジウムを共に本発明に開示する高い担持率で耐火性
無機酸化物上に共存させると、白金および／またはパラ
ジウムとロジウムの相互作用によって各々の貴金属が不
活性な状態へ化学変化することが抑制されることも見出
した。Furthermore, the present inventors have discovered that when platinum and/or palladium and rhodium are co-existed on the refractory inorganic oxide at the high loading rate disclosed in the present invention, each of the platinum and/or palladium interacts with rhodium. It has also been found that the chemical change of precious metals to an inactive state is suppressed.
このことも、排気ガス浄化用触媒においては、白金、パ
ラジウム、ロジウムが密接に存在すると、合金化するな
どして活性が失われるという従来の知見からは全く予見
しえなかったことである。This was also completely unexpected based on the conventional knowledge that when platinum, palladium, and rhodium are closely present in an exhaust gas purifying catalyst, they become alloyed and lose their activity.
［発明の構成］ 本発明の構成を以下に詳細に説明する。[Structure of the invention] The configuration of the present invention will be explained in detail below.
まず、貴金属のジルコニアへの高い担持率の範囲は、白
金および／またはパラジウムについては、５〜３０重量
％、好ましくは１０〜２０重量％。First, the range of high noble metal support on zirconia is 5 to 30% by weight, preferably 10 to 20% by weight for platinum and/or palladium.
ロジウムについては１〜２０重量％、好ましくは１〜１
０重量％である。白金および／またはパラジウムが５重
量％未満、またはロジウムが１重量％未満では通常の高
分散の状態に近くなり活性劣化が大きくなる。また、白
金および／またはパラジウムが３０重量％を超えたり、
ロジウムが２０重量％を超える場合は、反応に有効に寄
与する貴金属の活性点が増加せず、むしろ初期から少な
くなるため、触媒の初期性能が低く、また本発明の担持
率の範囲にある場合には見られない貴金属の粒子成長が
起こり、粒子が巨大化して触媒の活性は大幅に低下して
しまう。1-20% by weight for rhodium, preferably 1-1
It is 0% by weight. If the content of platinum and/or palladium is less than 5% by weight, or if the content of rhodium is less than 1% by weight, the content will approach a normal highly dispersed state, resulting in significant deterioration of activity. In addition, platinum and/or palladium exceeds 30% by weight,
If rhodium exceeds 20% by weight, the number of noble metal active sites that effectively contribute to the reaction will not increase, but rather decrease from the beginning, resulting in poor initial performance of the catalyst, and if the loading ratio is within the range of the present invention. Particle growth of the precious metal occurs, which is not seen in conventional methods, and the particles become huge, significantly reducing the activity of the catalyst.
また、白金および／またはパラジウムとロジウムを共に
高い担持率で担持することにより更に耐久性能が向上す
る。これは各々の貴金属の相互作用によって、例えば、
ロジウムが還元され難い酸化ロジウムを形成するといっ
た、不活性な状態への不可逆的な化学変化が抑制される
ためと考えられる。そして、本発明の担持率の範囲では
、驚くべきことに白金、パラジウム、ロジウムの合金化
による失活は見られなかった。Further, by supporting both platinum and/or palladium and rhodium at a high loading rate, durability performance is further improved. This is due to the interaction of each noble metal, e.g.
This is thought to be because an irreversible chemical change to an inactive state, such as rhodium forming rhodium oxide that is difficult to reduce, is suppressed. Surprisingly, within the loading ratio range of the present invention, no deactivation due to alloying of platinum, palladium, and rhodium was observed.
次に、貴金属が高い担持率で担持されたジルコニアを、
０．１〜２０μの比較的大きい平均粒子径をもつ凝集粒
子に調整された形で、他の多量の耐火性無機酸化物に分
散させることが本発明の特６一
徴である。この範囲の平均粒子径とすることによって、
排気ガス浄化反応の効率を阻害することな（、貴金属と
耐火性無機酸化物との相互作用や反応を緩和することが
出来る。Next, we made zirconia with a high loading rate of precious metals.
The sixth feature of the present invention is that it is dispersed in a large amount of other refractory inorganic oxide in a form that is adjusted to form agglomerated particles having a relatively large average particle diameter of 0.1 to 20 μm. By setting the average particle size in this range,
It can alleviate the interaction and reaction between noble metals and refractory inorganic oxides without impeding the efficiency of the exhaust gas purification reaction.
本発明に使用されるジルコニアは、少くとも１０ＴＩ１
．７ｇ、好ましくは６０〜１００ｍ／ｇの比表面積を有
し、かつ、２０００Å以下好ましくは５００Å以下の平
均−次粒子径を有するものが好適である。The zirconia used in the present invention is at least 10TI1
．． It is preferable to have a specific surface area of 7 g, preferably 60 to 100 m/g, and an average primary particle size of 2000 Å or less, preferably 500 Å or less.
上記物性を有するジルコニアであれば、市販のものを使
用しても良く、また、新たにジルコニウム塩の水溶液を
アンモニア等で中和し、水洗後乾燥焼成する方法等によ
っても調整されうるちのである。さらに、１０重量％以
下のイツトリウムまたはカルシウム等のアルカリ土類金
属によって安定化されたジルコニアも使用可能である。Commercially available zirconia having the above physical properties may be used, or it may be prepared by neutralizing a new aqueous solution of zirconium salt with ammonia, washing with water, drying and firing, etc. . Additionally, zirconia stabilized with up to 10% by weight of an alkaline earth metal such as yttrium or calcium can also be used.
こうしたジルコニアは、高い担持率で貴金属を担持した
際、良好な担持状態を与える。貴金属の担持は、貴金属
溶液をジルコニアと混合後乾燥し、焼成し、必要により
還元して行なわれるが、この操作においては複数の貴金
属溶液の混合溶液を用いてもよいし、または貴金属溶液
を一種類ずつジルコニアと混合し乾燥する操作を繰り返
しても良い。Such zirconia provides a good supporting state when noble metal is supported at a high loading rate. The noble metal is supported by mixing the noble metal solution with zirconia, drying it, firing it, and reducing it if necessary. In this operation, a mixed solution of multiple noble metal solutions may be used, or a mixture of multiple noble metal solutions may be used. The operation of mixing each type with zirconia and drying may be repeated.
この際、ジルコニアは凝集粒子として粒径が大きくなる
ので、これをミル等で粉砕して、平均粒子径を０．１〜
２０μとする。このようにして得られる粒子径を調整さ
れた貴金属含有ジルコニアを含むスラリーを一体構造を
有するハニカム担体にウォッシュコートし、乾燥し、必
要により焼成して完成触媒を得る。At this time, the particle size of zirconia becomes large as agglomerated particles, so this is ground with a mill etc. to reduce the average particle size to 0.1~
It is set to 20μ. The thus obtained slurry containing noble metal-containing zirconia whose particle size has been adjusted is wash-coated onto a honeycomb carrier having an integral structure, dried and, if necessary, calcined to obtain a finished catalyst.
一体構造を有するハニカム担体とは、コージエライ１〜
．ムライト、α−アルミナ等のセラミック担体およびス
テンレスまたはＦｅ −Ｃｒ −Ａ、ｉ合金等の酸化抵
抗性の耐熱金属を用いたメタルモノリス担体のことをい
う。A honeycomb carrier having an integral structure is a type of honeycomb carrier having a monolithic structure.
．． It refers to a metal monolith support using a ceramic support such as mullite or α-alumina and an oxidation-resistant heat-resistant metal such as stainless steel or Fe-Cr-A, i-alloy.
本発明に使用される貴金属源としては、塩化白金酸、ジ
ニトロジアンミン白金、塩化パラジウム。The noble metal sources used in the present invention include chloroplatinic acid, dinitrodiammine platinum, and palladium chloride.
硝酸パラジウム、塩化ロジウム、硝酸ロジウム。Palladium nitrate, rhodium chloride, rhodium nitrate.
硫酸ロジウム等が好ましい。Rhodium sulfate and the like are preferred.
本発明に使用される耐火性無機酸化物としては、アルミ
ナ、シリカ、チタニア、ジルコニア、マグネシアなどが
挙げられるが、アルミナ特に活性アルミナの使用が好ま
しい。アルミナの結晶形としては、γ、δ、θ、α、χ
、に、ηのいずれの形でも使用可能である。また、カル
シウム、バリウム等のアルカリ土類元素、さらに、クロ
ム、マンガン、鉄、コバルト、ニッケル、セリウム、ジ
ルコニウムなどの金属元素のうちの少くとも一種を酸化
物の形で、０．１〜３０重量％担持された活性アルミナ
も使用可能である。Examples of the refractory inorganic oxide used in the present invention include alumina, silica, titania, zirconia, magnesia, etc., and use of alumina, particularly activated alumina, is preferred. The crystal forms of alumina are γ, δ, θ, α, χ
, , and η can be used. In addition, at least one of alkaline earth elements such as calcium and barium, and metal elements such as chromium, manganese, iron, cobalt, nickel, cerium, and zirconium in the form of oxides of 0.1 to 30% by weight % loaded activated alumina can also be used.
以下、実施例にて本発明を更に詳細に説明するが、本発
明は、これら実施例のみに限定されるものではないこと
は言うまでもない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but it goes without saying that the present invention is not limited only to these Examples.
実施例１
市販コージェライト質モノリス担体（日本碍子株式会社
製）を用いて触媒を調整した。用いられたモノリス担体
は横断面が１インチ平方当り約４００個のガス流通セル
を有する外径３３醋φ。Example 1 A catalyst was prepared using a commercially available cordierite monolith carrier (manufactured by Nippon Insulators Co., Ltd.). The monolithic support used had an outer diameter of 33 mm with a cross section of approximately 400 gas flow cells per square inch.
長さ７６ ｍｍ ｌの円柱状のもので約６５ｄの体積を
有した。It had a cylindrical shape with a length of 76 mm l and a volume of about 65 d.
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 ）０．３ａを含
有する硝酸ロジウム水溶液の混合溶液と、比表面積６０
Ｔｄ／（］、平均粒径２００人を有するジルコニア（第
−稀元素化学製＞７．５ｇを混合し、１２０℃で一晩乾
燥した。その後、空気中４００℃で２時間焼成して１６
．１重量％ｐｔおよび３．２重量％Ｒｈ含有ジルコニア
粉体を調整した。A mixed solution of a nitric acid aqueous solution of dinitrodiammine platinum containing 1.5 g of platinum (Pt) and a rhodium nitrate aqueous solution containing 0.3a of rhodium (Rh), and a specific surface area of 60
Td/(], zirconia with an average particle size of 200 g (manufactured by Daiki Genso Kagaku Co., Ltd. > 7.5 g) was mixed and dried at 120°C overnight. Then, it was fired in air at 400°C for 2 hours to obtain 16
．． Zirconia powder containing 1% by weight PT and 3.2% by weight Rh was prepared.
上記ＰｔおよびＲｈ含有ジルコニア粉体を乳鉢で凝集粒
子の平均粒子径が約２０μとなるように粉砕した後、比
表面積１００ｍ／ｇの活性アルミナ１３９ｇと混合し、
ボールミルで２０時時間式粉砕することによってコーテ
ィング用水性スラリーを調整した。The above Pt and Rh-containing zirconia powder was ground in a mortar so that the average particle size of aggregated particles was about 20μ, and then mixed with 139g of activated alumina with a specific surface area of 100m/g,
An aqueous coating slurry was prepared by milling in a ball mill for 20 hours.
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圧縮空
気でブローして全ての目詰りを除去した。次いで１３０
℃で３時間乾燥して完成触媒を得た。The monolithic carrier was immersed in this aqueous slurry for coating, and after being taken out, the excess slurry in the cells was blown out with compressed air to remove all clogging. then 130
The finished catalyst was obtained by drying at ℃ for 3 hours.
この触媒のコーティング層をＥ １ｅｏｔｒｏｎＰｒｏ
ｂｅ Ｍｉｃｒｏ Ａｎａｌｙｓｉｓ （ＥＰＭ
Ａ）によって３０００倍の倍率のＰｔ、Ｒｈの分布写真
を無作為に３０ケ所撮影し分析したところ、Ｐｔおよび
Ｒｈ含有ジルコニアがそれぞれ平均粒子径７μで分散し
ていた。This catalyst coating layer is coated with E 1eotronPro.
be Micro Analysis (EPM
When Pt and Rh distribution photographs were taken at 30 random locations at 3000 times magnification using A) and analyzed, it was found that Pt and Rh-containing zirconia were each dispersed with an average particle size of 7 μm.
また、この触媒は、−個当りＰｔ ０．０６５（］ 。In addition, this catalyst has a Pt value of 0.065 (] per - piece.
Ｒｈ ０．０１３＋；ｌ含有していた。Contained Rh 0.013+;l.
実施例２
パラジウム（Ｐｄ ）１．５ａを含有する硝酸パラジウ
ム水溶液と、ロジウム０．３（！を含有する硝酸ロジウ
ム水溶液の混合溶液と、実施例１で用いたのと同じジル
コニア７．５ｇを混合し、１２０℃で一晩乾燥した。そ
の後、空気中４００℃で２時間焼成して、１６．１重量
％Ｐｄおよび３．２重量％Ｒｈ含有ジルコニア粉体を調
整した。Example 2 A mixed solution of a palladium nitrate aqueous solution containing 1.5a of palladium (Pd), a rhodium nitrate aqueous solution containing 0.3(!) of rhodium, and 7.5 g of the same zirconia used in Example 1 were mixed. The powder was dried overnight at 120° C. Thereafter, it was fired in air at 400° C. for 2 hours to prepare a zirconia powder containing 16.1% by weight of Pd and 3.2% by weight of Rh.
実施例１において、ｐｔおよびＲｈ含有ジルコニア粉体
の代わりに上記ＰｄおよびＲｈ含有ジルコニア粉体を用
いる以外は実施例１と同様な方法で完成触媒を得た。A finished catalyst was obtained in the same manner as in Example 1 except that the Pd and Rh containing zirconia powder was used instead of the pt and Rh containing zirconia powder.
この触媒のコーティング層をＥＰＭＡで分析したところ
ＰＣＩおよびＲｈ含有ジルコニアが平均粒子径３μで分
散していた。When the coating layer of this catalyst was analyzed by EPMA, it was found that PCI and Rh-containing zirconia were dispersed with an average particle size of 3 μm.
また、この触媒は一個当りＰｃｔ ０．０６５（１。Moreover, this catalyst has a Pct of 0.065 (1.
Ｒｈ ０．０１３（ｌ含有していた。Contained Rh 0.013 (l).
実施例３
Ｐｄ ０．９！ＩＩを含有する塩化白金酸水溶液と、Ｐ
ｄ ０．６ＣＩを含有する塩化パラジウム水溶液および
Ｒｈ ０．３！Ｉｔを含有する硝酸ロジウム水溶液の混
合溶液と、実施例１で用いたのと同じジルコニア７．５
ｇを混合し、１２０℃で一晩乾燥した。Example 3 Pd 0.9! A chloroplatinic acid aqueous solution containing P
d Palladium chloride aqueous solution containing 0.6 CI and Rh 0.3! A mixed solution of rhodium nitrate aqueous solution containing It and the same zirconia 7.5 as used in Example 1
g were mixed and dried at 120°C overnight.
その後、空気中４００℃で２時間焼成して、９．７重量
％Ｐｔ 、６．５重量％Ｐｄおよび３．２重量％Ｒｈ含
有ジルコニア粉体を調整した。Thereafter, it was fired in air at 400° C. for 2 hours to prepare a zirconia powder containing 9.7% by weight Pt, 6.5% by weight Pd, and 3.2% by weight Rh.
実施例１において、ｐｔおよびＲｈ含有ジルコニア粉体
の代わりに上記Ｐｔ、ＰｄおよびＲｈ含有ジルコニア粉
体を用いる以外は実施例１と同様な方法で完成触媒を得
た。A finished catalyst was obtained in the same manner as in Example 1, except that the Pt, Pd and Rh containing zirconia powder was used instead of the pt and Rh containing zirconia powder.
この触媒のコーティング層をＥＰＭＡで分析したところ
Ｐｔ、ＰｄおよびＲｈ含有ジルコニアは平均粒子径１３
μで分散していた。When the coating layer of this catalyst was analyzed by EPMA, the average particle size of zirconia containing Pt, Pd, and Rh was 13.
It was dispersed in μ.
この触媒は一個当りＰｔ ０．０３９（］ 、ＰｄＯ，
，０２６（１、Ｒｈ ０．０１３ｇ含有していた。This catalyst contains Pt 0.039(], PdO,
,026(1) Contained 0.013g of Rh.
実施例４
実施例１で用いたジルコニアの代わりに比表面積９０ｆ
ｆｌ／！ＩＩ 、平均粒径１５０人を有するジルコニア
（第−稀元素化学製）を用いる以外は実施例１と同様な
方法で完成触媒を得た。Example 4 Specific surface area 90f instead of zirconia used in Example 1
fl/! II. A finished catalyst was obtained in the same manner as in Example 1, except that zirconia (manufactured by Dai-Kigenso Kagaku) having an average particle size of 150 mm was used.
この触媒のコーティング層をＥＰＭＡで分析したところ
ｐｔおよびＲ１１含有ジルコニアは平均粒子径２μで分
散していた。When the coating layer of this catalyst was analyzed by EPMA, it was found that zirconia containing pt and R11 was dispersed with an average particle size of 2 μm.
こ（ＤＭ［は−１１Ｍ］当りＰｔ ０．０６５（＋ 、
Ｒｈ０．０１３（ｌ含有していた。This (DM [is -11M] per Pt 0.065 (+,
It contained Rh0.013 (l).
実施例５
厚さ６０μでアルミニウムを５重量％含有するフェライ
トステンレススチールの薄板と、この薄板をピッチ２．
５ｍｍの波形に成形した波板とを交互に重ねて積層し、
外径３３ｓφ、長さ７６ｍｍの円柱状の金属製モノリス
担体を成形した。この担１３一
体は横断面が１インチ平方当り約４７５個のガス流通セ
ルを有していた。Example 5 A thin plate of ferritic stainless steel having a thickness of 60 μm and containing 5% by weight of aluminum, and this thin plate having a pitch of 2.
Laminated by alternating layers of corrugated sheets formed into 5mm corrugated shapes,
A cylindrical metal monolith carrier having an outer diameter of 33 sφ and a length of 76 mm was molded. The carrier 13 had a cross section of approximately 475 gas flow cells per square inch.
実施例１においてコージェライト質モノリス担体の代わ
りに上記金属製モノリス担体を用いる以外は実施例１と
同様な方法で完成触媒を得た。A completed catalyst was obtained in the same manner as in Example 1 except that the above metal monolith support was used instead of the cordierite monolith support.
このコーティング層をＥＰＭＡで分析したところＰｔお
よびＲｈ含有ジルコニアは平均粒子径６μで分散してい
た。When this coating layer was analyzed by EPMA, it was found that Pt and Rh-containing zirconia were dispersed with an average particle size of 6 μm.
この触媒は一個当りＰｔ ０．０６５Ｇ 、Ｒｈ０．０
１３（ｌ含有していた。This catalyst has Pt 0.065G and Rh0.0 per piece.
It contained 13 (l).
実施例６
硝酸セリウム（Ｃｅ （Ｎｏ３）３ ・６Ｈ２０）２
５．２Ｑと、硝酸鉄（Ｆｅ （Ｎｏ：ｌ ）３ ・
９Ｈ２０）１０．１ｇを純水１００ｇに溶解し、比表面
積１００ＴＩｔ／ｇの活性アルミナ１２７ｇと混合して
１２０℃で一晩乾燥した。その後空気中７００℃で１時
間焼成してＣｅ ０２およびＦｅ２Ｏ：ｌ含有アルミナ
粉体を得た。Example 6 Cerium nitrate (Ce (No3)3 ・6H20)2
5.2Q and iron nitrate (Fe (No:l)3 ・
9H20) was dissolved in 100 g of pure water, mixed with 127 g of activated alumina having a specific surface area of 100 TIt/g, and dried at 120° C. overnight. Thereafter, it was calcined in air at 700° C. for 1 hour to obtain alumina powder containing Ce 02 and Fe 2 O:l.
実施例１において、１３９ｇの活性アルミナの代わりに
上記Ｃｅ ０２およびＦｅ ２０：ｌ含有アルミナを用
いる以外は実施例１と同様にして完成触媒を得た。A finished catalyst was obtained in the same manner as in Example 1, except that the above Ce 02 and Fe 20:1-containing alumina was used instead of 139 g of activated alumina.
この触媒のコーティング層をＥＰＭＡで分析したところ
ＰｔおよびＲｈ含有ジルコニアが平均粒子径５μで分散
していた。When the coating layer of this catalyst was analyzed by EPMA, it was found that Pt and Rh-containing zirconia were dispersed with an average particle size of 5 μm.
また、この触媒は一個当りＰｔ０．０６５（１。Moreover, this catalyst has Pt0.065 (1.
Ｒｈ ０．０１３！ＩＪ含有していた。Rh 0.013! It contained IJ.
比較例１
実施例１で用いた比表面積１００ｍ／ｑの活性アルミナ
１５０ｇをボールミルで２０時時間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整した。Comparative Example 1 An aqueous slurry for coating was prepared by milling 150 g of the activated alumina having a specific surface area of 100 m/q used in Example 1 for 20 hours in a ball mill.
このコーティング用水性スラリーと実施例１と同様な方
法でコージェライト質モノリス担体にアルミナとして６
．５ｇコーティングした。この活性アルミナコーティン
グ担体をジニトロジアンミン白金の硝酸水溶液と硝酸ロ
ジウム水溶液との混合溶液に浸漬し、引き出した後、圧
縮空気で余分な水溶液を除いた後、１３０℃で３時間乾
燥し、空気中４００℃で２時間焼成し完成触媒を得た。This coating aqueous slurry was applied to a cordierite monolithic support as alumina by the same method as in Example 1.
．． 5g coated. This activated alumina-coated carrier was immersed in a mixed solution of dinitrodiammine platinum in nitric acid and rhodium nitrate, pulled out, excess aqueous solution removed with compressed air, dried at 130°C for 3 hours, and heated to 400°C in air. A completed catalyst was obtained by calcining at ℃ for 2 hours.
この触媒のコーティング層をＥＰＭＡで分析したところ
Ｐｔ 、Ｒｈ共に０．５μ以上の粒子としては検出され
なかった。When this catalyst coating layer was analyzed by EPMA, neither Pt nor Rh particles were detected as particles larger than 0.5μ.
この触媒は一個当りＰｔ ０．０６５ｇ、Ｒｈ０．０１
３（＋含有していた。This catalyst has Pt 0.065g and Rh0.01 per piece.
3 (+).
比較例２
実施例１で用いた比表面積６０ＴＩｔ／（１，平均粒径
２００人のジルコニア１５０ｇをボールミルで２０時時
間式粉砕することによりコーティング用水性スラリーを
調整した。Comparative Example 2 An aqueous slurry for coating was prepared by milling 150 g of zirconia with a specific surface area of 60 TIt/(1 and an average particle size of 200) used in Example 1 for 20 hours in a ball mill.
このコーティング用水性スラリーと実施例１と同様な方
法でコージェライト質モノリス担体にジルコニアとして
６．５ｇコーティングした。このジルコニアコーティン
グ担体に比較例１と同様な方法でＰｔとＲｈを担持し完
成触媒を得た。A cordierite monolith carrier was coated with 6.5 g of zirconia using this aqueous coating slurry in the same manner as in Example 1. Pt and Rh were supported on this zirconia coated carrier in the same manner as in Comparative Example 1 to obtain a completed catalyst.
この触媒のコーティング層をＥＰＭＡで分析したところ
Ｐｔ、Ｒｈ共に０．５μ以上の粒子としては検出されな
かった。When this catalyst coating layer was analyzed by EPMA, neither Pt nor Rh particles were detected as particles larger than 0.5 μm.
この触媒は一個当りＰｔ ０．０６５ｇ、ＲｈＯ，０１
３ｑ含有していた。This catalyst contains 0.065g of Pt and 0.01g of RhO per piece.
It contained 3q.
［発明の効果］
実施例１から実施例６までの触媒と、比較例１゜比較例
２の触媒の電気炉エージング後における触媒性能を調べ
た。[Effects of the Invention] The catalyst performance of the catalysts of Examples 1 to 6 and the catalysts of Comparative Example 1 and Comparative Example 2 after aging in an electric furnace was investigated.
電気炉エージングは、空気中９００℃で１０時間触媒を
加熱するという、非常に厳しい高温酸化雰囲気で行なっ
た。The electric furnace aging was carried out in a very harsh high temperature oxidizing atmosphere by heating the catalyst in air at 900° C. for 10 hours.
エージング後の触媒性能の評価は、市販の電子制御方式
のエンジン（４気筒１８００ｃｃ）を使用し、各触媒を
充填したマルチコンバーターを、エンジンの排気系に連
設して行なった。空燃比をＡ／Ｆ＝１４．６に固定して
エンジンを運転し、エンジン排気系の触媒コンバーター
の前に熱交換器を取り付けて、触媒入口ガス温度を３０
０℃から５００℃まで連続的に変化させた時の触媒入口
及び出口ガス組成を分析してＣ○、ＨＣ及びＮｏの浄化
率を求めることにより触媒の低温での浄化性能を評価し
た。The catalyst performance after aging was evaluated using a commercially available electronically controlled engine (4 cylinders, 1800 cc), with a multi-converter filled with each catalyst connected to the exhaust system of the engine. The engine is operated with the air-fuel ratio fixed at A/F = 14.6, a heat exchanger is installed in front of the catalytic converter in the engine exhaust system, and the catalyst inlet gas temperature is set to 30.
The purification performance of the catalyst at low temperatures was evaluated by analyzing the catalyst inlet and outlet gas compositions when continuously changing from 0° C. to 500° C. and determining the purification rates of CO, HC, and No.
上記のようにして求めたＧｏ、ＨＣ及びＮｏの浄化率対
触媒入ロガス温度をグラフにプロットし、浄化率が５０
％を示す触媒入口ガス温度（Ｔｓｏ）を求めて、触媒の
低温での浄化性能を評価する基準とした。The purification rates of Go, HC, and No obtained as described above are plotted on a graph versus the temperature of the log gas containing the catalyst, and the purification rate is 50.
The catalyst inlet gas temperature (Tso) in % was determined and used as a standard for evaluating the purification performance of the catalyst at low temperatures.
以上の触媒性能評価方法により得られた結果を第１表に
示す。Table 1 shows the results obtained by the above catalyst performance evaluation method.
次に、実施例１から実施例６までの触媒と、比較例１．
比較例２の触媒のエンジン耐久走行後における触媒活性
を調べた。Next, the catalysts of Examples 1 to 6 and Comparative Example 1.
The catalytic activity of the catalyst of Comparative Example 2 was investigated after the engine was run for a long time.
市販の電子制御方式のエンジン（８気筒４７１００ＣＣ
）を使用し、各触媒を充填したマルチコンバーターをエ
ンジンの排気系に連設して耐久テストを行なった。エン
ジンは定常運転６０秒、減速６秒（減速時に燃料がカッ
トされて、触媒は高温酸化雰囲気の厳しい条件に曝され
る）というモード運転で運転し、触媒入口ガス温度が定
常運転時８００℃となる条件で５０時間触媒をエージン
グした。Commercially available electronically controlled engine (8 cylinders 47100CC)
), and a multi-converter filled with each catalyst was connected to the engine exhaust system for durability testing. The engine was operated in a mode of steady operation for 60 seconds and deceleration for 6 seconds (during deceleration, fuel is cut and the catalyst is exposed to severe conditions of a high temperature oxidizing atmosphere), and the catalyst inlet gas temperature was 800°C during steady operation. The catalyst was aged for 50 hours under the following conditions.
エンジン耐久走行後の触媒性能評価は、前記電気炉エー
ジング後の評価と全く同じ方法で行ない低温での浄化性
能を比較した。その結果を次に第２表に示す。Catalyst performance evaluation after engine endurance running was performed in exactly the same manner as the evaluation after electric furnace aging, and purification performance at low temperatures was compared. The results are shown in Table 2 below.
第２表 エンジン耐久走行後の触媒性能評価第１表およ
び第２表より明らかなように本発明に開示する白金、パ
ラジウムおよびロジウムを高い担持率で担持したジルコ
ニアを０．１〜２０μの範囲の平均粒子径を有する凝集
粒子としてコーティング層に分散させた実施例１から実
施例６の触媒はいずれも、貴金属を従来の担持状態とし
た比較例１および比較例２の触媒よりも非常にすぐれた
触媒性能を示した。Table 2 Evaluation of catalyst performance after engine endurance running As is clear from Tables 1 and 2, zirconia having a high loading rate of platinum, palladium and rhodium disclosed in the present invention was used in a range of 0.1 to 20μ. The catalysts of Examples 1 to 6, which were dispersed in the coating layer as agglomerated particles having an average particle size, were significantly superior to the catalysts of Comparative Examples 1 and 2, in which precious metals were conventionally supported. It showed catalytic performance.
以上の結果から、本発明に開示する触媒の通常のエンジ
ン走行条件はもちろん高温酸化雰囲気のような厳しい条
件下でも劣化の少ない優れた耐久性をもつ触媒であるこ
とが明らかである。From the above results, it is clear that the catalyst disclosed in the present invention has excellent durability with little deterioration even under severe conditions such as normal engine running conditions as well as high temperature oxidizing atmosphere.
特許出願人 日本触媒化学工業株式会社手続補正書 く
自発）
昭和６２年 Ｓ月夕日Patent applicant Nippon Shokubai Kagaku Kogyo Co., Ltd. Procedural Amendment (Spontaneous) Sunset in September 1988
Claims (5)
の範囲およびロジウムを１〜２０重量％の範囲担持せし
めてなるジルコニア（ａ）を０．１〜２０μの平均粒子
径の凝集粒子の形で含有せしめた触媒組成物を一体構造
を有するハニカム担体に被覆担持せしめてなることを特
徴とする排気ガス浄化用触媒。(1) 5 to 30% by weight of platinum and/or palladium
and a catalyst composition containing zirconia (a) carrying rhodium in the range of 1 to 20% by weight in the form of agglomerated particles with an average particle diameter of 0.1 to 20μ to a honeycomb carrier having an integral structure. An exhaust gas purifying catalyst characterized by being supported by a coating.
耐火性無機酸化物（ｂ）からなることを特徴とする特許
請求の範囲（１）記載の触媒。(2) The catalyst according to claim (1), wherein the catalyst composition comprises the zirconia (a) and the refractory inorganic oxide (b).
〜２０ｇ、当該耐火性無機酸化物（ｂ）を５０〜２００
ｇを担持せしめてなることを特徴とする特許請求の範囲
（２）記載の触媒。(3) Add 1 zirconia (a) per 1 liter of the carrier.
~20g, 50~200g of the refractory inorganic oxide (b)
The catalyst according to claim (2), characterized in that it supports g.
の比表面積を有し、かつその一次粒子の平均粒径が２０
００Å以下であることを特徴とする特許請求の範囲（１
）、（２）または（３）記載の触媒。(4) Zirconia used is at least 10 m^2/g
has a specific surface area of , and the average particle size of its primary particles is 20
00 Å or less (1
), (2) or (3).
ミナであることを特徴とする特許請求の範囲（２）、（
３）または（４）記載の触媒。(5) Claims (2) and (2) characterized in that the refractory inorganic oxide (b) used is activated alumina.
3) or the catalyst described in (4).
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62009110A JPS63178848A (en) | 1987-01-20 | 1987-01-20 | Catalyst for purifying exhaust gas |
| US07/134,363 US4904633A (en) | 1986-12-18 | 1987-12-17 | Catalyst for purifying exhaust gas and method for production thereof |
| DE3751403T DE3751403T2 (en) | 1986-12-18 | 1987-12-18 | Exhaust gas purification catalyst and process for its manufacture. |
| KR1019870014488A KR930000917B1 (en) | 1986-12-18 | 1987-12-18 | Catalyst for purifying exhaust gas and method for its production |
| EP87311178A EP0272136B1 (en) | 1986-12-18 | 1987-12-18 | Catalyst for purifying exhaust gas and method for its production |
| EP19930201246 EP0558159A3 (en) | 1986-12-18 | 1987-12-18 | Catalyst for purifying exhaust gas and method for production thereof |
| AU10648/88A AU604083B2 (en) | 1987-01-20 | 1988-01-19 | Catalyst for purifying exhaust gas and method for production thereof |
| CN91102032A CN1055302A (en) | 1987-01-20 | 1988-01-20 | The catalyst of purifying exhaust air and production method thereof |
| CN88100589A CN1013245B (en) | 1987-01-20 | 1988-01-20 | Catalyst for purifying exhaust gas and method for prodn. thereof |
| KR1019920016764A KR930000918B1 (en) | 1986-12-18 | 1992-09-15 | Catalyst for purifying exhaust gas and method for its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62009110A JPS63178848A (en) | 1987-01-20 | 1987-01-20 | Catalyst for purifying exhaust gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63178848A true JPS63178848A (en) | 1988-07-22 |
| JPH0578379B2 JPH0578379B2 (en) | 1993-10-28 |
Family
ID=11711488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62009110A Granted JPS63178848A (en) | 1986-12-18 | 1987-01-20 | Catalyst for purifying exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63178848A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185451A (en) * | 1986-09-05 | 1988-08-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for purifying exhaust gas |
| JPH01236942A (en) * | 1988-03-14 | 1989-09-21 | Mazda Motor Corp | Catalyst for purifying exhaust gas |
| WO1994025143A1 (en) * | 1993-04-28 | 1994-11-10 | Nippon Shokubai Co., Ltd. | Method of removing nitrogen oxides contained in exhaust gas |
| JP2006026635A (en) * | 1993-04-28 | 2006-02-02 | Nippon Shokubai Co Ltd | Method of removing nitrogen oxides contained in exhaust gas |
| JP2007005031A (en) * | 2005-06-21 | 2007-01-11 | Mitsubishi Heavy Ind Ltd | Catalyst for fuel gas combustion, fuel cell system, and combustion method of fuel gas |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185451A (en) * | 1986-09-05 | 1988-08-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for purifying exhaust gas |
-
1987
- 1987-01-20 JP JP62009110A patent/JPS63178848A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185451A (en) * | 1986-09-05 | 1988-08-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for purifying exhaust gas |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185451A (en) * | 1986-09-05 | 1988-08-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for purifying exhaust gas |
| JPH0578381B2 (en) * | 1986-09-05 | 1993-10-28 | Nippon Catalytic Chem Ind | |
| JPH01236942A (en) * | 1988-03-14 | 1989-09-21 | Mazda Motor Corp | Catalyst for purifying exhaust gas |
| WO1994025143A1 (en) * | 1993-04-28 | 1994-11-10 | Nippon Shokubai Co., Ltd. | Method of removing nitrogen oxides contained in exhaust gas |
| US5756057A (en) * | 1993-04-28 | 1998-05-26 | Nippon Shokubai Co., Ltd. | Method for removal of nitrogen oxides from exhaust gas |
| JP2006026635A (en) * | 1993-04-28 | 2006-02-02 | Nippon Shokubai Co Ltd | Method of removing nitrogen oxides contained in exhaust gas |
| JP2010184238A (en) * | 1993-04-28 | 2010-08-26 | Nippon Shokubai Co Ltd | Method of removing nitrogen oxides in exhaust gas |
| JP2012236193A (en) * | 1993-04-28 | 2012-12-06 | Nippon Shokubai Co Ltd | Method of removing nitrogen oxides in exhaust gas |
| JP2007005031A (en) * | 2005-06-21 | 2007-01-11 | Mitsubishi Heavy Ind Ltd | Catalyst for fuel gas combustion, fuel cell system, and combustion method of fuel gas |
| JP4699101B2 (en) * | 2005-06-21 | 2011-06-08 | 三菱重工業株式会社 | Fuel gas combustion catalyst, fuel cell system, and fuel gas combustion method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0578379B2 (en) | 1993-10-28 |
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